JP5412721B2 - Liquid crystal composition and liquid crystal display element - Google Patents

Description

  The present invention relates to a liquid crystal composition suitable mainly for an AM (active matrix) device and the like, and an AM device containing the composition. This composition has a nematic phase and a positive dielectric anisotropy.

  In the liquid crystal display element, the classification based on the operation mode of the liquid crystal includes PC (phase change), TN (twisted nematic), STN (super twisted nematic), ECB (electrically controlled birefringence), OCB (optically compensated bend), IPS ( in-plane switching) and VA (vertical alignment). The classification based on the element driving method is PM (passive matrix) and AM (active matrix). PM is classified into static and multiplex, and AM is classified into thin film transistor (TFT), metal insulator metal (MIM), and the like. TFTs are classified into amorphous silicon and polycrystalline silicon. The latter is classified into a high temperature type and a low temperature type according to the manufacturing process. The classification based on the light source includes a reflection type using natural light, a transmission type using backlight, and a semi-transmission type using both natural light and backlight.

  These devices contain a liquid crystal composition having appropriate characteristics. This liquid crystal composition has a nematic phase. In order to obtain an AM device having good general characteristics, the general characteristics of the composition are improved. The relationships in the two general characteristics are summarized in Table 1 below. The general characteristics of the composition will be further described based on a commercially available AM device. The temperature range of the nematic phase is related to the temperature range in which the device can be used. The preferable upper limit temperature of the nematic phase is 70 ° C. or higher, and the preferable lower limit temperature of the nematic phase is −10 ° C. or lower. The viscosity of the composition is related to the response time of the device. A short response time is preferred for displaying moving images on the device. Therefore, a small viscosity in the composition is preferred. Small viscosities at low temperatures are more preferred.

  The optical anisotropy of the composition is related to the contrast ratio of the device. The product (Δn · d) of the optical anisotropy (Δn) of the composition and the cell gap (d) of the device is designed to maximize the contrast ratio. The appropriate product value depends on the type of operation mode. For a device with a mode such as TN, a suitable value is about 0.45 μm. In this case, a composition having a large optical anisotropy is preferable for a device having a small cell gap. 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 preferable. 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 large specific resistance not only at room temperature but also at a high temperature in the initial stage is preferable. A composition having a large specific resistance not only at room temperature but also at a high temperature after being used for a long time is preferable. The stability of the composition against ultraviolet rays and heat relates to the lifetime of the liquid crystal display element. When their stability is high, the lifetime of the device is long. Such characteristics are preferable for an AM device used in a liquid crystal projector, a liquid crystal television, and the like.

Conventional compositions are disclosed in Patent Documents 1 to 6 below.
Japanese Patent Laid-Open No. 10-245559 Japanese Patent Laid-Open No. 11-349945 JP 2002-180050 A JP 2003-183656 A Special Table 2003-507526 Japanese Patent Laid-Open No. 10-095978

  Desirable AM elements have characteristics such as a wide usable temperature range, a short response time, a large contrast ratio, a low threshold voltage, a large voltage holding ratio, and a long lifetime. A shorter response time is desirable even at 1 millisecond. Therefore, desirable properties of the composition include a high maximum temperature of the nematic phase, a low minimum temperature of the nematic phase, a small viscosity, a large optical anisotropy, a large dielectric anisotropy, a large specific resistance, a high stability to ultraviolet light, a heat High stability against.

  The object of the present invention is to provide a high maximum temperature of the nematic phase, a low minimum temperature of the nematic phase, a large optical anisotropy, a large dielectric anisotropy, a large specific resistance, a high stability to ultraviolet light, a high stability to heat, etc. The characteristic is to provide a liquid crystal composition satisfying a plurality of characteristics. The object is to provide a liquid crystal composition having an appropriate balance regarding a plurality of characteristics. This object is also to provide a liquid crystal display device containing such a composition. Aspects of the present invention are compositions having a small viscosity, an optical anisotropy in the range of 0.13 to 0.25, a high stability to ultraviolet light, and the like, and a short response time, a large voltage holding ratio, a large contrast ratio. It is to provide an AM device having a long life.

ここで、Ｒ¹は炭素数１から１２のアルキルであり、Ｚ¹およびＺ²は独立して単結合またはエチレンであり、Ｘ¹は独立してフッ素、塩素、ＯＣＦ_３またはＯＣＦ_２Ｈであり、Ｙ¹は独立して水素またはフッ素であり、ｎは独立して１または２である。 The present invention provides at least one compound selected from the group of compounds represented by formulas (1-1) and (1-2) as the first component, and formulas (2-1) and ( A liquid crystal composition containing at least one compound selected from the group of compounds represented by 2-2) and having a nematic phase, and a liquid crystal display device containing this composition.

Here, R ¹ is alkyl having 1 to 12 carbons, Z ¹ and Z ² are independently a single bond or ethylene, and X ¹ is independently fluorine, chlorine, OCF ₃ or OCF ₂ H. Y ¹ is independently hydrogen or fluorine, and n is independently 1 or 2.

  The composition of the present invention has a high maximum temperature of the nematic phase, a low minimum temperature of the nematic phase, a small viscosity, a large optical anisotropy, a large dielectric anisotropy, a large specific resistance, a high stability to ultraviolet light, and a high heat resistance. A plurality of characteristics are satisfied in characteristics such as stability. This composition has an appropriate balance for multiple properties. The device of the present invention contains this composition. Many of these compositions have low viscosity, optical anisotropy in the range of 0.13 to 0.25, high stability to ultraviolet light, etc., short response time, large voltage holding ratio, large contrast ratio, long lifetime. Suitable for an AM device having

  Terms used in this specification are as follows. The liquid crystal composition of the present invention or the liquid crystal display device of the present invention may be abbreviated as “composition” or “device”, respectively. A liquid crystal display element is a general term for a liquid crystal display panel and a liquid crystal display module. “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 useful as a component of a composition. This useful compound contains a 6-membered ring such as 1,4-cyclohexylene and 1,4-phenylene, and has a rod-like molecular structure. An optically active compound may be added to the composition. Even if this compound is a liquid crystal compound, it is classified here as an additive. At least one compound selected from the group of compounds represented by formula (1-1) may be abbreviated as “compound (1-1)”. A group of compounds represented by formula (1-1) may also be abbreviated as “compound (1-1)”. The same applies to compounds represented by other formulas.

  The upper limit temperature of the nematic phase may be abbreviated as “upper limit temperature”. The lower limit temperature of the nematic phase may be abbreviated as “lower limit temperature”. “High specific resistance” means that the composition has a large specific resistance not only at room temperature but also at a high temperature in the initial stage, and has a large specific resistance not only at room temperature but also at a high temperature after long-term use. . “High voltage holding ratio” means that the device has a large voltage holding ratio not only at room temperature but also at a high temperature in the initial stage, and has a large voltage holding ratio not only at room temperature but also at a high temperature after long use. means. When describing characteristics such as optical anisotropy, values measured by the methods described in the examples are used. The “ratio of the first component” means a percentage by weight (% by weight) based on the total weight of the liquid crystal composition. The same applies to the ratio of the second component. The ratio of the additive mixed with the composition means a weight percentage (% by weight) based on the total weight of the liquid crystal composition.

ここで、Ｒ¹は炭素数１から１２のアルキルであり、Ｚ¹およびＺ²は独立して単結合またはエチレンであり、Ｘ¹は独立してフッ素、塩素、ＯＣＦ_３またはＯＣＦ_２Ｈであり、Ｙ¹は独立して水素またはフッ素であり、ｎは独立して１または２である。 Details of the present invention include the following items.
1. At least one compound selected from the group of compounds represented by formula (1-1) and formula (1-2) as the first component, and formula (2-1) and formula (2-2) as the second component A liquid crystal composition containing at least one compound selected from the group of compounds represented by formula (1) and having a nematic phase.

Here, R ¹ is alkyl having 1 to 12 carbons, Z ¹ and Z ² are independently a single bond or ethylene, and X ¹ is independently fluorine, chlorine, OCF ₃ or OCF ₂ H. Y ¹ is independently hydrogen or fluorine, and n is independently 1 or 2.

2. Item 2. The proportion of the first component is in the range of 5 to 50% by weight and the proportion of the second component is in the range of 30 to 95% by weight based on the total weight of the liquid crystal composition. Liquid crystal composition.

ここで、Ｒ²およびＲ³は独立して炭素数１から１２のアルキルであり、Ｙ²、Ｙ³、Ｙ⁴、およびＹ⁵は独立して水素またはフッ素である。 3. Item 2. The liquid crystal composition according to item 1, further comprising at least one compound selected from the group of compounds represented by formula (3-1) and formula (3-2) as a third component.

Here, R ² and R ³ are independently alkyl having 1 to 12 carbons, and Y ² , Y ³ , Y ⁴ , and Y ⁵ are independently hydrogen or fluorine.

