TWI812775B - Liquid crystal composition and use thereof, and liquid crystal display device - Google Patents

Abstract

The present invention provides a liquid crystal composition and an AM element containing the composition. The liquid crystal composition has high upper limit temperature, low lower limit temperature, low viscosity, appropriate optical anisotropy, large dielectric anisotropy, and large specific resistance. , high stability to light, high stability to heat, etc., fully satisfying at least one of the characteristics, or having an appropriate balance with respect to at least two characteristics. The liquid crystal composition of the present invention contains at least one compound selected from the group consisting of compounds having a monovalent group represented by formula (S) as a first additive, and may also contain a compound having large positive dielectric anisotropy as a first component. a specific compound having a high upper limit temperature or a small viscosity as the second component, or a specific compound having a large negative dielectric anisotropy as the third component.

Description

Liquid crystal compositions and their uses, and liquid crystal display elements

The present invention relates to a liquid crystal composition and its use, as well as a liquid crystal display element containing the composition, and the like. In particular, it relates to a liquid crystal composition with positive dielectric anisotropy, and a liquid crystal composition containing the composition and having twisted nematic (TN), electronically controlled birefringence (ECB), optically compensated bending (OCB), and in-plane switching (IPS). ), fringe field switching (FFS) or field-induced photoreactive alignment (FPA) active matrix (AM) components.

In liquid crystal display elements, the operating modes based on liquid crystal molecules are classified into phase change (PC), twisted nematic (TN), super twisted nematic (STN), electronically controlled birefringence ( electrically controlled birefringence (ECB), optically compensated bend (OCB), in-plane switching (IPS), vertical alignment (VA), fringe field switching (FFS), Field-induced photo-reactive alignment (FPA) and other modes. Component-based driving methods are classified into passive matrix (PM) and active matrix (AM). PM is classified into static type (static) and multiplex type (multiplex), etc., and AM is classified into thin film transistor (TFT), metal-insulator-metal (metal insulator metal, MIM), etc. TFTs are classified into amorphous silicon and polycrystal silicon. The latter are classified into high-temperature and low-temperature types based on the manufacturing process. Classification based on light source is reflective type that uses natural light, transmissive type that uses backlight, and semi-transmissive type that uses both natural light and backlight.

The liquid crystal display element contains a liquid crystal composition having a nematic phase. The composition has suitable properties. By improving the characteristics of the composition, AM elements with good characteristics can be obtained. The correlation among these characteristics is summarized in Table 1 below. The characteristics of the composition will be further described based on commercially available AM elements. The temperature range of the nematic phase is related to the temperature range in which the component can be used. 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 component. In order to display dynamic images using elements, a short response time is preferred. A response time of less than 1 millisecond is ideal. Therefore, it is preferable that the viscosity of the composition is small. Furthermore, it is preferable that the viscosity at low temperature is small. The elastic constant of the composition is related to the contrast of the element. In order to improve the contrast of the element, it is more preferable that the elastic constant of the composition is large.

[Table 1]

The optical anisotropy of the composition is related to the contrast of the element. Depending on the mode of the element, large optical anisotropy or small optical anisotropy, that is, appropriate optical anisotropy, is required. The product (Δn×d) of the optical anisotropy (Δn) of the composition and the cell gap (d) of the element is designed to maximize the contrast. The appropriate product value depends on the type of operating mode. For elements of the TN mode, the appropriate value is approximately 0.45 μm. In this case, a composition having a large optical anisotropy is preferable for an element with a small cell gap. The large dielectric anisotropy of the composition contributes to the low threshold voltage, small power consumption and large contrast ratio of the device. Therefore, large dielectric anisotropy is preferred. The large specific resistance of the composition contributes to the large voltage holding rate and large contrast ratio of the device. Therefore, a composition having a large specific resistance not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase in the initial stage is preferred. Preferably, a composition has a large specific resistance not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase after long-term use. The stability of the composition to light and heat is related to the life of the liquid crystal display element. When these stabilities are high, the component has a long life. Such characteristics are preferred for AM elements used in liquid crystal monitors, liquid crystal televisions, and the like.

AM elements having a TN mode use a composition having positive dielectric anisotropy. A composition having negative dielectric anisotropy is used in an AM element having a VA mode. AM elements having an IPS mode or an FFS mode use a composition having positive or negative dielectric anisotropy. Polymer sustained alignment (PSA) type AM devices use compositions with positive or negative dielectric anisotropy.

Furthermore, these liquid crystal display elements are required to have excellent display quality in which display defects such as burning marks and display unevenness are eliminated or suppressed. In order to realize this, attempts are being made to add various additives to the liquid crystal composition to improve the overall reliability of the Liquid Crystal Display (LCD) panel. [Prior art documents] [Patent Document]

[Patent Document 1] Japanese Patent Application Laid-Open No. 2017-105762

[Problem to be solved by the invention]

An object of the present invention is to provide a liquid crystal composition containing a compound having an effect of suppressing display defects such as line afterimage and an antistatic effect. Another subject is to provide a liquid crystal composition that satisfies the requirements of high upper limit temperature of the nematic phase, low lower limit temperature of the nematic phase, low viscosity, appropriate optical anisotropy, large positive dielectric anisotropy, large specific resistance, At least one of the characteristics of high stability to light, high stability to heat, and large elastic constant. Another subject is to provide a liquid crystal composition having an appropriate balance between at least two of these characteristics. Another subject is to provide a liquid crystal display element containing such a composition. Another object is to provide a liquid crystal display element with excellent display quality that eliminates or suppresses display defects such as burn marks and display unevenness by using such a composition. Another subject is to provide an AM element having characteristics such as short response time, high voltage retention, low threshold voltage, high contrast, and long life. [Technical means to solve problems]

The present inventors conducted research on various liquid crystal compounds and various chemical substances, found that the above problems can be solved by using specific compounds, and completed the present invention. That is, the present invention provides a liquid crystal composition containing at least one compound selected from the group consisting of compounds having a monovalent group represented by formula (S), and a liquid crystal display element using the composition. The first additive has a nematic phase and positive dielectric anisotropy. In the formula (S), R ^a is hydrogen, O·, OH, an alkyl group with 1 to 20 carbon atoms, an alicyclic hydrocarbon group with 3 to 20 carbon atoms, or an aromatic hydrocarbon group with 6 to 20 carbon atoms. Among these groups , at least one -CH ₂ - can be substituted by -O-, -NH-, -CO-, -COO- or -OCO-, at least one -CH ₂ -CH ₂ - can be substituted by -CH=CH- or -C≡ C-substituted, among these groups, at least one hydrogen can be substituted by an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, halogen, OH, NHR ^1b or NR ^1c R ^1d ; R ^1b , R ^1c and R ^1d is an alkyl group having 1 to 10 carbon atoms. [Effects of the invention]

An advantage of the present invention is to provide a liquid crystal composition containing a compound that has the effect of suppressing display defects such as line afterimages and the antistatic effect. Another advantage is to provide a liquid crystal composition that fully satisfies the requirements of high upper limit temperature of the nematic phase, low lower limit temperature of the nematic phase, low viscosity, appropriate optical anisotropy, large positive dielectric anisotropy, large specific resistance, At least one of the characteristics of high stability to light and high stability to heat. Another advantage is to provide a liquid crystal composition having an appropriate balance between at least two of these properties. Another advantage is to provide a liquid crystal display element containing such a composition. Another advantage is to provide a liquid crystal display element with excellent display quality that eliminates or suppresses display defects such as burn marks and display unevenness. Another advantage is to provide an AM element with characteristics such as short response time, large voltage holding rate, low threshold voltage, large contrast, and long life.

The terms used in this manual are as follows. The terms "liquid crystal composition" and "liquid crystal display element" are sometimes simply referred to as "composition" and "element" respectively. "Liquid crystal display element" is the general term for liquid crystal display panels and liquid crystal display modules. "Liquid crystalline compounds" are compounds that have a liquid crystal phase such as a nematic phase or a smectic phase, and compounds that do not have a liquid crystal phase but are used to adjust the temperature range, viscosity, and dielectric anisotropy of the nematic phase. A general term for compounds mixed into compositions for the purpose of such properties. The compound has a six-membered ring such as 1,4-cyclohexylene or 1,4-phenylene, and its molecule (liquid crystal molecule) is rod-like. A "polymerizable compound" is a compound added for the purpose of producing a polymer in the composition. Liquid crystalline compounds having an alkenyl group are not classified as polymeric compounds in their meaning.

A liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. Additives such as optically active compounds or polymerizable compounds may be added to the liquid crystal composition as necessary. Even when an additive is added, the proportion of the liquid crystal compound is expressed as a mass percentage (mass %) based on the mass of the liquid crystal composition not containing the additive. The proportion of the additive is expressed as a mass percentage (mass %) based on the mass of the liquid crystal composition not containing the additive. That is, the ratio of the liquid crystal compound or the additive is calculated based on the total mass of the liquid crystal compound.

Sometimes the "upper limit temperature of the nematic phase" is simply called the "upper limit temperature". Sometimes the "lower temperature limit of the nematic phase" is simply called the "lower limit temperature". The expression "increase dielectric anisotropy" means that the value increases positively when the dielectric anisotropy is positive in the composition, and means that the value becomes negative when the dielectric anisotropy is negative in the composition. Increase towards the ground. "Large voltage retention rate" means that the element has a large voltage retention 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, not only at room temperature, but also at temperatures close to the upper limit temperature. It also has a large voltage retention rate at temperatures close to the upper limit temperature. Sometimes the characteristics of a composition or component are studied through time-dependent changes.

The compound (1z) will be used as an example for explanation. In the formula (1z), the symbols α and β surrounded by hexagons correspond to the ring α and the ring β respectively, and represent rings such as six-membered rings and condensed rings. 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. The rule applies to any two rings α when the subscript 'x' is greater than 2. The same rules apply to other notations such as the bonding base Z. A diagonal line cutting across one side of ring β indicates that any hydrogen on ring β may be substituted by a substituent (-Sp-P). The subscript 'y' indicates the number of substituents substituted. When the subscript 'y' is 0, there is no such substitution. When the subscript 'y' is 2 or more, there are multiple substituents (-Sp-P) on ring β. In that case, the "may be the same or may be different" rule also applies. Furthermore, the above-mentioned rule also applies to the case where the notation R ^a is used for a plurality of compounds.

