CN114907865A

CN114907865A - Liquid crystal composition, liquid crystal display element and application of liquid crystal composition

Info

Publication number: CN114907865A
Application number: CN202111452681.1A
Authority: CN
Inventors: 杉泽美保; 宋依霖
Original assignee: JNC Corp; JNC Petrochemical Corp
Current assignee: JNC Corp; JNC Petrochemical Corp
Priority date: 2021-02-10
Filing date: 2021-12-01
Publication date: 2022-08-16
Also published as: TW202231850A; KR20220115502A

Abstract

The present invention provides a liquid crystal composition which satisfies at least one of the characteristics of high upper limit temperature, low lower limit temperature, low viscosity, large optical anisotropy, large negative dielectric anisotropy, large elastic constant, large specific resistance, high stability to light and high stability to heat, or has a suitable balance between at least two of the characteristics, a liquid crystal display element, and uses of the liquid crystal composition. A liquid crystal composition containing a specific compound having a high upper limit temperature and a large elastic constant as a component A, a specific compound having a large negative dielectric anisotropy and a large optical anisotropy or a large elastic constant as a component B, a specific compound having a large negative dielectric anisotropy as a component C, a specific compound having a high upper limit temperature or a small viscosity as a component D, or a specific compound having a polymerizable group as an additive X.

Description

Liquid crystal composition, liquid crystal display element and application of liquid crystal composition

Technical Field

The present invention relates to a liquid crystal composition, a liquid crystal display element containing the same, and a use of the liquid crystal composition. In particular, the present invention relates to a liquid crystal composition having negative dielectric anisotropy and a liquid crystal display device including the same and having in-plane switching (IPS), Vertical Alignment (VA), Fringe Field Switching (FFS), field-induced photo-reactive alignment (FPA) modes. Also relates to a liquid crystal display element of polymer stabilized alignment type.

Background

In a liquid crystal display device, the operation modes based on liquid crystal molecules are classified into Phase Change (PC), Twisted Nematic (TN), Super Twisted Nematic (STN), 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 the like. The driving methods of the elements are classified into Passive Matrix (PM) and Active Matrix (AM). The PM is classified into a static type (static) and a multiplexing type (multiplex), etc., and the AM is classified into a Thin Film Transistor (TFT), a Metal Insulator Metal (MIM), etc. TFTs are classified into amorphous silicon (amorphous silicon) and polycrystalline silicon (polysilicon). The latter is classified into a high temperature type and a low temperature type according to the manufacturing process. The light source is classified into a reflection type using natural light, a transmission type using a backlight, and a semi-transmission type using 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, an AM element having good characteristics can be obtained. The correlation between these properties is summarized in table 1 below. The properties of the composition are further illustrated based on commercially available AM elements. The temperature range of the nematic phase is associated with the temperature range in which the element can be used. The upper limit temperature of the nematic phase is preferably about 70 ℃ or higher, and the lower limit temperature of the nematic phase is preferably about-10 ℃ or lower. The viscosity of the composition correlates to the response time of the element. In order to display a moving image with the element, the response time is preferably short. Ideally shorter than 1 millisecond response time. Therefore, it is preferable that the viscosity of the composition is small. More preferably, the viscosity at low temperature is small.

TABLE 1 Properties of the compositions and AM elements

The optical anisotropy of the composition correlates with the contrast of the element. Depending on the mode of the element, a large optical anisotropy or a small optical anisotropy, that is, an appropriate optical anisotropy is required. The product (Δ n × d) of the optical anisotropy (Δ n) of the composition and the cell gap (d) of the element is designed to maximize the contrast. The value of the appropriate product depends on the type of operation mode. The VA mode element has a value in the range of about 0.30 μm to about 0.40 μm, and the IPS mode or FFS mode element has a value in the range of about 0.20 μm to about 0.30 μm. In these cases, a composition having a large optical anisotropy is preferable for an element having a small cell gap. The large dielectric anisotropy of the composition contributes to a low threshold voltage, small power consumption, and large contrast in the device. Therefore, a large dielectric anisotropy is preferable. The large specific resistance of the composition contributes to a large voltage holding ratio and a large contrast ratio of the element. Therefore, a composition having a large specific resistance in the initial stage is preferable. Preferred are compositions having a large specific resistance after long-term use. The stability of the composition to light or heat correlates with the lifetime of the component. When the stability is high, the life of the element is long. Such characteristics are preferable for AM elements used for liquid crystal monitors, liquid crystal televisions, and the like.

In a general-purpose liquid crystal display device, the vertical alignment of liquid crystal molecules can be achieved by using a specific polyimide alignment film. In a liquid crystal display element of a Polymer Sustained Alignment (PSA) type, a polymer is combined with an alignment film. First, a composition to which a small amount of a polymerizable compound is added is injected into an element. Then, the composition was irradiated with ultraviolet rays while applying a voltage between the substrates of the element. The polymerizable compound is polymerized to form a network structure of the polymer in the composition. In the composition, the alignment of the liquid crystal molecules can be controlled by the polymer, so that the response time of the element is shortened, and the burn mark of the image is improved. Such effects of the polymer can be expected in devices having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.

A composition having positive dielectric anisotropy is used for an AM element having a TN mode. A composition having negative dielectric anisotropy is used for an AM element having a VA mode. A composition having positive or negative dielectric anisotropy is used for an AM element having an IPS mode or an FFS mode. A composition having positive or negative dielectric anisotropy is used in an AM element of a Polymer Sustained Alignment (PSA) type.

Patent document 1 discloses a liquid crystal composition containing a tert-cyclohexyl compound, and patent document 2 discloses a liquid crystal composition containing a compound having a vinylidene bond and containing three cyclohexanes.

[ Prior art documents ]

[ patent document ]

[ patent document 1] German patent application laid-open No. 4414647

[ patent document 2] U.S. patent application publication No. 2007/0176146 specification

Disclosure of Invention

[ problems to be solved by the invention ]

The problem of the present invention is to provide a liquid crystal composition that sufficiently satisfies at least one of the characteristics of high upper limit temperature of a nematic phase, low lower limit temperature of the nematic phase, low viscosity, high optical anisotropy, high negative dielectric anisotropy, high elastic constant, high specific resistance, high stability to light, and high stability to heat. Another problem is to provide a liquid crystal composition having an appropriate balance between at least two of these characteristics. Another problem is to provide a liquid crystal display element containing such a composition. Another problem is to provide an AM device having characteristics such as a short response time, a high voltage holding ratio, a low threshold voltage, a high contrast ratio, and a long lifetime.

[ means for solving problems ]

The present invention relates to a liquid crystal composition containing at least one compound selected from compounds represented by formula (1) as component a and having negative dielectric anisotropy, and a liquid crystal display element containing the same.

In the formula (1), R ¹ Is alkyl of carbon number 1 to 12 or alkenyl of carbon number 2 to 12; r ² Alkenyl having 2 to 12 carbon atoms; z ¹ Is a single bond or vinylidene.

A polymer-stabilized alignment type liquid crystal display element is provided, which comprises the liquid crystal composition, wherein a polymerizable compound in the liquid crystal composition is polymerized.

The application of the liquid crystal composition is provided, and the liquid crystal composition is the liquid crystal composition and is used in a liquid crystal display element.

The application of the liquid crystal composition is provided, and the liquid crystal composition is used in a liquid crystal display element of a polymer stable orientation type.

[ Effect of the invention ]

An advantage of the present invention is to provide a liquid crystal composition that sufficiently satisfies at least one of characteristics such as a high upper limit temperature of a nematic phase, a low lower limit temperature of the nematic phase, a low viscosity, a large optical anisotropy, a large negative dielectric anisotropy, a large elastic constant, a large specific resistance, a high stability to light, and a high stability to heat. Another advantage is to provide a liquid crystal composition having an appropriate balance between at least two of these characteristics. Another advantage is to provide a liquid crystal display element containing such a composition. Another advantage is to provide an AM device having characteristics such as a short response time, a high voltage holding ratio, a low threshold voltage, a high contrast ratio, and a long lifetime.

Detailed Description

The usage of the terms in the present specification is as follows. The terms "liquid crystal composition" and "liquid crystal display element" may be simply referred to as "composition" and "element", respectively. The term "liquid crystal display element" is a generic term for liquid crystal display panels and liquid crystal display modules. The "liquid crystalline compound" is a general term for compounds having a liquid crystal phase such as a nematic phase or a smectic phase, and compounds which do not have a liquid crystal phase and are mixed in the composition for the purpose of adjusting characteristics such as a temperature range, viscosity, and dielectric anisotropy of a nematic phase. The compound has a six-membered ring such as 1, 4-cyclohexylene or 1, 4-phenylene, and the molecules (liquid crystal molecules) thereof are rod-like (rod like). The "polymerizable compound" is a compound added for the purpose of forming a polymer in the composition. The liquid crystalline compound having an alkenyl group is not classified into a polymerizable compound in terms of its meaning.

The liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. An additive such as an optically active compound or a polymerizable compound is added to the liquid crystal composition as needed. Even in the case where an additive is added, the proportion of the liquid crystalline compound is represented by a mass percentage (mass%) based on the mass of the liquid crystal composition containing no additive. The proportion of the additive is represented by mass percentage (mass%) based on the mass of the liquid crystal composition containing no additive. That is, the ratio of the liquid crystalline compound or the additive is calculated based on the total mass of the liquid crystalline compound. Parts per million (ppm) by mass are sometimes used. The proportions of the polymerization initiator and the polymerization inhibitor are exceptionally represented based on the mass of the polymerizable compound.

The "upper limit temperature of the nematic phase" may be simply referred to as "upper limit temperature". The "lower limit temperature of the nematic phase" may be simply referred to as "lower limit temperature". The expression "increase in dielectric anisotropy" means that the value increases positively in a composition having positive dielectric anisotropy, and increases negatively in a composition having negative dielectric anisotropy. "high voltage holding ratio" means that the device has a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature in the initial stage, and also has a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature after long-term use. The properties of the composition or the element are sometimes investigated by time-varying tests.

