TW201805409A - Liquid crystal composition and liquid crystal display element - Google Patents

Abstract

Provided are: a liquid crystal composition in which vertical alignment of liquid crystal molecules can be achieved by the action of a polymer; and a liquid crystal display element which comprises the composition. The liquid crystal composition, which is a nematic liquid crystal composition comprising a polar compound carrying at least one polymerizable group as a first additive and a polymerizable compound carrying at least three polymerizable groups as a second additive and having negative dielectric anisotropy, may comprise a specific liquid crystalline compound having largely negative dielectric anisotropy as a first component and a specific liquid crystalline compound having a high upper limit temperature or a low viscosity as a second component. The liquid crystal display element comprises the composition.

Description

Liquid crystal composition and liquid crystal display element

The present invention relates to a liquid crystal composition having a negative dielectric anisotropy, and a liquid crystal display element containing the composition. In particular, it relates to a liquid crystal composition containing a polar compound (or a polymer thereof) having a polymerizable group and a polymerizable compound (or the polymer), and the vertical alignment of liquid crystal molecules can be achieved by the action of these compounds. And liquid crystal display elements.

In liquid crystal display elements, the operation modes based on liquid crystal molecules are classified into phase change (PC), twisted nematic (TN), super twisted nematic (STN), and electrically controlled birefringence ( electrically controlled birefringence (ECB), optically compensated bend (OCB), in-plane switching (IPS), vertical alignment (VA), fringe field switching (FFS), Field-induced photo-reactive alignment (FPA) and other modes. The component-based driving methods are classified into a passive matrix (PM) and an active matrix (AM). PM is classified into static and 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 is classified into a high temperature type and a low temperature type according to manufacturing steps. The classification based on the light source is a reflection type using natural light, a transmission type using 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. This composition has appropriate characteristics. By improving the characteristics of the composition, an AM device having good characteristics can be obtained. The correlation between the characteristics of the two is summarized in Table 1 below. The characteristics of the composition will be further described based on a commercially available AM device. The temperature range of the nematic phase is related to the temperature range in which the element can be used. The preferable upper limit temperature of the nematic phase is about 70 ° C or higher, and the preferable lower limit temperature of the nematic phase is about -10 ° C or lower. The viscosity of a composition is related to the response time of the element. In order to display a moving image with a component, it is preferable that the response time is short. Ideally a response time shorter than 1 millisecond. Therefore, the viscosity of the composition is preferably small. Especially preferred is low viscosity at low temperatures.

The optical anisotropy of the composition is related to the contrast ratio of the element. Depending on the mode of the element, a large optical anisotropy or a small optical anisotropy is required, that is, an appropriate optical anisotropy. 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. The value of the appropriate product depends on the type of operation mode. In the VA mode device, the value ranges from about 0.30 μm to about 0.40 μm, and in the IPS mode or FFS mode devices, the value ranges from about 0.20 μm to about 0.30 μm. In these cases, a composition having a large optical anisotropy is preferred for a device having a small cell gap. The large dielectric anisotropy of the composition contributes to a low threshold voltage, a small power consumption, and a large contrast ratio in the device. Therefore, a large dielectric anisotropy is preferred. The large specific resistance of the composition contributes to the large voltage holding ratio and large contrast ratio of the device. Therefore, a composition having a large specific resistance not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase in the initial stage is preferred. A composition having a large specific resistance not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase after long-term use is preferred. The stability of the composition to ultraviolet rays or heat is related to the life of the device. When the stability is high, the life of the device is long. Such characteristics are preferred for AM elements used in liquid crystal projectors and liquid crystal televisions.

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

On the other hand, in a liquid crystal display element without an alignment film, a liquid crystal composition containing a polymer and a polar compound having no polymerizable group is used. First, a composition containing a small amount of a polymerizable compound and a small amount of a polar compound is injected into a device. Here, polar compounds are adsorbed and aligned on the substrate surface. The liquid crystal molecules are aligned according to the arrangement. Then, while applying a voltage between the substrates of the element, the composition was irradiated with ultraviolet rays. Here, the polymerizable compound is polymerized and the alignment of the liquid crystal molecules is stabilized. In this composition, polymers and polar compounds can be used to control the alignment of liquid crystal molecules, so the response time of the device is shortened, and the afterimage of the image is improved. Furthermore, a step of forming an alignment film is not necessary in an element having no alignment film. Since there is no alignment film, the resistance of the device does not decrease due to the interaction between the alignment film and the composition. Such an effect using a combination of a polymer and a polar compound can be expected for a device having a mode such as TN, ECB, OCB, IPS, VA, FFS, and FPA.

A composition having a positive dielectric anisotropy is used for an AM device having a TN mode. A composition having a negative dielectric anisotropy is used for an AM device having a VA mode. A composition having a positive or negative dielectric anisotropy is used for an AM device having an IPS mode or an FFS mode. A polymer stabilized alignment type AM device uses a composition having a positive or negative dielectric anisotropy. Examples of liquid crystal compositions having negative dielectric anisotropy are disclosed in Patent Documents 1 to 6 below. In the present invention, a polar compound (or a polymer thereof) having a polymerizable group and a polymerizable compound (or the polymer) are combined with a liquid crystal compound, and the composition is used for a liquid crystal display element without an alignment film. . [Prior Art Literature] [Patent Literature]

[Patent Literature 1] International Publication No. 2014/090362 [Patent Literature 2] International Publication No. 2014/094959 [Patent Literature 3] International Publication No. 2013/004372 [Patent Literature 4] International Publication No. 2012/104008 No. [Patent Document 5] International Publication No. 2012/038026 [Patent Document 6] Japanese Patent Laid-Open No. 50-35076