In the formula (1z), for example, the expression "R ^a and R ^b are alkyl, alkoxy or alkenyl" means that R ^a and R ^b are independently selected from the group of alkyl, alkoxy and alkenyl. group. Here, the group represented by R ^a and the group represented by R ^b may be the same or different. The rules also apply when the notation R ^a is used for multiple compounds. The rules also apply when more than one R ^a is used in a compound.

At least one compound selected from the compounds represented by formula (1z) may be simply referred to 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 group of 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' can be replaced by 'B'" means that when the number of 'A' is one, the position of 'A' is arbitrary, and when the number of 'A' is two or more, their position Unlimited options are also available. The expression "at least one _-CH2- may be substituted by -O-" is sometimes used. In this case, _-CH2 - _CH2 - _CH2- can be converted to -O- _CH2 -O- by substitution of a non-adjacent _-CH2- with -O-. However, there is no case where the adjacent _-CH2- is substituted with -O-. The reason is that -OO-CH ₂ - (peroxide) is generated during the substitution.

The alkyl group of the liquid crystal compound is linear or branched, and does not contain a cyclic alkyl group. Linear alkyl groups are preferred over branched alkyl groups. These conditions are also the same for terminal groups such as alkoxy groups and alkenyl groups. Regarding the configuration related to 1,4-cyclohexylene, in order to increase the upper limit temperature, the trans (trans) configuration is preferred over the cis (cis) configuration. Since the 2-fluoro-1,4-phenylene group is asymmetrical, it faces left (L) and right (R). The same applies to divalent radicals such as tetrahydropyran-2,5-diyl. Furthermore, in order to increase the upper limit temperature, it is preferable that the tetrahydropyran-2,5-diyl group faces right (R). The same goes for bonding groups such as carbonyloxy (-COO- or -OCO-).

The present invention includes the following items and the like.

Item 1. A liquid crystal composition containing at least one compound selected from compounds having a monovalent group represented by formula (S) as a first additive and having a nematic phase and positive dielectric anisotropy. In the formula (S), R ^a is hydrogen, O·, OH, an alkyl group with 1 to 20 carbon atoms, an alicyclic hydrocarbon group with 3 to 20 carbon atoms, or an aromatic hydrocarbon group with 6 to 20 carbon atoms. Among these groups , at least one -CH ₂ - can be substituted by -O-, -NH-, -CO-, -COO- or -OCO-, at least one -CH ₂ -CH ₂ - can be substituted by -CH=CH- or -C≡ C-substituted, among these groups, at least one hydrogen can be substituted by an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, halogen, OH, NHR ^1b or NR ^1c R ^1d ; R ^1b , R ^1c and R ^1d is an alkyl group having 1 to 10 carbon atoms.

Item 2. The liquid crystal composition according to Item 1, which contains at least one compound selected from the compounds represented by Formula (1) as a first additive. In formula (1), R ^b is hydrogen, fluorine, an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and at least one of these groups is -CH ₂ - may be substituted by -O-, -NH-, -CO-, -COO- or -OCO-, and at least one -CH ₂ -CH ₂ - may be substituted by -CH=CH- or -C≡C- , among these groups, at least one hydrogen may be substituted by an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, halogen, OH, NHR ^1b or NR ^1c R ^1d ; R ^1b , R ^1c and R ^1d is an alkyl group with 1 to 10 carbon atoms; M is a single bond, a tetravalent aliphatic hydrocarbon group with 1 to 20 carbon atoms, or a tetravalent aromatic hydrocarbon group with 6 to 20 carbon atoms. Among these groups, at least one -CH ₂ - can be substituted by -O- or -S-, one or two -CH=CH- can be substituted by -CH=N-, at least one hydrogen can be substituted by fluorine or chlorine; Z ^a and Z ^b are single bonds, -O-, -COO-, -OCO-, alkylene group with 1 to 20 carbon atoms, or alkenylene group with 2 to 20 carbon atoms. In these groups, at least one hydrogen can be substituted by fluorine, chlorine, or OH; Q ^a is a monovalent group represented by formula (S); n is 1, 2, 3 or 4; m is 4-n; where, when M is a single bond, n and m are 1; In the formula (S), R ^a is hydrogen, O·, OH, an alkyl group with 1 to 20 carbon atoms, an alicyclic hydrocarbon group with 3 to 20 carbon atoms, or an aromatic hydrocarbon group with 6 to 20 carbon atoms. Among these groups , at least one -CH ₂ - can be substituted by -O-, -NH-, -CO-, -COO- or -OCO-, at least one -CH ₂ -CH ₂ - can be substituted by -CH=CH- or -C≡ C-substituted, among these groups, at least one hydrogen can be substituted by an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, halogen, OH, NHR ^1b or NR ^1c R ^1d ; R ^1b , R ^1c and R ^1d is an alkyl group having 1 to 10 carbon atoms.

Item 3. The liquid crystal composition according to Item 1 or 2, which contains at least one compound selected from the compounds represented by Formula (1-1) to Formula (1-5) as a first additive. In Formula (1-1) to Formula (1-5), Z ^c is a single bond, an alkylene group with 1 to 5 carbon atoms, or an alkenylene group with 2 to 5 carbon atoms. In these groups, at least one hydrogen can Substituted by OH; R ^c is hydrogen, an alkyl group with 1 to 20 carbon atoms, an alicyclic hydrocarbon group with 3 to 20 carbon atoms, or an aromatic hydrocarbon group with 6 to 20 carbon atoms. Among these groups, at least one -CH ₂ - Can be substituted by -O-, -CO-, -COO- or -OCO-, at least one -CH ₂ -CH ₂ - can be substituted by -CH=CH- or -C≡C-, at least one of these groups is hydrogen Can be substituted by OH, an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, or an aromatic hydrocarbon group with 6 to 20 carbon atoms; s is an integer from 1 to 20; Q ^b is the formula (S- 1) The monovalent base represented; In formula (S-1), R ^d is hydrogen, O·, OH, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. Among these groups, , at least one hydrogen may be substituted by halogen.

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

Item 5. The liquid crystal composition according to any one of Items 1 to 4, which contains at least one compound selected from the compounds represented by Formula (2) as a first component. In formula (2), R ^2a is an alkyl group with 1 to 12 carbon atoms, an alkoxy group with 1 to 12 carbon atoms, or an alkenyl group with 2 to 12 carbon atoms; ring A is 1,4-cyclohexylene, 1 ,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyrimidine -2,5-diyl, 1,3-dioxane-2,5-diyl or tetrahydropyran-2,5-diyl; Z ^2a is a single bond, ethylene group, vinylene group, carbonyl ^{Oxygen or} difluoromethyleneoxy; X ^2a and or an alkoxy group having 1 to 12 carbon atoms substituted by chlorine, or an alkenyloxy group having 2 to 12 carbon atoms in which at least one hydrogen is substituted by fluorine or chlorine; a is 1, 2, 3 or 4.

Item 6. The liquid crystal composition according to any one of Items 1 to 5, which contains at least one compound selected from the compounds represented by Formula (2-1) to Formula (2-35) as a first component . In Formula (2-1) to Formula (2-35), R ^2a is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms.

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

Item 8. The liquid crystal composition according to any one of Items 1 to 7, which contains at least one compound selected from the compounds represented by Formula (3) as a second component. In formula (3), R ^3a and R ^3b are an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or at least one hydrogen substituted by fluorine or chlorine. Alkenyl group with 2 to 12 carbon atoms; ring B and ring C are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene or 2,5-difluoro- 1,4-phenylene; Z ^3a is a single bond, ethylene, vinylene, methyleneoxy or carbonyloxy; b is 1, 2 or 3.

Item 9. The liquid crystal composition according to any one of Items 1 to 8, which contains at least one compound selected from the compounds represented by Formula (3-1) to Formula (3-13) as a second component . In Formula (3-1) to Formula (3-13), R ^3a and R ^3b are an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or Alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen is substituted by fluorine or chlorine.

Item 10. The liquid crystal composition according to Item 8 or 9, wherein the proportion of the second component is in the range of 10 mass% to 85 mass%.

Item 11. The liquid crystal composition according to any one of Items 1 to 10, which contains at least one compound selected from the compounds represented by Formula (4) as a third component. In formula (4), R ^4a and R ^4b are hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms. Oxygen group; Ring D and Ring F are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, and at least one hydrogen 1,4-phenylene substituted with fluorine or chlorine, naphthalene-2,6-diyl, naphthalene-2,6-diyl with at least one hydrogen substituted with fluorine or chlorine, chroman-2,6-diyl base, or a chroman-2,6-diyl group in which at least one hydrogen is substituted by fluorine or 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-difluoro Chroman-2,6-diyl, 3,4,5,6-tetrafluorofluorene-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 ^4a and Z ^4b are single bonds, ethylene, and ethylene Vinyl, methyleneoxy or carbonyloxy; c is 0, 1, 2 or 3, d is 0 or 1; and the sum of c and d is 3 or less.

Item 12. The liquid crystal composition according to any one of Items 1 to 11, which contains at least one compound selected from the compounds represented by Formula (4-1) to Formula (4-35) as a third component . In Formula (4-1) to Formula (4-35), R ^4a and R ^4b are hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms. , or an alkenyloxy group having 2 to 12 carbon atoms.

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

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

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

Item 16. The liquid crystal display element according to item 15, wherein the operation mode of the liquid crystal display element is TN mode, ECB mode, OCB mode, IPS mode, FFS mode or FPA mode, and the driving mode of the liquid crystal display element is active matrix mode. .

Item 17. Use of a liquid crystal composition, which is the liquid crystal composition according to any one of Items 1 to 14, and is used in a liquid crystal display element.

The present invention also includes the following items. (a) The composition contains additives selected from the group consisting of optically active compounds, antioxidants, ultraviolet absorbers, matting agents, pigments, defoaming agents, polymerizable compounds, polymerization initiators, and polymerization inhibitors. One compound, two compounds, or three or more compounds. (b) An AM element containing the composition. (c) The composition further containing a polymerizable compound, and a polymer stable alignment (PSA) type AM element containing the composition. (d) A polymer stable alignment (PSA) type AM element, which contains the composition, and the polymerizable compound in the composition is polymerized. (e) A component containing the composition and having a pattern of PC, TN, STN, ECB, OCB, IPS, VA, FFS or FPA. (f) A transmission type element containing the composition. (g) Use of the composition as a composition having a nematic phase. (h) Use of an optically active composition obtained by adding an optically active compound to said composition.