The compound (1z) is exemplified. In formula (1z), the symbols α and β surrounded by a hexagon correspond to ring α and ring β, respectively, and represent a six-membered ring, a condensed ring, and the like. Where subscript 'x' is 2, there are two rings, α. The two groups represented by the two rings a may be the same or may also be different. The rule applies to any two rings a where subscript 'x' is greater than 2. The rules also apply to other tokens such as the bonding base Z. The diagonal line across one side of the loop β indicates that any hydrogen on the loop β can be substituted with a substituent (-Sp-P). The subscript 'y' indicates the number of substituents substituted. When subscript 'y' is 0, there is no such substitution. When the subscript 'y' is 2 or more, a plurality of substituents (-Sp-P) are present on the ring β. In that case, the rules "may be the same, or may also be different" also apply. Furthermore, the rules also apply to the use of the notation of Ra in a variety of compounds.

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

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

The expression "at least one ' a" means that the number of ' a's is arbitrary. The expression "at least one 'a' may be substituted with 'B' means that the position of 'a' is arbitrary when the number of 'a' is one, and the position thereof may be selected without limitation when the number of 'a' is two or more. Sometimes using "at least one-CH ₂ -may be substituted by-O-. In said case, -CH ₂ CH ₂ -CH ₂ Can pass through non-contiguous-CH ₂ Conversion to-O-CH by-O-substitution ₂ -O-. However, there is no contiguous-CH ₂ -substituted by-O-. The reason is that: in said substitution-O-CH is formed ₂ - (peroxides).

The alkyl group of the liquid crystalline compound is linear or branched and does not include a cyclic alkyl group. Straight chain alkyls are preferred over branched alkyls. The same applies to terminal groups such as alkoxy groups and alkenyl groups. For the configuration of 1, 4-cyclohexylene-related stereo-configuration, the trans-configuration is preferred to the cis-configuration in order to increase the upper limit temperature. Since the 2-fluoro-1, 4-phenylene group is asymmetric in the left-right direction, it is present in the left (L) and right (R) directions.

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

The present invention is the following items.

Item 1. a liquid crystal composition containing at least one compound selected from the compounds represented by formula (1) as component a and having negative dielectric anisotropy.

Item 2. the liquid crystal composition according to item 1, which contains at least one compound selected from the group consisting of the compounds represented by the formulae (1-1) and (1-2) as the component A.

In the formulae (1-1) and (1-2), R ¹ Is alkyl group having 1 to 12 carbon atoms or alkenyl group having 2 to 12 carbon atoms.

Item 3. the liquid crystal composition according to item 1 or item 2, wherein the proportion of the component A is in the range of 1 to 20% by mass.

Item 4. the liquid crystal composition according to any one of item 1 to item 3, which contains at least one compound selected from the group consisting of the compounds represented by formula (2) and formula (3) as component B.

In the formula (2), R ³ And R ⁴ Is alkyl group with carbon number of 1 to 12, alkoxy group with carbon number of 1 to 12 or alkenyl group with carbon number of 2 to 12; ring A and ring B are tetrahydropyran-2, 5-diyl, 1, 4-phenylene or 1, 4-phenylene in which at least one hydrogen is substituted by fluorine or chlorine; a is 1 or 2, b is 0 or 1; when a is 2, ring A is tetrahydropyran-2, 5-diyl or 1, 4-phenylene;

in the formula (3), R ⁵ And R ⁶ Is carbonAn alkyl group having a number of 1 to 12, an alkoxy group having a carbon number of 1 to 12, or an alkenyl group having a carbon number of 2 to 12; ring C and ring E are 1, 4-cyclohexylene, 1, 4-cyclohexenylene, tetrahydropyran-2, 5-diyl, 1, 4-phenylene in which at least one hydrogen is substituted by fluorine or chlorine, naphthalene-2, 6-diyl in which at least one hydrogen is substituted by fluorine or chlorine, chroman-2, 6-diyl, or chroman-2, 6-diyl in which at least one hydrogen is substituted by fluorine or chlorine; ring D 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-difluorochromane-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-tetrafluoroindan-2, 5-diyl; z is a linear or branched member ² And Z ³ Is a single bond, ethylene, vinylene, methyleneoxy or carbonyloxy; at least one of Z ² And Z ³ Is ethylene, vinylene, methyleneoxy or carbonyloxy; c is 1,2 or 3, d is 0 or 1; and the sum of c and d is 3 or less.

Item 5. the liquid crystal composition according to any one of items 1 to 4, which contains at least one compound selected from the group consisting of the compounds represented by formulae (2-1) to (2-4) and formulae (3-1) to (3-10) as the component B.

In the formulae (2-1) to (2-4), R ³ And R ⁴ Is alkyl with carbon number of 1 to 12, alkoxy with carbon number of 1 to 12 or alkenyl with carbon number of 2 to 12;

in the formulae (3-1) to (3-10), R ⁵ And R ⁶ Is alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms or alkenyl group having 2 to 12 carbon atoms.

Item 6. the liquid crystal composition according to item 4 or item 5, wherein the proportion of the component B is in the range of 5 to 40 mass%.

Item 7. the liquid crystal composition according to any one of items 1 to 6, which contains at least one compound selected from the compounds represented by formula (4) as the component C.

In the formula (4), R ⁷ And R ⁸ Is hydrogen, alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, alkenyl group having 2 to 12 carbon atoms, alkenyloxy group having 2 to 12 carbon atoms, or alkyl group having 1 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine; ring F and ring I are 1, 4-cyclohexylene, 1, 4-cyclohexenylene, tetrahydropyran-2, 5-diyl, 1, 4-phenylene in which at least one hydrogen is substituted by fluorine or chlorine, naphthalene-2, 6-diyl in which at least one hydrogen is substituted by fluorine or chlorine, chroman-2, 6-diyl in which at least one hydrogen is substituted by fluorine or chlorine, or chroman-2, 6-diyl in which at least one hydrogen is substituted by fluorine or chlorine; ring G 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-difluorochromane-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-tetrafluoroindan-2, 5-diyl; e is 0, 1,2 or 3, f is 0 or 1; and the sum of e and f is 3 or less; when the sum of e and F is 1 or more, at least one of ring F and ring I is 1, 4-cyclohexylene, 1, 4-cyclohexenylene, naphthalene-2, 6-diyl in which at least one hydrogen is substituted by fluorine or chlorine, chromane-2, 6-diyl, or chromane-2, 6-diyl in which at least one hydrogen is substituted by fluorine or chlorine; when the sum of e and f is 0, ring G is 4, 6-difluorodibenzofuran-3, 7-diyl or 4, 6-difluorodibenzothiophene-3, 7-diyl.

Item 8. the liquid crystal composition according to any one of item 1 to item 7, which contains at least one compound selected from the compounds represented by formulae (4-1) to (4-17) as component C.

In the formulae (4-1) to (4-17), R ⁷ And R ⁸ Is hydrogen, alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, alkenyl group having 2 to 12 carbon atoms, alkenyloxy group having 2 to 12 carbon atoms, or alkyl group having 1 to 12 carbon atoms wherein at least one hydrogen is substituted with fluorine or chlorine.

Item 9 the liquid crystal composition of item 7 or 8, wherein the proportion of component C is in a range of 10 to 60 mass%.

Item 10. the liquid crystal composition according to any one of item 1 to item 9, which contains at least one compound selected from the compounds represented by formula (5) as the component D.

In the formula (5), R ⁹ And R ¹⁰ Is 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, an alkyl group having 1 to 12 carbon atoms wherein at least one hydrogen is substituted with fluorine or chlorine, or an alkenyl group having 2 to 12 carbon atoms wherein at least one hydrogen is substituted with fluorine or chlorine; ring J and ring K are 1, 4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1, 4-phenylene or 2, 5-difluoro-1, 4-phenylene; z ⁴ Is a single bond, ethylene, methyleneoxy or carbonyloxy; g is 1,2 or 3; when g is 2 and Z ⁴ When it is a single bond, ring K is 1, 4-phenylene, 2-fluoro-1, 4-phenylene or 2, 5-difluoro-1, 4-phenylene.

Item 11. the liquid crystal composition according to any one of item 1 to item 10, which contains at least one compound selected from the compounds represented by formulae (5-1) to (5-13) as the component D.

In the formulae (5-1) to (5-13), R ⁹ And R ¹⁰ Is alkyl with carbon number of 1-12, C1-12An alkoxy group of 12 carbon atoms, an alkenyl group of 2 to 12 carbon atoms, an alkyl group of 1 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine, or an alkenyl group of 2 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine.

Item 12. the liquid crystal composition of item 10 or item 11, wherein the proportion of component D is in the range of 10 to 50 mass%.

Item 13. the liquid crystal composition according to any one of item 1 to item 12, which contains at least one compound selected from polymerizable compounds represented by formula (6) as an additive X.

In the formula (6), the ring L and the ring N are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1, 3-dioxan-2-yl, pyrimidin-2-yl or pyridin-2-yl, and in these rings, at least one hydrogen may be substituted with fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine; the ring M is 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, naphthalene-1, 2-diyl, naphthalene-1, 3-diyl, naphthalene-1, 4-diyl, naphthalene-1, 5-diyl, naphthalene-1, 6-diyl, naphthalene-1, 7-diyl, naphthalene-1, 8-diyl, naphthalene-2, 3-diyl, naphthalene-2, 6-diyl, naphthalene-2, 7-diyl, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl or pyridine-2, 5-diyl, in which at least one hydrogen may be substituted with fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, Or at least one hydrogen is substituted by a fluorine or chlorine substituted alkyl group of carbon number 1 to 12; z ⁵ And Z ⁶ Is a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group ₂ -may be substituted by-O-, -CO-, -COO-or-OCO-, at least one-CH ₂ CH ₂ -may be via-CH ═ CH-, -C (CH) ₃ )＝CH-、-CH＝C(CH ₃ ) -or-C (CH) ₃ )＝C(CH ₃ ) -substitution, of which at least one hydrogen may be substituted by fluorine or chlorine; p ¹ To P ³ Is a polymerizable group; sp ¹ To Sp ³ Is a single bond or of 1 to 10 carbon atomsAlkylene of which at least one-CH ₂ At least one-CH which may be substituted by-O-, -COO-, -OCO-or-OCOO-) ₂ CH ₂ -may be substituted by-CH ═ CH-or-C ≡ C-, in which groups at least one hydrogen may be substituted by fluoro or chloro; h is 0, 1 or 2; i. j and k are 0, 1,2, 3 or 4; and the sum of i, j and k is 1 or more.

