CN110461993A - Liquid crystal composition and liquid crystal display element - Google Patents

Abstract

The present invention provides a liquid crystal composition and an AM device comprising the composition. The liquid crystal composition satisfies the requirements of high upper limit temperature, low lower limit temperature, low viscosity, appropriate optical anisotropy, and large negative dielectric anisotropy. At least one of the properties of the class, or a suitable balance between at least two of these properties. A liquid crystal composition comprising a specific compound having a large dielectric anisotropy as a first component, a specific compound having a small viscosity or a large elastic constant as a second component, and may also contain a third component A specific compound having a large dielectric anisotropy, a specific compound having a high upper limit temperature as a fourth component, or a specific compound having a polymerizable group as a first additive.

Description

Liquid crystal composition and liquid crystal display element

technical field

The present invention relates to a liquid crystal composition, a liquid crystal display element containing the composition, and the like. In particular, it relates to a liquid crystal composition with negative dielectric anisotropy, and a liquid crystal display element containing the composition and having modes such as IPS, VA, FFS, and FPA. The present invention also relates to a polymer-stabilized alignment type liquid crystal display element.

Background technique

In liquid crystal display elements, the classification based on the operation mode of liquid crystal molecules is phase change (PC), twisted nematic (TN), super twisted nematic (STN), electronically controlled birefringence ( Electrically controlled birefringence (ECB), optically compensated bend (OCB), in-plane switching (IPS), vertical alignment (VA), fringe field switching (FFS), electric field induction Modes such as field-induced photo-reactive alignment (FPA). Component-based driving methods are classified into passive matrix (PM) and active matrix (AM). PM is classified into static type (static), multiplex type (multiplex), etc., AM is classified into thin film transistor (TFT), metal insulator metal (MIM) and the like. TFTs are classified into amorphous silicon and polycrystal silicon. The latter are classified into high temperature type and low temperature type according to the manufacturing process. The light source is classified into a reflective type using natural light, a transmissive type using a backlight, and a transflective 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 properties of the composition, an AM device having good properties can be obtained. The associations among these properties are summarized in Table 1 below. The properties of the composition will be further described based on a commercially available AM device. The temperature range of the nematic phase correlates to the temperature range over which the element can be used. The preferable upper limit temperature of the nematic phase is about 70°C or more, and the preferable lower limit temperature of the nematic phase is about -10°C or less. The viscosity of the composition correlates to the response time of the element. In order to display a moving image with an element, it is preferable that the response time is short. The ideal is a response time of less than 1 millisecond. Therefore, the viscosity of the composition is preferably small. Furthermore, it is preferable that the viscosity at low temperature is small.

Table 1. Properties of compositions and properties of AM devices

The optical anisotropy of the composition correlates to 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 (Δn×d) of the optical anisotropy (Δn) of the composition and the cell gap (d) of the element is designed to maximize the contrast ratio. An appropriate value of the product depends on the type of operation mode. In the element of the VA mode, the value is in the range of about 0.30 μm to about 0.40 μm, and in the element of the IPS mode or the FFS mode, the value is 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 with a small cell gap. The large dielectric anisotropy of the composition contributes to 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 the large voltage holding ratio and the large contrast ratio of the element. Therefore, a composition having a large specific resistance in the initial stage is preferable. A composition having a large specific resistance even after prolonged use is preferred. The stability of the composition to UV light or heat correlates with the lifetime of the element. 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 general-purpose liquid crystal display elements, the vertical alignment of liquid crystal molecules can be achieved using a specific polyimide alignment film. In a polymer sustained alignment (polymer sustained alignment, PSA) type liquid crystal display element, a polymer and an alignment film are combined. First, a composition to which a small amount of a polymerizable compound is added is injected into the element. Next, a voltage is applied between the substrates facing the element, and ultraviolet rays are irradiated on the composition. The polymerizable compound is polymerized to form a network structure of the polymer in the composition. In the composition, the polymer can be used to control the orientation of the liquid crystal molecules, so the response time of the element is shortened, and the afterimage of the image is improved. Such effects of polymers can be expected in elements having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.

A composition having a positive dielectric anisotropy is used in an AM element having a TN mode. A composition having a negative dielectric anisotropy is used in an AM element having a VA mode. A composition having a positive or negative dielectric anisotropy is used in an AM element having an IPS mode or an FFS mode. Compositions having positive or negative dielectric anisotropy are used in polymer-stabilized oriented AM devices. Patent Document 1 and Patent Document 2 disclose the compound contained in the first component of the present invention.

prior art literature

Patent Literature

Patent Document 1: International Publication No. 2015/129412

Patent Document 2: International Publication No. 2012/86437

SUMMARY OF THE INVENTION

problem to be solved by invention

An object of the present invention is to provide a liquid crystal composition that satisfies the requirements of high upper limit temperature of nematic phase, low minimum temperature of nematic phase, low viscosity, suitable optical anisotropy, large negative dielectric anisotropy, and high specific resistance. , at least one of the characteristics of high stability to ultraviolet rays and high stability to heat. Another subject is to provide a liquid crystal composition having an appropriate balance between at least two of these properties. Another subject is to provide a liquid crystal display element containing such a composition. Another subject is to provide an AM element having characteristics such as short response time (especially at low temperature), high voltage holding ratio, low threshold voltage, high contrast ratio, and long life.

Technical means to solve problems

The present invention relates to a liquid crystal composition containing, as a first component, at least one compound selected from the compounds represented by formula (1), and a liquid crystal display element containing the same, as a second component The component is at least one compound selected from the compounds represented by the formula (2), and has a negative dielectric anisotropy.

In formula (1) and formula (2), R ¹ and R ² are independently hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, carbon Alkenyloxy with 2 to 12 carbons, or alkyl with 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine; R ³ and R ⁴ are independently alkenyl with 2 to 12 carbons, 2 to 12 carbons Alkenyloxy of 12, or alkenyl of carbon number 2 to 12 in which at least one hydrogen is substituted by fluorine or chlorine; Ring A and Ring C are independently 1,4-cyclohexylene, 1,4-cyclohexene base, tetrahydropyran-2,5-diyl, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is substituted by fluorine or chlorine; ring B is fluorene-2,7-diyl , dibenzothiophene-3,7-diyl, phenanthrene-2,7-diyl, 9,10-dihydrophenanthrene-2,7-diyl, xanthene-2,6-diyl or indan- 2,5-diyl, in these rings, at least one hydrogen can be substituted by fluorine or chlorine; Z ¹ and Z ² are independently a single bond, ethylene, carbonyloxy or methyleneoxy; a is 0, 1, 2 or 3, b is 0 or 1, and the sum of a and b is 3 or less.

effect of invention

The advantages of the present invention are to provide a liquid crystal composition that satisfies the requirements of high upper limit temperature of nematic phase, low lower limit temperature of nematic phase, low viscosity, appropriate optical anisotropy, large negative dielectric anisotropy, and large specific resistance. , at least one of the characteristics of high stability to ultraviolet rays and high stability to heat. Another advantage is to provide a liquid crystal composition with a suitable balance between at least two of these properties. Another advantage is to provide a liquid crystal display element containing such a composition. Still another advantage is to provide an AM element with characteristics such as short response time, high voltage holding ratio, low threshold voltage, high contrast ratio, and long life.

Detailed ways

The usage method of the term in the said specification is as follows. The terms "liquid crystal composition" and "liquid crystal display element" may be abbreviated as "composition" and "element", respectively. A "liquid crystal display element" is a general term for a liquid crystal display panel and a liquid crystal display module. A "liquid crystal compound" is a compound having a liquid crystal phase such as a nematic phase or a smectic phase, and a compound that does not have a liquid crystal phase but is used for the purpose of adjusting the temperature range, viscosity, and dielectric anisotropy of the nematic phase. The general term for compounds mixed in the composition. The compound has a six-membered ring such as 1,4-cyclohexylene or 1,4-phenylene, and its molecular structure is rod-like. The "polymerizable compound" is a compound added for the purpose of producing a polymer in the composition. The liquid crystal compound having an alkenyl group is not polymerizable in its meaning.

The liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. Additives such as optically active compounds, antioxidants, ultraviolet absorbers, quenchers, pigments, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, and polar compounds are optionally added to the liquid crystal composition as required. . Even in the case where an additive is added, the ratio of the liquid crystal compound is represented by the weight percentage (% by weight) based on the weight of the liquid crystal composition not containing the additive. The ratio of the additive is represented by the weight percentage (% by weight) based on the weight of the liquid crystal composition not containing the additive. That is, the ratio of the liquid crystal compound or the additive is calculated based on the total weight of the liquid crystal compound. Parts per million by weight (ppm) are sometimes used. The ratios of the polymerization initiator and the polymerization inhibitor are expressed based on the weight of the polymerizable compound exceptionally.