The composition of the present invention will be described in the following order. First, the structure of the component compounds in the composition is explained. Second, the main characteristics of the component compounds and the main effects brought by the compounds to the composition or component are explained. Third, the combination of the component compounds in the composition, the preferred ratio of the component compounds, and their basis are explained. Fourth, preferred forms of the component compounds will be described. Fifth, preferred component compounds are shown. Sixth, additives that can be added to the composition will be described. Seventh, the synthesis method of the component compounds will be described. Finally, the use of the composition is explained.

First, the structure of the component compounds in the composition is explained. The composition contains a plurality of liquid crystal compounds. The composition may also contain additives. Additives include optically active compounds, antioxidants, ultraviolet absorbers, matting agents, pigments, defoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds, etc. From the viewpoint of liquid crystal compounds, the compositions are classified into composition A and composition B. Composition A may contain other liquid crystal compounds, additives, etc., in addition to the liquid crystal compound selected from the group consisting of compound (2), compound (3), and compound (4). "Other liquid crystal compounds" are liquid crystal compounds different from compound (2), compound (3), and compound (4). Such compounds are mixed into the composition for the purpose of further adjusting the properties.

Composition B substantially contains only a liquid crystal compound selected from the group consisting of compound (2), compound (3) and compound (4). "Substantially" means that although composition B may contain additives, it does not contain other liquid crystal compounds. Compared with composition A, composition B has a smaller number of components. From the viewpoint of cost reduction, composition B is superior to composition A. From the viewpoint that the characteristics can be further adjusted by mixing other liquid crystal compounds, composition A is superior to composition B.

Second, the main characteristics of the component compounds and the main effects brought by the compounds to the composition or component are explained. Based on the effects of the present invention, the main characteristics 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 smaller than S.

[Table 2]

The main effects of the component compounds are described below. The first additive functions as an inhibitor of display defects such as burn marks and display unevenness. The amount of compound (1) added is small, so in most cases, it does not affect characteristics such as upper limit temperature, optical anisotropy, and dielectric anisotropy. Compound (2) increases dielectric anisotropy and lowers the lower limit temperature. Compound (3) reduces the viscosity or increases the upper limit temperature. Compound (4) increases the dielectric constant in the short axis direction.

Display quality may significantly decrease due to long-term use of liquid crystal display elements. As one of the factors, the following is considered: a small amount of inherent charged particles in the liquid crystal composition are concentrated in a biased manner due to long-term driving, or potential is accumulated between element components other than the liquid crystal composition and the liquid crystal composition for some reason. , resulting in display defects such as burn marks or uneven display.

The first additive of the present invention is at least one compound selected from the group consisting of compounds having a monovalent group represented by formula (S). By adding the compound, the resistance of the liquid crystal display element can be extremely reduced without significantly reducing the specific resistance value of the liquid crystal composition. The amino group of the compound is attracted to the adsorption site of the peripheral material of the LCD panel (for example, the carbonyl group located on the surface of the alignment film), forming an adsorption layer. The layer has a low resistance value, thereby suppressing the deflection of charged particles or accumulation of potential, thereby suppressing display defects such as burn marks and display unevenness. Functions as a so-called topical antistatic agent.

Third, the combination of the component compounds in the composition, the preferred ratio of the component compounds, and their basis are explained. Preferred combinations of component compounds in the composition are first additive + compound (2), first additive + compound (3), first additive + compound (2) + compound (4), first additive + Compound (3) + compound (4), first additive + compound (2) + compound (3), first additive + compound (2) + compound (3) + compound (4). Further preferred combinations are first additive + compound (2) + compound (3) or first additive + compound (2) + compound (3) + compound (4).

The preferred proportion of the first additive is approximately 0.001% by mass or more. In order to lower the lower limit temperature, the preferred proportion of the first additive is approximately 2% by mass or less. A further preferred ratio is in the range of about 0.010% by mass to about 1.000% by mass. A particularly preferred ratio is in the range of about 0.020 mass% to about 0.150 mass%.

In order to improve the dielectric anisotropy, the preferred proportion of the compound (2) is about 10 mass % or more, and in order to lower the lower limit temperature or reduce the viscosity, the preferred proportion of the compound (2) is about 85 mass % or less. A further preferred ratio is in the range of about 20% by mass to about 80% by mass. A particularly preferred ratio is in the range of about 30% by mass to about 70% by mass.

In order to increase the upper limit temperature or to reduce the viscosity, the preferred proportion of compound (3) is about 10 mass % or more, and in order to increase the dielectric anisotropy, the preferred proportion of compound (3) is about 85 mass % or less. A further preferred ratio is in the range of about 20% by mass to about 80% by mass. A particularly preferred ratio is in the range of about 25% by mass to about 70% by mass.

In order to increase the dielectric constant in the short axis direction, the preferable proportion of compound (4) is about 3 mass % or more, and in order to lower the lower limit temperature, the preferable proportion of compound (4) is about 45 mass % or less. A further preferred ratio is in the range of about 5% by mass to about 40% by mass. A particularly preferred ratio is in the range of about 5% by mass to about 35% by mass.

Fourth, preferred forms of the component compounds will be described. In formula (1), R ^b is hydrogen, fluorine, an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and at least one of these groups is -CH ₂ - may be substituted by -O-, -NH-, -CO-, -COO- or -OCO-, and at least one -CH ₂ -CH ₂ - may be substituted by -CH=CH- or -C≡C- , among these groups, at least one hydrogen may be substituted by an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, halogen, OH, NHR ^1b or NR ^1c R ^1d . R ^1b , R ^1c and R ^1d are alkyl groups having 1 to 10 carbon atoms. Preferred R ^b is hydrogen, an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 6 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 15 carbon atoms. Preferably R ^1b , R ^1c or R ^1d is an alkyl group having 1 to 5 carbon atoms. M is a single bond, a tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a tetravalent aromatic hydrocarbon group having 6 to 20 carbon atoms. Among these groups, at least one -CH ₂ - can be passed through -O- or -S -Substituted, one or two -CH=CH- may be substituted by -CH=N-, and at least one hydrogen may be substituted by fluorine or chlorine. Preferably, M is a tetravalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, or a tetravalent aromatic hydrocarbon group having 6 to 10 carbon atoms. Z ^a and Z ^b are single bonds, -O-, -COO-, -OCO-, alkylene groups with 1 to 20 carbon atoms, or alkenylene groups with 2 to 20 carbon atoms. In these groups, at least one hydrogen can Substituted by fluorine, chlorine and OH. Preferred Z ^a or Z ^b is a single bond, -COO-, -OCO-, or an alkylene group having 1 to 5 carbon atoms. Q ^a is a monovalent base represented by formula (S). n is 1, 2, 3 or 4; m is 4-n. Preferred n is 2 or 4. In the formula (S), R ^a is hydrogen, O·, OH, an alkyl group with 1 to 20 carbon atoms, an alicyclic hydrocarbon group with 3 to 20 carbon atoms, or an aromatic hydrocarbon group with 6 to 20 carbon atoms. Among these groups , at least one -CH ₂ - can be substituted by -O-, -NH-, -CO-, -COO- or -OCO-, at least one -CH ₂ -CH ₂ - can be substituted by -CH=CH- or -C≡ C-substituted, in these groups, at least one hydrogen may be substituted by an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, halogen, OH, NHR ^1b or NR ^1c R ^1d . R ^1b , R ^1c and R ^1d are alkyl groups having 1 to 10 carbon atoms. Preferably R ^a is methyl. Preferably R ^1b , R ^1c or R ^1d is an alkyl group having 1 to 5 carbon atoms.

In Formula (1-1) to Formula (1-5), Z ^c is a single bond, an alkylene group with 1 to 5 carbon atoms, or an alkenylene group with 2 to 5 carbon atoms. In these groups, at least one hydrogen can Replaced by OH. Preferred Z ^c is a single bond, methylene or ethylene. R ^c is hydrogen, an alkyl group with 1 to 20 carbon atoms, an alicyclic hydrocarbon group with 3 to 20 carbon atoms, or an aromatic hydrocarbon group with 6 to 20 carbon atoms. Among these groups, at least one -CH ₂ - can be passed through -O -, -CO-, -COO- or -OCO- substituted, at least one -CH ₂ -CH ₂ - can be substituted by -CH=CH- or -C≡C-, in these groups, at least one hydrogen can be substituted by OH, Substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms. Preferred R ^c is an aromatic hydrocarbon group having 6 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms in which at least one hydrogen is substituted by OH. s is an integer from 1 to 20. Preferably s is an integer from 1 to 8. Q ^b is a monovalent base represented by formula (S-1). Here, R ^d is hydrogen, O·, OH, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. Among these groups, at least one hydrogen may be Substituted by halogen. Preferably R ^d is methyl.

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

In formula (2), formula (3) and formula (4), R ^2a is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms. In order to improve the stability to light or heat, it is preferred that R ^2a is an alkyl group having 1 to 12 carbon atoms. R ^3a and R ^3b are an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkyl group having 2 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine. alkenyl. In order to reduce the viscosity, it is preferable that R ^3a or R ^3b is an alkenyl group having 2 to 12 carbon atoms. In order to improve the stability against light or heat, it is preferable that R ^3a or R ^3b is an alkyl group having 1 to 12 carbon atoms. R ^4a and R ^4b are hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyloxy group having 2 to 12 carbon atoms. In order to improve the stability to light or heat, preferably R ^4a or R ^4b is an alkyl group with 1 to 12 carbon atoms. In order to improve the dielectric anisotropy, preferably R ^4a or R ^4b is an alkyl group with 1 to 12 carbon atoms. Oxygen group.

Preferred alkyl groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl. In order to reduce the viscosity, further preferred alkyl groups are methyl, ethyl, propyl, butyl or pentyl.

Preferred alkoxy groups are methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy or heptyloxy. In order to reduce the viscosity, the alkoxy group is more preferably a methoxy group or an ethoxy group.

Preferred alkenyl groups 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. In order to reduce the viscosity, further preferred alkenyl groups are vinyl, 1-propenyl, 3-butenyl or 3-pentenyl. The preferred stereoconfiguration of -CH=CH- in these alkenyl groups depends on the position of the double bond. In order to reduce viscosity, etc., in alkenyl groups such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl, and 3-hexenyl The trans form is preferred. Among alkenyl groups such as 2-butenyl, 2-pentenyl, and 2-hexenyl, the cis form is preferred.