[Problems to be Solved by the Invention] An object of the present invention is a liquid crystal composition containing a polar compound (or the polymer) having a polymerizable group and a polymerizable compound (or the polymer). Here, the polar compound and The polymerizable compound has high compatibility with a liquid crystal compound. Another object is a liquid crystal composition capable of achieving vertical alignment of liquid crystal molecules by the action of a polymer produced from the polar compound and the polymerizable compound. Another object is a liquid crystal composition, which has a high upper temperature in the nematic phase, a low lower temperature in the nematic phase, low viscosity, appropriate optical anisotropy, large negative dielectric anisotropy, large specific resistance, Among the characteristics such as high ultraviolet stability and high thermal stability, at least one characteristic is satisfied. Another object is a liquid crystal composition having a proper balance between at least two characteristics. Another object is a liquid crystal display element containing the composition. Still another object is an AM device having characteristics such as short response time, large voltage holding ratio, low threshold voltage, large contrast ratio, and long life. [Means for solving problems]

The present invention relates to a polar compound having at least one polymerizable group as a first additive and a polymerizable compound having at least three polymerizable groups as a second additive, and having negative dielectric anisotropy. A liquid crystal composition and a liquid crystal display element containing the composition. [Effect of the invention]

An advantage of the present invention is a liquid crystal composition containing a polar compound (or the polymer) having a polymerizable group and a polymerizable compound (or the polymer). Here, the polar compound and the polymerizable compound have a liquid crystal compound. High compatibility. Another advantage is a liquid crystal composition capable of achieving vertical alignment of liquid crystal molecules by the action of a polymer generated from the polar compound and the polymerizable compound. Another advantage is a liquid crystal composition, which has a high upper temperature in the nematic phase, a low lower temperature in the nematic phase, low viscosity, appropriate optical anisotropy, large negative dielectric anisotropy, large specific resistance, and Among the characteristics such as high ultraviolet stability and high thermal stability, at least one characteristic is satisfied. Another advantage is a liquid crystal composition having a suitable balance between at least two characteristics. Another advantage is a liquid crystal display element containing the composition. Still another advantage is an AM element with characteristics such as short response time, large voltage retention, low threshold voltage, large contrast ratio, and long life.

The terms used in this specification are described below. The terms "liquid crystal composition" and "liquid crystal display element" may be simply referred to as "composition" and "element", respectively. "Liquid crystal display element" is a generic term for liquid crystal display panels and liquid crystal display modules. A "liquid crystal compound" is a compound having a nematic phase and a smectic liquid crystal phase, and for the purpose of adjusting characteristics such as the temperature range, viscosity, and dielectric anisotropy of a nematic phase, although it does not have a liquid crystal phase. Generic term for compounds mixed in a composition. The compound has a six-membered ring such as 1,4-cyclohexyl or 1,4-phenylene, and its molecular structure is rod-like. The "polymerizable compound" is a compound added for the purpose of forming a polymer in the composition. The liquid crystal compound which has an alkenyl group is not polymerizable in the meaning.

The liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. To this liquid crystal composition, additives such as an optically active compound, an antioxidant, an ultraviolet absorber, a pigment, an antifoaming agent, a polymerizable compound, a polymerization initiator, a polymerization inhibitor, and a polar compound are added as needed. Liquid crystal compounds or additives are mixed in the above-mentioned order. That is, when it is convenient to add an additive, the ratio (content) of the liquid crystalline compound is also expressed by a weight percentage (% by weight) based on the weight of the liquid crystal composition not containing the additive. The ratio (addition amount) of the additive is expressed by a weight percentage (% by weight) based on the weight of the liquid crystal composition not containing the additive. Sometimes parts per million by weight (ppm) is used. The ratio of the polymerization initiator and the polymerization inhibitor is exceptionally expressed based on the weight of the polymerizable compound.

The "upper limit temperature of the nematic phase" may be simply referred to as the "upper limit temperature". The "lower limit temperature of the nematic phase" may be simply referred to as the "lower limit temperature". "High specific resistance" means that the composition has a large specific resistance not only at room temperature in the initial stage, but also at a temperature close to the upper limit temperature, and not only at room temperature, but also close to the temperature after long-term use. It also has a large specific resistance at the temperature of the upper limit. "Large voltage retention" means that the element has a large voltage retention not only at room temperature in the initial stage, but also at a temperature close to the upper limit temperature, and not only at room temperature but also after a long period of use. It also has a large voltage holding ratio at a temperature close to the upper limit temperature. In a composition or a device, characteristics may be studied before and after a change over time test (including an accelerated deterioration test). The expression "improving dielectric anisotropy" refers to a composition with a positive dielectric anisotropy, which means that its value increases positively, and a composition with a negative dielectric anisotropy means a negative value. Increase to the ground.

The compound represented by formula (1) may be simply referred to as "compound (1)". At least one kind of compound selected from the group of compounds represented by formula (1) may be simply referred to as "compound (1)". "Compound (1)" means one compound, a mixture of two compounds, or a mixture of three or more compounds represented by formula (1). The same applies to compounds represented by other formulas. The expression "at least one" A "" means that the number of "A" is arbitrary. The expression "at least one 'A' may be replaced by 'B'" means that when the number of 'A' is one, the position of 'A' is arbitrary, and when the number of 'A' is two or more, their positions are You can also choose unlimitedly. This rule also applies to the expression "at least one 'A' is replaced by 'B'".