The "upper limit temperature of the nematic phase" is sometimes simply referred to as the "upper limit temperature". The "lower limit temperature of the nematic phase" is sometimes simply referred to as the "lower limit temperature". "Large specific resistance" means that the composition has a large specific resistance in the initial stage, and, moreover, has a large specific resistance after being used for a long time. "Large voltage retention ratio" means that the element has a large voltage retention ratio not only at room temperature but also at a temperature close to the upper limit temperature in the initial stage, and not only at room temperature but also at a temperature close to the upper limit temperature after long-term use It has a large voltage holding ratio even at the temperature of the upper limit temperature. The properties of compositions or components are sometimes investigated before and after time-varying tests, including accelerated degradation tests. The expression "improving the dielectric anisotropy" means that the value of the composition with a positive dielectric anisotropy increases positively, and when the composition has a negative dielectric anisotropy, it means that the value is negative. increase to the ground.

The compound represented by formula (1) may be abbreviated as "compound (1)" in some cases. At least one compound selected from the compounds represented by the formula (1) may be abbreviated as "compound (1)" in some cases. "Compound (1)" refers to one compound represented by formula (1), a mixture of two compounds, or a mixture of three or more compounds. The same applies to compounds represented by other formulae. The expression "at least one 'A'" means that the number of 'A's is arbitrary. The expression "at least one 'A' may be substituted by 'B'" means that when the number of 'A' is one, the position of 'A' is arbitrary, and when the number of 'A' is two or more, their positions There are also unlimited options. The rules also apply to the expression "at least one 'A' is substituted with a 'B'".

Expressions such as "at least one -CH ₂ - may be substituted with -O-" are used in this specification. In that case, _-CH2 - _CH2 -CH2- can be converted to -O- _CH2 - _O- by substituting a non-adjacent _-CH2- with -O-. However, the adjacent _-CH2- is not substituted with -O-. This is because -OO-CH ₂ - (peroxide) is formed in the substitution. That is, the expression refers to both "one _-CH2- may be substituted with -O-" and "at least two non-adjacent _-CH2- may be substituted with -O-". The rules apply not only in the case of substitution with -O-, but also in the case of substitution with divalent groups such as -CH=CH- or -COO-.

In the chemical formulae of the component compounds, the notation of the terminal group R ¹ is used for various compounds. In these compounds, the two groups represented by any two R ¹ may be the same or different. For example, R ¹ of the compound (1-1) is an ethyl group, and R ¹ of the compound (1-2) is an ethyl group. There are cases where R ¹ of compound (1-1) is ethyl and R ¹ of compound (1-2) is propyl. The rules also apply to the notation of other end groups and the like. In formula (3), when the subscript 'c' is 2, there are two rings D. In the compound, the two rings represented by the two rings D may be the same or different. The rules also apply to any two rings D when the subscript 'c' is greater than 2. The rules also apply to the notation ^Z4 , ring G, etc. The rules also apply to the case of two -Sp ² -P ⁵ in compounds (5-27).

Symbols such as A, B, C, and D surrounded by hexagons correspond to rings such as ring A, ring B, ring C, and ring D, respectively, and represent rings such as six-membered rings and condensed rings. In compound (5), the oblique line crossing one side of the hexagon indicates that any hydrogen on the ring may be substituted by groups such as -Sp ¹ -P ¹ . Subscripts such as 'g' indicate the number of substituted groups. When the subscript 'g' is 0 (zero), there is no such substitution. When the subscript 'g' is 2 or more, a plurality of -Sp ¹ -P ¹ exist on the ring J. The plural bases represented by -Sp ¹ -P ¹ may be the same or different. In the expression "Ring A and Ring B are independently X, Y or Z", since the subject is plural, "independently" is used. When the subject is "Ring A", since the subject is singular, "independently" is not used.

2-Fluoro-1,4-phenylene refers to the following two divalent groups. In the chemical formula, fluorine can be left (L) or right (R). The rules also apply to left-right asymmetric divalent radicals such as tetrahydropyran-2,5-diyl, which are formed by removing two hydrogens from the ring. The same rules apply to divalent bonding groups such as carbonyloxy (-COO- or -OCO-).

The alkyl group of the liquid crystal compound is linear or branched, and does not contain a cyclic alkyl group. Straight chain alkyl groups are preferred over branched alkyl groups. The same applies to terminal groups such as an alkoxy group and an alkenyl group. To increase the upper temperature limit, the steric configuration associated with 1,4-cyclohexylene is the trans configuration over the cis configuration.

The present invention is the following items and the like.

Item 1. A liquid crystal composition comprising at least one compound selected from the compounds represented by the formula (1) as a first component, and a compound selected from the compounds represented by the formula (2) as a second component at least one compound having negative dielectric anisotropy,

In formula (1) and formula (2), R ¹ and R ² are independently hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, carbon Alkenyloxy with 2 to 12 carbons, or alkyl with 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine; R ³ and R ⁴ are independently alkenyl with 2 to 12 carbons, 2 to 12 carbons Alkenyloxy of 12, or alkenyl of carbon number 2 to 12 in which at least one hydrogen is substituted by fluorine or chlorine; Ring A and Ring C are independently 1,4-cyclohexylene, 1,4-cyclohexene base, tetrahydropyran-2,5-diyl, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is substituted by fluorine or chlorine; ring B is fluorene-2,7-diyl , dibenzothiophene-3,7-diyl, phenanthrene-2,7-diyl, 9,10-dihydrophenanthrene-2,7-diyl, xanthene-2,6-diyl or indan- 2,5-diyl, in these rings, at least one hydrogen can be substituted by fluorine or chlorine; Z ¹ and Z ² are independently a single bond, ethylene, carbonyloxy or methyleneoxy; a is 0, 1, 2 or 3, b is 0 or 1, and the sum of a and b is 3 or less.

Item 2. The liquid crystal composition according to Item 1, which contains, as the first component, at least one compound selected from the group of compounds represented by formula (1-1) to formula (1-38),

In formula (1-1) to formula (1-38), R ¹ and R ² are independently hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkoxy having 2 to 12 carbons alkenyl, alkenyloxy having 2 to 12 carbons, or alkyl having 1 to 12 carbons in which at least one hydrogen is substituted with fluorine or chlorine; X ¹ and X ² are independently hydrogen or fluorine.

Item 3. The liquid crystal composition according to Item 1 or Item 2, which contains, as a second component, at least one selected from the group consisting of compounds represented by formula (2-1) to formula (2-13) compound.

Item 4. The liquid crystal composition according to any one of Items 1 to 3, wherein the ratio of the first component is in the range of 3% by weight to 20% by weight.

Item 5. The liquid crystal composition according to any one of Items 1 to 4, wherein the ratio of the second component is in the range of 10% by weight to 70% by weight.

Item 6. The liquid crystal composition according to any one of Items 1 to 5, comprising at least one compound selected from the group consisting of compounds represented by formula (3) as a third component,

In formula (3), R ⁵ and R ⁶ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkenyl having 2 to 12 carbons Oxy group, or an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen is substituted by fluorine or chlorine; Ring D and Ring F are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydro Pyran-2,5-diyl, 1,4-phenylene, or 1,4-phenylene in which at least one hydrogen is substituted with fluorine or chlorine; Ring E is 2,3-difluoro-1,4- Phenylene, 2-chloro-3-fluoro-1,4-phenylene or 2,3-difluoro-5-methyl-1,4-phenylene; Z ³ and Z ⁴ are independently a single bond , ethylene, carbonyloxy or methyleneoxy; c is 1, 2 or 3, d is 0 or 1, and the sum of c and d is 3 or less.

Item 7. The liquid crystal composition according to any one of Items 1 to 6, which contains as a third component selected from the group of compounds represented by Formula (3-1) to Formula (3-25) at least one compound of

In formula (3-1) to formula (3-25), R ⁵ and R ⁶ are independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms. , an alkenyloxy group having 2 to 12 carbons, or an alkyl group having 1 to 12 carbons in which at least one hydrogen is substituted with fluorine or chlorine.

Item 8. The liquid crystal composition according to Item 6 or Item 7, wherein the ratio of the third component is in the range of 10% by weight to 70% by weight.

Item 9. The liquid crystal composition according to any one of Items 1 to 8, comprising at least one compound selected from the group consisting of compounds represented by formula (4) as the fourth component,

In formula (4), R ⁷ and R ⁸ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, at least one hydrogen is substituted with fluorine or chlorine The alkyl group with 1 to 12 carbon atoms, or the alkenyl group with 2 to 12 carbon atoms in which at least one hydrogen is substituted by fluorine or chlorine; Ring G and Ring I are independently 1,4-cyclohexylene, 1,4-cyclohexylene Phenyl, 2-fluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene; Z ⁵ is a single bond, ethylene or carbonyloxy; e is 1, 2 or 3; when e is 1, ring I is 1,4-phenylene.

Item 10. The liquid crystal composition according to any one of Items 1 to 9, comprising as a fourth component selected from the group of compounds represented by formula (4-1) to formula (4-12) at least one compound of

In formula (4-1) to formula (4-12), R ⁷ and R ⁸ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons , an alkyl group having 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine, or an alkenyl group having 2 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine.