Preferred alkenyloxy groups are vinyloxy, allyloxy, 3-butenoxy, 3-pentenyloxy or 4-pentenyloxy. In order to reduce the viscosity, further preferred alkenyloxy groups are allyloxy groups or 3-butenoxy groups.

Preferred examples of alkyl groups in which at least one hydrogen is substituted by fluorine or chlorine are fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl, 7- Fluoroheptyl or 8-fluorooctyl. In order to improve the dielectric anisotropy, further preferred examples are 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl or 5-fluoropentyl.

Preferred examples of alkenyl groups in which at least one hydrogen is substituted 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. In order to reduce the viscosity, further preferred examples are 2,2-difluorovinyl or 4,4-difluoro-3-butenyl.

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. In order to increase the optical anisotropy, preferred ring A is 1,4-phenylene or 2-fluoro-1,4-phenylene. Tetrahydropyran-2,5-diyl is or , preferably .

Ring B and ring C are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene. In order to reduce the viscosity, the preferred ring B or ring C is a 1,4-cyclohexylene group, and in order to improve the optical anisotropy, the preferred ring B or ring C is a 1,4-phenylene group. Ring D and ring F are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen is modified by fluorine or Chlorine-substituted 1,4-phenylene, naphthalene-2,6-diyl, at least one hydrogen substituted with fluorine or chlorine, naphthalene-2,6-diyl, chroman-2,6-diyl, or Chroman-2,6-diyl in which at least one hydrogen is substituted by fluorine or chlorine. Preferred examples of "1,4-phenylene in which at least one hydrogen is substituted by fluorine or chlorine" are 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene or 2 -Chloro-3-fluoro-1,4-phenylene. In order to reduce the viscosity, the preferred ring D or ring F is 1,4-cyclohexylene. In order to improve the dielectric anisotropy, the preferred ring D or ring F is tetrahydropyran-2,5-diyl. In order to improve the dielectric anisotropy, Optical anisotropy, preferred ring D or ring F is 1,4-phenylene. Ring E is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4- Phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, 7,8-difluorochroman-2,6-diyl, 3,4,5,6-tetrafluorofluorene- 2,7-diyl (FLF4), 4,6-difluorodibenzofuran-3,7-diyl (DBFF2), 4,6-difluorodibenzothiophene-3,7-diyl (DBTF2 ) or 1,1,6,7-tetrafluoroindan-2,5-diyl (InF4). In order to reduce the viscosity, the preferred ring E is 2,3-difluoro-1,4-phenylene. In order to reduce the optical anisotropy, the preferred ring E is 2-chloro-3-fluoro-1,4-phenylene. In order to improve the dielectric anisotropy, the preferred ring E is 7,8-difluorochroman-2,6-diyl.

Z ^2a is a single bond, ethylene group, vinylene group, carbonyloxy group or difluoromethyleneoxy group. In order to reduce the viscosity, Z ^2a is preferably a single bond, and in order to increase the dielectric anisotropy, Z ^2a is preferably a difluoromethyleneoxy group. Z ^3a is a single bond, ethylene group, vinylene group, methyleneoxy group or carbonyloxy group. In order to reduce the viscosity, it is preferred that Z ^3a is a single bond. Z ^4a and Z ^4b are single bonds, ethylene groups, vinylene groups, methyleneoxy groups or carbonyloxy groups. In order to reduce the viscosity, Z ^4a or Z ^4b is preferably a single bond. In order to lower the lower limit temperature, Z ^4a or Z ^4b is preferably an ethylene group. In order to improve the dielectric anisotropy, Z ^4a or Z ^4b is preferably a methylene group. Oxygen group.

Bivalent groups such as methyleneoxy are asymmetrical from left to right. Among the methyleneoxy groups, -CH ₂ O- is preferred to -OCH ₂ -. Among carbonyloxy groups, -COO- is preferred to -OCO-. Among the difluoromethyleneoxy groups, -CF ₂ O- is preferred to -OCF ₂ -.

X ^2a and X ^2b are hydrogen or fluorine. In order to improve the dielectric anisotropy, it is preferable that X ^2a or X ^2b is fluorine.

Y ^2a is fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine, an alkoxy group having 1 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine, or at least one hydrogen is substituted with fluorine Or chlorine-substituted alkenyloxy group having 2 to 12 carbon atoms. In order to lower the minimum temperature, Y ^2a is preferably fluorine.

A preferred example of an alkyl group in which at least one hydrogen is substituted by fluorine or chlorine is trifluoromethyl. A preferred example of an alkoxy group in which at least one hydrogen is substituted by fluorine or chlorine is trifluoromethoxy. A preferred example of an alkenyloxy group in which at least one hydrogen is substituted by fluorine or chlorine is trifluoroethyleneoxy.

a is 1, 2, 3 or 4. In order to lower the lower limit temperature, a is preferably 2, and in order to increase the dielectric anisotropy, a is preferably 3. b is 1, 2 or 3. In order to reduce the viscosity, b is preferably 1, and in order to increase the upper limit temperature, b is preferably 2 or 3. c is 0, 1, 2 or 3, d is 0 or 1, and the sum of c and d is 3 or less. In order to reduce the viscosity, c is preferably 1, and in order to increase the upper limit temperature, c is preferably 2 or 3. In order to lower the viscosity, d is preferably 0, and in order to lower the lower limit temperature, d is preferably 1.

Fifth, preferred component compounds are shown. Preferred compounds (1) are compounds (1-1) to (1-5) described in item 3. Among these compounds, compound (1-1) or compound (1-2) is preferred.

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

Preferred compounds (3) are compounds (3-1) to (3-13) described in item 9. Among these compounds, it is preferable that at least one second component is compound (3-1), compound (3-3), compound (3-5), compound (3-6), or compound (3-7). At least two preferred second components are compound (3-1) and compound (3-5), compound (3-1) and compound (3-6), compound (3-1) and compound (3-7) ), combinations of compound (3-3) and compound (3-5), compound (3-3) and compound (3-6), compound (3-3) and compound (3-7).

Preferred compounds (4) are compounds (4-1) to (4-35) described in Item 12. Among these compounds, at least one preferred third component is compound (4-1), compound (4-3), compound (4-6), compound (4-8), compound (4-10), compound ( 4-14) or compound (4-16). Preferred at least two third components are compound (4-1) and compound (4-8), compound (4-1) and compound (4-14), compound (4-3) and compound (4-8) ), compound (4-3) and compound (4-14), compound (4-3) and compound (4-16), compound (4-6) and compound (4-8), compound (4-6) and combinations of compound (4-10), compound (4-6) and compound (4-16), compound (4-10) and compound (4-16).

Sixth, additives that can be added to the composition will be described. Such additives include optically active compounds, antioxidants, ultraviolet absorbers, matting agents, pigments, defoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds, etc. The optically active compound is added to the composition for the purpose of inducing a helical structure of the liquid crystal molecules and imparting a torsion angle. Examples of such compounds are compound (5-1) to compound (5-5). The preferred proportion of the optically active compound is about 5% by mass or less. A further preferred ratio is in the range of about 0.01% by mass to about 2% by mass.

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 temperatures close to the upper limit temperature after using the element for a long time, it is also possible to further Antioxidants such as compounds (6-1) to (6-3) are added to the composition.

Since the compound (6-2) has low volatility, it is effective in maintaining a large voltage holding ratio not only at room temperature but also at temperatures close to the upper limit temperature after the device is used for a long time. In order to obtain the effect, the preferred ratio of the antioxidant is about 50 ppm or more, and in order not to lower the upper limit temperature or to raise the lower limit temperature, the preferred ratio of the antioxidant is about 600 ppm or less. A further preferred ratio is in the range of about 100 ppm to about 300 ppm.

Preferred examples of ultraviolet absorbers include benzophenone derivatives, benzoate derivatives, triazole derivatives, and the like. In addition, light stabilizers such as sterically hindered amines are also preferred. Preferred examples of the light stabilizer include compounds (7-1) to compounds (7-16) and the like. In order to obtain the effect, the preferred ratio of these absorbents or stabilizers is about 50 ppm or more, and in order not to lower the upper limit temperature or to not increase the lower limit temperature, the preferred ratio of these absorbers or stabilizers is about 10,000 ppm or less. A further preferred ratio is in the range of about 100 ppm to about 10,000 ppm.

The matting agent is a compound that prevents the decomposition of the liquid crystal compound by receiving light energy absorbed by the liquid crystal compound and converting it into thermal energy. Preferred examples of the matting agent include compounds (8-1) to compounds (8-7) and the like. In order to obtain the effect, the preferred ratio of these matting agents is about 50 ppm or more, and in order to reduce the lower limit temperature, the preferred ratio of these matting agents is about 20,000 ppm or less. A further preferred ratio is in the range of about 100 ppm to about 10,000 ppm.

In order to be suitable for guest host (GH) mode components, dichroic dyes (dichroic dyes) such as azo dyes and anthraquinone dyes are added to the composition. The preferable ratio of the pigment is in the range of about 0.01% by mass to about 10% by mass. In order to prevent bubbling, defoaming agents such as dimethyl silicone oil and methyl phenyl silicone oil are added to the composition. In order to obtain the above effects, the preferred ratio of the defoaming agent is about 1 ppm or more, and in order to prevent display defects, the preferred ratio of the defoaming agent is about 1000 ppm or less. A further preferred ratio is in the range of about 1 ppm to about 500 ppm.

In order to be suitable for a polymer stable alignment (PSA) type device, a polymerizable compound is added to the composition. Preferred examples of the polymerizable compound include compounds such as acrylates, methacrylates, vinyl compounds, vinyloxy compounds, allyl ethers, epoxy compounds (oxirane, oxetane), and vinyl ketones. Further preferred examples are derivatives of acrylate or methacrylate. In order to obtain the above-mentioned effects, the preferable proportion of the polymerizable compound is about 0.05 mass % or more, and in order to prevent display defects, the preferable proportion of the polymerizable compound is about 10 mass % or less. A further preferred ratio is in the range of about 0.1% by mass to about 2% by mass. The polymerizable compound is polymerized by ultraviolet irradiation. Polymerization can also be performed in the presence of an initiator such as a photopolymerization initiator. Suitable conditions for carrying out polymerization, suitable types of starters, and suitable amounts are known to those skilled in the art and are documented in the literature. For example, as photopolymerization initiators, Irgacure 651 (registered trademark; BASF), Irgacure 184 (registered trademark; BASF) or Darocur 1173 (registered trademark) Trademark; BASF) is suitable for free radical polymerization. The preferred proportion of the photopolymerization initiator is in the range of about 0.1 mass % to about 5 mass % based on the mass of the polymerizable compound. A further preferred ratio is in the range of about 1% by mass to about 3% by mass.