The expression "at least one -CH ₂ -may be substituted with -O-" is used in this specification. In this case, -CH ₂ -CH ₂ -CH ₂ -can be converted to -O-CH ₂ -O- by non-adjacent -CH ₂ -substituted with -O-. However, adjacent -CH ₂ -will not be replaced by -O-. This is because -OO-CH _2- (peroxide) is formed during the substitution. That is, the expression refers to both "one -CH ₂ -may be substituted with -O-" and "at least two non-adjacent -CH ₂ -may be substituted with -O-". This rule applies not only to the case of substitution with -O-, but also to the case of substitution with a divalent radical such as -CH = CH- or -COO-. In the alkyl group, at least one -CH ₂ -may be substituted with a cycloalkylene group having 3 to 8 carbon atoms. The carbon number of the alkyl group is increased by this substitution. At this time, the maximum carbon number is 30. This rule applies not only to monovalent groups such as alkyl groups, but also to divalent groups such as alkylene groups.

In the chemical formula of the component compound, the symbol 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, there may be a case where 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 also cases where R ¹ of compound (1-1) is ethyl and R ¹ of compound (1-2) is propyl. This rule applies to other tokens. In formula (1), when a is 2, there are two rings A. In this compound, the two rings represented by the two rings A may be the same or different. This rule also applies to any two rings A when a is greater than 2. This rule applies to other tokens. This rule also applies to the case of the two -Sp ¹¹ -P ⁵ of compound (5-7).

Symbols 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 the formula (3), a diagonal line crossing the hexagon indicates that any hydrogen on the ring may be substituted with a group such as -Sp ¹ -P ¹ . Subscripts such as 'k' indicate the number of substituted groups. When the subscript 'k' is 0, there is no such substitution. When the subscript 'k' is 2 or more, there are multiple -Sp ¹ -P ¹ on the ring J. The multiple radicals represented by -Sp ¹ -P ¹ may be the same or different. In the expression "ring A and ring C are independently X, Y, or Z", since there are multiple subjects, "independently" is used. When the subject is "ring A", "independently" is not used because the subject is singular. When "Ring A" is used in multiple formulas, the "may be the same or different" rule applies to "Ring A". The same is true for other bases.

2-Fluoro-1,4-phenylene refers to two types of divalent groups described below. In the chemical formula, fluorine may be leftward (L) or rightward (R). This rule also applies to asymmetric divalent groups such as tetrahydropyran-2,5-diyl, which are generated by removing two hydrogens from the ring. This rule also applies 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 include a cyclic alkyl group. Linear alkyl groups are preferred over branched alkyl groups. The same applies to terminal groups such as an alkoxy group and an alkenyl group. In order to raise the upper limit temperature, the stereo configuration associated with 1,4-cyclohexyl is a trans configuration that is better than a cis configuration.

The present invention includes the following items.

Item 1. A liquid crystal composition containing a polar compound having at least one polymerizable group as a first additive and a polymerizable compound having at least three polymerizable groups as a second additive, and having a negative dielectric Anisotropy.

式（1）中，R¹ 及R² 獨立地為碳數1至12的烷基、碳數1至12的烷氧基、碳數2至12的烯基、至少一個氫經氟或氯取代的碳數2至12的烯基、或者碳數2至12的烯氧基；環A及環C獨立地為1,4-伸環己基、1,4-伸環己烯基、四氫吡喃-2,5-二基、1,4-伸苯基、至少一個氫經氟或氯取代的1,4-伸苯基、萘-2,6-二基、至少一個氫經氟或氯取代的萘-2,6-二基、色原烷-2,6-二基、或者至少一個氫經氟或氯取代的色原烷-2,6-二基；環B為2,3-二氟-1,4-伸苯基、2-氯-3-氟-1,4-伸苯基、2,3-二氟-5-甲基-1,4-伸苯基、3,4,5-三氟萘-2,6-二基或7,8-二氟色原烷-2,6-二基；Z¹ 及Z² 獨立地為單鍵、-CH₂ CH₂ -、-CH₂ O-、-OCH₂ -、-COO-或-OCO-；a為1、2或3，b為0或1，而且a與b之和為3以下。Item 2. The liquid crystal composition according to Item 1, comprising as a first component at least one compound selected from the group of compounds represented by formula (1),

In formula (1), R ¹ and R ^{2 are} independently 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, and at least one hydrogen is substituted with fluorine or chlorine Alkenyl having 2 to 12 carbon atoms, or alkenyloxy having 2 to 12 carbon atoms; ring A and ring C are independently 1,4-cyclohexyl, 1,4-cyclohexenyl, tetrahydropyridine Ran-2,5-diyl, 1,4-phenylene, at least one hydrogen substituted by fluorine or chlorine, 1,4-phenylene, naphthalene-2,6-diyl, at least one hydrogen substituted by fluorine or chlorine Substituted naphthalene-2,6-diyl, chromogen-2,6-diyl, or chromogen-2,6-diyl with at least one hydrogen substituted by fluorine or chlorine; ring B 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 or 7,8-difluorochromogen-2,6-diyl; Z ¹ and Z ^{2 are} independently a single bond, -CH ₂ CH ₂ -,- CH ₂ O-, -OCH _2- , -COO-, or -OCO-; a is 1, 2 or 3, b is 0 or 1, and the sum of a and b is 3 or less.

式（1-1）至式（1-22）中，R¹ 及R² 獨立地為碳數1至12的烷基、碳數1至12的烷氧基、碳數2至12的烯基、至少一個氫經氟或氯取代的碳數2至12的烯基、或者碳數2至12的烯氧基。Item 3. The liquid crystal composition according to Item 1 or 2, which contains, as a first component, at least one compound selected from the group of compounds represented by formula (1-1) to formula (1-22),

In formulae (1-1) to (1-22), R ¹ and R ^{2 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. , At least one hydrogen substituted with fluorine or chlorine, an alkenyl group having 2 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms.