4). Based on the total weight of the liquid crystal composition, the proportion of the first component is in the range of 5 wt% to 50 wt%, the proportion of the second component is in the range of 30 wt% to 95 wt%, and the third component Item 4. The liquid crystal composition according to item 3, wherein the ratio of is in the range of 5 wt% to 40 wt%.

5. Item 2. The liquid crystal composition according to item 1, wherein n in Formula (1-1) and Formula (1-2) is 2.

6). Item 6. The proportion of the first component is in the range of 5 to 50% by weight and the proportion of the second component is in the range of 30 to 95% by weight based on the total weight of the liquid crystal composition. Liquid crystal composition.

ここで、Ｒ²およびＲ³は独立して炭素数１から１２のアルキルであり、Ｙ²、Ｙ³、Ｙ⁴、およびＹ⁵は独立して水素またはフッ素である。 7). Item 6. The liquid crystal composition according to item 5, further containing at least one compound selected from the group of compounds represented by formulas (3-1) and (3-2) as a third component.

Here, R ² and R ³ are independently alkyl having 1 to 12 carbons, and Y ² , Y ³ , Y ⁴ , and Y ⁵ are independently hydrogen or fluorine.

ここで、Ｒ¹、Ｒ²およびＲ³は独立しては炭素数１から１２のアルキルであり、Ｚ¹およびＺ²は独立して単結合またはエチレンであり、Ｘ¹は独立してフッ素、塩素、ＯＣＦ_３またはＯＣＦ_２Ｈであり、Ｙ¹、Ｙ²、Ｙ³、Ｙ⁴およびＹ⁵は独立して水素またはフッ素であり、ｎは独立して１または２である。 8). At least one compound selected from the group of compounds represented by formula (1-1) and formula (1-2) as the first component, and formula (2-1) and formula (2-2) as the second component And at least one compound selected from the group of compounds represented by formula (3-1) and formula (3-2) as the third component A liquid crystal composition substantially comprising only a first component, a second component, and a third component, and having a nematic phase.

Here, R ¹ , R ² and R ³ are independently alkyl having 1 to 12 carbons, Z ¹ and Z ² are independently a single bond or ethylene, X ¹ is independently fluorine, Chlorine, OCF ₃ or OCF ₂ H, Y ¹ , Y ² , Y ³ , Y ⁴ and Y ⁵ are independently hydrogen or fluorine, and n is independently 1 or 2.

ここで、Ｒ⁴は炭素数１から１２のアルキルであり、Ｘ²はフッ素またはＯＣＦ_３であり、そしてＹ⁶は水素またはフッ素である。 9. Item 8. The liquid crystal composition according to item 3 or 7, further comprising at least one compound selected from the group of compounds represented by formula (4) as a fourth component.

Here, R ⁴ is alkyl having 1 to 12 carbons, X ² is fluorine or OCF ₃ , and Y ⁶ is hydrogen or fluorine.

10. Item 10. The liquid crystal composition according to item 9, wherein the ratio of the fourth component is in the range of 1% by weight to 30% by weight based on the total weight of the liquid crystal composition.

11. Item 8. The liquid crystal composition according to any one of items 1 to 7, further comprising an ultraviolet absorber.

12 Item 9. A liquid crystal display device comprising the liquid crystal composition according to any one of items 1 to 8.

  The present invention also includes the following items. 1) The above-described composition further containing an optically active compound, 2) the above-mentioned composition further containing additives such as an antioxidant, an ultraviolet absorber, and an antifoaming agent. 3) an AM device containing the above composition, 4) a device containing the above composition and having a mode of TN, ECB, OCB, or IPS, 5) a transmissive device containing the above composition 6) Use of the above composition as a composition having a nematic phase, 7) Use of the above composition as an optically active composition by adding an optically active compound to the above composition.

  The composition of the present invention will be described in the following order. First, the constitution of component compounds in the composition will be described. Second, the main characteristics of the component compounds and the main effects of the compounds on the composition will be explained. Third, the preferred ratio of the component compounds and the basis thereof will be described. Fourth, a preferred form of the component compound will be described. Fifth, specific examples of component compounds are shown. Sixth, a method for synthesizing the component compounds will be described. Seventh, additives that may be mixed into the composition will be described. Finally, the use of the composition will be described.

  First, the constitution of component compounds in the composition will be described. The composition of the present invention is classified into Composition A and Composition B. The composition A may further contain other liquid crystal compounds, additives, impurities and the like. “Other liquid crystal compounds” include compound (1-1), compound (1-2), compound (2-1), compound (2-2), compound (3-1), and compound (3-2). And a liquid crystal compound different from the compound (4). Such compounds are mixed into the composition for the purpose of further adjusting the properties. Additives include optically active compounds, dyes, antioxidants, ultraviolet absorbers and the like. Impurities are compounds mixed in processes such as synthesis of component compounds

  Composition B is substantially compound (1-1), compound (1-2), compound (2-1), compound (2-2), compound (3-1), compound (3-2), And a compound selected from the compound (4) only. “Substantially” means that the composition does not contain a liquid crystal compound different from these compounds. “Substantially” also means that the composition may further contain additives, impurities and the like. Composition B has fewer components than composition A. Composition B is preferred over Composition A because it reduces costs. Since the physical properties can be further adjusted by mixing other liquid crystal compounds, the composition A is preferable to the composition B.

  Second, the main characteristics of the component compounds and the main effects of the compounds on the characteristics of the composition will be explained. The main properties of the component compounds are summarized in Table 2 according to the purpose of the present invention. In the symbols in Table 2, L means large or high, M means moderate, and S means small or low. The symbols L, M, and S are classifications based on a qualitative comparison among the component compounds.

  When component compounds are mixed into the composition, the main effects of the component compounds on the properties of the composition are as follows. Compound (1-1) and compound (1-2) increase the optical anisotropy and increase the dielectric anisotropy. Compound (2-1) and compound (2-2) increase the dielectric anisotropy. Compound (2-2) increases the maximum temperature. Compound (3-1) and compound (3-2) increase the optical anisotropy and decrease the viscosity. Compound (3-2) increases the maximum temperature. Compound (4) particularly increases the dielectric anisotropy of the composition.

  Third, the preferred ratio of the component compounds and the basis thereof will be described. A desirable ratio of the first component is approximately 5% by weight or more for increasing the optical anisotropy and increasing the dielectric anisotropy, and is approximately 50% by weight or less for decreasing the minimum temperature. A more desirable ratio is in the range of 5% to 40% by weight. A particularly desirable ratio is in the range of 10% to 35% by weight.

  A desirable ratio of the second component is approximately 30% by weight or more for increasing the dielectric anisotropy, and is approximately 95% by weight or less for decreasing the minimum temperature. A more desirable ratio is in the range of 30% to 70% by weight. A particularly desirable ratio is in the range of 40% to 65% by weight.

  A desirable ratio of the third component is 5% by weight or more for increasing the optical anisotropy, increasing the maximum temperature, and decreasing the viscosity, and 40% by weight for decreasing the minimum temperature and increasing the dielectric anisotropy. % Or less. A more desirable ratio is in the range of 5% to 35% by weight. A particularly desirable ratio is in the range of 10% by weight to 35% by weight.

  The fourth component is particularly suitable for preparing a composition having a large dielectric anisotropy. This component has a large effect of increasing the dielectric anisotropy, but a smaller amount is preferable in order to maintain stability against ultraviolet rays. Therefore, the fourth component is used when it is particularly desired to increase the dielectric anisotropy. The appropriate proportion of the fourth component depends on the use of the composition and is determined by the balance between large dielectric anisotropy and stability to ultraviolet light. A desirable ratio of this component is 30% by weight or less. A more desirable ratio is 15% by weight or less. A particularly desirable ratio is 10% by weight or less.

  In the composition A, a preferable ratio of the total of the first component, the second component, the third component, and the fourth component is 70% by weight or more in order to obtain good characteristics. A more desirable ratio is 90% by weight or more. The total of the four components in composition B is 100% by weight.

Fourth, a preferred form of the component compound will be described. R ¹ is alkyl having 1 to 12 carbons. Preferred R ¹ is straight-chain alkyl having 1 to 10 carbons. R ² , R ³ and R ⁴ are independently alkyl having 1 to 12 carbons. Preferred R ² , R ³ and R ⁴ are linear alkyl having 1 to 10 carbon atoms.

  Preferred alkyl is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl. More preferable alkyl is ethyl, propyl, butyl, pentyl, or heptyl from the viewpoint of small viscosity.

  Preferred alkenyl is vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl. Further preferred alkenyl is vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl from the viewpoint of small viscosity. The preferred configuration of —CH═CH— in these alkenyls depends on the position of the double bond. Trans is preferable in alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl and 3-hexenyl for decreasing the viscosity. Cis is preferable in alkenyl such as 2-butenyl, 2-pentenyl and 2-hexenyl. In these alkenyl, linear alkenyl is preferable to branching.