Item 14 the liquid crystal composition of item 13, wherein, in formula (6), P ¹ To P ³ Is a group selected from the polymerizable groups represented by the formulae (P-1) to (P-5).

In the formulae (P-1) to (P-5), M ¹ To M ³ Hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine.

Item 15 the liquid crystal composition according to any one of item 1 to item 14, which contains at least one compound selected from the polymerizable compounds represented by formulae (6-1) to (6-29) as the additive X.

In formulae (6-1) to (6-29), Sp ¹ To Sp ³ Is a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group ₂ At least one-CH which may be substituted by-O-, -COO-, -OCO-or-OCOO-) ₂ CH ₂ -may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being substituted by fluorine or chlorine; p ⁴ To P ⁶ Is a polymerizable group selected from the group represented by the formulae (P-1) to (P-3);

in the formulae (P-1) to (P-3), M ¹ To M ³ Hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine.

Item 16. the liquid crystal composition of any one of items 13 to 15, wherein the proportion of the additive X is in the range of 0.03 to 10 mass%.

Item 17. a liquid crystal display element containing the liquid crystal composition according to any one of items 1 to 16.

The liquid crystal display device of item 17, wherein the operation mode is an IPS mode, a VA mode, an FFS mode, or an FPA mode, and the driving method is an active matrix method.

Item 19. A polymer stable alignment type liquid crystal display element comprising the liquid crystal composition according to any one of items 13 to 16, in which a polymerizable compound is polymerized.

Item 20. use of a liquid crystal composition according to any one of items 1 to 16 in a liquid crystal display element.

Item 21. use of a liquid crystal composition according to any one of items 13 to 16 in a liquid crystal display element of a polymer stabilized alignment type.

The present invention also includes the following items. (a) The composition contains one compound, two compounds or three or more compounds selected from additives such as an optically active compound, an antioxidant, an ultraviolet absorber, a delustering agent, a pigment, an antifoaming agent, a polymerizable compound, a polymerization initiator and a polymerization inhibitor. (b) An AM element comprising the composition. (c) The composition further contains a polymerizable compound, and a polymer-stabilized oriented (PSA) AM element containing the composition. (d) An AM element of Polymer Stable Alignment (PSA) type, comprising the composition, wherein a polymerizable compound in the composition is polymerized. (e) An element comprising said composition and having a pattern of PC, TN, STN, ECB, OCB, IPS, VA, FFS or FPA. (f) A permeable element comprising the composition. (g) Use of said composition as a composition having a nematic phase. (h) Use of an optically active composition obtained by adding an optically active compound to the composition.

The composition of the present invention is illustrated in the following order. First, the composition is explained. Second, the main characteristics of the component compounds and the main effects of the compounds on the composition or element will be described. Thirdly, combinations, preferable ratios and their references of the component compounds in the composition are explained. Fourthly, preferred forms of the component compounds will be explained. Fifth, preferred component compounds are shown. Sixth, additives that can be added to the composition will be described. Seventh, a method for synthesizing the component compound will be explained. Finally, the use of the composition is illustrated.

First, the composition is explained. The composition contains a plurality of liquid crystalline compounds. The composition may also contain additives. The additive is an optically active compound, an antioxidant, an ultraviolet absorber, a matting agent, a coloring matter, an antifoaming agent, a polymerizable compound, a polymerization initiator, a polymerization inhibitor, a polar compound, or the like. From the viewpoint of the liquid crystalline compound, the compositions are classified into a composition (a) and a composition (b). The composition (a) may contain other liquid crystalline compounds, additives, and the like in addition to the liquid crystalline compound selected from the group consisting of the compound (1), the compound (2), the compound (3), the compound (4), and the compound (5). The "other liquid crystalline compound" is a liquid crystalline compound different from the compound (1), the compound (2), the compound (3), the compound (4) and the compound (5). Such compounds are mixed in the composition for the purpose of further adjusting the properties.

The composition (b) substantially contains only a liquid crystalline compound selected from the group consisting of the compound (1), the compound (2), the compound (3), the compound (4) and the compound (5). "substantially" means that the composition (b) may contain additives but does not contain other liquid crystalline compounds. The amount of the component of composition (b) is small compared to composition (a). From the viewpoint of cost reduction, the composition (b) is superior to the composition (a). The composition (a) is superior to the composition (b) in that the properties can be further adjusted by mixing other liquid crystalline compounds.

In order to prepare a liquid crystal composition having an appropriate balance between at least two of the characteristics of a high upper limit temperature of a nematic phase, a low lower limit temperature of a nematic phase, a small viscosity, a large optical anisotropy, a large negative dielectric anisotropy, a large elastic constant, a large specific resistance, a high stability to light and a high stability to heat, it is preferable that the compound represented by the formula (S) and the compound represented by the formula (T) are not contained.

In the formula (S), R ^S1 And R ^S2 Is alkyl group with carbon number of 1 to 12, alkoxy group with carbon number of 1 to 12 or alkenyl group with carbon number of 2 to 12; ring A ^S Is 1, 4-cyclohexylene, 1, 4-cyclohexenylene, tetrahydropyran-2, 5-diyl, 1, 4-phenylene in which at least one hydrogen is substituted by fluorine or chlorine, or 1, 4-phenylene in which at least one hydrogen is substituted by trifluoromethyl or difluoromethyl;

in the formula (T), R ^T1 And R ^T2 Is alkyl group with carbon number of 1 to 12, alkoxy group with carbon number of 1 to 12 or alkenyl group with carbon number of 2 to 12; l is ^T1 、L ^T2 And L ^T3 Is fluorine, chlorine, trifluoromethyl, trifluoromethoxy or difluoromethyl.

Second, the main characteristics of the component compounds and the main effects of the compounds on the composition or element will be described. The main properties of the component compounds based on the effects of the present invention are summarized in Table 2. In the notation of Table 2, L means large or high, M means medium, and S means small or low. The notation L, M, S is a classification based on qualitative comparisons between component compounds, with 0 (zero) meaning less than S.

TABLE 2 Properties of liquid crystalline Compounds

Compound (I)	Compound (1)	Compound (2)	Compound (3)	Compound (4)	Compound (5)
						Upper limit temperature	L	S～M	S～L	S～L	S～L
Viscosity of the oil	M	M～L	M～L	M～L	S～M
						Optical anisotropy	S	L	M～L	M～L	S～L
Dielectric anisotropy	0	M～L ¹⁾	M～L ¹⁾	M～L ¹⁾	0
						Specific resistance	L	L	L	L	L

1) The dielectric anisotropy is negative, and the sign indicates the magnitude of the absolute value.

The main effects of the component compounds are as follows. The compound (1) increases the upper limit temperature and the elastic constant. The compound (2) improves optical anisotropy and dielectric anisotropy. The compound (3) improves the elastic constant and the dielectric anisotropy. The compound (4) increases the dielectric anisotropy and lowers the lower limit temperature. The compound (5) raises the upper limit temperature or lowers the viscosity.

Thirdly, combinations of the component compounds in the composition, preferable ratios and their basis are explained. Preferred combinations of the component compounds in the composition are compound (1) + compound (2), compound (1) + compound (3), compound (1) + compound (2) + compound (4), compound (1) + compound (2) + compound (5), compound (1) + compound (3) + compound (4), compound (1) + compound (3) + compound (5), compound (1) + compound (2) + compound (4) + compound (5), compound (1) + compound (3) + compound (4) + compound (5), compound (1) + compound (2) + compound (3) + compound (4), compound (1) + compound (2) + compound (3) + compound (5), and compound (5), Compound (1) + compound (2) + compound (4) + compound (5) + compound (6), compound (1) + compound (3) + compound (4) + compound (5) + compound (6), compound (1) + compound (2) + compound (3) + compound (4) + compound (5) or compound (1) + compound (2) + compound (3) + compound (4) + compound (5) + compound (6). Further preferred combinations are compound (1) + compound (2) + compound (4) + compound (5), compound (1) + compound (3) + compound (4) + compound (5), or compound (1) + compound (2) + compound (3) + compound (4) + compound (5).

The preferable proportion of the compound (1) is about 1% by mass or more in order to increase the upper limit temperature and the elastic constant, and the preferable proportion of the compound (1) is about 20% by mass or less in order to decrease the lower limit temperature. Further, the preferable ratio is in the range of about 3 to about 15 mass%. A particularly preferred ratio is in the range of about 3% to about 10% by mass.

The component B contains at least one of the compound (2) and the compound (3). The compound (2) may be contained alone or the compound (3) may be contained alone. The compound (2) and the compound (3) may be contained at the same time. The preferred proportion of component B is about 5 mass% or more and about 40 mass% or less.

The preferable proportion of the compound (2) is about 15% by mass or more in order to improve the optical anisotropy and the dielectric anisotropy, and the preferable proportion of the compound (2) is about 35% by mass or less in order to lower the lower limit temperature. Further, the preferable ratio is in the range of about 15% by mass to about 30% by mass. A particularly preferred ratio is in the range of about 20% by mass to about 30% by mass.

The preferable proportion of the compound (3) is about 5% by mass or more in order to improve the elastic constant and the dielectric anisotropy, and the preferable proportion of the compound (3) is about 40% by mass or less in order to lower the lower limit temperature. A more preferable ratio is in the range of about 10% by mass to about 40% by mass. A particularly preferred ratio is in the range of about 15% to about 40% by mass.

The preferable proportion of the compound (4) is about 10% by mass or more for improving the dielectric anisotropy, and the preferable proportion of the compound (4) is about 60% by mass or less for lowering the lower limit temperature. Further, the preferable ratio is in the range of about 15% by mass to about 50% by mass. A particularly preferred ratio is in the range of about 20% by mass to about 50% by mass.

The preferable proportion of the compound (5) is about 10% by mass or more in order to raise the upper limit temperature or to lower the viscosity, and the preferable proportion of the compound (5) is about 50% by mass or less in order to lower the lower limit temperature. Further, the preferable ratio is in the range of about 20 to about 50 mass%. A particularly preferred ratio is in the range of about 30% by mass to about 50% by mass.

The compound (6) is added to the composition for the purpose of being suitable for a polymer stable alignment type element. The preferable proportion of the compound (6) is about 0.03% by mass or more for aligning liquid crystal molecules, and about 10% by mass or less for preventing display defects of the device. Further, the preferable ratio is in the range of about 0.1% by mass to about 2% by mass. A particularly preferred ratio is in the range of about 0.2% to about 1.0% by mass.