Item 4. The liquid crystal composition according to any one of Items 1 to 3, wherein the proportion of the first component is in a range of 10% by weight to 90% by weight based on the weight of the liquid crystal composition.

式（2）中，R³ 及R⁴ 獨立地為碳數1至12的烷基、碳數1至12的烷氧基、碳數2至12的烯基、至少一個氫經氟或氯取代的碳數1至12的烷基、或者至少一個氫經氟或氯取代的碳數2至12的烯基；環D及環E獨立地為1,4-伸環己基、1,4-伸苯基、2-氟-1,4-伸苯基或2,5-二氟-1,4-伸苯基；Z³ 為單鍵、-CH₂ CH₂ -、-CH₂ O-、-OCH₂ -、-COO-或-OCO-；c為1、2或3。Item 5. The liquid crystal composition according to any one of Items 1 to 4, which contains, as a second component, at least one compound selected from the group of compounds represented by formula (2),

In formula (2), R ³ and R ^{4 are} independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, an alkenyl group having 2 to 12 carbons, and at least one hydrogen is substituted with fluorine or chlorine Alkyl group having 1 to 12 carbon atoms, or alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine; ring D and ring E are independently 1,4-cyclohexyl, 1,4-cyclohexyl Phenyl, 2-fluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene; Z ³ is a single bond, -CH ₂ CH _2- , -CH ₂ O-,- OCH _2- , -COO- or -OCO-; c is 1, 2 or 3.

式（2-1）至式（2-13）中，R³ 及R⁴ 獨立地為碳數1至12的烷基、碳數1至12的烷氧基、碳數2至12的烯基、至少一個氫經氟或氯取代的碳數1至12的烷基、或者至少一個氫經氟或氯取代的碳數2至12的烯基。Item 6. The liquid crystal composition according to any one of Items 1 to 5, which contains at least one compound selected from the group of compounds represented by Formula (2-1) to Formula (2-13) as The second component,

In the formulae (2-1) to (2-13), R ³ and R ^{4 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. , At least one hydrogen having 1 to 12 carbons substituted with fluorine or chlorine, or at least one hydrogen having 2 to 12 carbons substituted with fluorine or chlorine.

Item 7. The liquid crystal composition according to Item 5 or 6, wherein the proportion of the second component is in a range of 10% by weight to 70% by weight based on the weight of the liquid crystal composition.

Item 8. The liquid crystal composition according to any one of Items 1 to 7, wherein the first additive is a polar compound having a hetero atom selected from nitrogen, oxygen, sulfur, and phosphorus.

式（3）中，R⁷ 為氫、氟、氯或碳數1至25的烷基，該烷基中，至少一個-CH₂ -可經-NR⁰ -、-O-、-S-、-CO-、-CO-O-、-O-CO-、-O-CO-O-或碳數3至8的伸環烷基取代，而且至少一個三級碳（＞CH-）可經氮（＞N-）取代，該些基中，至少一個氫可經氟或氯取代，此處，R⁰ 為氫或碳數1至12的烷基；R⁸ 為具有OH結構的氧原子、SH結構的硫原子、及一級、二級或三級胺結構的氮原子中的至少一種的極性基；環J、環K及環L獨立地為1,4-伸環己基、1,4-伸環己烯基、1,4-伸苯基、萘-1,2-二基、萘-1,3-二基、萘-1,4-二基、萘-1,5-二基、萘-1,6-二基、萘-1,7-二基、萘-1,8-二基、萘-2,3-二基、萘-2,6-二基、萘-2,7-二基、四氫吡喃-2,5-二基、1,3-二噁烷-2,5-二基、嘧啶-2,5-二基或吡啶-2,5-二基，該些環中，至少一個氫可經氟、氯、碳數1至12的烷基、碳數1至12的烷氧基、或者至少一個氫經氟或氯取代的碳數1至12的烷基取代；Z⁷ 及Z⁸ 獨立地為單鍵或碳數1至10的伸烷基，該伸烷基中，至少一個-CH₂ -可經-O-、-CO-、-COO-或-OCO-取代，而且至少一個-CH₂ CH₂ -可經-CH=CH-、-C(CH₃ )=CH-、-CH=C(CH₃ )-或-C(CH₃ )=C(CH₃ )-取代，該些基中，至少一個氫可經氟或氯取代；P¹ 、P² 及P³ 為聚合性基；Sp¹ 、Sp² 及Sp³ 獨立地為單鍵或碳數1至10的伸烷基，該伸烷基中，至少一個-CH₂ -可經-O-、-COO-、-OCO-或-OCOO-取代，而且至少一個-CH₂ CH₂ -可經-CH=CH-或-C≡C-取代，該些基中，至少一個氫可經氟或氯取代；g及h獨立地為0、1、2、3或4，而且g及h之和為0、1、2、3或4；k及p獨立地為0、1、2、3或4，o為1、2、3或4； 式（4）中，R⁹ 為氫、氟、氯、碳數1至12的烷基、碳數1至12的烷氧基、碳數2至12的烯基、至少一個氫經氟或氯取代的碳數1至12的烷基、或者至少一個氫經氟或氯取代的碳數2至12的烯基；R¹⁰ 為-OH、-OR⁰ 、-NH₂ 、-NHR⁰ 或-N(R⁰ )₂ 所表示的基，此處，R⁰ 為氫或碳數1至12的烷基；環M及環N獨立地為1,4-伸環己基、1,4-伸環己烯基、1,4-伸苯基、萘-1,2-二基、萘-1,3-二基、萘-1,4-二基、萘-1,5-二基、萘-1,6-二基、萘-1,7-二基、萘-1,8-二基、萘-2,3-二基、萘-2,6-二基、萘-2,7-二基、四氫吡喃-2,5-二基、1,3-二噁烷-2,5-二基、嘧啶-2,5-二基、吡啶-2,5-二基、茀-2,7-二基、菲-2,7-二基或蒽-2,6-二基，該些環中，至少一個氫可經氟、氯、碳數1至12的烷基、碳數1至12的烷氧基、或者至少一個氫經氟或氯取代的碳數1至12的烷基取代；Z⁹ 為單鍵、-CH₂ CH₂ -、-CH=CH-、-C≡C-、-COO-、-OCO-、-CF₂ O-、-OCF₂ -、-CH₂ O-、-OCH₂ -或-CF=CF-；Sp⁴ 及Sp⁵ 獨立地為單鍵或碳數1至7的伸烷基，該伸烷基中，至少一個-CH₂ -可經-O-、-COO-或-OCO-取代，至少一個-CH₂ CH₂ -可經-CH=CH-取代，該些基中，至少一個氫可經氟取代；j為0、1、2、3或4。Item 9. The liquid crystal composition according to any one of Items 1 to 8, comprising as a first addition at least one compound selected from the group of polar compounds represented by formula (3) and formula (4) Things