Item 11. The liquid crystal composition according to Item 9 or Item 10, wherein the ratio of the fourth component is in the range of 2% by weight to 50% by weight.

Item 12. The liquid crystal composition according to any one of Items 1 to 11, which contains, as a first additive, at least one compound selected from the group consisting of polymerizable compounds represented by formula (5),

In formula (5), ring J and ring L are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxyl Alkyl-2-yl, pyrimidin-2-yl or pyridin-2-yl, in these rings, at least one hydrogen can be replaced by fluorine, chlorine, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, Or at least one hydrogen is substituted by an alkyl group having 1 to 12 carbon atoms substituted by fluorine or chlorine; ring K 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 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 these rings, at least one hydrogen can be replaced by fluorine, chlorine, carbon number 1 to 12 alkyl groups, alkoxy groups of carbon numbers from 1 to 12, or alkyl groups of carbon numbers from 1 to 12 in which at least one hydrogen is substituted by fluorine or chlorine; Z ⁶ and Z ⁷ are independently a single bond or carbon number 1 to 10 alkylene groups, in the alkylene group, at least one -CH ₂ - can be substituted by -O-, -CO-, -COO- or -OCO-, and at least one -CH ₂ -CH ₂ - can be substituted by -CH=CH-, -C(CH ₃ )=CH-, -CH=C(CH ₃ )- or -C(CH ₃ )=C(CH ₃ )- substituted, in these groups, at least one hydrogen may be replaced by Fluorine or chlorine substitution; P ¹ , P ² and P ³ are independently polymerizable groups; Sp ¹ , Sp ² and Sp ³ are independently a single bond or an alkylene group having 1 to 10 carbon atoms, in the alkylene group , at least one -CH ₂ - can be substituted by -O-, -COO-, -OCO- or -OCOO-, at least one -CH ₂ -CH ₂ - can be substituted by -CH=CH- or -C≡C-, In these groups, at least one hydrogen may be substituted with fluorine or chlorine; f is 0, 1 or 2; g, h and i are independently 0, 1, 2, 3 or 4, and the sum of g, h and i is 1 above.

Item 13. The liquid crystal composition according to Item 12, wherein in formula (5), P ¹ , P ² and P ³ are independently polymers selected from the group consisting of polymers represented by formula (P-1) to formula (P-5). The base in the sex-based group,

In formula (P-1) to formula (P-5), M ¹ , M ² and M ³ are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or carbon wherein at least one hydrogen is substituted with fluorine or chlorine 1 to 5 alkyl groups.

Item 14. The liquid crystal composition according to any one of Items 1 to 13, which contains as a first additive a compound selected from the group consisting of polymerizable compounds represented by formula (5-1) to formula (5-29) at least one compound in the group,

In formula (5-1) to formula (5-29), P ⁴ , P ⁵ and P ⁶ are independently selected from the group of polymerizable groups represented by formula (P-1) to formula (P-3) base in;

Here, M ¹ , M ² and M ³ are independently hydrogen, fluorine, an alkyl group with 1 to 5 carbon atoms, or an alkyl group with 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine; Sp ¹ , Sp ² and Sp ³ are independently a single bond or an alkylene group having 1 to 10 carbon atoms, and in the alkylene group, at least one -CH ₂ - may be via -O-, -COO-, -OCO- or -OCOO- Substitution, at least one -CH ₂ -CH ₂ - may be substituted with -CH=CH- or -C≡C-, and in these groups, at least one hydrogen may be substituted with fluorine or chlorine.

Item 15. The liquid crystal composition according to any one of Items 12 to 14, wherein the ratio of the first additive is in the range of 0.03 wt % to 10 wt %.

Item 16. A liquid crystal display element comprising the liquid crystal composition according to any one of Items 1 to 15.

Item 17. The liquid crystal display element according to item 16, wherein the operation mode of the liquid crystal display element is IPS mode, VA mode, FFS mode or FPA mode, and the driving mode of the liquid crystal display element is an active matrix mode.

Item 18. A polymer-stabilized alignment-type liquid crystal display element comprising the liquid crystal composition according to any one of Items 12 to 15, wherein the first additive contained in the liquid crystal composition is polymerized .

Item 19. Use of a liquid crystal composition, which is the liquid crystal composition according to any one of Items 1 to 15, in a liquid crystal display element.

Item 20. Use of a liquid crystal composition, which is the liquid crystal composition according to any one of Items 1 to 15, in a polymer-stabilized alignment type liquid crystal display element.

The present invention also includes the following items. (a) The composition further contains an optically active compound as a second additive, an antioxidant, an ultraviolet absorber, a quencher, a pigment, an antifoaming agent, a polymerizable compound different from the compound (5), and a polymerization initiator , at least one of additives such as polymerization inhibitors and polar compounds. (b) An AM device comprising the composition. (c) A polymer stabilized orientation (PSA) type AM device comprising the composition. (d) A polymer-stabilized orientation (PSA) type AM device comprising the composition, wherein the polymerizable compound in the composition is polymerized. (e) An element comprising the composition and having a mode of PC, TN, STN, ECB, OCB, IPS, VA, FFS or FPA. (f) A transmissive element comprising the composition. (g) Using the composition as a composition having a nematic phase. (h) A composition prepared by adding an optically active compound to the composition is used as an optically active composition.

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

First, the constitution of the composition will be described. The composition contains various liquid crystal compounds. The composition may also contain additives. The additives are optically active compounds, antioxidants, ultraviolet absorbers, pigments, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds, and the like. The compositions are classified into composition A and composition B from the viewpoint of the liquid crystal compound. Composition A may contain other liquid crystal compounds, additives, and the like in addition to the liquid crystal compound selected from the group consisting of compound (1), compound (2), compound (3), and compound (4). The "other liquid crystal compound" is a liquid crystal compound different from compound (1), compound (2), compound (3), and compound (4). Such a compound is mixed in the composition for the purpose of further adjusting the properties.

Composition B contains substantially only the liquid crystal compound selected from the group consisting of compound (1), compound (2), compound (3) and compound (4). "Substantially" means that although the composition B may contain additives, it does not contain other liquid crystal compounds. Compared with composition A, composition B has a small number of ingredients. Composition B is superior to Composition A from the viewpoint of cost reduction. The composition A is superior to the composition B in that the characteristics can be further adjusted by mixing other liquid crystal compounds.

Second, the main characteristics of the component compounds and the main effects that the compounds bring to the composition or the device will be described. Based on the effects of the present invention, the main characteristics of the component compounds are summarized in Table 2. In the notation in Table 2, L means large or high, M means medium, and S means small or low. The symbols L, M, and S are classifications based on qualitative comparison between the constituent compounds, and the symbol 0 (zero) means extremely small.

Table 2. Characteristics of liquid crystal compounds

characteristic Compound (1) Compound (2) Compound (3) Compound (4) upper limit temperature M～L S～M S～L S～L Viscosity M～L S M～L S～M optical anisotropy M～L S M～L S～L Dielectric Anisotropy M～L¹⁾ 0 M～L¹⁾ 0 specific resistance L L L L

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

When the component compounds are mixed in the composition, the main effects of the component compounds on the properties of the composition are as follows. Compound (1) increases the dielectric anisotropy. Compound (2) increases the elastic constant, or decreases the viscosity. Compound (3) increases the dielectric anisotropy and lowers the minimum temperature. Compound (4) increases the upper limit temperature, or lowers the viscosity. Compound (5), by polymerization, provides a polymer that shortens the response time of the element and also improves the afterimage of the image.

Third, the combination of components in the composition, the preferred ratio of the component compounds, and the basis thereof will be described. Preferred combinations of components in the composition are compound (1)+compound (2), compound (1)+compound (2)+compound (3), compound (1)+compound (2)+compound (4), compound (1)+Compound (2)+Compound (5), Compound (1)+Compound (2)+Compound (3)+Compound (4), Compound (1)+Compound (2)+Compound (3)+Compound (5), compound (1)+compound (2)+compound (4)+compound (5) or compound (1)+compound (2)+compound (3)+compound (4)+compound (5). Further preferred combinations are compound (1)+compound (2)+compound (3)+compound (4) or compound (1)+compound (2)+compound (3)+compound (4)+compound (5).

In order to increase the dielectric anisotropy, the preferred ratio of the compound (1) is about 3% by weight or more, and the preferred ratio of the compound (1) is about 20% by weight or less in order to lower the minimum temperature. A further preferred ratio is in the range of about 3% by weight to about 18% by weight. A particularly preferred ratio is in the range of about 3% by weight to about 15% by weight.

The preferred ratio of the compound (2) is about 10 wt% or more for increasing the elastic constant or for decreasing the viscosity, and about 70 wt% or less for increasing the dielectric anisotropy. A further preferred ratio is in the range of about 15% by weight to about 60% by weight. A particularly preferred ratio is in the range of about 20% by weight to about 50% by weight.