Fourthly, preferred forms of the component compounds will be explained. In the formulae (1), (2), (3), (4) and (5), R ¹ An alkyl group having 1 to 12 carbon atoms or an alkenyl group having 2 to 12 carbon atoms. For improved stability, R is preferred ¹ Is alkyl of carbon number 1 to 12, and R is preferably selected to reduce viscosity ¹ Is an alkenyl group having 2 to 12 carbon atoms. Particularly preferred R ¹ Is an alkyl group having 3 to 5 carbon atoms, and among them, a propyl group is most preferable. R is ² Is an alkenyl group having 2 to 12 carbon atoms. Preferred R ² Is a vinyl group. R ³ And R ⁴ Is alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms or alkenyl group having 2 to 12 carbon atoms. For improved stability, R is preferred ³ Or R ⁴ Is alkyl having 1 to 12 carbon atoms, and R is preferably selected to reduce viscosity ³ Or R ⁴ Is alkenyl group having 2 to 12 carbon atoms, and R is preferably selected to improve dielectric anisotropy ³ Or R ⁴ Is alkoxy with 1 to 12 carbon atoms. R ⁵ And R ⁶ Is alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms or alkenyl group having 2 to 12 carbon atoms. For improved stability, R is preferred ⁵ Or R ⁶ Is alkyl of carbon number 1 to 12, for reducingViscosity, preferably R ⁵ Or R ⁶ R is an alkenyl group having 2 to 12 carbon atoms and is preferable for improving the dielectric anisotropy ⁵ Or R ⁶ Is an alkoxy group having 1 to 12 carbon atoms. R ⁷ And R ⁸ Is hydrogen, alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, alkenyl group having 2 to 12 carbon atoms, alkenyloxy group having 2 to 12 carbon atoms, or alkyl group having 1 to 12 carbon atoms wherein at least one hydrogen is substituted with fluorine or chlorine. For improved stability, R is preferred ⁷ Or R ⁸ Is alkyl of carbon number 1 to 12, and R is preferably selected to reduce viscosity ⁷ Or R ⁸ R is an alkenyl group having 2 to 12 carbon atoms and is preferable for improving the dielectric anisotropy ⁷ Or R ⁸ Is an alkoxy group having 1 to 12 carbon atoms. R ⁹ And R ¹⁰ Is 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, an alkyl group having 1 to 12 carbon atoms wherein at least one hydrogen is substituted with fluorine or chlorine, or an alkenyl group having 2 to 12 carbon atoms wherein at least one hydrogen is substituted with fluorine or chlorine. For improved stability, R is preferred ⁹ And R ¹⁰ Is alkyl having 1 to 12 carbon atoms, and R is preferably selected to reduce viscosity ⁹ And R ¹⁰ Is an alkenyl group having 2 to 12 carbon atoms.

Preferred alkyl groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl. Further preferred alkyl groups for reducing the viscosity are methyl, ethyl, propyl, butyl or pentyl.

Preferred alkoxy groups are methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy or heptoxy. Further preferred alkoxy groups for reducing the viscosity are methoxy or ethoxy.

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. Further preferred alkenyl groups for reducing the viscosity are vinyl, 1-propenyl, 3-butenyl or 3-pentenyl. The preferred steric configuration of-CH ═ CH-in these alkenyl groups depends on the position of the double bond. For reasons of viscosity reduction and the like, the trans configuration is preferred among alkenyl groups such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl, 3-hexenyl. Among alkenyl groups such as 2-butenyl, 2-pentenyl, 2-hexenyl, the cis configuration is preferred.

Preferred alkenyloxy groups are vinyloxy, allyloxy, 3-butenyloxy, 3-pentenyloxy or 4-pentenyloxy. Further preferred alkenyloxy groups are allyloxy or 3-butenyloxy groups in order to reduce the viscosity.

Preferred examples of alkyl groups in which at least one hydrogen is replaced by fluorine or chlorine are fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl, 7-fluoroheptyl or 8-fluorooctyl. Further preferable examples of the compound for improving the dielectric anisotropy include 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl and 5-fluoropentyl.

Preferred examples of alkenyl groups in which at least one hydrogen is substituted by fluorine or chlorine are 2, 2-difluorovinyl, 3-difluoro-2-propenyl, 4-difluoro-3-butenyl, 5-difluoro-4-pentenyl or 6, 6-difluoro-5-hexenyl. Further preferable examples for lowering the viscosity are 2, 2-difluorovinyl group and 4, 4-difluoro-3-butenyl group.

Ring A and ring B are tetrahydropyran-2, 5-diyl, 1, 4-phenylene or 1, 4-phenylene in which at least one hydrogen is substituted by fluorine or chlorine. The ring A or B is preferably a 1, 4-phenylene group for the purpose of improving optical anisotropy and reducing viscosity, and is preferably tetrahydropyran-2, 5-diyl group for the purpose of improving dielectric anisotropy. Tetrahydropyran-2, 5-diyl in ring A and ring B is

Or

Preferably a

Ring C, ring E, ring F and ring I are 1, 4-cyclohexylene, 1, 4-cyclohexenylene, tetrahydropyran-2, 5-diyl, 1, 4-phenylene in which at least one hydrogen is substituted by fluorine or chlorine, naphthalene-2, 6-diyl in which at least one hydrogen is substituted by fluorine or chlorine, chromane-2, 6-diyl in which at least one hydrogen is substituted by fluorine or chlorine, or chromane-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. The ring C, ring E, ring F or ring I is preferably a 1, 4-cyclohexylene group for lowering the viscosity, the ring C, ring E, ring F or ring I is preferably a tetrahydrofuran-2, 5-diyl group for improving the dielectric anisotropy, and the ring C, ring E, ring F or ring I is preferably a 1, 4-phenylene group for improving the optical anisotropy. Tetrahydropyran-2, 5-diyl in ring C and ring E is

Or

Preferably, it is

And ring D and ring G are 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-difluorochromane-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 (InF 4).

The preferred ring D or G is 2, 3-difluoro-1, 4-phenylene for viscosity reduction and 4, 6-difluorodibenzothiophene-3, 7-diyl for dielectric anisotropy improvement.

Ring J and ring K are 1, 4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1, 4-phenylene or 2, 5-difluoro-1, 4-phenylene. For lowering the viscosity or for increasing the upper temperature limit, the preferred ring J or ring K is 1, 4-cyclohexylene, and for lowering the lower temperature limit, the preferred ring J or ring K is 1, 4-phenylene.

Z ¹ Is a single bond or vinylidene. Z ² And Z ³ Is a single bond, ethylene, vinylene, methyleneoxy or carbonyloxy, at least one Z ² And Z ³ Is ethylene, vinylene, methyleneoxy or carbonyloxy. For lowering the lower limit temperature, Z is preferable ² Or Z ³ Is ethylene, and Z is preferably selected to improve the dielectric anisotropy ² Or Z ³ Is methyleneoxy. In the presence of a plurality of Z ² Or Z ³ In the case of (2), one of them is preferably a single bond. Z ⁴ Is a single bond, ethylene, methyleneoxy or carbonyloxy. For reducing the viscosity, preferred is Z ⁴ Is a single bond.

Divalent radicals such as methyleneoxy are asymmetric to the left and right. In the methyleneoxy group, -CH ₂ O-is superior to-OCH ₂ -. In the carbonyloxy group, -COO-is preferable to-OCO-.

a is 1 or 2, and b is 0 or 1. In order to reduce the viscosity, a is preferably 1, and in order to improve the optical anisotropy, a is preferably 2. For lowering the viscosity, b is preferably 0, and for improving the optical anisotropy, b is preferably 1. c is 1,2 or 3, d is 0 or 1, and the sum of c and d is 3 or less. For lowering the viscosity, c is preferably 1, and for raising the upper limit temperature, c is preferably 2. For lowering the viscosity, d is preferably 0, and for raising the upper limit temperature, d is preferably 1. e is 0, 1,2 or 3, f is 0 or 1, and the sum of e and f is 3 or less. For lowering the viscosity, e is preferably 1, and for raising the upper limit temperature, e is preferably 2. For lowering the viscosity, f is preferably 0, and for raising the upper limit temperature, f is preferably 1. g is 1,2 or 3. For lowering the viscosity, g is preferably 1, and for raising the upper limit temperature, g is preferably 2 or 3.

In the formula (2), when a is 2, ring A is tetrahydropyran-2, 5-diyl or 1, 4-phenylene.

In the formula (4), when the sum of e and F is 1 or more, at least one of ring F and ring I is 1, 4-cyclohexylene group, 1, 4-cyclohexenylene group, naphthalene-2, 6-diyl group in which at least one hydrogen is substituted with fluorine or chlorine, chromane-2, 6-diyl group, or chromane-2, 6-diyl group in which at least one hydrogen is substituted with fluorine or chlorine.

In the formula (4), when the sum of e and f is 0, the ring G is 4, 6-difluorodibenzofuran-3, 7-diyl or 4, 6-difluorodibenzothiophene-3, 7-diyl.

In the formula (5), when g is 2 and Z ⁴ When it is a single bond, ring K is 1, 4-phenylene, 2-fluoro-1, 4-phenylene or 2, 5-difluoro-1, 4-phenylene.

In the formula (6), the ring L and the ring N are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1, 3-dioxan-2-yl, pyrimidin-2-yl or pyridin-2-yl, and in these rings, at least one hydrogen may be substituted with fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine. Preferably, ring L or ring N is phenyl. The ring M is 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, naphthalene-1, 2-diyl, naphthalene-1, 3-diyl, naphthalene-1, 4-diyl, naphthalene-1, 5-diyl, naphthalene-1, 6-diyl, naphthalene-1, 7-diyl, naphthalene-1, 8-diyl, naphthalene-2, 3-diyl, naphthalene-2, 6-diyl, naphthalene-2, 7-diyl, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl or pyridine-2, 5-diyl, and in these rings, at least one hydrogen may be replaced with fluorine, chlorine, an alkyl group having a carbon number of 1 to 12, an alkoxy group having a carbon number of 1 to 12, Or at least one hydrogen is substituted with a fluorine or chlorine substituted alkyl group having 1 to 12 carbon atoms. Preferred ring M is 1, 4-phenylene or 2-fluoro-1, 4-phenylene.