In the formula (3), R ⁷ is hydrogen, fluorine, chlorine, or an alkyl group having 1 to 25 carbon atoms. In the alkyl group, at least one -CH ₂ -may pass through -NR ^0- , -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- or a cycloalkyl group having 3 to 8 carbon atoms, and at least one tertiary carbon (> CH-) may be substituted with nitrogen (> N-) substitution. Among these groups, at least one hydrogen may be substituted by fluorine or chlorine. Here, R ⁰ is hydrogen or an alkyl group having 1 to 12 carbons; R ⁸ is an oxygen atom having an OH structure, and SH A polar group of at least one of a sulfur atom of the structure and a nitrogen atom of the primary, secondary or tertiary amine structure; the ring J, the ring K and the ring L are independently 1,4-cyclohexyl, 1,4-cyclohexyl Cyclohexenyl, 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, these In the ring, at least one hydrogen may be substituted with fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or carbon having at least one hydrogen substituted with fluorine or chlorine. 1 to 12 alkyl substitution; Z ⁷ and Z ^{8 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, and at least one of the alkylene groups may be -CH ₂ -via -O-, -CO- , -COO- or -OCO-, and at least one -CH ₂ CH ₂ -can be via -CH = CH-, -C (CH ₃ ) = CH-, -CH = C (CH ₃ )-or -C ( CH ₃ ) = C (CH ₃ ) -substitution, among these groups, at least one hydrogen may be substituted by fluorine or chlorine; P ¹ , P ² and P ³ are polymerizable groups; Sp ¹ , Sp ² and Sp ^{3 are} independently Is a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one -CH ₂ -may be substituted with -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ CH ₂ -may be substituted by -CH = CH- or -C≡C-. Among these groups, at least one hydrogen may be substituted by fluorine or chlorine; g and h are independently 0, 1, 2, 3, or 4, And the sum of g and h is 0, 1, 2, 3, or 4; k and p are independently 0, 1, 2, 3, or 4, and o is 1, 2, 3, or 4; in formula (4), R ⁹ is hydrogen, fluorine, chlorine, 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, and at least one hydrogen having 1 to 12 carbon atoms substituted with fluorine or chlorine Alkyl, or at least one hydrogen alkenyl having 2 to 12 carbons substituted with fluorine or chlorine; R ¹⁰ is- A group represented by OH, -OR ⁰ , -NH ₂ , -NHR ⁰ or -N (R ⁰ ) ₂ , where R ⁰ is hydrogen or an alkyl group having 1 to 12 carbons; ring M and ring N are independently 1,4-cyclohexyl, 1,4-cyclohexenyl, 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, pyridine-2,5-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, or anthracene-2,6-diyl, at least one of these rings may be fluorinated , Chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen substituted with fluorine or chlorine and alkyl having 1 to 12 carbons; Z ⁹ is a single bond, -CH ₂ CH _2- , -CH = CH-, -C≡C-, -COO-, -OCO-, -CF ₂ O-, -OCF _2- , -CH ₂ O-, -OCH ₂ -or -CF = CF-; Sp ⁴ and Sp ^{5 are} independently a single bond or an alkylene group having 1 to 7 carbon atoms. At least one -CH ₂ -in the alkylene group may be substituted with -O-, -COO-, or -OCO- at least one -CH ₂ CH ₂ - may be replaced by -CH = CH-, the plurality of groups, at least one hydrogen may be Fluoro-substituted; J is 0, 1 or 4.