Z ¹ and Z ² are each independently a single bond or ethylene (—CH ₂ CH ₂ —). Preferred Z ¹ is a single bond from the viewpoint of small viscosity.

X ¹ is fluorine, chlorine, OCF ₃ or OCF ₂ H. Desirable X ¹ is fluorine from the viewpoint of large dielectric anisotropy and high stability to ultraviolet rays. X ² is fluorine or OCF ₃ . Desirable X ² is fluorine from the viewpoint of large dielectric anisotropy and high stability to ultraviolet rays.

Y ¹ , Y ² , Y ³ , Y ⁴ , and Y ⁵ are hydrogen or fluorine.

Fifth, specific examples of component compounds are shown. In the following preferred compounds, R ¹ is straight-chain alkyl having 1 to 10 carbon atoms. Preferred R ² , R ³ and R ⁴ are independently straight-chain alkyl having 1 to 10 carbon atoms. In these compounds, trans is preferable to cis for the configuration of 1,4-cyclohexylene from the viewpoint of a high maximum temperature. In the chemical formulas of component compounds, the symbol R ¹ is used for a plurality of compounds. In these compounds, the meanings of R ¹ may be the same or different. For example, there is a case where R ^{1 of} the compound (1-1) is ethyl and R ¹ of the compound (1-2) is ethyl. In some cases, R ^{1 of} compound (1-1) is ethyl and R ¹ of compound (1-2) is propyl. This rule also applies to R ² , R ^3, etc.

  Desirable compounds (1-1) are the compounds (1-1-9) to (1-1-16) from the viewpoints of a high maximum temperature and a low viscosity. Desirable compounds (1-2) are from the compound (1-2-9) to the compound (1-2-16) from the viewpoint of a high maximum temperature and a high dielectric anisotropy. Desirable compounds (2-1) are the compounds (2-1-1) to (2-1-4). A more desirable compound (2-1) is the compound (2-1-1) from the viewpoints of a high maximum temperature and a low minimum temperature. Desirable compounds (2-2) are from the compound (2-2-1) to the compound (2-2-4). More desirable compound (2-2) is a formula (2-2-1) from a viewpoint of a high maximum temperature and a low minimum temperature.

  Desirable compounds (3-1) are the compounds (3-1-1) to (3-1-3). More desirable compounds (3-1) are the compound (3-1-1) and the compound (3-1-3) from the viewpoint of a high maximum temperature and a low minimum temperature. Desirable compounds (3-2) are the compound (3-2-1) and the compound (3-2-2). More desirable compound (3-2) is compound (3-2-2) from the viewpoints of a high maximum temperature and a low minimum temperature. . Desirable compounds (4) are the compound (4-1) and the compound (4-4). More desirable compound (4) is compound (4-1) from the viewpoint of large dielectric anisotropy.

  Sixth, a method for synthesizing the component compounds will be described. These compounds can be synthesized by known methods. The synthesis method is illustrated. Compound (1-1) is synthesized by the method described in JP-T-8-530888. Compound (2-1-1) and compound (2-1-2) are synthesized by the method described in JP-A-2-233626. Compound (2-2-1) and compound (2-2-2) are synthesized by the method described in JP-A-2-233626. Compound (3-1-1) is synthesized by the method described in JP-A-60-51135. Compound (3-1-3) is synthesized by the method described in JP-A-4-257535. Compound (3-2-2) is synthesized by the method described in JP-A-2-237949. Compound (4-1) to Compound (4-4) are synthesized by the method described in JP-A-10-251186.

  Compounds that have not been described as synthetic methods include Organic Syntheses (John Wiley & Sons, Inc), Organic Reactions (John Wiley & Sons, Inc), Comprehensive Organic Synthesis (Comprehensive Organic Synthesis) Synthesis, Pergamon Press) and new experimental chemistry course (Maruzen). A compound in which n in Formula (6) is 1 is commercially available. This compound is sold, for example, by the company Aldrich. Compound (6) where n is 7, and the like are synthesized by the method described in US Pat. No. 3,660,505. The composition is prepared from the compound thus obtained by known methods. For example, the component compounds are mixed and dissolved in each other by heating.

  Seventh, additives that may be mixed into the composition will be described. Such additives are optically active compounds, dyes, antioxidants, ultraviolet absorbers and the like. An optically active compound is mixed with the composition for the purpose of inducing a helical structure of liquid crystal to give a twist angle. Examples of such a compound are the compound (5-1) to the compound (5-4). A desirable ratio of the optically active compound is 5% or less. A more desirable ratio is in the range of 0.01% to 2% by weight.

  A dichroic dye such as an azo dye or an anthraquinone dye is mixed with the composition in order to adapt to a GH (Guest host) mode element. A preferred ratio of the dye is in the range of 0.01% by weight to 10% by weight. In order to prevent a decrease in specific resistance due to heating in the atmosphere or to maintain a large voltage holding ratio not only at room temperature but also at a high temperature after using the device for a long time, an antioxidant is added to the composition. Mixed. A desirable ratio of the antioxidant is 50 ppm or more for achieving its effect, and is 600 ppm or less for avoiding a decrease in the maximum temperature or avoiding an increase in the minimum temperature. A more desirable ratio is in the range of 100 ppm to 300 ppm.

  A preferred example of the antioxidant is a compound (6) wherein n is an integer of 1 to 9. In the compound (6), preferred n is 1, 3, 5, 7, or 9. Further preferred n is 1 or 7. Since the compound (6) in which n is 1 has high volatility, it is effective in preventing a decrease in specific resistance due to heating in the atmosphere. Since the compound (6) in which n is 7 has low volatility, it is effective for maintaining a large voltage holding ratio not only at room temperature but also at a high temperature after the device has been used for a long time.

  Preferred examples of the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. A desirable ratio of the ultraviolet absorber is 50 ppm or more for obtaining the effect thereof, and is 10,000 ppm or less for avoiding a decrease in the maximum temperature or avoiding an increase in the minimum temperature. A more desirable ratio is in the range of 100 ppm to 1000 ppm.

  Finally, the use of the composition will be described. Most compositions have a minimum temperature of −10 ° C. or lower, a maximum temperature of 70 ° C. or higher, and an optical anisotropy in the range of 0.13 to 0.25. A device containing this composition has a large voltage holding ratio. This composition is suitable for an AM device. This composition is particularly suitable for a transmissive AM device. A composition having an optical anisotropy in the range of 0.15 to 0.25, or 0.12 to 0.30 by controlling the ratio of the component compounds or by mixing other liquid crystal compounds. You may prepare the composition which has the optical anisotropy of the range of these. This composition can be used as a composition having a nematic phase, or can be used as an optically active composition by adding an optically active compound.

  This composition can be used for an AM device. Further, it can be used for PM elements. This composition can also be used for devices having modes such as PC, TN, STN, ECB, OCB, IPS, and VA. Use for a device having a TN or OCB mode is particularly preferable. These elements may be reflective, transmissive, or transflective. Use in a transmissive element is preferred. It can also be used for an amorphous silicon-TFT device or a polycrystalline silicon-TFT device. NCAP (nematic curvilinear aligned phase) elements produced by microencapsulating this composition, and PD (polymer dispersed) elements in which a three-dimensional network polymer is formed in the composition, for example, PN (polymer network) elements Can also be used.

The present invention will be described in detail by examples. The present invention is not limited by the following examples. The compounds in Comparative Examples and Examples were represented by symbols based on the definitions in Table 3 below.
In Table 3, the configuration regarding 1,4-cyclohexylene and 1,3-dioxane-2,5-diyl is trans. The configuration regarding the bonding group of —CH═CH— is trans. In the examples, the number in parentheses after the symbol corresponds to the number of the preferred compound. The symbol (−) means other liquid crystal compounds. The ratio (percentage) of the liquid crystal compound is a weight percentage (% by weight) based on the total weight of the liquid crystal compound. Finally, the characteristic values of the composition are summarized.

  The composition is prepared by measuring the weight of components such as a liquid crystal compound and then mixing them. Therefore, it is easy to calculate the weight percentage of the component. However, it is not easy to accurately calculate the ratio of components by gas chromatographic analysis of the composition. This is because the correction coefficient depends on the type of liquid crystal compound. Fortunately, the correction factor is approximately 1. Furthermore, the influence of the 1% by weight difference in the component compounds on the properties of the composition is small. Therefore, in the present invention, the area ratio of the component peak in the gas chromatograph can be regarded as the weight percent of the component compound. In other words, the result of gas chromatographic analysis (peak area ratio) can be considered to be equivalent to the weight percent of the liquid crystal compound without correction.