In order to increase the dielectric anisotropy, the preferred ratio of the compound (3) is about 10% by weight or more, and the preferred ratio of the compound (3) is about 70% by weight or less in order to lower the minimum temperature. A further preferred ratio is in the range of about 15% by weight to about 65% by weight. A particularly preferred ratio is in the range of about 20% by weight to about 60% by weight.

The preferred ratio of compound (4) is about 2 wt % or more for increasing the upper limit temperature or for reducing viscosity, and about 50 wt % or less for increasing dielectric anisotropy. A further preferred ratio is in the range of about 2% by weight to about 40% by weight. A particularly preferred ratio is in the range of about 4% by weight to about 30% by weight.

The compound (5) is added to the composition for the purpose of being suitable for a polymer-stabilized oriented device. The preferred ratio of compound (5) is about 0.03% by weight or more in order to align liquid crystal molecules, and the preferred ratio of compound (5) is about 10% by weight or less in order to prevent display failure of the device. A further preferred ratio is in the range of about 0.1% by weight to about 2% by weight. A particularly preferred ratio is in the range of about 0.2% by weight to about 1.0% by weight.

Fourth, preferred forms of the component compounds will be described. In formula (1), formula (2), formula (3) and formula (4), R ¹ and R ² are independently hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, An alkenyl group having 2 to 12 carbons, an alkenyloxy group having 2 to 12 carbons, or an alkyl group having 1 to 12 carbons in which at least one hydrogen is substituted with fluorine or chlorine. In order to improve the stability to ultraviolet light or heat, preferably R ¹ or R ² is an alkyl group having 1 to 12 carbon atoms, and in order to improve the dielectric anisotropy, preferably R ¹ or R ² is an alkyl group having 1 to 12 carbon atoms. Oxygen. R ³ and R ⁴ are independently an alkenyl group having 2 to 12 carbons, an alkenyloxy group having 2 to 12 carbons, or an alkenyl group having 2 to 12 carbons in which at least one hydrogen is substituted with fluorine or chlorine. In order to reduce viscosity, preferable R ³ or R ⁴ is an alkenyl group having 2 to 12 carbons. R ⁵ and R ⁶ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkenyloxy having 2 to 12 carbons, or at least one An alkyl group having 1 to 12 carbons in which hydrogen is substituted with fluorine or chlorine. In order to improve the stability to ultraviolet light or heat, preferably R ⁵ or R ⁶ is an alkyl group with 1 to 12 carbon atoms, and in order to improve the dielectric anisotropy, preferably R ⁵ or R ⁶ is an alkyl group with 1 to 12 carbon atoms Oxygen. R ⁷ and R ⁸ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, 1 to 12 carbons in which at least one hydrogen is substituted with fluorine or chlorine , or an alkenyl group having 2 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine. In order to improve the stability against ultraviolet rays or heat, preferable R ⁷ or R ⁸ is an alkyl group having 1 to 12 carbons.

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

Preferred alkoxy groups are methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy or heptyloxy. Further preferred alkoxy groups are methoxy groups or ethoxy groups in order to lower the viscosity.

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 are vinyl, 1-propenyl, 3-butenyl or 3-pentenyl in order to reduce viscosity. The preferred stereoconfiguration of -CH=CH- in these alkenyl groups depends on the position of the double bond. For reasons such as viscosity reduction, among alkenyl groups such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl, and 3-hexenyl, trans is preferable. formula configuration. Among alkenyl groups such as 2-butenyl, 2-pentenyl, and 2-hexenyl, the cis configuration is preferred.

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

Preferred examples of the alkenyl group in which at least one hydrogen is substituted with fluorine or chlorine are 2,2-difluorovinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro-3-butenyl, 5 ,5-difluoro-4-pentenyl or 6,6-difluoro-5-hexenyl. In order to reduce viscosity, a more preferable example is 2,2-difluorovinyl or 4,4-difluoro-3-butenyl.

Ring A and Ring C are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen Fluorine or chlorine substituted 1,4-phenylene. In order to reduce viscosity, preferred ring A or ring C is 1,4-cyclohexylene, and in order to increase dielectric anisotropy, preferred ring A or ring C is tetrahydropyran-2,5-diyl, in order to increase dielectric anisotropy Optically anisotropic, preferred ring A or ring C is 1,4-phenylene. Ring B is fluorene-2,7-diyl, dibenzothiophene-3,7-diyl, phenanthrene-2,7-diyl, 9,10-dihydrophenanthrene-2,7-diyl, xanthene -2,6-diyl or indan-2,5-diyl, in these rings, at least one hydrogen may be substituted by fluorine or chlorine. In order to increase the dielectric anisotropy, the preferred ring B is fluorene-2,7-diyl with at least one hydrogen substituted with fluorine, phenanthrene-2,7-diyl with at least one hydrogen substituted with fluorine, at least one hydrogen with fluorine Substituted 9,10-dihydrophenanthrene-2,7-diyl, xanthene-2,6-diyl with at least one hydrogen substituted with fluorine or indan-2,5-diyl with at least one hydrogen substituted with fluorine . A particularly preferred ring B is fluorene-2,7-diyl in which at least one hydrogen is substituted with fluorine. Tetrahydropyran-2,5-diyl is

or

preferably

Ring D and Ring F are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen via Fluorine or chlorine substituted 1,4-phenylene. In order to reduce the viscosity, the preferred ring D or ring F is 1,4-cyclohexylene, and in order to increase the dielectric anisotropy, the preferred ring D or ring F is tetrahydropyran-2,5-diyl, in order to increase the dielectric anisotropy Optically anisotropic, preferred ring D or ring F is 1,4-phenylene. Ring E is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene or 2,3-difluoro-5-methyl-1,4- phenylene. In order to increase the dielectric anisotropy, the preferred ring E is 2,3-difluoro-1,4-phenylene.

Ring G and Ring I are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene . In order to lower the viscosity or to increase the upper limit temperature, the preferred ring G or ring I is 1,4-cyclohexylene, and in order to lower the lower limit temperature, the preferred ring G or ring I is 1,4-phenylene.

Z ¹ , Z ² , Z ³ and Z ⁴ are independently a single bond, ethylene, carbonyloxy or methyleneoxy. In order to lower the viscosity, preferably Z ¹ , Z ² , Z ³ or Z ⁴ is a single bond, in order to lower the lower limit temperature, preferably Z ¹ , Z ² , Z ³ or Z ⁴ is an ethylene group, in order to improve the dielectric anisotropy Anisotropic, preferably Z ¹ , Z ² , Z ³ or Z ⁴ is a methyleneoxy group. Z ⁵ is a single bond, ethylene or carbonyloxy. In order to improve the stability against ultraviolet light or heat, preferably Z ⁵ is a single bond.

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

In formula (5), P ¹ , P ² and P ³ are independently polymerizable groups. Preferable P ¹ , P ² or P ³ is a polymerizable group selected from the group of groups represented by formula (P-1) to formula (P-5). Further preferred P ¹ , P ² or P ³ is the formula (P-1) or the formula (P-2). A particularly preferred formula (P-1) is -OCO-CH=CH ₂ or -OCO-C(CH ₃ )=CH ₂ . The wavy lines of the formula (P-1) to the formula (P-5) indicate the bonding site.

In formula (P-1) to formula (P-5), M ¹ , M ² and M ³ are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or carbon wherein at least one hydrogen is substituted with fluorine or chlorine 1 to 5 alkyl groups. In order to increase reactivity, preferred M ¹ , M ² or M ³ is hydrogen or methyl. Still more preferred M ¹ is methyl, and still more preferred M ² or M ³ is hydrogen.

In formula (5-1) to formula (5-29), P ⁴ , P ⁵ and P ⁶ are independently groups represented by formula (P-1) to formula (P-3). Preferred P4, ^P5 or P6 are of formula (P ^{- 1} ) or formula (P-2). A more preferable formula (P-1) is -OCO-CH=CH ₂ or -OCO-C(CH ₃ )=CH ₂ . The wavy lines of the formula (P-1) to the formula (P-3) indicate the bonding site.

In formula (5), Sp ¹ , Sp ² and Sp ³ are independently a single bond or an alkylene group having 1 to 10 carbon atoms, and in the alkylene group, at least one -CH ₂ - may be passed through -O-, - COO-, -OCO- or -OCOO- is substituted, at least one -CH ₂ -CH ₂ - can be substituted by -CH=CH- or -C≡C-, and in these groups, at least one hydrogen can be substituted by fluorine or chlorine. Preferred Sp ¹ , Sp ² or Sp ³ are single bonds, -CH ₂ CH ₂ -, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CO-CH=CH- or -CH =CH-CO-. Further preferred Sp ¹ , Sp ² or Sp ³ is a single bond.