Z ⁵ And Z ⁶ Is a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group ₂ -may be substituted by-O-, -CO-, -COO-or-OCO-, at least one-CH ₂ CH ₂ -may be via-CH ═ CH-, -C (CH) ₃ )＝CH-、-CH＝C(CH ₃ ) -or-C (CH) ₃ )＝C(CH ₃ ) -substitution, of which at least one hydrogen may be substituted by fluorine or chlorine. Preferred Z ⁵ Or Z ⁶ Is a single bond, -CH ₂ CH ₂ -、-CH ₂ O-、-OCH ₂ -, -COO-or-OCO-. Further preferred is Z ⁵ Or Z ⁶ Is a single bond.

Sp ¹ To Sp ³ Is a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group ₂ At least one-CH which may be substituted by-O-, -COO-, -OCO-or-OCOO-) ₂ CH ₂ -may be substituted by-CH ═ CH-or-C ≡ C-, in which groups at least one hydrogen may be substituted by fluorine or chlorine. Preferred is Sp ¹ To Sp ³ Is a single bond, -CH ₂ CH ₂ -、-CH ₂ O-、-OCH ₂ -, -COO-, -OCO-, -CO-CH-or-CH-CO-. Further preferred is Sp ¹ To Sp ³ Is a single bond.

h is 0, 1 or 2. Preferably h is 0 or 1. i. j and k are 0, 1,2, 3 or 4, and the sum of i, j and k is 1 or more. Preferably i, j or k is 1 or 2.

P ¹ To P ³ Is a polymerizable group. Preferred P ¹ To P ³ Is a polymerizable group selected from the group represented by the formulae (P-1) to (P-5). Further preferred is P ¹ To P ³ Is a group represented by the formula (P-1), the formula (P-2) or the formula (P-3). Particularly preferred P ¹ To P ³ Is a group represented by the formula (P-1) or (P-2). Most preferred P ¹ To P ³ Is a group represented by the formula (P-1). A preferred group represented by formula (P-1) is-OCO-CH ═ CH ₂ or-OCO-C (CH) ₃ )＝CH ₂ . The wavy lines of the formulae (P-1) to (P-5) indicate the bonding sites.

In the formulae (P-1) to (P-5), M ¹ To M ³ Hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine. For the purpose of enhancing reactivity, M is preferred ¹ To M ³ Is hydrogen or methyl. Further preferred is M ¹ Is hydrogen or methyl, and further preferred M ² Or M ³ Is hydrogen.

In formulae (6-1) to (6-29), P ⁴ To P ⁶ Are a group represented by the formulae (P-1) to (P-3). Preferred P ⁴ To P ⁶ Is represented by formula (P-1) or formula (P-2). Still more preferred formula (P-1) is-OCO-CH ═ CH ₂ or-OCO-C (CH) ₃ )＝CH ₂ . The wavy lines of the formulae (P-1) to (P-3) indicate the bonding sites.

Fifth, preferred component compounds are shown. Preferred compound (1) is the compound (1-1) and the compound (1-2) described in the above item 2.

Preferred compound (2) is the compound (2-1) to the compound (2-4) described in the item 5. Of these compounds, it is preferable that at least one of the components B is the compound (2-1) or the compound (2-3). It is particularly preferable that at least one of the components B is the compound (2-1). The proportion of the compound (2-1) is preferably 15% by mass or more, and particularly preferably 20% by mass or more.

Preferred compound (3) is the compound (3-1) to the compound (3-10) described in the item 5. Of these compounds, it is preferable that at least one of the components B is the compound (3-1), the compound (3-2), the compound (3-3) or the compound (3-4). Preferably, at least two of the components B are a combination of the compound (3-1) and the compound (3-3) or the compound (3-2) and the compound (3-4).

Preferred compound (4) is compound (4-1) to compound (4-17) described in item 8. Of these compounds, it is preferable that at least one of the components C is the compound (4-1), the compound (4-3), the compound (4-6) or the compound (4-7). Preferably, at least two of the components C are a combination of the compound (4-1) and the compound (4-3), the compound (4-1) and the compound (4-7), the compound (4-3) and the compound (4-6), the compound (4-3) and the compound (4-7), or the compound (4-6) and the compound (4-7). Preferably at least one of the components C is R ⁵ A compound which is a vinyl group. Among them, R is particularly preferable ⁵ A compound (4-3) or a compound (4-7) which is a vinyl group.

Preferred compounds (5) areThe compound (5-1) to the compound (5-13) according to item 11. Of these compounds, it is preferable that at least one of the components D is the compound (5-1), the compound (5-3), the compound (5-5), the compound (5-6), the compound (5-7), the compound (5-8) or the compound (5-10). It is particularly preferable that at least one of the components D is the compound (5-1), the compound (5-3), the compound (5-5) or the compound (5-10). Preferably, at least two of the components D are a combination of the compound (5-1) and the compound (5-3), the compound (5-1) and the compound (5-5), the compound (5-1) and the compound (5-6), the compound (5-1) and the compound (5-10), the compound (5-3) and the compound (5-5), the compound (5-3) and the compound (5-6), or the compound (5-5) and the compound (5-6). It is particularly preferred that at least one of the components D is R ⁷ Is propyl or vinyl and R ⁸ The compound (5-1) is a vinyl group or 1-propenyl group, and the proportion thereof is preferably 30% by mass or more. Particularly preferably R ⁷ Is propyl and R ⁸ Compound (5-1) being a vinyl group and R ⁷ Is vinyl and R ⁸ A compound (5-1) which is 1-propenyl group or R ⁷ Is propyl and R ⁸ Compound (5-1) which is a vinyl group and R ⁷ Is propyl and R ⁸ A combination of the compound (5-1) which is 1-propenyl group.

Preferred compound (6) is the compound (6-1) to the compound (6-29) described in the item 15. Of these compounds, it is preferable that at least one of the additives X is the compound (6-1), the compound (6-2), the compound (6-24), the compound (6-25), the compound (6-26) or the compound (6-27). Preferably, at least two of the additives X are a combination of the compound (6-1) and the compound (6-2), the compound (6-1) and the compound (6-18), the compound (6-2) and the compound (6-24), the compound (6-2) and the compound (6-25), the compound (6-2) and the compound (6-26), the compound (6-25) and the compound (6-26), or the compound (6-18) and the compound (6-24).

Sixth, additives that can be added to the composition will be described. Such additives include optically active compounds, antioxidants, ultraviolet absorbers, delustering agents, pigments, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds, and the like. An optically active compound is added to the composition for the purpose of inducing a helical structure of liquid crystal molecules to impart a twist angle (torsion angle). Examples of such compounds are compound (7-1) to compound (7-5). The preferable proportion of the optically active compound is about 5% by mass or less. Further, the preferable ratio is in the range of about 0.01 to about 2 mass%.

In order to prevent a decrease in specific resistance due to heating in the atmosphere or to maintain a large voltage holding ratio at room temperature and also at a temperature close to the upper limit temperature after the device is used for a long time, an antioxidant such as the compound (8-1) to the compound (8-3) may be further added to the composition.

Since the compound (8-2) has low volatility, it is effective for maintaining a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature after the device is used for a long time. In order to obtain the above effects, the preferable proportion of the antioxidant is about 50ppm or more, and in order not to lower the upper limit temperature or to raise the lower limit temperature, the preferable proportion of the antioxidant is about 600ppm or less. Even more preferred ratios range from about 100ppm to about 300 ppm.

Preferable examples of the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Light stabilizers such as sterically hindered amines are also preferred. Preferable examples of the light stabilizer are compound (9-1) to compound (9-16) and the like. The preferable proportion of these absorbents or stabilizers is about 50ppm or more in order to obtain the above effects, and about 10000ppm or less in order not to lower the upper limit temperature or not to raise the lower limit temperature. Further preferred ratios range from about 100ppm to about 10000 ppm.

The matting agent is a compound that receives light energy absorbed by the liquid crystalline compound and converts the light energy into thermal energy to prevent decomposition of the liquid crystalline compound. Preferable examples of the matting agent are a compound (10-1) to a compound (10-7) and the like. The preferable proportion of these matting agents is about 50ppm or more in order to obtain the above effects, and about 20000ppm or less in order not to raise the lower limit temperature. Even more preferred ratios range from about 100ppm to about 10000 ppm.

In order to be suitable for a guest-host (GH) mode element, a dichroic dye (dichromatic dye) such as an azo dye or an anthraquinone dye is added to the composition. The preferable ratio of the pigment ranges from about 0.01% by mass to about 10% by mass. In order to prevent bubbling, an antifoaming agent such as dimethylsilicone oil or methylphenylsilicone oil is added to the composition. The preferable ratio of the defoaming agent is about 1ppm or more in order to obtain the above effects, and about 1000ppm or less in order to prevent display failure. Even more preferred ratios range from about 1ppm to about 500 ppm.

Polymerizable compounds are used to adapt to polymer-stabilized alignment (PSA) type devices. The compound (6) is suitable for the purpose. A polymerizable compound different from the compound (6) may be added to the composition together with the compound (6). Preferable examples of such polymerizable compounds are compounds such as acrylic acid esters, methacrylic acid esters, vinyl compounds, vinyloxy compounds, propenyl ethers, epoxy compounds (oxetane ) and vinyl ketones. Further preferred are derivatives of acrylic acid esters or methacrylic acid esters. The preferable proportion of the compound (6) is 10% by mass or more based on the total mass of the polymerizable compounds. Further, the preferable ratio is 50% by mass or more. The ratio is particularly preferably 80% by mass or more. The most preferable ratio is 100 mass%.

The polymerizable compound such as the compound (6) is polymerized by ultraviolet irradiation. The polymerization may be carried out in the presence of an appropriate initiator such as a photopolymerization initiator. Suitable conditions for carrying out the polymerization, suitable types of initiators, and suitable amounts are known to those skilled in the art and are described in the literature. For example, brilliant good solid (Irgacure)651 (registered trademark; Basf), brilliant good solid (Irgacure)184 (registered trademark; Basf), or Delocur (Darocur)1173 (registered trademark; Basf) as a photopolymerization initiator is suitable for radical polymerization. The preferable proportion of the photopolymerization initiator ranges from about 0.1% by mass to about 5% by mass based on the total mass of the polymerizable compound. Further, the preferable ratio is in the range of about 1% by mass to about 3% by mass.