式（A1）至式（A4）中，Sp⁶ 、Sp⁸ 及Sp⁹ 獨立地為單鍵或碳數1至12的伸烷基，該伸烷基中，至少一個-CH₂ -可經-O-、-S-、-NH-、-N(R⁰ )-、-CO-、-CO-O-、-O-CO、-O-CO-O-、-S-CO-、-CO-S-、-N(R⁰ )-CO-O-、-O-CO-N(R⁰ )-、-N(R⁰ )-CO-N(R⁰ )-、-CH=CH-或-C≡C-取代，該些基中，至少一個氫可經氟或氯取代，此處，R⁰ 為氫或碳數1至12的烷基；Sp⁷ 為＞CH-、＞CR⁰ -、＞N-或＞C＜，此處，R⁰ 為氫或碳數1至12的烷基；X¹⁷ 為-OH、-OR⁰ 、-COOH、-NH₂ 、-NHR⁰ 、-N(R⁰ )₂ 、-SH、-SR⁰ 、

， 此處，R⁰ 為氫或碳數1至12的烷基；X¹⁸ 為-O-、-CO-、-NH-、-NR⁰ -、-S-或單鍵，此處，R⁰ 為氫或碳數1至12的烷基；Z¹⁰ 為單鍵或碳數1至15的伸烷基，該伸烷基中，至少一個-CH₂ -可經-C≡C-、-CH=CH-、-COO-、-OCO-、-CO-或-O-取代，該些基中，至少一個氫可經氟或氯取代；環P為碳數6至25的芳基，該芳基中，一個至三個氫可經-OH、-(CH₂ )_q -OH、氟、氯、碳數1至5的烷基、或者至少一個氫經氟或氯取代的碳數1至5的烷基取代，此處，q為1、2、3或4；n為0、1、2或3；m為1、2、3、4或5。Item 10. The liquid crystal composition according to Item 9, wherein in formula (3) according to item 9, R ⁸ is selected from the group of polar groups represented by formula (A1) to formula (A4) base,

In the formulae (A1) to (A4), Sp ⁶ , Sp ⁸ and Sp ^{9 are} independently a single bond or an alkylene group having 1 to 12 carbon atoms. In the alkylene group, at least one of -CH ₂ -may pass through- O-, -S-, -NH-, -N (R ⁰ )-, -CO-, -CO-O-, -O-CO, -O-CO-O-, -S-CO-, -CO -S-, -N (R ⁰ ) -CO-O-, -O-CO-N (R ⁰ )-, -N (R ⁰ ) -CO-N (R ⁰ )-, -CH = CH- or -C≡C- substitution. Among these groups, at least one hydrogen may be substituted by fluorine or chlorine. Here, R ⁰ is hydrogen or an alkyl group having 1 to 12 carbon atoms; Sp ⁷ is>CH-,> CR ^0- ,> N- or> C <, where R ⁰ is hydrogen or an alkyl group having 1 to 12 carbons; X ¹⁷ is -OH, -OR ⁰ , -COOH, -NH ₂ , -NHR ⁰ , -N ( R ⁰ ) ₂ , -SH, -SR ⁰ ,

Here, R ⁰ is hydrogen or an alkyl group having 1 to 12 carbons; X ¹⁸ is -O-, -CO-, -NH-, -NR ^0- , -S-, or a single bond; here, R ⁰ Is hydrogen or an alkyl group having 1 to 12 carbon atoms; Z ¹⁰ is a single bond or an alkylene group having 1 to 15 carbon atoms, at least one of -CH ₂ -may pass through -C≡C-, -CH = CH-, -COO-, -OCO-, -CO- or -O-, at least one of these groups may be substituted by fluorine or chlorine; ring P is an aryl group having 6 to 25 carbon atoms, the aromatic group In the radical, one to three hydrogens may be substituted by -OH,-(CH ₂ ) _q -OH, fluorine, chlorine, an alkyl group having 1 to 5 carbons, or at least one hydrogen substituted by fluorine or chlorine having 1 to 5 carbons. Alkyl substitution, where q is 1, 2, 3 or 4; n is 0, 1, 2 or 3; m is 1, 2, 3, 4 or 5.

式（P-1）至式（P-5）中，M¹ 、M² 及M³ 獨立地為氫、氟、碳數1至5的烷基、或者至少一個氫經氟或氯取代的碳數1至5的烷基。Item 11. The liquid crystal composition according to Item 9, wherein in the formula (3) according to Item 9, P ¹ , P ^2, and P ^{3 are} independently selected from the formula (P-1) to the formula (P- 5) a group in the group of polymerizable groups represented,

In the formulae (P-1) to (P-5), M ¹ , M ² and M ^{3 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbons, or a carbon in which at least one hydrogen is replaced by fluorine or chlorine. Number 1 to 5 alkyl.

式（3-1）至式（3-15）中，R⁷ 為氫、氟、氯或碳數1至25的烷基，該烷基中，至少一個-CH₂ -可經-NR⁰ -、-O-、-S-、-CO-、-CO-O-、-O-CO-、-O-CO-O-或碳數3至8的伸環烷基取代，而且至少一個三級碳（＞CH-）可經氮（＞N-）取代，該些基中，至少一個氫可經氟或氯取代，此處，R⁰ 為氫或碳數1至12的烷基；Sp² 為單鍵或碳數1至10的伸烷基，該伸烷基中，至少一個-CH₂ -可經-O-、-COO-、-OCO-或-OCOO-取代，而且至少一個-CH₂ CH₂ -可經-CH=CH-或-C≡C-取代，該些基中，至少一個氫可經氟或氯取代；Sp¹⁰ 為單鍵或碳數1至10的伸烷基，該伸烷基中，至少一個-CH₂ -可經-O-、-COO-、-OCO-或-OCOO-取代，而且至少一個-CH₂ CH₂ -可經-CH=CH-或-C≡C-取代，該些基中，至少一個氫可經氟或氯取代；L¹ 、L² 、L³ 及L⁴ 獨立地為氫、氟、甲基或乙基；R¹¹ 及R¹² 獨立地為氫或甲基。Item 12. The liquid crystal composition according to any one of Items 1 to 11, wherein the first additive is selected from the group of polar compounds represented by the formula (3-1) to the formula (3-15) At least one compound of