Ring J and Ring L are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, Pyrimidine-2-yl or pyridin-2-yl, in these rings, at least one hydrogen can be fluorine, chlorine, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, or at least one hydrogen with fluorine or chlorine-substituted alkyl group having 1 to 12 carbon atoms. Preferred ring J or ring L is phenyl. Ring K 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 these rings, at least one hydrogen can be replaced by fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen Substituted with alkyl having 1 to 12 carbons substituted with fluorine or chlorine. Preferred ring K is 1,4-phenylene or 2-fluoro-1,4-phenylene.

Z ⁶ and Z ⁷ are independently a single bond or an alkylene group having 1 to 10 carbon atoms, and in the alkylene group, at least one -CH ₂ - may be via -O-, -CO-, -COO- or -OCO -Substituted, 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 these groups, at least one hydrogen may be replaced by fluorine or chlorine. Preferred Z ⁶ or Z ⁷ is a single bond, -CH ₂ -CH ₂ -, -CH ₂ O-, -OCH ₂ -, -COO- or -OCO-. Further preferred Z ⁶ or Z ⁷ is a single bond.

f is 0, 1 or 2. Preferred f is 0 or 1. g, h and i are independently 0, 1, 2, 3 or 4, and the sum of g, h and i is 1 or more. Preferred g, h or i are 1 or 2.

Fifth, preferred constituent compounds are shown. Preferred compounds (1) are the compounds (1-1) to (1-38) described in item 2. Among these compounds, at least one of the first components is preferably compound (1-1), compound (1-2), compound (1-7), compound (1-8), compound (1-11), compound (1-12), compound (1-15), compound (1-22), compound (1-28), compound (1-30), compound (1-32), compound (1-33) or compound ( 1-36). Preferably, at least two of the first components are compound (1-1) and compound (1-2), compound (1-1) and compound (1-7), compound (1-8) and compound (1-11) ), compound (1-8) and compound (1-12) or a combination of compound (1-33) and compound (1-36).

Preferred compounds (2) are the compounds (2-1) to (2-13) described in item 3. Among these compounds, at least one of the second component is preferably compound (2-1), compound (2-2), and compound (2-3). Preferably, at least two of the second components are compound (2-1) and compound (2-2), compound (2-1) and compound (2-3), or compound (2-2) and compound (2-3) )The combination.

Preferred compounds (3) are the compounds (3-1) to (3-25) described in item 7. Among these compounds, preferably at least one of the third component is compound (3-1), compound (3-2), compound (3-3), compound (3-6), compound (3-8), compound (3-9), compound (3-10) or compound (3-14). Preferably, at least two of the third components are compound (3-1) and compound (3-6), compound (3-1) and compound (3-8), compound (3-1) and compound (3-10) ), compound (3-1) and compound (3-14), compound (3-3) and compound (3-8), compound (3-3) and compound (3-10), compound (3-3) and compound (3-14), compound (3-6) and compound (3-8), compound (3-6) and compound (3-9), compound (3-6) and compound (3-10) or A combination of compound (3-6) and compound (3-14).

Preferred compounds (4) are the compounds (4-1) to (4-12) described in item 10. Among these compounds, at least one of the fourth component is preferably compound (4-2), compound (4-4), compound (4-5) or compound (4-6). Preferably, at least two of the fourth components are compound (4-2) and compound (4-4), compound (4-2) and compound (4-5), or compound (4-2) and compound (4- 6) combination.

Preferred compounds (5) are the compounds (5-1) to (5-29) described in item 14. Among these compounds, preferably at least one of the first additives is compound (5-1), compound (5-2), compound (5-24), compound (5-25), compound (5-26), Compound (5-27) or Compound (5-29). Preferably, at least two of the first additives are compound (5-1) and compound (5-2), compound (5-1) and compound (5-19), compound (5-2) and compound (5- 24), compound (5-2) and compound (5-25), compound (5-2) and compound (5-26), compound (5-27) and compound (5-26) or compound (5-18) ) and a combination of compounds (5-24).

Sixth, additives that can be added to the composition will be described. Such additives are optically active compounds, antioxidants, ultraviolet absorbers, quenchers, pigments, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds, and the like. The optically active compound is added to the composition for the purpose of imparting a torsion angle by inducing a helical structure of liquid crystal molecules. Examples of such compounds are compound (6-1) to compound (6-5). A preferable ratio of the optically active compound is about 5% by weight or less. A further preferred ratio is in the range of about 0.01% by weight to about 2% by weight.

In order to prevent a decrease in specific resistance caused by heating in the atmosphere or to maintain a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature after using the element for a long time, an antioxidant is added to in the composition. Preferable examples of the antioxidant are compound (7-1) to compound (7-3) and the like.

Since the compound (7-2) 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 using the device for a long time. In order to obtain the effect, the preferable ratio of the antioxidant is about 50 ppm or more, and the preferable ratio of the antioxidant is about 600 ppm or less in order not to lower the upper limit temperature or not to raise the lower limit temperature. A further preferred ratio is in the range of about 100 ppm to about 300 ppm.

Preferable examples of the ultraviolet absorber are benzophenone derivatives, benzoate derivatives, triazole derivatives, and the like. Light stabilizers such as sterically hindered amines are also preferred. Preferred examples of the light stabilizer are compound (8-1) to compound (8-16) and the like. The preferable ratio of these absorbents or stabilizers is about 50 ppm or more in order to obtain the effect, and about 10000 ppm or less in order not to lower the upper limit temperature or not to raise the lower limit temperature. A further preferred ratio is in the range of about 100 ppm to about 10,000 ppm.

The quencher is a compound that prevents the liquid crystal compound from decomposing by accepting the light energy absorbed by the liquid crystal compound and converting it into heat energy. Preferred examples of the quencher are compound (9-1) to compound (9-7) and the like. In order to obtain the above-mentioned effects, the preferable ratio of the quenching agent is about 50 ppm or more, and the preferable ratio of these quenching agents is about 20000 ppm or less so as not to raise the minimum temperature. A further preferred ratio is in the range of about 100 ppm to about 10,000 ppm.

Dichroic dyes such as azo-based dyes, anthraquinone-based dyes, and the like are added to the composition in order to be suitable for a guest host (GH) mode device. The preferred proportion of the pigment is in the range of about 0.01% by weight to about 10% by weight. In order to prevent foaming, antifoaming agents such as dimethyl silicone oil and methyl phenyl silicone oil are added to the composition. In order to obtain the above-mentioned effects, the preferable ratio of the antifoaming agent is about 1 ppm or more, and the preferable ratio of the antifoaming agent is about 1000 ppm or less in order to prevent poor display. A further preferred ratio is in the range of about 1 ppm to about 500 ppm.

A polymerizable compound is used in order to be suitable for a polymer-stabilized orientation (PSA) type element. Compound (5) is suitable for this purpose. Compound (5) and a polymerizable compound different from compound (5) may be added to the composition together. In place of the compound (5), a polymerizable compound different from the compound (5) may be added to the composition. Preferred examples of such polymerizable compounds are acrylates, methacrylates, vinyl compounds, vinyloxy compounds, propenyl ethers, epoxy compounds (oxiranes, oxetanes), vinyl ketones, and the like compound. Further preferred examples are derivatives of acrylate or methacrylate. The reactivity of the polymerizable compound and the pretilt angle of the liquid crystal molecules can be adjusted by changing the type of the compound (5) or by combining a polymerizable compound different from the compound (5) with the compound (5) in an appropriate ratio. By optimizing the pretilt angle, a short response time of the element can be achieved. Since the alignment of the liquid crystal molecules is stabilized, a large contrast ratio or a long life can be achieved.

The polymerizable compound is polymerized by ultraviolet irradiation. The polymerization can also be carried out in the presence of a polymerization initiator such as a photopolymerization initiator. Appropriate conditions for carrying out the polymerization or appropriate types and amounts of polymerization initiators are known to those skilled in the art and are described in the literature. For example, as a photopolymerization initiator, Irgacure 651 (registered trademark; BASF), Irgacure 184 (registered trademark; BASF), or Darocur 1173 (registered trademark; BASF) trademark; BASF) is suitable for free radical polymerization. The preferable ratio of the photopolymerization initiator is in the range of about 0.1% by weight to about 5% by weight based on the weight of the polymerizable compound. A further preferred ratio is in the range of about 1% by weight to about 3% by weight.

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

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

Seventh, the synthesis method of the component compounds will be described. These compounds can be synthesized by known methods. Synthetic methods are exemplified. Compound (1-8) was synthesized by the method described in Japanese Patent Laid-Open No. 2016-47905. Compound (2-1) was synthesized by the method described in Japanese Patent Laid-Open No. 9-77692. Compound (3-8) was synthesized by the method described in JP-A-2-503441. Compound (4-4) was synthesized by the method described in Japanese Patent Laid-Open No. Sho 59-176221. Compound (5-19) was synthesized by the method described in Japanese Patent Laid-Open No. 7-101900. Antioxidants are commercially available. Compound (7-1) can be obtained from Sigma-Aldrich Corporation. Compound (7-2) and the like were synthesized by the method described in the specification of US Pat. No. 3,660,505.