When a polymerizable compound such as the compound (6) is stored, a polymerization inhibitor may be added to prevent polymerization. The polymerizable compound is usually added to the composition in a state where the polymerization inhibitor is not removed. Examples of the polymerization inhibitor are hydroquinone derivatives such as hydroquinone and methyl hydroquinone, 4-t-butyl catechol, 4-methoxyphenol, phenothiazine and the like.

Seventh, a method for synthesizing the component compound will be explained. These compounds can be synthesized using known methods. A synthesis method is exemplified. The compound (1) is synthesized by the method described in the specification of German patent application laid-open No. 4414647. The compound (2-3) was synthesized by the method described in "Molecular Crystals and Liquid Crystals" (2011, volume 542, No. 1, p.16-27). The compound (3-2) is synthesized by the method described in Japanese patent laid-open No. Hei 2-503568. The compound (4-1) was synthesized by the method described in Japanese patent application laid-open No. 2-503441. The compound (5-1) is synthesized by the method described in Japanese patent laid-open No. 9-77692. The compound (6-18) is synthesized by the method described in Japanese patent laid-open No. Hei 7-101900. Antioxidants are commercially available. Compound (8-1) is available from Sigma Aldrich Corporation. The compound (8-2) and the like were synthesized by the method described in U.S. Pat. No. 3660505.

Compounds not described in the synthesis method can be synthesized by the method described in the following protocol: organic Synthesis (Organic Syntheses, John Wiley & Sons, Inc.), "Organic Reactions (Organic Reactions, John Wiley & Sons, Inc.)," Comprehensive Organic Synthesis (Pergamon Press, Pegman Press), "New Experimental chemistry lecture (Bolus)), and the like. The compositions are prepared from the compounds obtained in the manner described, using known methods. For example, the component compounds are mixed and then dissolved in each other by heating.

Finally, the use of the composition is illustrated. The composition has a major amount of optical anisotropy having a lower temperature limit of about-10 ℃ or less, an upper temperature limit of about 70 ℃ or more, and a range of about 0.07 to about 0.20. A composition having an optical anisotropy in the range of about 0.08 to about 0.25 may be prepared by controlling the ratio of the component compounds, or by mixing other liquid crystalline compounds. Compositions having optical anisotropy in the range of about 0.10 to about 0.30 may also be prepared by trial and error. The device containing the composition has a large voltage holding ratio. The composition is suitable for AM elements. The composition is particularly suitable for transmissive 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 elements. And can also be used for PM elements. The composition can be used for AM elements and PM elements having modes such as PC, TN, STN, ECB, OCB, IPS, FFS, VA, FPA and the like. Particularly preferably for AM elements having TN, OCB, IPS mode or FFS mode. In an AM element having an IPS mode or an FFS mode, the alignment of liquid crystal molecules may be parallel to a glass substrate or may be perpendicular to the glass substrate when no voltage is applied. These elements may be reflective, transmissive or transflective. Preferably for use in transmissive devices. It can also be used for an amorphous silicon-TFT element or a polysilicon-TFT element. The composition may be used for a device of a Nematic Curvilinear Aligned Phase (NCAP) type prepared by microencapsulation (microencapsulation) or a device of a Polymer Dispersed (PD) type in which a three-dimensional network polymer is formed in the composition.

[ examples ]

The present invention will be further described in detail by way of examples. The present invention is not limited by these examples. The invention comprises a mixture of the composition of example 1 and the composition of example 2. The invention also includes mixtures of at least two of the compositions of the examples. The synthesized compound is identified by Nuclear Magnetic Resonance (NMR) analysis or the like. The properties of the compounds, compositions and devices were measured by the methods described below.

NMR analysis: DRX-500 manufactured by Bruker BioSpin was used for the measurement. ¹ In the measurement of H-NMR, a sample was dissolved in CDCl ₃ The measurement was performed in the deuterated solvent at room temperature under conditions of 500MHz and 16 cumulative times. Tetramethylsilane was used as an internal standard. ¹⁹ In the measurement of F-NMR, CFCl was used ₃ As an internal standard, the number of times is accumulated to 24 times. In the description of the nmr spectra, s is a singlet (singlet), d is a doublet (doublt), t is a triplet (triplet), q is a quartet (quatet), quin is a quintet (quintet), sex is a sextant (sextet), m is a multiplet (multiplet), and br is a broad (broad).

Gas chromatography analysis: for measurement, a GC-14B gas chromatograph manufactured by Shimadzu corporation was used. The carrier gas was helium (2 mL/min). The sample vaporizer was set at 280 ℃ and the detector (flame ionization detector, FID) was set at 300 ℃. The separation of the component compounds was carried out by using a capillary column DB-1 (length 30m, inner diameter 0.32mm, film thickness 0.25 μm; stationary liquid phase is dimethylpolysiloxane; non-polar) manufactured by Agilent Technologies Inc. After the column was held at 200 ℃ for 2 minutes, the temperature was raised to 280 ℃ at a rate of 5 ℃/min. After preparing a sample into an acetone solution (0.1 mass%), 1. mu.L of the acetone solution was injected into a sample vaporizing chamber. The record is a chromatograph module (Chromatopac) model C-R5A manufactured by Shimadzu corporation or an equivalent thereof. The obtained gas chromatogram showed the retention time of the peak corresponding to the component compound and the area of the peak.

As a solvent for diluting the sample, chloroform, hexane, etc. can be used. To separate the constituent compounds, the following capillary column may be used. HP-1 (length 30m, inner diameter 0.32mm, film thickness 0.25 μm) manufactured by Agilent Technologies Inc., Rtx-1 (length 30m, inner diameter 0.32mm, film thickness 0.25 μm) manufactured by Rasteck Corporation, BP-1 (length 30m, inner diameter 0.32mm, film thickness 0.25 μm) manufactured by Australian SGE International Pty.Ltd. For the purpose of preventing overlapping of the compound peaks, a capillary column CBP1-M50-025 (length 50M, inner diameter 0.25mm, film thickness 0.25 μ M) manufactured by Shimadzu corporation was used.

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

Measurement of the sample: in the measurement of the properties of the composition or the element, the composition is used as a sample as it is. In order to measure the characteristics of the compound, a sample for measurement was prepared by mixing the compound (15 mass%) in a mother liquid crystal (85 mass%). From the values obtained by the measurement, the characteristic values of the compounds were calculated by an extrapolation method (extrapolation method). (extrapolated value) { (measured value of sample) — 0.85 × (measured value of mother liquid crystal) }/0.15. When the smectic phase (or crystals) precipitates at 25 ℃ at the ratio, the ratio of the compound to the mother liquid crystal is set at 10 mass%: 90% by mass and 5% by mass: 95% by mass and 1% by mass: the order of 99 mass% was changed. The values of the upper limit temperature, optical anisotropy, viscosity and dielectric anisotropy relating to the compound were determined by the extrapolation method.

The following mother liquid crystal was used. The proportion of the component compounds is represented by mass%.

The determination method comprises the following steps: the characteristics were measured by the following methods. These methods are mostly described in JEITA standard (JEITA. ED-2521B) examined and established by the Japan electronic Information Technology Industries Association (JEITA), or modified. The TN element used for the measurement was not provided with a Thin Film Transistor (TFT).

(1) Upper limit temperature of nematic phase (NI;. degree. C.): the sample was placed on a hot plate of a melting point measuring apparatus equipped with a polarizing microscope, and heated at a rate of 1 ℃/min. The temperature at which a portion of the sample changes from a nematic phase to an isotropic liquid is measured. The upper limit temperature of the nematic phase may be simply referred to as "upper limit temperature".

(2) Lower limit temperature (T) of nematic phase _C (ii) a C): a sample having a nematic phase was placed in a glass bottle, and the liquid crystal phase was observed after 10 days of storage in a freezer at 0 ℃, -10 ℃, -20 ℃, -30 ℃, and-40 ℃. For example, when the sample is kept in a nematic phase at-20 ℃ and changed to a crystalline or smectic phase at-30 ℃, T is set _C Is reported as < -20 ℃. The lower limit temperature of the nematic phase may be simply referred to as "lower limit temperature".

(3) Viscosity (. eta.; measured at 20 ℃ C.; mPas): for the measurement, an E-type rotational viscometer manufactured by tokyo counter gmbh was used.

(4) Viscosity (rotational viscosity; γ 1; measured at 25 ℃; mPas): for the measurement, a rotational viscosity ratio measuring system LCM-2 of Toyang technical products Co. A VA device having a gap (cell gap) of 10 μm between two glass substrates was used as a sample. A rectangular wave (55V, 1ms) was applied to the element. The peak current (peak current) and peak time (peak time) of the transient current (transient current) generated by the application are measured. The values of rotational viscosity were obtained using these measured values and dielectric anisotropy. The dielectric anisotropy was measured by the method described in measurement (6).

(5) Optical anisotropy (refractive index anisotropy; Δ n; measured at 25 ℃): the measurement was performed using light having a wavelength of 589nm by an Abbe refractometer having a polarizing plate attached to an eyepiece lens. After rubbing the surface of the main prism in one direction, the sample was dropped 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 the polarized light is perpendicular to the direction of the friction. The value of the optical anisotropy is calculated from the formula Δ n ═ n/n ″.

(6) Dielectric anisotropy (. DELTA.. di-elect cons.; measured at 25 ℃): the value of the dielectric anisotropy is calculated according to the formula Δ ∈/∈ j. The dielectric constants (. epsilon./. epsilon. mu.j) were measured in the following manner.

1) Measurement of dielectric constant (. epsilon. /): a solution of octadecyltriethoxysilane (0.16mL) in ethanol (20mL) was coated on the well-cleaned glass substrate. The glass substrate was rotated by a rotator and then heated at 150 ℃ for 1 hour. A VA cell having a gap (cell gap) of 4 μm between two glass substrates was loaded with a sample, and the cell was sealed with an adhesive cured by ultraviolet rays. A sine wave (0.5V, 1kHz) was applied to the cell, and the dielectric constant (. epsilon. /) in the long axis direction of the liquid crystal molecules was measured after 2 seconds.