In the formulae (3-1) to (3-15), R ⁷ is hydrogen, fluorine, chlorine, or an alkyl group having 1 to 25 carbon atoms. At least one of the alkyl groups may be -CH ₂ -via -NR ^0- -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, or cycloalkylene with 3 to 8 carbon atoms, and at least one third order Carbon (> CH-) may be substituted with nitrogen (> N-). Among these groups, at least one hydrogen may be substituted with fluorine or chlorine. Here, R ⁰ is hydrogen or an alkyl group having 1 to 12 carbons; Sp ² Is a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one -CH ₂ -may be substituted with -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ CH ₂ -may be substituted by -CH = CH- or -C≡C-. Among these groups, at least one hydrogen may be substituted by fluorine or chlorine; Sp ¹⁰ is a single bond or an alkylene group having 1 to 10 carbon atoms, In the alkylene group, at least one -CH ₂ -may be substituted by -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ CH ₂ -may be -CH = CH- or -C. ≡C- substitution, in these groups, at least one hydrogen may be substituted by fluorine or chlorine; L ¹ , L ² , L ³ and L ^{4 are} independently hydrogen, fluorine, methyl or ethyl; R ¹¹ and R ^{12 are} independent Ground is hydrogen or methyl.

式（4-1）至式（4-9）中，R⁹ 為氫、氟、氯、碳數1至12的烷基、碳數1至12的烷氧基、碳數2至12的烯基、至少一個氫經氟或氯取代的碳數1至12的烷基、或者至少一個氫經氟或氯取代的碳數2至12的烯基；Z⁹ 為單鍵、-CH₂ CH₂ -、-CH=CH-、-C≡C-、-COO-、-OCO-、-CF₂ O-、-OCF₂ -、-CH₂ O-、-OCH₂ -或-CF=CF-；Sp⁴ 及Sp⁵ 獨立地為單鍵或碳數1至7的伸烷基，該伸烷基中，至少一個-CH₂ -可經-O-、-COO-或-OCO-取代，至少一個-CH₂ CH₂ -可經-CH=CH-取代，該些基中，至少一個氫可經氟取代；L⁵ 、L⁶ 、L⁷ 、L⁸ 、L⁹ 、L¹⁰ 、L¹¹ 、L¹² 、L¹³ 、L¹⁴ 、L¹⁵ 及L¹⁶ 獨立地為氫、氟、甲基或乙基。Item 13. The liquid crystal composition according to any one of Items 1 to 12, wherein the first additive is selected from the group of polar compounds represented by formula (4-1) to formula (4-9) At least one compound of

In the formulae (4-1) to (4-9), R ⁹ is hydrogen, fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an olefin having 2 to 12 carbon atoms. Group, at least one hydrogen group having 1 to 12 carbon atoms substituted with fluorine or chlorine, or at least one hydrogen group having 2 to 12 carbon atoms substituted with fluorine or chlorine; Z ⁹ is a single bond, -CH ₂ CH ₂ -, -CH = CH-, -C≡C-, -COO-, -OCO-, -CF ₂ O-, -OCF _2- , -CH ₂ O-, -OCH _2- , or -CF = CF-; Sp ⁴ and Sp ^{5 are} independently a single bond or an alkylene group having 1 to 7 carbon atoms. In this alkylene group, at least one -CH ₂ -may be substituted with -O-, -COO-, or -OCO-, and at least one -CH ₂ CH ₂ -may be substituted by -CH = CH-, in these groups, at least one hydrogen may be substituted by fluorine; L ⁵ , L ⁶ , L ⁷ , L ⁸ , L ⁹ , L ¹⁰ , L ¹¹ , L ^{12, L 13, L 14,} L 15 and L ¹⁶ are independently hydrogen, fluoro, methyl or ethyl.

Item 14. The liquid crystal composition according to any one of Items 1 to 13, wherein the proportion of the first additive is in a range of 0.05% by weight to 10% by weight based on the weight of the liquid crystal composition.

式（5）中，環T及環V獨立地為環己基、環己烯基、苯基、1-萘基、2-萘基、四氫吡喃-2-基、1,3-二噁烷-2-基、嘧啶-2-基或吡啶-2-基，該些環中，至少一個氫可經氟、氯、碳數1至12的烷基、碳數1至12的烷氧基、或者至少一個氫經氟或氯取代的碳數1至12的烷基取代；環U為1,4-伸環己基、1,4-伸環己烯基、1,4-伸苯基、萘-1,2-二基、萘-1,3-二基、萘-1,4-二基、萘-1,5-二基、萘-1,6-二基、萘-1,7-二基、萘-1,8-二基、萘-2,3-二基、萘-2,6-二基、萘-2,7-二基、四氫吡喃-2,5-二基、1,3-二噁烷-2,5-二基、嘧啶-2,5-二基或吡啶-2,5-二基，該些環中，至少一個氫可經氟、氯、碳數1至12的烷基、碳數1至12的烷氧基、或者至少一個氫經氟或氯取代的碳數1至12的烷基取代；Z¹¹ 及Z¹² 獨立地為單鍵或碳數1至10的伸烷基，該伸烷基中，至少一個-CH₂ -可經-O-、-CO-、-COO-或-OCO-取代，而且至少一個-CH₂ CH₂ -可經-CH=CH-、-C(CH₃ )=CH-、-CH=C(CH₃ )-或-C(CH₃ )=C(CH₃ )-取代，該些基中，至少一個氫可經氟或氯取代；P⁴ 、P⁵ 及P⁶ 為聚合性基；Sp¹⁰ 、Sp¹¹ 及Sp¹² 獨立地為單鍵或碳數1至10的伸烷基，該伸烷基中，至少一個-CH₂ -可經-O-、-COO-、-OCO-或-OCOO-取代，而且至少一個-CH₂ CH₂ -可經-CH=CH-或-C≡C-取代，該些基中，至少一個氫可經氟或氯取代；t為0、1或2；u、v及w獨立地為0、1、2、3或4，而且u、v及w之和為3以上。Item 15. The liquid crystal composition according to any one of Items 1 to 14, which contains, as a second additive, at least one compound selected from the group of polymerizable compounds represented by Formula (5),