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

Finally, the use of the composition will be explained. Most compositions have a lower limit temperature of about -10°C or lower, an upper limit temperature of about 70°C or higher, and an optical anisotropy in the range of about 0.07 to about 0.20. The composition having the optical anisotropy in the range of about 0.08 to about 0.25 can be prepared by controlling the ratio of the constituent compounds or by mixing other liquid crystal compounds. Furthermore, compositions having an optical anisotropy in the range of about 0.10 to about 0.30 can also be prepared by trial and error. The element containing the composition has a large voltage holding ratio. The composition is suitable for AM devices. The composition is particularly suitable for transmissive AM devices. The composition can be used as a composition having a nematic phase, or can be used as an optically active composition by adding an optically active compound.

The composition can be used in AM devices. Furthermore, it 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, etc. It is particularly preferred for AM elements with VA, OCB, IPS or FFS modes. In the AM element having the IPS mode or the FFS mode, when no voltage is applied, the alignment of the liquid crystal molecules may be parallel or perpendicular to the glass substrate. These elements can be reflective, transmissive or transflective. It is preferably used for the element of the transmissive type. Can also be used for amorphous silicon-TFT elements or polysilicon-TFT elements. The composition can also be used for a nematic curvilinear aligned phase (NCAP) type element produced by microencapsulation or a polymer formed by forming a three-dimensional network polymer in the composition Dispersed (polymer dispersed, PD) type components.

An example of a method of producing a polymer-stabilized orientation type element is as follows. Assembling a component comprising two substrates referred to as an array substrate and a color filter substrate. The substrate has an alignment film. At least one of the substrates has an electrode layer. The liquid crystal compound is mixed to prepare a liquid crystal composition. A polymerizable compound is added to the composition. Additives can be further added as needed. The composition is injected into the element. Light irradiation is performed in a state where a voltage is applied to the element. Ultraviolet rays are preferred. The polymerizable compound is polymerized by light irradiation. A polymer-containing composition is produced by the polymerization. The polymer-stabilized orientation type elements are fabricated in the sequence described above.

In the above procedure, when a voltage is applied, the liquid crystal molecules are aligned by the action of the alignment film and the electric field. According to the orientation, the molecules of the polymerizable compound are also oriented. Since the polymerizable compound is polymerized by ultraviolet rays in the above-described state, a polymer maintaining the above-described orientation is produced. Through the effect of the polymer, the response time of the element is shortened. Since the afterimage of the image is caused by the malfunction of the liquid crystal molecules, the afterimage is also simultaneously improved by the effect of the polymer. In addition, the polymerizable compound in the composition may be polymerized in advance, and the composition may be disposed between the substrates of the liquid crystal display element.

Example

The present invention will be further described in detail by means of examples. The present invention is not limited by these examples. The present invention comprises a mixture of the composition of Example 1 and the composition of Example 2. The present invention also includes mixtures obtained by mixing at least two of the compositions of the examples. The synthesized compounds were identified by methods such as nuclear magnetic resonance (NMR) analysis. The properties of compounds, compositions, and devices were measured by the methods described below.

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

Gas chromatographic analysis: A GC-14B gas chromatograph manufactured by Shimadzu Corporation was used for the measurement. The carrier gas was helium (2 mL/min). The sample vaporization chamber was set to 280°C, and the detector (flameionization detector (FID)) was set to 300°C. For the separation of component compounds, a capillary column DB-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by Agilent Technologies Inc. was used; the stationary liquid phase was dimethylpolysiloxane ; no polarity). After the column was held at 200°C for 2 minutes, the temperature was raised to 280°C at a rate of 5°C/min. After the sample was prepared as an acetone solution (0.1% by weight), 1 μL of the solution was injected into the sample vaporization chamber. The recorder is a C-R5A type chromatograph package (Chromatopac) manufactured by Shimadzu Corporation or its equivalent. The obtained gas chromatogram showed the retention time of the peak and the area of the peak corresponding to the component compounds.

As a solvent for diluting the sample, chloroform, hexane, or the like can be used. In order to separate the component compounds, the following capillary columns can be used. HP-1 manufactured by Agilent Technologies Inc. (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm), Rtx-1 manufactured by Restek Corporation (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm), BP-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by SGE International Pty. Ltd, Australia. For the purpose of preventing overlapping of compound peaks, a capillary column CBP1-M50-025 (length 50 m, inner diameter 0.25 mm, film thickness 0.25 μm) manufactured by Shimadzu Corporation was used.

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

Measurement sample: When measuring the properties of the composition and the element, the composition was directly used as a sample. When measuring the properties of the compound, a sample for measurement was prepared by mixing the compound (15 wt %) in mother liquid crystal (85 wt %). From the value obtained by the measurement, the characteristic value of the compound was calculated by an extrapolation method. (Extrapolated value)={(Measured value of sample)−0.85×(Measured value of mother liquid crystal)}/0.15. When the smectic phase (or crystal) is precipitated at 25°C under the stated ratio, the ratio of the compound to the mother liquid crystal is 10% by weight: 90% by weight, 5% by weight: 95% by weight, 1% by weight: 99% by weight The order of weight % is changed. The values of the upper limit temperature, optical anisotropy, viscosity, and dielectric anisotropy related to the compound were obtained by the above-mentioned extrapolation method.

The following mother liquid crystals were used. The proportions of the constituent compounds are expressed in % by weight.

Measurement method: The measurement of the characteristic was performed by the following method. Most of these methods are methods described in the JEITA standard (JEITA·ED-2521B) reviewed and formulated by the Japan Electronics and Information Technology Industries Association (JEITA) or modified methods. . In the TN element used for the measurement, a thin film transistor (TFT) was not mounted.

(1) Upper limit temperature of nematic phase (NI;° 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° C./min. The temperature at which a part of the sample changes from the nematic phase to the isotropic liquid is measured. The upper limit temperature of the nematic phase is sometimes simply referred to as the "upper limit temperature".

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

(3) Viscosity (bulk viscosity; η; measured at 20°C; mPa·s): An E-type rotational viscometer manufactured by Tokyo Keiki Co., Ltd. was used for the measurement.

(4) Viscosity (rotational viscosity; γ1; measured at 25°C; mPa·s): According to "Molecular Crystals and Liquid Crystals", No. 259, by M. Imai et al. The measurement was carried out by the method described in page 37 (1995). The sample was put in the VA element whose space|interval (cell gap) of two glass substrates was 20 micrometers. A voltage in the range of 39 volts to 50 volts was applied stepwise in units of 1 volt to the element. After no voltage application for 0.2 seconds, application of only one rectangular wave (rectangular pulse; 0.2 seconds) and no voltage application (2 seconds) were repeated. The peak current and peak time of the transient current generated by the application were measured. The value of rotational viscosity was obtained from these measured values and the calculation formula (8) on page 40 of the paper by M. Imai et al. The dielectric anisotropy required for the calculation is determined in assay (6).

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

(6) Dielectric anisotropy (Δε; measured at 25° C.): The value of the dielectric anisotropy was calculated according to the formula of Δε=ε∥−ε⊥. The dielectric constants (ε∥ and ε⊥) were measured as follows.

1) Measurement of dielectric constant (ε∥): A solution of octadecyltriethoxysilane (0.16 mL) in ethanol (20 mL) was applied on a sufficiently washed glass substrate. After the glass substrate was rotated with a spinner, it was heated at 150° C. for 1 hour. A sample was placed in a VA element having a distance (cell gap) between two glass substrates of 4 μm, and the element was sealed with an adhesive cured by ultraviolet rays. A sine wave (0.5 V, 1 kHz) was applied to the element, and the dielectric constant (ε∥) in the long axis direction of the liquid crystal molecules was measured after 2 seconds.

2) Measurement of dielectric constant (ε⊥): A polyimide solution was applied on a sufficiently washed glass substrate. After calcining the glass substrate, a rubbing process is performed on the obtained alignment film. A sample was placed in a TN element with a gap (cell gap) of two glass substrates of 9 μm and a twist angle of 80 degrees. A sine wave (0.5 V, 1 kHz) was applied to the element, and the dielectric constant (ε⊥) in the short axis direction of the liquid crystal molecules was measured after 2 seconds.

(7) Threshold voltage (Vth; measured at 25° C.; V): An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source is a halogen lamp. A sample was placed in a normally black mode VA element in which the distance between two glass substrates (cell gap) was 4 μm and the rubbing direction was anti-parallel, and the above-mentioned adhesive was hardened with ultraviolet rays. Elements are sealed. The voltage (60 Hz, rectangular wave) applied to the element was increased in steps from 0V to 20V in units of 0.02V. At this time, the element was irradiated with light from a 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 the voltage at which the transmittance reaches 10%.