  When the sample was a composition, it was measured as it was and the obtained value was described. When the sample was a compound, the sample was prepared by mixing 15% by weight compound and 85% by weight mother liquid crystals. 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) is precipitated at 25 ° C. at this ratio, the ratio of the compound and the mother liquid crystal is 10% by weight: 90% by weight, 5% by weight: 95% by weight, 1% by weight: 99% by weight in this order. changed. By this extrapolation method, the maximum temperature, optical anisotropy, viscosity, and dielectric anisotropy values for the compound were determined.

The composition (% by weight) of the mother liquid crystals is as follows.

  The characteristic values were measured according to the following method. Many of them are the method described in the Standard of Electric Industries Association of Japan EIAJ ED-2521A or a modified method thereof. No TFT was attached to the TN device used for measurement.

  Maximum 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 a part of the sample changed from a nematic phase to an isotropic liquid. The upper limit temperature of the nematic phase may be abbreviated as “upper limit temperature”.

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

  Viscosity (η; measured at 20 ° C .; mPa · s): An E-type viscometer was used for measurement.

  Rotational viscosity (γ1; measured at 25 ° C .; mPa · s): Measurement was according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). A sample was put in a device in which the twist angle was 0 ° and the distance between two glass substrates (cell gap) was 5 μm. The voltage was applied to the TN device in steps of 0.5V in the range of 16V to 19.5V. After no application for 0.2 seconds, the application was repeated under the condition 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. The value of rotational viscosity was obtained from these measured values and the paper by M. Imai et al., Formula (8) on page 40. The value of dielectric anisotropy necessary for this calculation was determined by the method described below using the element whose rotational viscosity was measured.

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

  Dielectric anisotropy (Δε; measured at 25 ° C.): A sample was put in a TN device in which the distance between two glass substrates (cell gap) was 9 μm and the twist angle was 80 degrees. Sine waves (10 V, 1 kHz) were applied to the device, and after 2 seconds, the dielectric constant (ε‖) in the major axis direction of the liquid crystal molecules was measured. Sine waves (0.5 V, 1 kHz) were applied to the device, and the dielectric constant (ε 誘 電) in the minor axis direction of the liquid crystal molecules was measured after 2 seconds. The value of dielectric anisotropy was calculated from the equation: Δε = ε∥−ε⊥.

  Threshold voltage (Vth; measured at 25 ° C .; V): An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement. The light source is 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 about 0.45 / Δn (μm) and the twist angle was 80 degrees. The voltage (32 Hz, rectangular wave) applied to this element was increased stepwise from 0V to 10V by 0.02V. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. A voltage-transmittance curve was created in which the transmittance was 100% when the light amount reached the maximum and the transmittance was 0% when the light amount was the minimum. The threshold voltage is a voltage when the transmittance reaches 90%.

  Voltage holding ratio (VHR-1; 25 ° C .;%): The TN device used for the measurement has a polyimide alignment film, and the distance between two glass substrates (cell gap) is 5 μm. This element was sealed with an adhesive polymerized by ultraviolet rays after putting a sample. The TN device was charged by applying a pulse voltage (60 microseconds at 5 V). The decaying voltage was measured for 16.7 milliseconds with a high-speed voltmeter, and the area A between the voltage curve and the horizontal axis in a unit cycle was determined. The area B is an area when it is not attenuated. The voltage holding ratio is a percentage of the area A with respect to the area B.

  Stability against ultraviolet rays: After irradiation with ultraviolet rays, the voltage holding ratio (VHR-2; 25 ° C .;%) and the upper limit temperature (NI (UV)) were measured to evaluate the stability against ultraviolet rays. A composition having a large VHR-2 has a large stability to ultraviolet light. The TN device used for measurement has a polyimide alignment film, and the cell gap is 5 μm. A sample was injected into this device and irradiated with light for 200 minutes. The light source is an ultra high pressure mercury lamp USH-500D (manufactured by USHIO), and the distance between the element and the light source is 20 cm. In the measurement of VHR-2, the decreasing voltage was measured for 1667 milliseconds.

  Stability against heat: TN device injected with sample was heated in a thermostatic chamber at 120 ° C. for 500 hours, and then voltage holding ratio (VHR-3; 25 ° C .;%) and upper limit temperature (NI (H)) were measured. The stability against heat was evaluated. A composition having a large VHR-3 has a large stability to heat. A composition having a small difference between NI and NI (H) has a large stability to heat. In the measurement of VHR-3, the decreasing voltage was measured for 1667 milliseconds.

  Response time (τ; measured at 25 ° C .; millisecond): An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement. The light source is a halogen lamp. The low-pass filter was set to 5 kHz. A sample was put in a normally white mode TN device in which the distance between two glass substrates (cell gap) 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 element. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. The transmittance is 100% when the light amount is maximum, and the transmittance is 0% when the light amount is minimum. The rise time (τr: rise time) is the time required for the transmittance to change from 90% to 10%. The fall time (τf: fall time) is the time required to change the transmittance from 10% to 90%. The response time is the sum of the rise time and the fall time obtained in this way.

  Gas chromatographic 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. For separation of the component compounds, capillary column DB-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm; stationary liquid phase is dimethylpolysiloxane; nonpolar) manufactured by Agilent Technologies Inc. was used. The column was held at 200 ° C. for 2 minutes and then heated to 280 ° C. at a rate of 5 ° C./min. A sample was prepared in an acetone solution (0.1% by weight), and 1 μl thereof was injected into the sample vaporization chamber. The recorder is a C-R5A type Chromatopac manufactured by Shimadzu Corporation or an equivalent thereof. The obtained gas chromatogram showed the peak retention time and peak area corresponding to the component compounds.

  As a solvent for diluting the sample, chloroform, hexane or the like may be used. In order to separate the component compounds, the following capillary column may be used. HP-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by Agilent Technologies Inc., Rtx-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by Restek Corporation, BP-1 made by SGE International Pty. Ltd (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm). In order to prevent compound peaks from overlapping, 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 area ratio of peaks in the gas chromatogram corresponds to the ratio of component compounds. The weight percentage of the component compounds is not completely the same as the area ratio of each peak. However, in the present invention, when these capillary columns are used, the weight percentage of the component compounds may be considered to be the same as the area ratio of each peak. This is because there is no significant difference in the correction coefficients of the component compounds.

Comparative Example 1
Example 12 was selected from the compositions disclosed in JP-A-11-349945. The reason is that this composition contains the compound (2) and has the largest optical anisotropy. The components and properties of this composition are as follows.
3-B (F) B (F) B-CL (-) 12%
5-B (F) B (F) B-CL (-) 12%
3-BB (2F) B (2F) -CL (-) 8%
2-BB (F) B (F) -F (-) 6%
3-BB (F) B (F) -F (-) 8%
2-B (F) B2B-CL (-) 12%
3-B (F) B2B-CL (-) 6%
3-HB (F) B (F, F) -F (2-1-3) 9%
3-HBB (F) -F (-) 6%
5-HBB (F) -F (-) 8%
3-HHB (F) B (F, F) -F (2-2-3) 6%
3-HBBH-3 (-) 3%
5-HBBH-3 (-) 3%
5-HBBH-5 (-) 1%
NI = 108.8 ° C .; Tc ≦ 0 ° C .; Δn = 0.214; Δε = 6.1; η = 35.8 mPa · s; Vth = 1.85 V; VHR-1 = 99.6%

Comparative Example 2
Example 1 was selected from the compositions disclosed in JP-A-2002-180050. The reason is that this composition contains the compound (2) and has the largest optical anisotropy. The components and properties of this composition are as follows.
2-HB (F) B (F, F) -F (2-1-3) 8%
3-HB (F) B (F, F) -F (2-1-3) 7%
3-HHB (F, F) -F (-) 5%
V-HHB-1 (-) 8%
V-HHB (F) -F (-) 10%
3-HB-O2 (-) 8%
V-HVHB-1 (-) 5%
V-HVHB-O1 (-) 5%
1V-HVHB-O1 (-) 5%
2-BB (F) B (F, F) -F (-) 8%
3-BB (F) B (F, F) -F (-) 8%
5-BB (F) B (F, F) -F (-) 8%
1-BTB-O2 (-) 5%
2-BTB-O1 (-) 3%
3-HBTB-O1 (-) 4%
3-HBTB-O2 (-) 3%
NI = 97.3 ° C .; Tc ≦ −20 ° C .; Δn = 0.164; Δε = 5.3; η = 28.6 mPa · s; Vth = 1.90 V; VHR-1 = 99.3%.