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

Polar compounds are organic compounds that have polarity. Here, compounds having ionic bonds are not included. Atoms such as oxygen, sulfur, and nitrogen are electrically negative and tend to have a partial negative charge. Carbon and hydrogen tend to be neutral or have a partial positive charge. Polarity results from the uneven distribution of partial charges among different kinds of atoms in a compound. For example, the polar compound has at least one partial structure such as -OH, -COOH, -SH, -NH ₂ , >NH, >N-.

Seventh, the synthesis method of the component compounds will be explained. These compounds can be synthesized using known methods. Example synthesis method. Compound (1-A) is available from Tokyo Chemical Industry (TCI). Compound (2-4) was synthesized by the method described in Japanese Patent Application Laid-Open No. 10-204016. Compound (3-1) was synthesized by the method described in Japanese Patent Application Laid-Open No. Sho 59-176221. Compound (4-1) is synthesized by the method described in Japanese Patent Application Laid-Open No. 2000-053602. Antioxidants are commercially available. Compounds of formula (6) in which n is 1 are available from Sigma-Aldrich Corporation. Compound (6) in which n is 7 and the like are synthesized by the method described in U.S. Patent No. 3660505.

Compounds whose synthesis methods are not documented can be synthesized using the methods described in the following books: Organic Syntheses (John Wiley & Sons, Inc), Organic Reactions (Organic Reactions, John Wiley & Sons, Inc), "Comprehensive Organic Synthesis" (Pergamon Press), New Experimental Chemistry Lectures (Maruzen), etc. The composition is prepared from the compound obtained in the above manner using a known method. For example, the component compounds are mixed and then heated to dissolve each other.

Finally, the use of the composition is explained. The composition mainly has a lower limit temperature of about -10°C or lower, an upper limit temperature of about 70°C or higher, 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 can be prepared by controlling the ratio of the component compounds or by mixing other liquid crystal compounds. Compositions having an optical anisotropy in the range of about 0.10 to about 0.30 can also be prepared by trial and error. Elements containing the composition have a large voltage retention rate. The composition is suitable for AM components. The composition is particularly suitable for transmission-type AM elements. The composition can be used as a composition having a nematic phase, and can be used as an optically active composition by adding an optically active compound.

The composition can be used in AM components. Furthermore, it can also be used for PM elements. The composition can be used for AM components and PM components having PC, TN, STN, ECB, OCB, IPS, FFS, VA, FPA and other modes. It is especially preferred for AM elements having TN, OCB, IPS mode or FFS mode. In an AM element with an IPS mode or an FFS mode, when no voltage is applied, the arrangement of liquid crystal molecules may be parallel or perpendicular to the glass substrate. These elements can be reflective, transmissive or semi-transmissive. It is preferably used for transmission type elements. It can also be used for amorphous silicon-TFT devices or polycrystalline silicon-TFT devices. The composition can also be used for nematic curvilinear aligned phase (NCAP) type devices produced by microencapsulation, or for forming a three-dimensional network of polymers in the composition. Polymer dispersed (PD) type components. [Example]

The present invention will be explained in more detail by examples. The present invention is not limited by these examples. The present invention includes a mixture of the composition of Example 1 and the composition of Example 2. The present invention also includes a mixture obtained by mixing at least two of the compositions of the Examples. The synthesized compounds are identified through Nuclear Magnetic Resonance (NMR) analysis and other methods. The characteristics of compounds, compositions, and devices are measured by the methods described below.

NMR analysis: DRX-500 manufactured by Bruker BioSpin was used for measurement. In the measurement of ¹ H-NMR, the sample is dissolved in a deuterated solvent such as CDCl ₃ and measured at room temperature under conditions of 500 MHz and a cumulative count of 16 times. Tetramethylsilane was used as an internal standard. In the measurement of ¹⁹ F-NMR, CFCl ₃ was used as an internal standard, and the measurement was performed with a cumulative count of 24 times. In the description of nuclear magnetic resonance spectrum, s refers to singlet, d refers to doublet, t refers to triplet, q refers to quartet, and quin refers to quintet. (quintet), sex refers to sextet, m refers to multiplet (multiplet), and br refers to broad peak (broad).

Gas chromatography analysis: A GC-14B gas chromatograph manufactured by Shimadzu Corporation was used for measurement. The carrier gas was helium (2 mL/min). The sample vaporization chamber was set to 280°C, and the detector (flame ionization detector (FID)) was set to 300°C. When separating component compounds, 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 dimethyl polysiloxane ; non-polar). After the column was maintained at 200°C for 2 minutes, the temperature was increased to 280°C at a rate of 5°C/min. After preparing the sample into an acetone solution (0.1 mass%), 1 μL of it was injected into the sample vaporization chamber. The recorder is a C-R5A chromatograph unit (Chromatopac) manufactured by Shimadzu Corporation or its equivalent. The obtained gas chromatogram shows the retention time of the peak corresponding to the component compound and the area of the peak.

Chloroform, hexane, etc. can be used as a solvent for diluting the sample. In order to separate the component compounds, the following capillary column can be used. 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) diameter 0.32 mm, film thickness 0.25 μm), BP-1 manufactured by Australia's SGE International Pty. Ltd (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm). 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) can be used.

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

Measurement sample: When measuring the characteristics of a composition or component, the composition is used directly as a sample. When measuring the characteristics of a compound, a measurement sample is prepared by mixing the compound (15 mass%) with mother liquid crystal (85 mass%). Based on the values obtained by measurement, the characteristic values of the compounds are calculated using an extrapolation method. (Extrapolated value) = {(measured value of sample)-0.85×(measured value of mother liquid crystal)}/0.15. When the smectic phase (or crystal) precipitates at 25°C under the stated ratio, the ratio of the compound to the mother liquid crystal is 10 mass%: 90 mass%, 5 mass%: 95 mass%, 1 mass%: 99 The order of mass % is changed. The extrapolation method is used to find compound-related upper temperature limit, optical anisotropy, viscosity, and dielectric anisotropy values.

Use the following mother liquid crystal. The ratio of component compounds is expressed in mass %.

Measurement method: Use the following method to measure the characteristics. Most of these methods are methods described in the JEITA standard (JEITA·ED-2521B) reviewed and established by the Japan Electronics and Information Technology Industries Association (JEITA) or modified methods. The TN element used for measurement does not have a thin film transistor (TFT) mounted on it.

(1) Upper limit temperature of nematic phase (NI; °C): Place the sample on the hot plate of a melting point measuring device equipped with a polarizing microscope, and heat at a rate of 1 °C/min. Measure the temperature at which a part of the sample changes from a nematic phase to an isotropic liquid. The upper limit temperature of the nematic phase is sometimes simply referred to as the "upper limit temperature".

(2) Lower limit temperature of nematic phase (TC; ℃): Add the sample with nematic phase into a glass bottle and freeze in a freezer at 0°C, -10°C, -20°C, -30°C and -40°C After 10 days of storage, the liquid crystal phase was observed. For example, when the sample maintains the nematic phase at -20°C and changes to the crystalline or smectic phase at -30°C, it is recorded as TC < -20°C. The lower temperature limit of the nematic phase is sometimes simply referred to as the "lower temperature limit".

(3) Viscosity (volume viscosity; eta; 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): According to "Molecular Crystals and Liquid Crystals" (Vol. 259) by M. Imai et al. , 37 (1995)). A sample was added to a TN element with a twist angle of 0° and a distance (cell gap) between two glass substrates of 5 μm. A voltage was applied to the element in steps of 0.5 V in the range of 16 V to 19.5 V. After no voltage was applied for 0.2 seconds, the voltage was repeatedly applied with only one rectangular wave (rectangular pulse; 0.2 seconds) and without application (2 seconds). The peak current and peak time of the transient current generated by the application are measured. The rotational viscosity value was obtained based on 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 the calculation is determined by the method described below using an element that measures the rotational viscosity.

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

(6) Dielectric anisotropy (Δε; measured at 25°C): A sample was added to 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 the element, and the dielectric constant (ε∥) in the long axis direction of the liquid crystal molecules was measured after 2 seconds. A sine wave (0.5 V, 1 kHz) was applied to the element, and the dielectric constant (ε⊥) in the short axis direction of the liquid crystal molecules was measured after 2 seconds. The value of dielectric anisotropy is calculated according to the formula Δε=ε∥-ε⊥.

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

(8) Voltage holding rate (VHR-9; measured at 25°C; %): The TN element used for measurement has a polyimide alignment film, and the distance (cell gap) between two glass substrates is 5 μm. The components are sealed using an adhesive that hardens with UV rays after adding the sample. The TN element is charged by applying a pulse voltage (1 V, 60 microseconds). The attenuated voltage was measured with a high-speed voltmeter during a period of 16.67 milliseconds, and the area A between the voltage curve per unit period and the horizontal axis was found. Area B is the area without attenuation. The voltage retention rate is expressed as the percentage of area A relative to area B.

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

(10) Voltage retention rate (VHR-11; measured at 60°C; %): After irradiation with ultraviolet rays, the voltage retention rate was measured and the stability against ultraviolet rays was evaluated. The TN element used for measurement has a polyimide alignment film and a cell gap of 5 μm. The sample was injected into the device and irradiated with ultraviolet light of 5 mW/cm ² for 167 minutes. The light source is a black light manufactured by Eye Graphics Co., Ltd., F40T10/BL (peak wavelength 369 nm), and the distance between the component and the light source is 5 mm. In the measurement of VHR-11, the attenuated voltage is measured within a period of 16.67 milliseconds. Compositions with a large VHR-11 have a large stability to ultraviolet light.

(11) Voltage holding rate (VHR-12; measured at 60°C; %): After heating the TN element with the sample injected in a constant temperature bath at 120°C for 20 hours, measure the voltage holding rate and evaluate the resistance to heat. Stability. In the measurement of VHR-12, the attenuated voltage is measured within a period of 16.67 milliseconds. Compositions with large VHR-12 have large stability to heat.