(8) Voltage holding ratio (VHR-1; measured at 25° C.; %): The TN element used for the measurement had a polyimide alignment film, and the distance (cell gap) between two glass substrates was 5 μm. After the element is placed in the sample, it is sealed with an adhesive that is cured by ultraviolet rays. The TN element was charged by applying a pulse voltage (5V, 60 microseconds). Using a high-speed voltmeter, the decayed voltage was measured for 16.7 milliseconds, and the area A between the voltage curve and the horizontal axis in a unit cycle was obtained. Area B is the area without attenuation. Voltage retention is expressed as the percentage of area A relative to area B.

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

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

(11) Voltage holding ratio (VHR-4; measured at 25° C.; %): After heating the TN element injected with the sample in a constant temperature bath at 80° C. for 500 hours, the voltage holding ratio was measured, and the resistance to heat was evaluated. stability. In the measurement of VHR-4, the decayed voltage was measured during 16.7 milliseconds. Compositions with large VHR-4 have large thermal stability.

(12) Response time (τ(25); measured at 25° C.; ms): LCD5100 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source is a halogen lamp. The low-pass filter is set to 5kHz. A sample was placed in a normally black mode FFS element in which the distance between two glass substrates (cell gap) was 3.2 μm and the rubbing direction was antiparallel. The elements are sealed with an adhesive that hardens with UV light. At 25° C., a voltage (60 Hz, rectangular wave) was applied to the element while increasing stepwise from 0 V to 20 V in units of 0.02 V. At this time, the element was irradiated with light from a vertical direction, and the amount of light transmitted through the element was measured. A voltage-transmittance curve was prepared in which the transmittance was 100% when the light amount reached the maximum, and the transmittance was 0% when the light amount was the minimum. The voltage at which the transmittance was 95% was expressed by V95(V), and was used as the applied voltage when measuring the response time. Next, a rectangular wave (60 Hz, V95, 0.5 seconds) was applied to the element. At this time, the element was irradiated with light from a vertical direction, and the amount of light transmitted through the element was measured. The transmittance was regarded as 100% when the light amount was the maximum, and the transmittance was regarded as 0% when the light amount was the minimum. The response time is the time required for the transmittance to change from 10% to 90% (rise time; rise time; milliseconds) and the time required for the transmittance to change from 90% to 10% (fall time; fall time; milliseconds) ) to represent the total.

(13) Response time (τ(-20); measured at -20°C; ms): LCD5100 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source is a halogen lamp. The low-pass filter is set to 5kHz. A sample was placed in a normally black mode FFS element in which the distance between two glass substrates (cell gap) was 3.2 μm and the rubbing direction was antiparallel. The elements are sealed with an adhesive that hardens with UV light. A rectangular wave (60 Hz, V95, 2 seconds) was applied to the element. Here, V95 was measured by the same method as described above. 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 was the maximum, and the transmittance was regarded as 0% when the light amount was the minimum. The response time is the time required for the transmittance to change from 10% to 90% (rise time; rise time; milliseconds) and the time required for the transmittance to change from 90% to 10% (fall time; fall time; milliseconds) ) to represent the total.

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

(15) Elastic constant (K11: splay elastic constant, K33: bend elastic constant; measured at 25°C; pN): EC manufactured by TOYO Corporation was used in the measurement -1 type elastic constant tester. A sample was placed in a vertical alignment element whose interval (cell gap) between two glass substrates was 20 μm. A charge of 20 volts to 0 volts was applied to the element, and the electrostatic capacitance and the applied voltage were measured. Using the equations (2.98) and (2.101) on page 75 of the "Handbook of Liquid Crystal Devices" (Nikkan Kogyo Shimbun), the measured electrostatic capacitance (C) and the value of the applied voltage (V) were fitted, and according to the equation (2.100) to obtain the value of the elastic constant.

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 steric configuration related to 1,4-cyclohexylene is trans configuration. The number in parentheses following the notated compound indicates the formula to which the compound belongs. The symbol (-) refers to other liquid crystal compounds. The ratio (percentage) of the liquid crystal compound is the weight percentage (% by weight) based on the weight of the liquid crystal composition without additives. Finally, the property values of the composition are summarized.

Table 3. Representation of compounds using symbols

R-(A ₁ )-Z ₁ -·····-Z _n -(A _n )-R'

[Comparative Example 1]

Example 16 of International Publication No. 2012/86437 was selected as Comparative Example 1. This is because this composition contains the compound (1-24) as the first component of the present invention, and has the smallest viscosity (?).

NI=74.8℃; η=22.8mPa·s; Δn=0.094; Δε=-4.4.

[Example 1]

The composition of Comparative Example 1 was prepared by substituting 2-HH-5, 3-HH-4 and 3-HH-5 for the second component of the present invention.

NI=70.2℃; η=19.0mPa·s; Δn=0.099; Δε=-4.4.

[Example 2]

NI=71.1℃; Tc<-20℃; η=14.1mPa·s; Δn=0.104; Δε=-2.8; γ1=47.3mPa·s; K11=12.7pN; K33=12.7pN.

[Example 3]

NI=78.2℃; Tc<-20℃; η=15.2mPa·s; Δn=0.108; Δε=-2.9; γ1=52.1mPa·s; K11=13.7pN; K33=13.2pN.

[Example 4]

NI=82.2℃; η=19.0mPa·s; Δn=0.106; Δε=-3.5; γ1=64.2mPa·s; K11=13.5pN; K33=13.1pN; V95=4.64V; τ(25)=44.9ms ;τ(-20)=845.6ms.

[Example 5]

NI=83.4℃; Tc<-20℃; η=19.0mPa·s; Δn=0.104; Δε=-3.6; γ1=64.2mPa·s; V95=4.53V; τ(25)=44.3ms; τ(- 20)=844.6ms.

[Example 6]

NI=74.2℃; η=17.5mPa·s; Δn=0.100; Δε=-3.3.

[Example 7]

NI=78.6℃; Tc<-20℃; η=17.0mPa·s; Δn=0.100; Δε=-2.7.

[Example 8]

NI=83.0℃; Tc<-20℃; η=15.9mPa·s; Δn=0.106; Δε=-3.2.

[Example 9]

NI=84.5℃; η=17.5mPa·s; Δn=0.101; Δε=-3.2.

[Example 10]

NI=75.0℃; Tc<-20℃; η=18.4mPa·s; Δn=0.107; Δε=-3.1.

[Example 11]

NI=75.0℃; Tc<-20℃; η=18.1mPa·s; Δn=0.106; Δε=-3.1.

[Example 12]

NI=79.5℃; Tc<-20℃; η=17.3mPa·s; Δn=0.102; Δε=-3.0.

[Example 13]

NI=72.5℃; η=18.4mPa·s; Δn=0.111; Δε=-3.5.

[Example 14]

NI=72.7℃; Tc<-20℃; η=15.8mPa·s; Δn=0.105; Δε=-3.0.

[Example 15]

NI=72.2℃; Tc<-20℃; η=17.7mPa·s; Δn=0.101; Δε=-3.2.

[Example 16]

NI=72.1℃; η=18.2mPa·s; Δn=0.110; Δε=-3.0.

[Example 17]

NI=74.0℃; Tc<-20℃; η=17.3mPa·s; Δn=0.100; Δε=-3.3.

[Example 18]

NI=74.2℃; Tc<-20℃; η=14.0mPa·s; Δn=0.096; Δε=-3.5.

[Example 19]

NI=83.3℃; Tc<-20℃; η=16.0mPa·s; Δn=0.102; Δε=-3.5.

[Example 20]

NI=76.1℃; Tc<-20℃; η=14.7mPa·s; Δn=0.101; Δε=-3.5.

The viscosity of the composition of Comparative Example 1 was 22.8 mPa·s. On the other hand, the viscosity of the composition of Example 1 was 19.0 mPa·s. As described above, the compositions of Examples had smaller viscosities than the compositions of Comparative Examples. Therefore, it can be concluded that the liquid crystal composition of the present invention has excellent characteristics.

Industrial Availability

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

Claims (20)

1. a kind of liquid-crystal composition is changed containing at least one of the compound represented by formula (1) that is selected from as first composition It closes object, be selected from least one of compound represented by formula (2) compound as second composition, and have negative dielectric each Anisotropy.

In formula (1) and formula (2), R¹And R²Independently be hydrogen, the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12, carbon number 2 to The alkyl for the carbon number 1 to 12 that 12 alkenyl, the alkenyl oxygroup of carbon number 2 to 12 or at least one hydrogen replace through fluorine or chlorine；R³And R⁴It independently is the carbon that the alkenyl of carbon number 2 to 12, the alkenyl oxygroup of carbon number 2 to 12 or at least one hydrogen replace through fluorine or chlorine The alkenyl of number 2 to 12；Ring A and ring C independently be 1,4- cyclohexylidene, 1,4- cyclohexadienylidene, oxinane -2,5- diyl, The 1,4- phenylene that 1,4- phenylene, at least one hydrogen replace through fluorine or chlorine；Ring B be fluorenes -2,7- diyl, dibenzothiophenes -3, 7- diyl, phenanthrene -2,7- diyl, 9,10- dihydro phenanthrene -2,7- diyl, xanthene -2,6- diyl or indane -2,5- diyl, these rings In, at least one hydrogen can replace through fluorine or chlorine；Z¹And Z²It independently is singly-bound, ethylidene, carbonyl oxygroup or methylene oxygroup；A is 0,1,2 or 3, b be 0 or 1, and a and b's and be 3 or less.