Comparative Example 3
Example M8 was selected from the compositions disclosed in JP-A-2003-183656. The reason is that this composition has the largest optical anisotropy. The components and properties of this composition are as follows.
2-HHB (F, F) -F (-) 10%
3-HHB (F, F) -F (-) 10%
2-HHB (F) -OCF3 (-) 11%
3-HHB (F) -OCF3 (-) 11%
5-HHB (F) -OCF3 (-) 5%
3-HHB-OCF3 (-) 8%
4-HHB-OCF3 (-) 6%
5-HHB-OCF3 (-) 8%
1-HB (F) B (F, F) -F (2-1-3) 8%
2-HB (F) B (F, F) -F (2-1-3) 10%
3-HB (F) B (F, F) -F (2-1-3) 9%
3-HHB (F) B (F, F) -F (2-2-3) 4%
NI = 82.3 ° C .; Tc ≦ −20 ° C .; Δn = 0.095; Δε = 7.2; η = 31.3 mPa · s; Vth = 1.35 V; VHR-1 = 99.6%.

Comparative Example 4
Example 11 was selected from the compositions disclosed in JP-T-2003-507526. This is because this composition has the highest NI point and has a large optical anisotropy. The components and properties of this composition are as follows.
2-B (F, F) TBB-3 (-) 23%
2-BB (F) B (F, F) -F (-) 9%
3-BB (F) B (F, F) -F (-) 9%
5-BB (F) B (F, F) -F (-) 6%
2-HB (F) B (F, F) -F (2-1-3) 10%
3-HB (F) B (F, F) -F (2-1-3) 8%
3-HB-O1 (-) 16%
3-HB (F) BH-3 (-) 5%
5-HB (F) BH-3 (-) 5%
V-HHB (F) -F (-) 9%
NI = 94.7 ° C .; Tc ≦ 0 ° C .; Δn = 0.197; Δε = 5.8; η = 29.1 mPa · s; Vth = 1.77 V; VHR-1 = 99.5%.

Comparative Example 5
Example 9 was selected from the compositions disclosed in Japanese Patent No. 3216550. The basis is that this composition has the largest NI point. The components and properties of this composition are as follows.
3-BB (F, F) BB (F, F) -OCF2H (-) 2%
3-BB (F, F) 2B (F, F) -OCF2H (-) 2%
3-BB (F) B (F, F) -F (-) 4%
3-HBB (F, F) -F (2-1-1) 8%
5-HBB (F, F) -F (2-1-1) 9%
3-HHB (F, F) -F (-) 6%
3-HH2B (F, F) -F (-) 8%
5-HH2B (F, F) -F (-) 8%
3-HH2B (F) -F (-) 2%
3-H2HB (F, F) -F (-) 10%
4-H2HB (F, F) -F (-) 9%
5-H2HB (F, F) -F (-) 9%
2-HHB (F) -F (-) 4%
3-HHB (F) -F (-) 5%
5-HHB (F) -F (-) 5%
2-HBEB (F, F) -F (-) 3%
3-HBEB (F, F) -F (-) 3%
5-HBEB (F, F) -F (-) 3%
NI = 83.6 ° C .; Tc ≦ −30 ° C .; Δn = 0.094; Δε = 7.4; η = 34.2 mPa · s; Vth = 1.01 V; VHR-1 = 98.9%.

Example 1
V2-BB (F) B (F, F) -F (1-1-1) 10%
1V2-BB (F) B (F, F) -F (1-2-1) 10%
2-HBB (F, F) -F (2-1-1) 10%
3-HBB (F, F) -F (2-1-1) 10%
5-HBB (F, F) -F (2-1-1) 10%
2-HB (F) B (F, F) -F (2-1-3) 10%
3-HB (F) B (F, F) -F (2-1-3) 10%
2-HHBB (F, F) -F (2-2-1) 5%
4-HHBB (F, F) -F (2-2-1) 5%
3-HHB (F) B (F, F) -F (2-2-3) 5%
5-HHB (F) B (F, F) -F (2-2-3) 5%
3-HHBB (F, F) -CL (2-2-5) 5%
5-HHB (F) B (F, F) -CL (2-2-7) 5%
NI = 91.1 ° C .; Tc ≦ −30 ° C .; Δn = 0.127; Δε = 8.5; η = 44.9 mPa · s; Vth = 1.36 V; VHR-1 = 99.5%.

Example 2
V2-BB (F) B (F, F) -CL (1-1-2) 2%
V2-BB (F) B (F, F) -OCF3 (1-1-3) 2%
V2-BB (F) B (F, F) -OCF2H (1-1-4) 2%
V2-B (F) B (F) B (F, F) -F (1-1-5) 2%
V2-B (F) B (F) B (F, F) -CL (1-1-6) 2%
1V2-BB (F) B (F, F) -CL (1-2-2) 2%
1V2-BB (F) B (F, F) -OCF3 (1-2-3) 2%
1V2-BB (F) B (F, F) -OCF2H (1-2-4) 2%
1V2-B (F) B (F) B (F, F) -F (1-2-5) 2%
1V2-B (F) B (F) B (F, F) -CL (1-2-6) 2%
3-HBB (F, F) -F (2-1-1) 5%
5-HBB (F, F) -F (2-1-1) 5%
4-H2BB (F, F) -F (2-1-2) 5%
2-HB (F) B (F, F) -F (2-1-3) 5%
3-HB (F) B (F, F) -F (2-1-3) 5%
3-H2B (F) B (F, F) -F (2-1-4) 5%
2-HBB (F, F) -CL (2-1-5) 5%
3-H2BB (F, F) -CL (2-1-6) 5%
2-HB (F) B (F, F) -CL (2-1-7) 5%
3-H2B (F) B (F, F) -CL (2-1-8) 5%
2-HHBB (F, F) -F (2-2-1) 5%
4-HHBB (F, F) -F (2-2-1) 5%
3-HHB (F) B (F, F) -F (2-2-3) 5%
5-HHB (F) B (F, F) -F (2-2-3) 5%
3-HHBB (F, F) -CL (2-2-5) 5%
5-HHB (F) B (F, F) -CL (2-2-7) 5%
NI = 92.0 ° C .; Tc ≦ −30 ° C .; Δn = 0.126; Δε = 8.7; η = 42.8 mPa · s; Vth = 1.39 V; VHR-1 = 99.6%.

Example 3
V2-BB (F) B (F, F) -F (1-1-1) 5%
V2-B (F) B (F) B (F, F) -F (1-1-5) 5%
V2-B (F) B (F) B (F, F) -OCF3 (1-1-7) 5%
V2-B (F) B (F) B (F, F) -OCF2H (1-1-8) 5%
1V2-BB (F) B (F, F) -F (1-2-1) 5%
1V2-B (F) B (F) B (F, F) -F (1-2-5) 5%
1V2-B (F) B (F) B (F, F) -OCF3 (1-2-7) 5%
1V2-B (F) B (F) B (F, F) -OCF2H (1-2-8) 5%
3-HBB (F, F) -OCF3 (2-1-9) 8%
4-H2BB (F, F) -OCF3 (2-1-10) 8%
5-HB (F) B (F, F) -OCF3 (2-1-11) 9%
3-HBB (F, F) -OCF3 (2-1-13) 8%
4-H2BB (F, F) -OCF3 (2-1-14) 8%
5-HB (F) B (F, F) -OCF3 (2-1-15) 9%
2-HHB (F) B (F, F) -F (2-2-3) 10%
NI = 65.9 ° C .; Tc ≦ −40 ° C .; Δn = 0.162; Δε = 14.9; η = 31.8 mPa · s; Vth = 0.91 V; VHR-1 = 99.7%.

Example 4
V2-BB (F) B (F, F) -F (1-1-1) 3%
1V2-BB (F) B (F, F) -F (1-2-1) 3%
5-HBB (F, F) -F (2-1-1) 10%
1-H2BB (F, F) -F (2-1-2) 5%
3-HB (F) B (F, F) -F (2-1-3) 10%
4-HBB (F, F) -CL (2-1-5) 10%
3-HB (F) B (F, F) -CL (2-1-7) 10%
3-H2B (F) B (F, F) -OCF3 (2-1-12) 7%
2-H2B (F) B (F, F) -OCF2H (2-2-16) 7%
3-HH2BB (F, F) -CL (2-2-6) 5%
3-HH2B (F) B (F, F) -CL (2-2-8) 5%
2-HH2BB (F, F) -OCF3 (2-2-10) 5%
4-HHB (F) B (F, F) -OCF3 (2-2-11) 5%
2-HH2B (F) B (F, F) -OCF3 (2-2-12) 5%
3-HHB (F) B (F, F) -OCF2H (2-2-11) 5%
3-HH2B (F) B (F, F) -OCF2H (2-2-12) 5%
NI = 92.6 ° C .; Tc ≦ −30 ° C .; Δn = 0.138; Δε = 13.6; η = 35.7 mPa · s; Vth = 1.05 V; VHR-1 = 99.6%.