2) Measurement of dielectric constant (. epsilon. DELTA. -): the polyimide solution was coated on the well-cleaned glass substrate. After the glass substrate is fired, the obtained alignment film is subjected to rubbing treatment. A sample was placed in a TN cell having a cell gap of 9 μm between two glass substrates and a twist angle of 80 degrees. Sine wave (0.5V, 1kHz) was applied to the element, and the dielectric constant (∈ ∈ in the short axis direction of the liquid crystal molecules was measured after 2 seconds.

(7) Threshold voltage (Vth; measured at 25 ℃; V): for the measurement, a Liquid Crystal Display (LCD) 5100 type luminance meter manufactured by Otsuka electronics Ltd was used. The light source is a halogen lamp. A VA element in a normally black mode (normal black mode) in which the gap between two glass substrates (cell gap) was 4 μm and the rubbing directions were antiparallel was loaded with a sample, and the element was sealed using an adhesive cured with ultraviolet rays. The voltage applied to the element (60Hz, rectangular wave) was increased stepwise from 0V to 20V in units of 0.02V. At this time, the element was irradiated with light from the vertical direction, and the amount of light transmitted through the element was measured. A voltage-transmittance curve is prepared 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 a voltage at which the transmittance reaches 10%.

(8) Voltage holding ratio (VHR-1; measured at 25;%): the TN element used for the measurement had a polyimide alignment film, and the interval (cell gap) between the two glass substrates was 5 μm. The element is sealed with an adhesive cured with ultraviolet rays after the sample is placed. The TN cell is charged by applying a pulse voltage (5V, 60 μ sec). The decayed voltage was measured by a high-speed voltmeter for a period of 16.7 milliseconds, and the area a between the voltage curve and the horizontal axis in the unit cycle was determined. The area B is the area when not attenuated. The voltage holding ratio is expressed by a percentage of the area a to the area B.

(9) Voltage holding ratio (VHR-2; measured at 80 ℃.): the voltage holding ratio was measured in the same procedure as described except that the measurement was performed at 80 ℃ instead of 25 ℃. The obtained value is denoted by VHR-2.

(10) Voltage holding ratio (VHR-3; measured at 25 ℃.): after irradiation with ultraviolet rays, the voltage holding ratio was measured, and stability to ultraviolet rays was evaluated. The TN cells used for the measurement had a polyimide alignment film and a cell gap of 5 μm. The sample was injected into the cell and irradiated with light for 20 minutes. The light source was an ultra-high pressure mercury lamp USH-500D (manufactured by Ushio motor), and the spacing between the elements and the light source was 20 cm. In the measurement of VHR-3, the voltage at decay was measured during 16.7 milliseconds. Compositions with large VHR-3 have a large stability to UV light. VHR-3 is preferably 90% or more, more preferably 95% or more.

(11) Voltage holding ratio (VHR-4; measured at 25;%): after heating the TN element having the sample injected therein in a thermostatic bath at 80 ℃ for 500 hours, the voltage holding ratio was measured, and the stability to heat was evaluated. In the measurement of VHR-4, the voltage decay was measured during 16.7 milliseconds. Compositions with large VHR-4 have a large stability to heat.

(12) Response time (. tau.; measured at 25 ℃ C.; ms): for the measurement, an LCD5100 type luminance meter manufactured by Otsuka electronics Co., Ltd was used. The light source is a halogen lamp. The Low-pass filter (Low-pass filter) is set to 5 kHz. A sample was placed in a VA element of a normally black mode (normal black mode) in which the gap between two glass substrates (cell gap) was 4 μm and the rubbing directions were antiparallel. The element is sealed using an adhesive hardened with ultraviolet rays. A square wave (60Hz, 10V, 0.5 sec) was applied to the element. At this time, the element was irradiated with light from the vertical direction, and the amount of light transmitted through the element was measured. The transmittance was regarded as 100% when the light amount reached the maximum, and as 0% when the light amount was the minimum. The response time is represented by the time (fall time; millisecond) required for the transmittance to change from 90% to 10%.

(13) Specific resistance (. rho.; measured at 25 ℃ C.;. OMEGA.cm): 1.0mL of the sample was injected into a container equipped with an electrode. A DC voltage (10V) was applied to the vessel, and a DC current after 10 seconds was measured. The specific resistance is calculated according to the following equation. (specific resistance) { (voltage) × (capacitance of container) }/{ (direct current) × (dielectric constant of vacuum) }.

(14) Line afterimage (Line Image learning Parameter; LISP;%): the liquid crystal display element is electrically stressed to generate a line residual image. The luminance of the region where the line afterimage exists and the luminance of the remaining region are measured. The ratio of the decrease in luminance due to the line afterimage is calculated, and the size of the line afterimage is represented by the ratio.

14a) Measurement of luminance: an image of the element was taken using an imaging color luminance meter (PM-1433F-0, manufactured by radial Zemax). The brightness of each region of the element was calculated by analyzing the image using software (Prometric 9.1, manufactured by radiation Imaging). Average luminance of 3500cd/m used for light source ² A Light-Emitting Diode (LED) backlight.

14b) Setting of stress voltage: a sample was put into an FFS cell (16 cells of 4 vertical cells × 4 horizontal cells) having a cell gap of 3.5 μm and a matrix structure, and the cell was sealed with an adhesive cured with ultraviolet rays. Polarizing plates are disposed on the upper surface and the lower surface of the element so that the polarizing axes are orthogonal to each other. Light was irradiated to the element and a voltage (rectangular wave, 60Hz) was applied. The voltage was in the range of 0V to 7.5V, and the luminance of the transmitted light at each voltage was measured while increasing stepwise in units of 0.1V. The voltage at which the luminance reaches the maximum is simply referred to as V255. The voltage at which the luminance reaches 21.6% of V255 (i.e., 127 gradations) is simply referred to as V127.

14c) Conditions of stress: v255 (square wave, 30Hz) and 0.5V (square wave, 30Hz) were applied to the element at 60 ℃ for 23 hours, and a checkerboard pattern was displayed. Next, V127 (square wave, 0.25Hz) was applied, and the brightness was measured under the condition of an exposure time of 4000 milliseconds.

14d) Calculation of line afterimage: for the calculation, 4 units (vertical 2 units × horizontal 2 units) in the center of 16 units were used. The 4 units were divided into 25 regions (vertical 5 units × horizontal 5 units). The average luminance of 4 areas (2 cells in vertical direction × 2 cells in horizontal direction) located at four corners is simply referred to as luminance a. The area formed by removing the four corner areas from the 25 areas is a cross. Of the 4 regions obtained by removing the central intersection region from the cross-shaped region, the minimum value of the luminance is simply referred to as luminance B. The line residual image is calculated according to the following equation. (line afterimage) (luminance a-luminance B)/luminance a × 100.

(15) Expansibility: the spreadability of the additive was qualitatively evaluated by applying a voltage to the element and measuring the luminance. The measurement of the luminance was performed in the same manner as in the item 14 a. The voltage (V127) is set in the same manner as in the above-described item 14 b. In which VA elements are used instead of FFS elements. The luminance was measured in the following manner. First, a dc voltage (2V) was applied to the element for 2 minutes. Next, V127 (square wave, 0.05Hz) was applied, and the brightness was measured under the condition of an exposure time of 4000 milliseconds. And evaluating the expansibility according to the result.

(16) Response time (. tau. -2; measured at-20 ℃ C.; ms): for the measurement, an LCD5100 type luminance meter manufactured by Otsuka electronics Co., Ltd was used. The light source is a halogen lamp. The Low-pass filter (Low-pass filter) is set to 5 kHz. A sample was placed in a VA element of a normally black mode (normal black mode) in which the gap between two glass substrates (cell gap) was 4 μm and the rubbing directions were antiparallel. The element is sealed using an adhesive hardened with ultraviolet rays. A square wave (60Hz, 10V, 0.5 sec) was applied to the element. At this time, the element was irradiated with light from the vertical direction, and the amount of light transmitted through the element was measured. The transmittance was regarded as 100% when the light amount reached the maximum, and as 0% when the light amount was the minimum. The response time is represented by the time (fall time; millisecond) required for the transmittance to change from 90% to 10%.

(17) Response time (. tau. -3; measured at-30 ℃ C.; ms): for the measurement, an LCD5100 type luminance meter manufactured by Otsuka electronics Co., Ltd was used. The light source is a halogen lamp. The Low pass filter (Low-pass filter) was set to 5 kHz. A sample was placed in a VA element of a normally black mode (normal black mode) in which the gap between two glass substrates (cell gap) was 4 μm and the rubbing directions were antiparallel. The element is sealed using an adhesive hardened with ultraviolet rays. A square wave (60Hz, 10V, 0.5 sec) was applied to the element. At this time, the element was irradiated with light from the vertical direction, and the amount of light transmitted through the element was measured. The transmittance was regarded as 100% when the light amount reached the maximum, and as 0% when the light amount was the minimum. The response time is represented by the time (fall time; millisecond) required for the transmittance to change from 90% to 10%.

(18) Elastic constant (K11: splay elastic constant, K33: bend elastic constant; measured at 25 ℃ C.; pN): for the measurement, an EC-1 elastic constant measuring instrument manufactured by Toyang Technica (Toyo technical) Co., Ltd was used. A sample was placed in a vertical alignment cell having a gap (cell gap) of 20 μm between two glass substrates. A charge of 20 to 0V was applied to the cell, and the electrostatic capacitance and applied voltage were measured. The values of the measured electrostatic capacitance (C) and the applied voltage (V) were fitted using the equations (2.98) and (2.101) on page 75 of the handbook of liquid crystal devices (journal industries, press), and the value of the elastic constant was obtained from the equation (2.100).

Examples of compositions are shown below. The component compounds are represented by symbols based on the definitions in table 3 below. In Table 3, the configuration of the 1, 4-cyclohexylene group is trans. The numbers in parentheses after the symbols correspond to the numbers of the compounds. The symbol (-) indicates other liquid crystalline compounds. The proportion (percentage) of the liquid crystalline compound is a mass percentage (mass%) based on the mass of the liquid crystal composition. Finally, the values of the properties of the composition are summarized.

TABLE 3 expression of compounds using symbols

R-(A ₁ )-Z ₁ -·····-Z _n -(A _n )-R’

Comparative example 1

A composition not containing the compound (1) as the component a of the present invention was prepared.