2. liquid-crystal composition according to claim 1, containing being selected from formula (1-1) to formula (1-38) institute as first composition At least one of group of compound of expression compound.

Formula (1-1) is into formula (1-38), R¹And R²It independently is hydrogen, the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12, carbon The alkane for the carbon number 1 to 12 that the alkenyl of number 2 to 12, the alkenyl oxygroup of carbon number 2 to 12 or at least one hydrogen replace through fluorine or chlorine Base；X¹And X²It independently is hydrogen or fluorine.

3. liquid-crystal composition according to claim 1 or 2, containing as second composition selected from formula (2-1) to formula (2- 13) at least one of group of compound represented by compound.

4. liquid-crystal composition according to any one of claim 1 to 3, the ratio of first composition is 3 weight % to 20 weights Measure the range of %.

5. liquid-crystal composition according to any one of claim 1 to 4, the ratio of second composition is 10 weight % to 70 weights Measure the range of %.

6. liquid-crystal composition according to any one of claim 1 to 5, containing ternary being selected from formula (3) institute as the At least one of compound of expression compound.

In formula (3), R⁵And R⁶It independently is the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12, the alkenyl of carbon number 2 to 12, carbon The alkyl for the carbon number 1 to 12 that the alkenyl oxygroup of number 2 to 12 or at least one hydrogen replace through fluorine or chlorine；Ring D and ring F are independently It is 1,4- cyclohexylidene, 1,4- cyclohexadienylidene, oxinane -2,5- diyl, 1,4- phenylene or at least one hydrogen through fluorine Or the 1,4- phenylene that chlorine replaces；Ring E is that the fluoro- 1,4- phenylene of 2,3- bis-, the fluoro- 1,4- phenylene of the chloro- 3- of 2- or 2,3- bis- are fluoro- 5- methyl-1,4- phenylene；Z³And Z⁴It independently is singly-bound, ethylidene, carbonyl oxygroup or methylene oxygroup；C is 1,2 or 3, and d is 0 or 1, and c and d's and be 3 or less.

7. liquid-crystal composition according to any one of claim 1 to 6, comprising ternary being selected from formula (3-1) as the To at least one of the group of compound represented by formula (3-25) compound.

Formula (3-1) is into formula (3-25), R⁵And R⁶It independently is the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12, carbon number 2 To 12 alkenyl, carbon number 2 to 12 alkenyl oxygroup or the alkyl of carbon number 1 to 12 that replaces through fluorine or chlorine of at least one hydrogen.

8. liquid-crystal composition according to claim 6 or 7, ternary ratio is the model of 10 weight % to 70 weight % It encloses.

9. liquid-crystal composition according to any one of claim 1 to 8, containing being selected from formula (4) institute as the 4th ingredient At least one of compound of expression compound.

In formula (4), R⁷And R⁸It independently is the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12, the alkenyl of carbon number 2 to 12, extremely The carbon number 2 to 12 that the alkyl or at least one hydrogen for the carbon number 1 to 12 that few hydrogen replaces through fluorine or chlorine replace through fluorine or chlorine Alkenyl；Ring G and ring I independently is the fluoro- 1,4- phenylene of 1,4- cyclohexylidene, 1,4- phenylene, 2- or the fluoro- 1,4- of 2,5- bis- is sub- Phenyl；Z⁵For singly-bound, ethylidene or carbonyl oxygroup；E is 1,2 or 3；When e is 1, ring I is Isosorbide-5-Nitrae-phenylene.

10. liquid-crystal composition according to any one of claim 1 to 9, comprising being selected from formula (4-1) as the 4th ingredient To at least one of the group of compound represented by formula (4-12) compound.

Formula (4-1) is into formula (4-12), R⁷And R⁸It independently is the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12, carbon number 2 Replace to the alkyl of 12 carbon number 1 to 12 of alkenyl, at least one hydrogen through fluorine or chlorine substitution or at least one hydrogen through fluorine or chlorine Carbon number 2 to 12 alkenyl.

11. liquid-crystal composition according to claim 9 or 10, the ratio of the 4th ingredient is 2 weight % to 50 weight %'s Range.

12. liquid-crystal composition according to any one of claim 1 to 11, containing being selected from formula as the first additive (5) at least one of polymerizable compound represented by compound.

In formula (5), ring J and ring L independently be cyclohexyl, cyclohexenyl group, phenyl, 1- naphthalene, 2- naphthalene, oxinane -2- base, 1,3- dioxanes -2- base, pyrimidine -2-base or pyridine -2- base, in these rings, at least one hydrogen can be through fluorine, chlorine, carbon number 1 to 12 The alkyl for the carbon number 1 to 12 that alkyl, the alkoxy of carbon number 1 to 12 or at least one hydrogen replace through fluorine or chlorine replaces；Ring K is 1,4- cyclohexylidene, 1,4- cyclohexadienylidene, 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, oxinane -2,5- diyl, 1,3- dioxanes -2,5- diyl, pyrimidine -2,5- diyl or pyridine -2,5- diyl, this In a little rings, at least one hydrogen can be passed through through fluorine, chlorine, the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12 or at least one hydrogen The alkyl for the carbon number 1 to 12 that fluorine or chlorine replace replaces；Z⁶And Z⁷It independently is the alkylidene of singly-bound or carbon number 1 to 10, the alkylene In base, at least one-CH₂It can replace through-O- ,-CO- ,-COO- or-OCO-, at least one-CH₂-CH₂It can be through-CH= CH-、-C(CH₃)=CH- ,-CH=C (CH₃)-or-C (CH₃)=C (CH₃)-replace, in these bases, at least one hydrogen can be through fluorine Or chlorine replaces；P¹、P²And P³It independently is polymerism base；Sp¹、Sp²And Sp³It independently is the alkylidene of singly-bound or carbon number 1 to 10, In the alkylidene, at least one-CH₂It can replace through-O- ,-COO- ,-OCO- or-OCOO-, at least one-CH₂-CH₂It can Replace through-CH=CH- or-C ≡ C-, in these bases, at least one hydrogen can replace through fluorine or chlorine；F is 0,1 or 2；G, h and i is independent Ground be 0,1,2,3 or 4, and g, h and i and be 1 or more.

13. liquid-crystal composition according to claim 12, in the formula (5), P¹、P²And P³It independently is selected from formula (P-1) Base into the group of polymerism base represented by formula (P-5).

Formula (P-1) is into formula (P-5), M¹、M²And M³It independently is hydrogen, fluorine, the alkyl of carbon number 1 to 5 or at least one hydrogen warp The alkyl for the carbon number 1 to 5 that fluorine or chlorine replace.

14. liquid-crystal composition according to any one of claim 1 to 13, comprising being selected from formula as the first additive At least one of the group of polymerizable compound represented by (5-1) to formula (5-29) compound.

Formula (5-1) is into formula (5-29), P⁴、P⁵And P⁶It independently is and is selected from polymerism base represented by formula (P-1) to formula (P-3) Group in base；

Wherein, M¹、M²And M³It independently is the carbon that hydrogen, fluorine, the alkyl of carbon number 1 to 5 or at least one hydrogen replace through fluorine or chlorine The alkyl of number 1 to 5；Sp¹、Sp²And Sp³It independently is the alkylidene of singly-bound or carbon number 1 to 10, in the alkylidene, at least one A-CH₂It can replace through-O- ,-COO- ,-OCO- or-OCOO-, at least one-CH₂-CH₂It can be taken through-CH=CH- or-C ≡ C- In generation, in these bases, at least one hydrogen can replace through fluorine or chlorine.

15. liquid-crystal composition described in any one of 2 to 14 according to claim 1, the ratio of the first additive is 0.03 weight Measure the range of % to 10 weight %.

16. a kind of liquid crystal display element, containing according to claim 1 to liquid-crystal composition described in any one of 15.

17. liquid crystal display element according to claim 16, wherein the operating mode of liquid crystal display element is coplanar switching Mode, vertical alignment mode, fringe field switching mode or electric field induction light reaction alignment mode, the driving of liquid crystal display element Mode is active matrix mode.

18. a kind of liquid crystal display element of polymer stabilizing orientating type includes according to claim 1 described in any one of 2 to 15 Liquid-crystal composition, and the first additive contained in the liquid-crystal composition is polymerize.

19. a kind of purposes of liquid-crystal composition, the liquid-crystal composition is according to claim 1 to liquid described in any one of 15 Brilliant composition, in liquid crystal display element.

20. a kind of purposes of liquid-crystal composition, the liquid-crystal composition is according to claim 1 to liquid described in any one of 15 Brilliant composition, in the liquid crystal display element for polymer stabilizing orientating type.