Example 5
V2-BB (F) B (F, F) -F (1-1-1) 10%
1V2-BB (F) B (F, F) -F (1-2-1) 10%
2-HBB (F, F) -F (2-1-1) 10%
3-HBB (F, F) -F (2-1-1) 10%
5-HBB (F, F) -F (2-1-1) 10%
2-HB (F) B (F, F) -F (2-1-3) 10%
3-HB (F) B (F, F) -F (2-1-3) 10%
2-HHBB (F, F) -F (2-2-1) 5%
4-HHBB (F, F) -F (2-2-1) 5%
3-HHB (F) B (F, F) -F (2-2-3) 5%
5-HHB (F) B (F, F) -F (2-2-3) 5%
3-HHBB (F, F) -CL (2-2-5) 5%
5-HHB (F) B (F, F) -CL (2-2-7) 5%
NI = 93.1 ° C .; Tc ≦ −30 ° C .; Δn = 0.131; Δε = 8.6; η = 44.3 mPa · s; Vth = 1.31 V; VHR-1 = 99.5%.

Example 6
V2-BB (F) B (F, F) -CL (1-1-2) 2%
V2-BB (F) B (F, F) -OCF3 (1-1-3) 2%
V2-BB (F) B (F, F) -OCF2H (1-1-4) 2%
V2-B (F) B (F) B (F, F) -F (1-1-5) 2%
V2-B (F) B (F) B (F, F) -CL (1-1-6) 2%
1V2-BB (F) B (F, F) -CL (1-2-2) 2%
1V2-BB (F) B (F, F) -OCF3 (1-2-3) 2%
1V2-BB (F) B (F, F) -OCF2H (1-2-4) 2%
1V2-B (F) B (F) B (F, F) -F (1-2-5) 2%
1V2-B (F) B (F) B (F, F) -CL (1-2-6) 2%
3-HBB (F, F) -F (2-1-1) 5%
5-HBB (F, F) -F (2-1-1) 5%
4-H2BB (F, F) -F (2-1-2) 5%
2-HB (F) B (F, F) -F (2-1-3) 5%
3-HB (F) B (F, F) -F (2-1-3) 5%
3-H2B (F) B (F, F) -F (2-1-4) 5%
2-HBB (F, F) -CL (2-1-5) 5%
3-H2BB (F, F) -CL (2-1-6) 5%
2-HB (F) B (F, F) -CL (2-1-7) 5%
3-H2B (F) B (F, F) -CL (2-1-8) 5%
4-HHBB (F, F) -F (2-2-1) 5%
3-HH2BB (F, F) -F (2-2-2) 5%
5-HH2B (F) B (F, F) -F (2-2-4) 5%
3-HHBB (F, F) -OCF3 (2-2-9) 5%
2-HHBB (F, F) -OCF3 (2-2-13) 5%
5-HH2BB (F, F) -OCF3 (2-2-14) 5%
NI = 93.2 ° C .; Tc ≦ −30 ° C .; Δn = 0.129; Δε = 8.8; η = 42.5 mPa · s; Vth = 1.33 V; VHR-1 = 99.6%.

Example 7
V2-BB (F) B (F, F) -F (1-1-1) 5%
V2-B (F) B (F) B (F, F) -F (1-1-5) 5%
V2-B (F) B (F) B (F, F) -OCF3 (1-1-7) 5%
V2-B (F) B (F) B (F, F) -OCF2H (1-1-8) 5%
1V2-BB (F) B (F, F) -F (1-2-1) 5%
1V2-B (F) B (F) B (F, F) -F (1-2-5) 5%
1V2-B (F) B (F) B (F, F) -OCF3 (1-2-7) 5%
1V2-B (F) B (F) B (F, F) -OCF2H (1-2-8) 5%
3-HBB (F, F) -OCF3 (2-1-9) 8%
4-H2BB (F, F) -OCF3 (2-1-10) 8%
5-HB (F) B (F, F) -OCF3 (2-1-11) 9%
3-HBB (F, F) -OCF2H (2-1-13) 8%
4-H2BB (F, F) -OCF2H (2-1-14) 8%
5-HB (F) B (F, F) -OCF3 (2-1-15) 9%
2-HHB (F) B (F, F) -F (2-2-3) 10%
NI = 66.8 ° C .; Tc ≦ −40 ° C .; Δn = 0.165; Δε = 15.1; η = 38.9 mPa · s; Vth = 0.89 V; VHR-1 = 99.5%.

Example 8
V2-BB (F) B (F, F) -F (1-1-1) 3%
1V2-BB (F) B (F, F) -F (1-2-1) 3%
5-HBB (F, F) -F (2-1-1) 10%
1-H2BB (F, F) -F (2-1-2) 5%
3-HB (F) B (F, F) -F (2-1-3) 10%
4-HBB (F, F) -CL (2-1-5) 10%
3-HB (F) B (F, F) -CL (2-1-7) 10%
3-H2B (F) B (F, F) -OCF3 (2-1-12) 7%
2-H2B (F) B (F, F) -OCF2H (2-1-16) 7%
3-HH2BB (F, F) -CL (2-2-6) 5%
3-HH2B (F) B (F, F) -CL (2-2-8) 5%
2-HH2BB (F, F) -OCF3 (2-2-10) 5%
4-HHB (F) B (F, F) -OCF3 (2-2-11) 5%
2-HH2B (F) B (F, F) -OCF3 (2-2-12) 5%
3-HHB (F) B (F, F) -OCF3 (2-2-15) 5%
3-HH2B (F) B (F, F) -OCF3 (2-2-16) 5%
NI = 93.6 ° C .; Tc ≦ −30 ° C .; Δn = 0.140; Δε = 13.7; η = 37.7 mPa · s; Vth = 1.03 V; VHR-1 = 99.7%.

Example 9
V2-BB (F) B (F, F) -F (1-1-1) 10%
1V2-BB (F) B (F, F) -F (1-2-1) 10%
2-HBB (F, F) -F (2-1-1) 10%
3-HBB (F, F) -F (2-1-1) 10%
1-HB (F) B (F, F) -F (2-1-3) 5%
3-HB (F) B (F, F) -F (2-1-3) 5%
2-HHBB (F, F) -F (2-2-1) 5%
4-HHBB (F, F) -F (2-2-1) 5%
3-HHB (F) B (F, F) -F (2-2-3) 5%
5-HHB (F) B (F, F) -F (2-2-3) 5%
3-HHBB (F, F) -CL (2-2-5) 5%
5-HHB (F) B (F, F) -CL (2-2-7) 5%
3-BB (F) B-4 (3-1-1) 5%
2-BB (F) B-4 (3-1-1) 5%
5-HBB (F) B-2 (3-2-2) 5%
5-HBB (F) B-3 (3-2-2) 5%
NI = 112.2 ° C .; Tc ≦ −30 ° C .; Δn = 0.173; Δε = 12.6; η = 45.1 mPa · s; Vth = 1.12 V; VHR-1 = 99.6%.

Example 10
V2-BB (F) B (F, F) -F (1-1-1) 10%
1V2-BB (F) B (F, F) -F (1-2-1) 10%
1-HBB (F, F) -F (2-1-1) 5%
3-HBB (F, F) -F (2-1-1) 5%
5-HBB (F, F) -F (2-1-1) 5%
1-HB (F) B (F, F) -F (2-1-3) 5%
2-HB (F) B (F, F) -F (2-1-3) 5%
3-HB (F) B (F, F) -F (2-1-3) 5%
2-HHBB (F, F) -F (2-2-1) 5%
4-HHBB (F, F) -F (2-2-1) 5%
3-HHB (F) B (F, F) -F (2-2-3) 5%
5-HHB (F) B (F, F) -F (2-2-3) 5%
2-HHBB (F, F) -CL (2-2-5) 5%
3-HHB (F) B (F, F) -CL (2-2-7) 5%
1-BB (F) B-6 (3-1-1) 5%
3-BBB (2F) -1 (3-1-2) 5%
5-BB (2F, 5F) B-2 (3-1-3) 5%
3-HBBB-2 (3-2-1) 3%
1-HBBB-4 (3-2-1) 2%
NI = 121.6 ° C .; Tc ≦ −20 ° C .; Δn = 0.171; Δε = 12.8; η = 42.2 mPa · s; Vth = 1.21 V; VHR-1 = 99.5%.

Example 11
V2-BB (F) B (F, F) -F (1-1-1) 10%
1V2-BB (F) B (F, F) -F (1-2-1) 10%
3-HBB (F, F) -F (2-1-1) 10%
5-HBB (F, F) -F (2-1-1) 10%
2-HB (F) B (F, F) -F (2-1-3) 5%
3-HB (F) B (F, F) -F (2-1-3) 5%
3-HHBB (F, F) -F (2-2-1) 5%
5-HHBB (F, F) -F (2-2-1) 5%
3-HHB (F) B (F, F) -F (2-2-3) 5%
5-HHB (F) B (F, F) -F (2-2-3) 5%
3-HHBB (F, F) -CL (2-2-5) 5%
5-HHB (F) B (F, F) -CL (2-2-7) 5%
V-HH-4 (-) 5%
1V-HH-3 (-) 5%
V-HHB-1 (-) 10%
NI = 102.0 ° C .; Tc ≦ −30 ° C .; Δn = 0.165; Δε = 11.3; η = 32.0 mPa · s; Vth = 1.33 V; VHR-1 = 99.7%.