(12) Voltage retention rate (VHR-13; measured at 60°C; %): After irradiating light emitting diode (LED) light, the voltage retention rate is measured and the stability to LED light is evaluated. The LED light used is light (visible light) irradiated by a typical 32-inch TV backlight unit using LEDs as light-emitting elements. The measured brightness value in the irradiation surface is 3500 cd/m ² to 3970 cd/m ² . Regarding the test, TN elements into which the sample was injected were arranged on a backlight unit and irradiated for 4 weeks, and then the voltage retention rate was measured and the stability to LED light was evaluated. In the measurement of VHR-13, the attenuated voltage is measured within a period of 16.67 milliseconds. Compositions with large VHR-13 have great stability to LED light.

(13) Response time (τ; measured at 25°C; ms): The LCD5100 model luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement. The light source is a halogen lamp. The low-pass filter is set to 5 kHz. A sample was added to a normally white mode TN element with a distance (cell gap) of 5.0 μm between two glass substrates and a twist angle of 80 degrees. A square wave (60 Hz, 5 V, 0.5 sec) was applied to the element. At this time, the element is irradiated with light from the vertical direction, and the amount of light transmitted through the element is measured. When the light amount reaches the maximum, the transmittance is considered to be 100%, and when the light amount reaches the minimum, the transmittance is considered to be 0%. Rise time (τr: rise time; milliseconds) is the time required for the transmittance to change from 90% to 10%. Fall time (τf: fall time; milliseconds) is the time required for the transmittance to change from 10% to 90%. The response time is represented by the sum of the rise time and fall time found in the manner described.

(14) Elastic constant (K; measured at 25°C; pN): HP4284A type LCR meter manufactured by Yokogawa Hewlett-Packard Co., Ltd. was used for measurement. Add the sample to a horizontal alignment element with a distance (cell gap) of 20 μm between two glass substrates. A charge of 0 to 20 volts was applied to the element, and the electrostatic capacitance and applied voltage were measured. The measured electrostatic capacitance (C) and applied voltage (V) values were measured using equations (2.98) and equation (2.101) on page 75 of "Liquid crystal device handbook" (Nikkan Kogyo Shimbun) Fitting, and obtain the values of K11 and K33 according to equation (2.99). Then, the previously calculated values of K11 and K33 are used in equation (3.18) on page 171 of "Liquid Crystal Device Handbook" to calculate K22. The elastic constant is represented by the average value of K11, K22, and K33 calculated as described above.

(15) Specific resistance (ρ; measured at 25°C; Ωcm): Inject 1.0 mL of sample into a container equipped with an electrode. A DC voltage (10 V) was applied to the container, and the DC current after 10 seconds was measured. The specific resistance is calculated according to the following formula. (Specific resistance) = {(voltage) × (capacitance of the container)}/{(DC current) × (dielectric constant of vacuum)}.

(16) Pitch (P; measured at room temperature; μm): The pitch is measured using the wedge method. Refer to "LCD Handbook", page 196 (published in 2000, Maruzen). The sample was injected into a wedge-shaped box and left to stand at room temperature for 2 hours, and then the distance between the disclination lines (d2-d1) was observed using a polarizing microscope (Nikon Corporation, trade name: MM40/60 series). The pitch (P) is calculated based on the following equation in which the angle of the wedge box is expressed as θ. P=2×(d2-d1)×tanθ.

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

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

(19) Line afterimage (Line Image Sticking Parameter; LISP; %): Line afterimage is generated by applying electrical stress to the liquid crystal display element. The brightness of the area where the line residual image exists and the brightness of the remaining areas are measured. The ratio of brightness decrease is calculated from the line afterimage, and the size of the line afterimage is expressed by the ratio.

(19a) Measurement of brightness: Use an imaging color luminance meter (manufactured by Radiant Zemax, PM-1433F-0) to capture the image of the component. The image was analyzed using software (Prometric 9.1, manufactured by Radiant Imaging Co., Ltd.) to calculate the brightness of each area of the element.

(19b) Setting of stress voltage: A sample is added to a liquid crystal display element having a matrix structure (16 cells, 4 vertical cells × 4 horizontal cells), and the element is sealed using an adhesive hardened by ultraviolet rays. Polarizing plates are respectively arranged on the upper surface and lower surface of the element in such a manner that the polarization axes are orthogonal to each other. The element is irradiated with light and a voltage is applied. The brightness of transmitted light at each voltage was measured. The voltage at maximum brightness is abbreviated as V255. The voltage when the brightness is 21.6% of V255 (i.e. 127 steps) is abbreviated as V127.

(19c) Stress conditions: Apply V255 and 0.5 V to the component at 60°C for 23 hours to display a checker pattern. Next, apply V127, light up the entire surface, and measure the brightness.

(19d) Calculation of line afterimage: The calculation uses the central 4 units (2 vertical units × 2 horizontal units) among the 16 units. The four units are divided into 25 areas (5 units vertically × 5 units horizontally). The average brightness of the four areas (2 units vertically x 2 units horizontally) located at the four corners is abbreviated as brightness A. The area excluding the four corner areas from the 25 areas is a cross shape. The minimum value of brightness among the four regions excluding the central intersection region from the cross-shaped region is abbreviated as brightness B. The line afterimage is calculated according to the following equation. (Line residual image) = (Brightness A-Brightness B)/Brightness A×100.

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

[table 3]

[Comparative example 1] 3-HHXB(F,F)-CF3 (2-5) 12% 3-GB(F,F)XB(F,F)-F (2-14) 8% 3-GBB(F)B(F,F)-F (2-22) 3% 4-GBB(F)B(F,F)-F (2-22) 2% 3-HBBXB(F,F)-F (2-23) 3% 4-GB(F)B(F,F)XB(F,F)-F (2-27) 5% 5-GB(F)B(F,F)XB(F,F)-F (2-27) 5% 5-BB(F)B(F,F)XB(F,F)-F (2-29) 12% 3-HH-V (3-1) 23% 3-HH-V1 (3-1) 10% 1V2-HH-3 (3-1) 9% V2-HHB-1 (3-5) 8% NI＝89.0℃; Tc＜-20℃; Δn＝0.101; Δε＝13.4; Vth＝1.34 V; γ1＝123.7 mPa·s; LISP＝9.5%

[Example 1] A composition obtained by adding the compound (1-A) to the composition of Comparative Example 1 was used as Example 1. 3-HHXB(F,F)-CF3 (2-5) 12% 3-GB(F,F)XB(F,F)-F (2-14) 8% 3-GBB(F)B(F, F)-F (2-22) 3% 4-GBB(F)B(F,F)-F (2-22) 2% 3-HBBXB(F,F)-F (2-23) 3% 4 -GB(F)B(F,F)XB(F,F)-F (2-27) 5% 5-GB(F)B(F,F)XB(F,F)-F (2-27 ) 5% 5-BB(F)B(F,F)XB(F,F)-F (2-29) 12% 3-HH-V (3-1) 23% 3-HH-V1 (3- 1) 10% 1V2-HH-3 (3-1) 9% V2-HHB-1 (3-5) 8% Compound (1-A) was added to the composition in a proportion of 0.100 mass %. NI＝89.0℃; Tc＜-20℃; Δn＝0.101; Δε＝13.4; Vth＝1.34 V; γ1＝123.7 mPa·s; LISP＝2.5%

[Example 2] A composition obtained by adding the compound (1-C) to the composition of Comparative Example 1 was used as Example 2. 3-HHXB(F,F)-CF3 (2-5) 12% 3-GB(F,F)XB(F,F)-F (2-14) 8% 3-GBB(F)B(F, F)-F (2-22) 3% 4-GBB(F)B(F,F)-F (2-22) 2% 3-HBBXB(F,F)-F (2-23) 3% 4 -GB(F)B(F,F)XB(F,F)-F (2-27) 5% 5-GB(F)B(F,F)XB(F,F)-F (2-27 ) 5% 5-BB(F)B(F,F)XB(F,F)-F (2-29) 12% 3-HH-V (3-1) 23% 3-HH-V1 (3- 1) 10% 1V2-HH-3 (3-1) 9% V2-HHB-1 (3-5) 8% Compound (1-C) was added to the composition at a ratio of 0.100 mass %. NI＝89.0℃; Tc＜-20℃; Δn＝0.101; Δε＝13.4; Vth＝1.34 V; γ1＝123.7 mPa·s; LISP＝1.5%

Furthermore, in order to confirm the effect on burn marks, display unevenness, etc., line afterimages were observed. The liquid crystal compositions of Comparative Example 1, Example 1 and Example 2 were added to a liquid crystal display element, and line afterimages were observed. Line afterimages were observed in the initial state before stress was applied and in the state after stress was applied (Table 4).

In the initial state, it was found that no display defects such as burn marks or uneven display occurred. After application, it was found that in Comparative Example 1, line afterimages were clearly observed between the electrodes, and burn marks in a checkerboard pattern were subtle but visible. On the other hand, in Examples 1 and 2, no lines were generated. Afterimage and unchanged from the initial state.