[ example 1]

[ example 2]

[ example 3]

[ example 4]

[ example 5]

[ example 6]

[ example 7]

[ example 8]

[ example 9]

[ example 10]

[ example 11]

[ example 12]

[ example 13]

[ example 14]

[ example 15]

[ example 16]

[ example 17]

[ example 18]

[ example 19]

[ example 20]

[ example 21]

[ example 22]

[ example 23]

The rotational viscosity of the composition of comparative example 1 was 130 mPas. On the other hand, the rotational viscosity of the compositions of examples 1 to 23 was 72 to 115mPa · s. As described above, the compositions of examples have a small rotational viscosity as compared with the compositions of comparative examples. Therefore, it was concluded that the liquid crystal composition of the present invention has excellent characteristics.

[ industrial applicability ]

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

Claims

1. A liquid crystal composition containing at least one compound selected from the group consisting of compounds represented by the formula (1) as a component A and having a negative dielectric anisotropy;

in the formula (1), R ¹ Is alkyl of carbon number 1 to 12 or alkenyl of carbon number 2 to 12; r ² Alkenyl having 2 to 12 carbon atoms; z is a linear or branched member ¹ Is a single bond or vinylidene.

2. The liquid crystal composition according to claim 1, which comprises at least one compound selected from the group consisting of compounds represented by the formulae (1-1) and (1-2) as the component A;

in the formulae (1-1) and (1-2), R ¹ An alkyl group having 1 to 12 carbon atoms or an alkenyl group having 2 to 12 carbon atoms.

3. The liquid crystal composition according to claim 1 or 2, wherein the proportion of the component a is in the range of 1 to 20% by mass.

4. The liquid crystal composition according to claim 1 or 2, which contains at least one compound selected from the group consisting of compounds represented by formula (2) and formula (3) as component B;

in the formula (2), R ³ And R ⁴ Is alkyl with carbon number of 1 to 12, alkoxy with carbon number of 1 to 12 or alkenyl with carbon number of 2 to 12; ring A and ring B are tetrahydropyran-2, 5-diyl, 1, 4-phenylene, or 1, 4-phenylene in which at least one hydrogen is substituted by fluorine or chlorine; a is 1 or 2, b is 0 or 1; when a is 2, ring A is tetrahydropyran-2, 5-diyl or 1, 4-phenylene;

in the formula (3), R ⁵ And R ⁶ Is alkyl group with carbon number of 1 to 12, alkoxy group with carbon number of 1 to 12 or alkenyl group with carbon number of 2 to 12; ring C and ring E are 1, 4-cyclohexylene, 1, 4-cyclohexenylene, tetrahydropyran-2, 5-diyl, 1, 4-phenylene in which at least one hydrogen is substituted by fluorine or chlorine, naphthalene-2, 6-diyl in which at least one hydrogen is substituted by fluorine or chlorine, chroman-2, 6-diyl, or chroman-2, 6-diyl in which at least one hydrogen is substituted by fluorine or chlorine; ring D 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-difluorochromane-2, 6-diyl, 3,4,5, 6-tetrafluorofluorene-2, 7-diyl, 46-difluorodibenzofuran-3, 7-diyl, 4, 6-difluorodibenzothiophene-3, 7-diyl, or 1,1,6, 7-tetrafluoroindan-2, 5-diyl; z ² And Z ³ Is a single bond, ethylene, vinylidene, methyleneoxy or carbonyloxy; at least one of Z ² And Z ³ Is ethylene, vinylene, methyleneoxy or carbonyloxy; c is 1,2 or 3, d is 0 or 1; and the sum of c and d is 3 or less.

5. The liquid crystal composition according to claim 1 or 2, which contains at least one compound selected from the group consisting of compounds represented by formulae (2-1) to (2-4) and formulae (3-1) to (3-10) as the component B;

in the formulae (2-1) to (2-4), R ³ And R ⁴ Is alkyl group with carbon number of 1 to 12, alkoxy group with carbon number of 1 to 12 or alkenyl group with carbon number of 2 to 12;

6. The liquid crystal composition according to claim 4, wherein the proportion of the component B is in the range of 5 to 40% by mass.

7. The liquid crystal composition according to claim 1 or 2, which contains at least one compound selected from the group consisting of compounds represented by formula (4) as component C;

in the formula (4), the reaction mixture is,R ⁷ and R ⁸ Is hydrogen, alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, alkenyl group having 2 to 12 carbon atoms, alkenyloxy group having 2 to 12 carbon atoms, or alkyl group having 1 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine; ring F and ring I are 1, 4-cyclohexylene, 1, 4-cyclohexenylene, tetrahydropyran-2, 5-diyl, 1, 4-phenylene in which at least one hydrogen is substituted by fluorine or chlorine, naphthalene-2, 6-diyl in which at least one hydrogen is substituted by fluorine or chlorine, chroman-2, 6-diyl in which at least one hydrogen is substituted by fluorine or chlorine, or chroman-2, 6-diyl in which at least one hydrogen is substituted by fluorine or chlorine; ring G 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-difluorochromane-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-tetrafluoroindan-2, 5-diyl; e is 0, 1,2 or 3, f is 0 or 1; and the sum of e and f is 3 or less; when the sum of e and F is 1 or more, at least one of ring F and ring I is 1, 4-cyclohexylene, 1, 4-cyclohexenylene, naphthalene-2, 6-diyl in which at least one hydrogen is substituted by fluorine or chlorine, chromane-2, 6-diyl, or chromane-2, 6-diyl in which at least one hydrogen is substituted by fluorine or chlorine; when the sum of e and f is 0, ring G is 4, 6-difluorodibenzofuran-3, 7-diyl or 4, 6-difluorodibenzothiophene-3, 7-diyl.

8. The liquid crystal composition according to claim 1 or 2, which contains at least one compound selected from the group consisting of compounds represented by formulae (4-1) to (4-17) as component C;

in the formulae (4-1) to (4-17), R ⁷ And R ⁸ Is hydrogen, alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, carbon atomAn alkenyl group having 2 to 12 carbon atoms, an alkenyloxy group having 2 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine.

9. The liquid crystal composition according to claim 7, wherein the proportion of the component C is in the range of 10 to 60 mass%.

10. The liquid crystal composition according to claim 1 or 2, which contains at least one compound selected from the group consisting of compounds represented by formula (5) as component D;

11. The liquid crystal composition according to claim 1 or 2, which contains at least one compound selected from the group consisting of compounds represented by formulae (5-1) to (5-13) as the component D;

in the formulae (5-1) to (5-13), R ⁹ And R ¹⁰ Is alkyl with carbon number of 1-12, alkoxy with carbon number of 1-12, alkenyl with carbon number of 2-12, alkyl with carbon number of 1-12 with at least one hydrogen substituted by fluorine or chlorine, or alkenyl with carbon number of 2-12 with at least one hydrogen substituted by fluorine or chlorine。

12. The liquid crystal composition according to claim 10, wherein the proportion of the component D is in the range of 10 to 50% by mass.

13. The liquid crystal composition according to claim 1 or 2, which contains at least one compound selected from polymerizable compounds represented by formula (6) as an additive X;

in the formula (6), the ring L and the ring N are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1, 3-dioxan-2-yl, pyrimidin-2-yl or pyridin-2-yl, and in these rings, at least one hydrogen may be substituted with fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine; the ring M is 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, naphthalene-1, 2-diyl, naphthalene-1, 3-diyl, naphthalene-1, 4-diyl, naphthalene-1, 5-diyl, naphthalene-1, 6-diyl, naphthalene-1, 7-diyl, naphthalene-1, 8-diyl, naphthalene-2, 3-diyl, naphthalene-2, 6-diyl, naphthalene-2, 7-diyl, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl or pyridine-2, 5-diyl, and in these rings, at least one hydrogen may be replaced with fluorine, chlorine, an alkyl group having a carbon number of 1 to 12, an alkoxy group having a carbon number of 1 to 12, Or at least one hydrogen is substituted by a fluorine or chlorine substituted alkyl group of carbon number 1 to 12; z is a linear or branched member ⁵ And Z ⁶ Is a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group ₂ -may be substituted by-O-, -CO-, -COO-or-OCO-, at least one-CH ₂ CH ₂ -may be via-CH ═ CH-, -C (CH) ₃ )＝CH-、-CH＝C(CH ₃ ) -or-C (CH) ₃ )＝C(CH ₃ ) -substituted, in which at least one hydrogen may be substituted by fluorine or chlorine; p ¹ To P ³ Is a polymerizable group; sp ¹ To Sp ³ Is a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group ₂ At least one-CH which may be substituted by-O-, -COO-, -OCO-or-OCOO-) ₂ CH ₂ -may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being substituted by fluorine or chlorine; h is 0, 1 or 2; i. j and k are 0, 1,2, 3 or 4; and the sum of i, j and k is 1 or more.

14. The liquid crystal composition according to claim 13, wherein in formula (6), P ¹ To P ³ Is a group selected from the polymerizable groups represented by the formulae (P-1) to (P-5);

15. The liquid crystal composition according to claim 1 or 2, which contains at least one compound selected from the polymerizable compounds represented by formulae (6-1) to (6-29) as an additive X;

in formulae (6-1) to (6-29), Sp ¹ To Sp ³ Is a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group ₂ At least one-CH which may be substituted by-O-, -COO-, -OCO-or-OCOO-) ₂ CH ₂ Can be passed through-CH-or-C ≡ C-substituted, of which groups at least one hydrogen may be substituted by fluoro or chloro; p ⁴ To P ⁶ Is a polymerizable group selected from the group represented by the formulae (P-1) to (P-3);

16. The liquid crystal composition according to claim 13, wherein the proportion of the additive X is in the range of 0.03 to 10 mass%.

17. A liquid crystal display element comprising the liquid crystal composition according to any one of claims 1 to 16.

18. The liquid crystal display element according to claim 17, wherein the operation mode is an in-plane switching mode, a vertical alignment mode, a fringe field switching mode, or an electric field induced photo-response alignment mode, and the driving method is an active matrix method.

19. A polymer-stabilized alignment type liquid crystal display element comprising the liquid crystal composition according to any one of claims 13 to 16, wherein the polymerizable compound in the liquid crystal composition is polymerized.

20. Use of a liquid crystal composition according to any one of claims 1 to 16 in a liquid crystal display element.

21. Use of a liquid crystal composition according to any one of claims 13 to 16 in a liquid crystal display element of a polymer-stabilized alignment type.