Example 12
V2-BB (F) B (F, F) -F (1-1-1) 10%
1V2-BB (F) B (F, F) -F (1-2-1) 10%
2-HBB (F, F) -F (2-1-1) 5%
3-HBB (F, F) -F (2-1-1) 5%
5-HBB (F, F) -F (2-1-1) 5%
2-HB (F) B (F, F) -F (2-1-3) 5%
3-HB (F) B (F, F) -F (2-1-3) 5%
5-HB (F) B (F, F) -F (2-1-3) 5%
3-HHBB (F, F) -F (2-2-1) 5%
5-HHBB (F, F) -F (2-2-1) 5%
3-HHB (F) B (F, F) -F (2-2-3) 5%
5-HHB (F) B (F, F) -F (2-2-3) 5%
3-HHBB (F, F) -CL (2-2-5) 5%
5-HHB (F) B (F, F) -CL (2-2-7) 5%
3-BB (F) B-4 (3-1-1) 5%
5-HBB (F) B-3 (3-2-2) 5%
V-HH-5 (-) 5%
2-HBB-F (-) 2%
3-HBB-F (-) 3%
NI = 108.4 ° C .; Tc ≦ −30 ° C .; Δn = 0.174; Δε = 11.5; η = 37.5 mPa · s; Vth = 1.25 V; VHR-1 = 99.5%.

Example 13
V2-BB (F) B (F, F) -F (1-1-1) 10%
1V2-BB (F) B (F, F) -F (1-2-1) 10%
2-HBB (F, F) -F (2-1-1) 5%
3-HBB (F, F) -F (2-1-1) 5%
5-HBB (F, F) -F (2-1-1) 5%
2-HB (F) B (F, F) -F (2-1-3) 5%
3-HB (F) B (F, F) -F (2-1-3) 5%
5-HB (F) B (F, F) -F (2-1-3) 5%
3-HHBB (F, F) -F (2-2-1) 5%
5-HHBB (F, F) -F (2-2-1) 5%
3-HHB (F) B (F, F) -F (2-2-3) 5%
5-HHB (F) B (F, F) -F (2-2-3) 5%
1-BB (F) B-5 (3-1-1) 5%
5-BB (2F, 5F) B-5 (3-1-3) 5%
V-HH-1 (-) 5%
1V-HH-4 (-) 5%
V-HHB-1 (-) 5%
2-HBB-F (-) 2%
3-HBB-F (-) 3%
NI = 99.6 ° C .; Tc ≦ −30 ° C .; Δn = 0.177; Δε = 12.1; η = 38.9 mPa · s; Vth = 1.18 V; VHR-1 = 99.5%.

Example 14
V2-BB (F) B (F, F) -F (1-1-1) 10%
1V2-BB (F) B (F, F) -F (1-2-1) 10%
2-HBB (F, F) -F (2-1-1) 5%
3-HBB (F, F) -F (2-1-1) 5%
5-HBB (F, F) -F (2-1-1) 5%
2-HB (F) B (F, F) -F (2-1-3) 5%
3-HB (F) B (F, F) -F (2-1-3) 5%
5-HB (F) B (F, F) -F (2-1-3) 5%
3-HHBB (F, F) -F (2-2-1) 5%
5-HHBB (F, F) -F (2-2-1) 5%
3-HHB (F) B (F, F) -F (2-2-3) 5%
5-HHB (F) B (F, F) -F (2-2-3) 5%
3-HHBB (F, F) -CL (2-2-5) 5%
5-HHB (F) B (F, F) -CL (2-2-7) 5%
5-BB (F) B-2 (3-1-1) 5%
3-BB (F, F) CF2OB (F, F) -F (4-1) 5%
V-HH-5 (-) 5%
V-HHB-1 (-) 5%
NI = 95.9 ° C .; Tc ≦ −30 ° C .; Δn = 0.169; Δε = 13.1; η = 41.2 mPa · s; Vth = 1.09 V; VHR-1 = 99.5%.

Example 15
V2-BB (F) B (F, F) -F (1-1-1) 10%
1V2-BB (F) B (F, F) -F (1-2-1) 10%
2-HBB (F, F) -F (2-1-1) 5%
3-HBB (F, F) -F (2-1-1) 5%
5-HBB (F, F) -F (2-1-1) 5%
2-HB (F) B (F, F) -F (2-1-3) 5%
3-HB (F) B (F, F) -F (2-1-3) 5%
5-HB (F) B (F, F) -F (2-1-3) 5%
3-HHBB (F, F) -F (2-2-1) 5%
5-HHBB (F, F) -F (2-2-1) 5%
3-HHB (F) B (F, F) -F (2-2-3) 5%
5-HHB (F) B (F, F) -F (2-2-3) 5%
2-BB (F) B-3 (3-1-1) 5%
5-BB (F, F) CF2OB (F) -F (4-2) 5%
4-BB (F, F) CF2OB (F, F) -OCF3 (4-3) 5%
2-BB (F, F) CF2OB (F) -OCF3 (4-4) 5%
V-HH-4 (-) 5%
V-HHB-3 (-) 5%
NI = 96.3 ° C .; Tc ≦ −30 ° C .; Δn = 0.168; Δε = 13.0; η = 40.5 mPa · s; Vth = 1.12 V; VHR-1 = 99.7%.

Example 16
V2V2-BB (F) B (F, F) -F (1-1-9) 10%
1V2V2-BB (F) B (F, F) -F (1-2-9) 10%
2-HBB (F, F) -F (2-1-1) 10%
3-HBB (F, F) -F (2-1-1) 10%
1-HB (F) B (F, F) -F (2-1-3) 5%
3-HB (F) B (F, F) -F (2-1-3) 5%
2-HHBB (F, F) -F (2-2-1) 5%
4-HHBB (F, F) -F (2-2-1) 5%
3-HHB (F) B (F, F) -F (2-2-3) 5%
5-HHB (F) B (F, F) -F (2-2-3) 5%
3-HHBB (F, F) -CL (2-2-5) 5%
5-HHB (F) B (F, F) -CL (2-2-7) 5%
3-BB (F) B-4 (3-1-1) 5%
2-BB (F) B-4 (3-1-1) 5%
5-HBB (F) B-2 (3-2-2) 5%
5-HBB (F) B-3 (3-2-2) 5%
NI = 123.1 ° C .; Tc ≦ −20 ° C .; Δn = 0.174; Δε = 12.6; η = 40.6 mPa · s; Vth = 1.32 V; VHR-1 = 99.6%.

Example 17
V2V2-BB (F) B (F, F) -F (1-1-9) 10%
1V2V2-BB (F) B (F, F) -F (1-2-9) 10%
1-HBB (F, F) -F (2-1-1) 5%
3-HBB (F, F) -F (2-1-1) 5%
5-HBB (F, F) -F (2-1-1) 5%
1-HB (F) B (F, F) -F (2-1-3) 5%
2-HB (F) B (F, F) -F (2-1-3) 5%
3-HB (F) B (F, F) -F (2-1-3) 5%
2-HHBB (F, F) -F (2-2-1) 5%
4-HHBB (F, F) -F (2-2-1) 5%
3-HHB (F) B (F, F) -F (2-2-3) 5%
5-HHB (F) B (F, F) -F (2-2-3) 5%
2-HHBB (F, F) -CL (2-2-5) 5%
3-HHB (F) B (F, F) -CL (2-2-7) 5%
1-BB (F) B-6 (3-1-1) 5%
3-BBB (2F) -1 (3-1-2) 5%
5-BB (2F, 5F) B-2 (3-1-3) 5%
3-HBBB-2 (3-2-1) 3%
1-HBBB-4 (3-2-1) 2%
NI = 103.8 ° C .; Tc ≦ −30 ° C .; Δn = 0.167; Δε = 11.0; η = 31.5 mPa · s; Vth = 1.40 V; VHR-1 = 99.7%.

Example 18
V2V2-BB (F) B (F, F) -F (1-1-9) 10%
1V2V2-BB (F) B (F, F) -F (1-2-9) 10%
3-HBB (F, F) -F (2-1-1) 10%
5-HBB (F, F) -F (2-1-1) 10%
2-HB (F) B (F, F) -F (2-1-3) 5%
3-HB (F) B (F, F) -F (2-1-3) 5%
3-HHBB (F, F) -F (2-2-1) 5%
5-HHBB (F, F) -F (2-2-1) 5%
3-HHB (F) B (F, F) -F (2-2-3) 5%
5-HHB (F) B (F, F) -F (2-2-3) 5%
3-HHBB (F, F) -CL (2-2-5) 5%
5-HHB (F) B (F, F) -CL (2-2-7) 5%
V-HH-4 (-) 5%
1V-HH-3 (-) 5%
V-HHB-1 (-) 10%
NI = 110.1 ° C; Tc ≤ -30 ° C; Δn = 0.176; Δε = 11.2; η = 35.9 mPa · s; Vth = 1.29 V; VHR-1 = 99.5%.