[Table 4]

[Example 3] 3-HHXB(F,F)-F (2-4) 6% 3-BB(F,F)XB(F,F)-F (2-18) 13% 3-HHBB(F ,F)-F (2-19) 4% 4-HHBB(F,F)-F (2-19) 5% 3-HBBXB(F,F)-F (2-23) 3% 3-BB( F)B(F,F)XB(F)-F (2-28) 2% 4-BB(F)B(F,F)XB(F,F)-F (2-29) 8% 5- BB(F)B(F,F)XB(F,F)-F (2-29) 7% 3-HH-V (3-1) 44% V-HHB-1 (3-5) 6% 2 -BB(F)B-3 (3-8) 2% Compound (1-B) was added to the composition in a proportion of 0.050 mass%. NI＝80.2℃; Tc＜-30℃; Δn＝0.106; Δε＝8.1; Vth＝1.45 V; η＝11.6 mPa·s; γ1＝60.0 mPa·s; LISP＝1.8%

[Example 4] 5-HXB(F,F)-F (2-1) 3% 3-HHXB(F,F)-F (2-4) 3% 3-HHXB(F,F)-CF3 ( 2-5) 3% 3-HGB(F,F)-F (2-6) 3% 5-HB(F)B(F,F)-F (2-9) 1% 3-BB(F, F)XB(F,F)-F (2-18) 6% 3-HHBB(F,F)-F (2-19) 6% 5-BB(F)B(F,F)XB(F) B(F,F)-F (2-31) 1% 3-BB(2F,3F)XB(F,F)-F (2-32) 4% V2-B(2F,3F)BXB(F, F)-F (2-33) 1% 3-HHB(F,F)XB(F,F)-F (2) 1% 3-HB-CL (2) 3% 3-HHB-OCF3 (2) 3% 3-HH-V (3-1) 28% 3-HH-V1 (3-1) 14% 5-HB-O2 (3-2) 5% 3-HHEH-3 (3-4) 3% 3-HBB-2 (3-6) 9% 5-B(F)BB-3 (3-7) 3% Compound (1-C) was added to the composition in a proportion of 0.070 mass %. NI＝74.2℃; Tc＜-20℃; Δn＝0.091; Δε＝3.7; Vth＝2.87 V; η＝5.8 mPa·s; γ1＝40.9 mPa·s; LISP=2.1%

[Example 5] 5-HXB(F,F)-F (2-1) 6% 3-HHXB(F,F)-F (2-4) 6% 5-HB(F)B(F,F )-F (2-9) 5% 3-HHB(F)B(F,F)-F (2-20) 7% 2-BB(F)B(F,F)XB(F)-F ( 2-28) 3% 3-BB(F)B(F,F)XB(F)-F (2-28) 3% 4-BB(F)B(F,F)XB(F)-F ( 2-28) 4% 5-HB-CL (2) 5% 2-HH-5 (3-1) 8% 3-HH-V (3-1) 10% 3-HH-V1 (3-1) 7% 4-HH-V (3-1) 10% 4-HH-V1 (3-1) 8% 5-HB-O2 (3-2) 7% 4-HHEH-3 (3-4) 3% 1-BB(F)B-2V (3-8) 3% 1O1-HBBH-3 (-) 5% Compound (1-C) was added to the composition in a proportion of 0.080 mass %. NI＝80.3℃; Tc＜-20℃; Δn＝0.091; Δε＝4.2; Vth＝1.50 V; η＝8.4 mPa·s; γ1＝54.2 mPa·s; LISP＝1.9%

[Example 6] 3-HHEB(F,F)-F (2-3) 5% 3-HHXB(F,F)-F (2-4) 7% 5-HBEB(F,F)-F ( 2-10) 5% 3-BB(F,F)XB(F,F)-F (2-18) 10% 2-HHB(F)B(F,F)-F (2-20) 3% 3-HB(2F,3F)BXB(F,F)-F (2-34) 3% 3-BB(2F,3F)BXB(F,F)-F (2-35) 2% 5-HHB( F,F)XB(F,F)-F (2) 6% 2-HH-3 (3-1) 8% 2-HH-5 (3-1) 20% 3-HH-V (3-1 ) 6% 4-HH-V (3-1) 6% V-HH-V (3-1) 1% 5-HB-O2 (3-2) 5% V2-B2BB-1 (3-9) 3 % 3-HHEBH-3 (3-11) 5% 3-HHEBH-5 (3-11) 5% Compound (1-B) was added to the composition in a proportion of 0.075% by mass. NI＝90.8℃; Tc＜-20℃; Δn＝0.084; Δε＝5.4; Vth＝1.65 V; η＝13.6 mPa·s; γ1＝60.1 mPa·s; LISP＝2.5%

[Example 7] 3-BBXB(F,F)-F (2-17) 1% 3-BB(F,F)XB(F,F)-F (2-18) 11% 3-HHBB(F ,F)-F (2-19) 5% 4-HHBB(F,F)-F (2-19) 3% 5-HHBB(F,F)-F (2-19) 1% 3-HBBXB( F,F)-F (2-23) 2% 3-HBB(F,F)XB(F,F)-F (2-24) 1% 3-BB(F)B(F,F)XB( F)-F (2-28) 3% 3-BB(F)B(F,F)XB(F,F)-F (2-29) 3% 4-BB(F)B(F,F) XB(F,F)-F (2-29) 5% 5-BB(F)B(F,F)XB(F,F)-F (2-29) 4% 2-HH-3 (3- 1) 6% 3-HH-5 (3-1) 6% 3-HH-V (3-1) 24% 3-HH-VFF (3-1) 6% V-HH-V1 (3-1) 1% 3-HB-O2 (3-2) 2% 5-HB-O2 (3-2) 5% V-HHB-1 (3-5) 6% V-HBB-2 (3-6) 5% Compound (1-B) was added to the composition at a ratio of 0.090% by mass. NI＝79.6℃; Tc＜-20℃; Δn＝0.105; Δε＝6.8; Vth＝1.55 V; η＝11.6 mPa·s; γ1＝55.6 mPa·s; LISP＝2.4%

[Example 8] 3-HGB(F,F)-F (2-6) 3% 5-GHB(F,F)-F (2-7) 4% 3-GB(F,F)XB(F ,F)-F (2-14) 5% 3-BB(F)B(F,F)-CF3 (2-16) 2% 3-HHBB(F,F)-F (2-19) 4% 3-GBB(F)B(F,F)-F (2-22) 2% 2-dhBB(F,F)XB(F,F)-F (2-25) 4% 3-GB(F) B(F,F)XB(F,F)-F (2-27) 3% 3-HGB(F,F)XB(F,F)-F (2) 5% 7-HB(F,F) -F (2) 3% 2-HH-3 (3-1) 14% 2-HH-5 (3-1) 4% 3-HH-V (3-1) 26% 1V2-HH-3 (3 -1) 5% 1-BB-3 (3-3) 3% 2-BB(F)B-3 (3-8) 3% 3-HB(F)HH-2 (3-10) 4% 5 -HBB(F)B-2 (3-13) 6% Compound (1-C) was added to the composition in a proportion of 0.080 mass%. NI＝79.3℃; Tc＜-20℃; Δn＝0.099; Δε＝5.2; Vth＝1.45 V; η＝11.5 mPa·s; γ1＝61.7 mPa·s; LISP＝1.8%

[Example 9] 3-HBB(F,F)-F (2-8) 5% 5-HBB(F,F)-F (2-8) 4% 3-BB(F)B(F,F )-F (2-15) 3% 3-BB(F)B(F,F)XB(F,F)-F (2-29) 3% 4-BB(F)B(F,F)XB (F,F)-F (2-29) 5% 3-BB(F,F)XB(F)B(F,F)-F (2-30) 3% 5-BB(F)B(F ,F)XB(F)B(F,F)-F (2-31) 1% 3-HH2BB(F,F)-F (2) 3% 4-HH2BB(F,F)-F (2) 3% 2-HH-5 (3-1) 9% 3-HH-V (3-1) 28% 3-HH-V1 (3-1) 10% 4-HH-V1 (3-1) 9% 5-HB-O2 (3-2) 5% 7-HB-1 (3-2) 5% VFF-HHB-O1 (3-5) 1% VFF-HHB-1 (3-5) 3% Compound (1-C) was added to the above composition in a proportion of 0.075% by mass. NI＝71.5℃; Tc＜-20℃; Δn＝0.0894; Δε＝3.0; Vth＝2.62 V; η＝10.0 mPa·s; γ1＝45.0 mPa·s; LISP＝2.1%

[Example 10] 3-HHB(F,F)-F (2-2) 8% 3-GB(F)B(F)-F (2-11) 1% 3-GB(F)B(F) ,F)-F (2-12) 2% 3-BB(F,F)XB(F,F)-F (2-18) 9% 3-GB(F)B(F,F)XB(F ,F)-F (2-27) 6% 5-GB(F)B(F,F)XB(F,F)-F (2-27) 6% 3-HH-V (3-1) 30 % 3-HH-V1 (3-1) 10% 1V2-HH-3 (3-1) 8% 3-HH-VFF (3-1) 8% 1-BB-3 (3-3) 2% 5 -HB(F)BH-3 (3-12) 10% Compound (1-B) was added to the composition in a proportion of 0.070 mass%. NI＝79.5℃; Tc＜-20℃; Δn＝0.087; Δε＝6.5; Vth＝1.85 V; η＝13.9 mPa·s; γ1＝66.9 mPa·s; LISP＝2.5%

[Example 11] 3-HHEB(F,F)-F (2-3) 4% 5-HHEB(F,F)-F (2-3) 3% 3-HBEB(F,F)-F ( 2-10) 3% 5-HBEB(F,F)-F (2-10) 3% 3-GB(F,F)XB(F)-F (2-13) 1% 3-BB(F) B(F,F)-F (2-15) 2% 3-GB(F)B(F,F)XB(F,F)-F (2-27) 5% 4-GB(F)B( F,F)XB(F,F)-F (2-27) 5% 5-HB-CL (2) 5% 3-HHB-OCF3 (2) 4% 3-HHB(F,F)XB(F ,F)-F (2) 5% 5-HHB(F,F)XB(F,F)-F (2) 3% 3-HGB(F,F)XB(F,F)-F (2) 5% 2-HH-5 (3-1) 3% 3-HH-5 (3-1) 5% 3-HH-V (3-1) 24% 4-HH-V (3-1) 5% 1V2-HH-3 (3-1) 5% 3-HHEH-3 (3-4) 5% 5-B(F)BB-2 (3-7) 3% 5-B(F)BB-3 ( 3-7) 2% Compound (1-C) is added to the composition at a ratio of 0.060 mass%. NI＝82.9℃; Tc＜-20℃; Δn＝0.093; Δε＝6.9; Vth＝1.50 V; η＝16.3 mPa·s; γ1＝65.2 mPa·s; LISP＝2.2%

[Example 12] 3-HHEB(F,F)-F (2-3) 4% 3-HBEB(F,F)-F (2-10) 3% 5-HBEB(F,F)-F ( 2-10) 3% 3-BB(F)B(F,F)-F (2-15) 3% 3-HBBXB(F,F)-F (2-23) 6% 4-GBB(F, F)XB(F,F)-F (2-26) 2% 5-GBB(F,F)XB(F,F)-F (2-26) 2% 3-GB(F)B(F, F)XB(F,F)-F (2-27) 5% 4-GB(F)B(F,F)XB(F,F)-F (2-27) 5% 5-HHB(F, F)XB(F,F)-F (2) 3% 3-HGB(F,F)XB(F,F)-F (2) 3% 5-HB-CL (2) 2% 3-HHB- OCF3 (2) 4% 3-HH-5 (3-1) 4% 3-HH-V (3-1) 21% 3-HH-V1 (3-1) 3% 4-HH-V (3- 1) 4% 1V2-HH-3 (3-1) 6% 5-B(F)BB-2 (3-7) 3% 5-B(F)BB-3 (3-7) 2% 3- HB(2F,3F)-O2 (4-1) 3% 3-BB(2F,3F)-O2 (4-6) 2% 3-HHB(2F,3F)-O2 (4-8) 4% F3 -HH-V (-) 3% Compound (1-C) was added to the composition in a proportion of 0.080 mass%. NI＝78.2℃; Tc＜-20℃; Δn＝0.101; Δε＝6.7; Vth＝1.45 V; η＝17.8 mPa·s; γ1＝67.8 mPa·s; LISP＝1.8%