Example 19
V2V2-BB (F) B (F, F) -F (1-1-9) 10%
1V2V2-BB (F) B (F, F) -F (1-2-9) 10%
2-HBB (F, F) -F (2-1-1) 5%
3-HBB (F, F) -F (2-1-1) 5%
5-HBB (F, F) -F (2-1-1) 5%
2-HB (F) B (F, F) -F (2-1-3) 5%
3-HB (F) B (F, F) -F (2-1-3) 5%
5-HB (F) B (F, F) -F (2-1-3) 5%
3-HHBB (F, F) -F (2-2-1) 5%
5-HHBB (F, F) -F (2-2-1) 5%
3-HHB (F) B (F, F) -F (2-2-3) 5%
5-HHB (F) B (F, F) -F (2-2-3) 5%
3-HHBB (F, F) -CL (2-2-5) 5%
5-HHB (F) B (F, F) -CL (2-2-7) 5%
3-BB (F) B-4 (3-1-1) 5%
5-HBB (F) B-3 (3-2-2) 5%
V-HH-5 (-) 5%
2-HBB-F (-) 2%
3-HBB-F (-) 3%
NI = 100.6 ° C .; Tc ≦ −30 ° C .; Δn = 0.179; Δε = 11.8; η = 38.0 mPa · s; Vth = 1.23 V; VHR-1 = 99.6%.

Example 20
V2V2-BB (F) B (F, F) -F (1-1-9) 10%
1V2V2-BB (F) B (F, F) -F (1-2-9) 10%
2-HBB (F, F) -F (2-1-1) 5%
3-HBB (F, F) -F (2-1-1) 5%
5-HBB (F, F) -F (2-1-1) 5%
2-HB (F) B (F, F) -F (2-1-3) 5%
3-HB (F) B (F, F) -F (2-1-3) 5%
5-HB (F) B (F, F) -F (2-1-3) 5%
3-HHBB (F, F) -F (2-2-1) 5%
5-HHBB (F, F) -F (2-2-1) 5%
3-HHB (F) B (F, F) -F (2-2-3) 5%
5-HHB (F) B (F, F) -F (2-2-3) 5%
1-BB (F) B-5 (3-1-1) 5%
5-BB (2F, 5F) B-5 (3-1-3) 5%
V-HH-1 (-) 5%
1V-HH-4 (-) 5%
V-HHB-1 (-) 5%
2-HBB-F (-) 2%
3-HBB-F (-) 3%
NI = 96.9 ° C .; Tc ≦ −30 ° C .; Δn = 0.171; Δε = 12.8; η = 39.2 mPa · s; Vth = 1.15 V; VHR-1 = 99.7%.

Example 21
V2V2-BB (F) B (F, F) -F (1-1-9) 10%
1V2V2-BB (F) B (F, F) -F (1-2-9) 10%
2-HBB (F, F) -F (2-1-1) 5%
3-HBB (F, F) -F (2-1-1) 5%
5-HBB (F, F) -F (2-1-1) 5%
2-HB (F) B (F, F) -F (2-1-3) 5%
3-HB (F) B (F, F) -F (2-1-3) 5%
5-HB (F) B (F, F) -F (2-1-3) 5%
3-HHBB (F, F) -F (2-2-1) 5%
5-HHBB (F, F) -F (2-2-1) 5%
3-HHB (F) B (F, F) -F (2-2-3) 5%
5-HHB (F) B (F, F) -F (2-2-3) 5%
3-HHBB (F, F) -CL (2-2-5) 5%
5-HHB (F) B (F, F) -CL (2-2-7) 5%
5-BB (F) B-2 (3-1-1) 5%
3-BB (F, F) CF2OB (F, F) -F (4-1) 5%
V-HH-5 (-) 5%
V-HHB-1 (-) 5%
NI = 97.5 ° C .; Tc ≦ −30 ° C .; Δn = 0.170; Δε = 12.8; η = 38.5 mPa · s; Vth = 1.18 V; VHR-1 = 99.6%.

Example 22
V2V2-BB (F) B (F, F) -F (1-1-9) 10%
1V2V2-BB (F) B (F, F) -F (1-2-9) 10%
2-HBB (F, F) -F (2-1-1) 5%
3-HBB (F, F) -F (2-1-1) 5%
5-HBB (F, F) -F (2-1-1) 5%
2-HB (F) B (F, F) -F (2-1-3) 5%
3-HB (F) B (F, F) -F (2-1-3) 5%
5-HB (F) B (F, F) -F (2-1-3) 5%
3-HHBB (F, F) -F (2-2-1) 5%
5-HHBB (F, F) -F (2-2-1) 5%
3-HHB (F) B (F, F) -F (2-2-3) 5%
5-HHB (F) B (F, F) -F (2-2-3) 5%
2-BB (F) B-3 (3-1-1) 5%
5-BB (F, F) CF2OB (F) -F (4-2) 5%
4-BB (F, F) CF2OB (F, F) -OCF3 (4-3) 5%
2-BB (F, F) CF2OB (F) -OCF3 (4-4) 5%
V-HH-4 (-) 5%
V-HHB-3 (-) 5%
NI = 124.4 ° C .; Tc ≦ −20 ° C .; Δn = 0.176; Δε = 12.4; η = 39.1 mPa · s; Vth = 1.39 V; VHR-1 = 99.5%.

Claims (8)

At least one compound selected from the group of compounds represented by formula (1-1) and formula (1-2) as the first component, and formula (2-1) and formula (2-2) as the second component ) Containing at least one compound selected from the group of compounds represented by the formula: wherein the proportion of the first component is in the range of 5% to 50% by weight and the proportion of the second component is 30% to 95% by weight. % of the range, the liquid crystal composition having a nematic phase and its.

Here, R ¹ is alkyl having 1 to 12 carbons, Z ¹ and Z ² are independently a single bond or ethylene, and X ¹ is independently fluorine, chlorine, OCF ₃ or OCF ₂ H. Y ¹ is independently hydrogen or fluorine, and n is independently 1 or 2. It further contains at least one compound selected from the group of compounds represented by formula (3-1) and formula (3-2) as the third component, and the proportion of the third component is 5 wt% to 40 wt% The liquid crystal composition according to claim 1, which is in the range of

Here, R ² and R ³ are independently alkyl having 1 to 12 carbons, and Y ² , Y ³ , Y ⁴ , and Y ⁵ are independently hydrogen or fluorine.   The liquid crystal composition according to claim 1, wherein n in Formula (1-1) and Formula (1-2) is 2. It further contains at least one compound selected from the group of compounds represented by formulas (3-1) and (3-2) as a third component, and the proportion of the third component is 5 wt% to 40 wt% The liquid crystal composition according to claim 3 , which is in a range .

Here, R ² and R ³ are independently alkyl having 1 to 12 carbons, and Y ² , Y ³ , Y ⁴ , and Y ⁵ are independently hydrogen or fluorine. At least one compound selected from the group of compounds represented by formula (1-1) and formula (1-2) as the first component, and formula (2-1) and formula (2-2) as the second component And at least one compound selected from the group of compounds represented by formula (3-1) and formula (3-2) as the third component The proportion of the first component is in the range of 5% to 50% by weight, the proportion of the second component is in the range of 30% to 95% by weight and the proportion of the third component is from 5% by weight. A liquid crystal composition having a nematic phase in the range of 40% by weight and containing no liquid crystal compound different from these compounds.

Here, R ¹ , R ² and R ³ are independently alkyl having 1 to 12 carbons, Z ¹ and Z ² are independently a single bond or ethylene, X ¹ is independently fluorine, Chlorine, OCF ₃ or OCF ₂ H, Y ¹ , Y ² , Y ³ , Y ⁴ and Y ⁵ are independently hydrogen or fluorine, and n is independently 1 or 2. At least one compound further contains selected from the group of compounds represented by formula (4) as a fourth component, according to claim 2 or 4 ratio of the fourth component is from 1 wt% to 30 wt% The liquid crystal composition described in 1.

Here, R ⁴ is alkyl having 1 to 12 carbons, X ² is fluorine or OCF ₃ , and Y ⁶ is hydrogen or fluorine. The liquid crystal composition according to any one of claims 1, further comprising an ultraviolet absorber 4. The liquid crystal display element containing the liquid-crystal composition of any one of Claim 1 to 5 .