[Example 13] 3-HHXB(F,F)-F (2-4) 9% 3-BB(F)B(F,F)-F (2-15) 14% 3-HH-V (3 -1) 39% 3-HH-V1 (3-1) 10% 1V2-HH-3 (3-1) 6% V-HHB-1 (3-5) 3% V2-HHB-1 (3-5 ) 3% 2-HBB(2F,3F)-O2 (4-14) 3% 3-HBB(2F,3F)-O2 (4-14) 7% 4-HBB(2F,3F)-O2 (4- 14) 3% 3-dhBB(2F,3F)-O2 (4-16) 2% 2-BB(2F,3F)B-3 (4-19) 1% In the composition, 0.070 mass% Add compound (1-C) proportionally. NI＝82.2℃; Tc＜-20℃; Δn＝0.099; Δε＝2.0; Vth＝2.94 V; η＝9.9 mPa·s; γ1＝37.0 mPa·s; LISP＝2.1%

The LISP of the composition of Comparative Example 1 was 9.5%. On the other hand, the LISP of the compositions of Examples 1 to 13 was in the range of 1.5% to 2.5%. In addition, according to the observation results of line afterimages, line afterimages and burn marks were observed in the device containing the composition of Comparative Example 1. On the other hand, in the device containing the compositions of Examples 1 and 2 , no line afterimages or burn marks were observed. Therefore, the following conclusion is drawn: the liquid crystal composition of the present invention has more excellent characteristics, and by using the liquid crystal composition of the present invention, a liquid crystal display element with excellent display quality can be obtained.

The specific resistance of the liquid crystal compositions of Comparative Example 1, Example 1 and Example 2 was measured. In addition, these liquid crystal compositions were added to a liquid crystal display element, and the resistance value of the liquid crystal display element was measured. The results are summarized in Table 5. It can be seen that the specific resistance values of Examples 1 and 2 are slightly lower than those of Comparative Example 1, and the resistance values of the liquid crystal display elements of Examples 1 and 2 are significantly lower than those of Comparative Example 1. Therefore, it was concluded that by using the liquid crystal composition of the present invention, a liquid crystal display element in which charging is further suppressed can be obtained.

[table 5] [Industrial availability]

The liquid crystal composition of the present invention can be used in liquid crystal monitors, liquid crystal televisions, etc.

without

FIG. 1A shows the observation results of line afterimages before stress voltage application (initial) in Comparative Example 1. FIG. 1B shows the observation results of line afterimages after stress voltage application (after application) in Comparative Example 1. FIG. 2A is an observation result of a line afterimage before stress voltage application (initial) in Example 1. FIG. 2B is an observation result of a line afterimage after application of the stress voltage in Example 1 (after application). FIG. 3A shows the observation results of line afterimages before stress voltage application (initial) in Example 2. FIG. 3B shows the observation results of line afterimages after stress voltage application (after application) in Example 2.

Claims (16)

A liquid crystal composition containing at least one compound selected from the compounds represented by formula (1) as a first additive and having a nematic phase and positive dielectric anisotropy:

In formula (1), R ^b is hydrogen, fluorine, an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and at least one of these groups is -CH ₂ - may be substituted by -O-, -NH-, -CO-, -COO- or -OCO-, and at least one -CH ₂ -CH ₂ - may be substituted by -CH=CH- or -C≡C- , among these groups, at least one hydrogen may be substituted by an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, halogen, OH, NHR ^1b or NR ^1c R ^1d ; R ^1b , R ^1c and R ^1d is an alkyl group with 1 to 10 carbon atoms; M is a single bond, a tetravalent aliphatic hydrocarbon group with 1 to 20 carbon atoms, or a tetravalent aromatic hydrocarbon group with 6 to 20 carbon atoms. Among these groups, at least one -CH ₂ - can be substituted by -O- or -S-, one or two -CH=CH- can be substituted by -CH=N-, at least one hydrogen can be substituted by fluorine or chlorine; Z ^a and Z ^b are single bonds, -O-, -COO-, -OCO-, alkylene group with 1 to 20 carbon atoms, or alkenylene group with 2 to 20 carbon atoms. In these groups, at least one hydrogen can be substituted by fluorine, chlorine, or OH; Q ^a is a monovalent group represented by formula (S); n is 1, 2, 3 or 4; m is 4-n; where, when M is a single bond, n and m are 1;

In the formula (S), R ^a is hydrogen, O‧, OH, an alkyl group with 1 to 20 carbon atoms, an alicyclic hydrocarbon group with 3 to 20 carbon atoms, or an aromatic hydrocarbon group with 6 to 20 carbon atoms. Among these groups , at least one -CH ₂ - can be substituted by -O-, -NH-, -CO-, -COO- or -OCO-, at least one -CH ₂ -CH ₂ - can be substituted by -CH=CH- or -C≡ C-substituted, among these groups, at least one hydrogen can be substituted by an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, halogen, OH, NHR ^1b or NR ^1c R ^1d ; R ^1b , R ^1c and R ^1d is an alkyl group having 1 to 10 carbon atoms. The liquid crystal composition as described in item 1 of the patent application, which includes at least one compound selected from the compounds represented by formula (1-1) to formula (1-5) as the first additive:

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

In formula (S-1), R ^d is hydrogen, O‧, OH, an alkyl group with 1 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, or an alkoxy group with 1 to 10 carbon atoms. Among these groups, , at least one hydrogen may be substituted by halogen. As for the liquid crystal composition described in Item 1 or Item 2 of the patent application, the proportion of the first additive is in the range of 0.001 mass% to 2 mass%. The liquid crystal composition described in Item 1 or Item 2 of the patent application includes at least one compound selected from the compounds represented by formula (2) as the first component:

In formula (2), R ^2a is an alkyl group with 1 to 12 carbon atoms, an alkoxy group with 1 to 12 carbon atoms, or an alkenyl group with 2 to 12 carbon atoms; ring A is 1,4-cyclohexylene, 1 ,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyrimidine -2,5-diyl, 1,3-dioxane-2,5-diyl or tetrahydropyran-2,5-diyl; Z ^2a is a single bond, ethylene group, vinylene group, carbonyl ^{Oxygen or} difluoromethyleneoxy; X ^2a and or an alkoxy group having 1 to 12 carbon atoms substituted by chlorine, or an alkenyloxy group having 2 to 12 carbon atoms in which at least one hydrogen is substituted by fluorine or chlorine; a is 1, 2, 3 or 4. The liquid crystal composition described in Item 1 or Item 2 of the patent application includes at least one compound selected from the compounds represented by Formula (2-1) to Formula (2-35) as the first component:

In Formula (2-1) to Formula (2-35), R ^2a is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms. As for the liquid crystal composition described in item 4 of the patent application, the proportion of the first component is in the range of 10 mass% to 85 mass%. The liquid crystal composition as described in item 1 or 2 of the patent application, which includes at least one compound selected from the compounds represented by formula (3) as the second component:

In formula (3), R ^3a and R ^3b are an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or at least one hydrogen substituted with fluorine or chlorine. Alkenyl group with 2 to 12 carbon atoms; ring B and ring C are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene or 2,5-difluoro- 1,4-phenylene; Z ^3a is a single bond, ethylene, vinylene, methyleneoxy or carbonyloxy; b is 1, 2 or 3. The liquid crystal composition as described in item 1 or 2 of the patent application, which includes at least one compound selected from the compounds represented by formula (3-1) to formula (3-13) as the second component:

In Formula (3-1) to Formula (3-13), R ^3a and R ^3b are an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or Alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen is substituted by fluorine or chlorine. As for the liquid crystal composition described in item 7 of the patent application, the proportion of the second component is in the range of 10 mass% to 85 mass%. The liquid crystal composition as described in item 1 or 2 of the patent application, which includes at least one compound selected from the compounds represented by formula (4) as a third component:

In formula (4), R ^4a and R ^4b are hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms. Oxygen group; Ring D and Ring F are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, and at least one hydrogen 1,4-phenylene substituted with fluorine or chlorine, naphthalene-2,6-diyl, naphthalene-2,6-diyl with at least one hydrogen substituted with fluorine or chlorine, chroman-2,6-diyl base, or a chroman-2,6-diyl group in which at least one hydrogen is substituted by fluorine or 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-difluoro Chroman-2,6-diyl, 3,4,5,6-tetrafluorofluorene-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 ^4a and Z ^4b are single bonds, ethylene, and ethylene Vinyl, methyleneoxy or carbonyloxy; c is 0, 1, 2 or 3, d is 0 or 1; and the sum of c and d is 3 or less. The liquid crystal composition as described in item 1 or 2 of the patent application, which includes at least one compound selected from the compounds represented by formula (4-1) to formula (4-35) as a third component:

In Formula (4-1) to Formula (4-35), R ^4a and R ^4b are hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms. , or an alkenyloxy group having 2 to 12 carbon atoms. As for the liquid crystal composition described in item 10 of the patent application, the proportion of the third component is in the range of 3 mass% to 45 mass%. For example, the liquid crystal composition described in Item 1 or 2 of the patent application scope has an upper limit temperature of the nematic phase of 70°C or more, and the optical anisotropy at a wavelength of 589 nm is 0.07 or more when measured at 25°C, and the frequency The dielectric anisotropy at 1 kHz is 2 or more when measured at 25°C. A liquid crystal display element comprising the liquid crystal composition described in any one of items 1 to 13 of the patent application scope. The liquid crystal display element as described in item 14 of the patent application, wherein the operation mode of the liquid crystal display element is a twisted nematic mode, an electronically controlled birefringence mode, an optically compensated bending mode, an in-plane switching mode, a fringe field switching mode, or The electric field induces light reaction alignment mode, and the driving mode of the liquid crystal display element is an active matrix mode. A use of a liquid crystal composition, which includes the use of the liquid crystal composition as described in any one of items 1 to 13 of the patent application in a liquid crystal display element.