In formula (5), ring T and ring V are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane Alk-2-yl, pyrimidin-2-yl or pyridin-2-yl, in these rings, at least one hydrogen may pass through fluorine, chlorine, alkyl having 1 to 12 carbons, and alkoxy having 1 to 12 carbons Or at least one hydrogen is substituted by fluorine or chlorine alkyl group having 1 to 12 carbons; ring U is 1,4-cyclohexyl, 1,4-cyclohexenyl, 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-di Group, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, at least one of these rings may be fluorine, chlorine, carbon 1 to 12 alkyl groups, 1 to 12 carbon alkoxy groups, or at least one hydrogen substituted with fluorine or chlorine 1 to 12 alkyl groups; Z ¹¹ and Z ^{12 are} independently a single bond or carbon 1 to 10 alkylene groups in which at least one -CH ₂ -may be substituted with -O-, -CO-, -COO-, or -OCO-, and at least one -CH ₂ CH ₂ -can be substituted with -CH = CH-, -C (CH ₃ ) = CH-, -CH = C (CH ₃ )-, or -C (CH ₃ ) = C (CH ₃ )- At least one hydrogen may be substituted by fluorine or chlorine; P ⁴ , P ⁵ and P ⁶ are polymerizable groups; Sp ¹⁰ , Sp ¹¹ and Sp ^{12 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms. In the alkyl group, at least one -CH ₂ -may be substituted by -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ CH ₂ -may be -CH = CH- or -C≡C. -Substitution, in these groups, at least one hydrogen may be substituted by fluorine or chlorine; t is 0, 1 or 2; u, v and w are independently 0, 1, 2, 3 or 4, and u, v and w The sum is 3 or more.

式（P-1）至式（P-5）中，M¹ 、M² 及M³ 獨立地為氫、氟、碳數1至5的烷基、或者至少一個氫經氟或氯取代的碳數1至5的烷基。Item 16. The liquid crystal composition according to Item 15, wherein in the formula (5) according to Item 15, P ⁴ , P ^5, and P ^{6 are} independently selected from the formula (P-1) to the formula (P- 5) a group in the group of polymerizable groups represented,

In the formulae (P-1) to (P-5), M ¹ , M ² and M ^{3 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbons, or a carbon in which at least one hydrogen is replaced by fluorine or chlorine. Number 1 to 5 alkyl.

式（5-1）至式（5-7）中，P⁴ 、P⁵ 及P⁶ 獨立地為選自式（P-1）至式（P-3）所表示的聚合性基的群組中的基，

此處，M¹ 、M² 及M³ 獨立地為氫、氟、碳數1至5的烷基、或者至少一個氫經氟或氯取代的碳數1至5的烷基；Sp¹⁰ 、Sp¹¹ 及Sp¹² 獨立地為單鍵或碳數1至10的伸烷基，該伸烷基中，至少一個-CH₂ -可經-O-、-COO-、-OCO-或-OCOO-取代，而且至少一個-CH₂ CH₂ -可經-CH=CH-或-C≡C-取代，該些基中，至少一個氫可經氟或氯取代。Item 17. The liquid crystal composition according to any one of Items 1 to 16, which contains at least one selected from the group consisting of a polymerizable compound represented by Formula (5-1) to Formula (5-7). Compound as a second additive,

In Formulas (5-1) to (5-7), P ⁴ , P ^5, and P ^{6 are} independently selected from the group of polymerizable groups represented by Formulas (P-1) to (P-3) In the base,

Here, M ¹ , M ² and M ^{3 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbons, or an alkyl group having 1 to 5 carbons in which at least one hydrogen is replaced with fluorine or chlorine; Sp ¹⁰ , Sp ¹¹ and Sp ^{12 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, and at least one of -CH ₂ -may be substituted with -O-, -COO-, -OCO-, or -OCOO- Moreover, at least one -CH ₂ CH ₂ -may be substituted by -CH = CH- or -C≡C-. Among these groups, at least one hydrogen may be substituted by fluorine or chlorine.

Item 18. The liquid crystal composition according to any one of Items 15 to 17, wherein a ratio of the second additive is in a range of 0.03% by weight to 10% by weight based on the weight of the liquid crystal composition.

Item 19. A liquid crystal display element comprising the liquid crystal composition according to any one of Items 1 to 18.

Item 20. The liquid crystal display element according to item 19, wherein the operation mode of the liquid crystal display element is an IPS mode, a VA mode, an FFS mode, or an FPA mode, and the driving method of the liquid crystal display element is an active matrix method.

Item 21. A polymer stabilized alignment type liquid crystal display device comprising the liquid crystal composition according to any one of items 1 to 18, and the first additive and the second additive in the liquid crystal composition are polymerization.

Item 22. A liquid crystal display element without an alignment film, comprising the liquid crystal composition according to any one of items 1 to 18, and polymerizing the first additive and the second additive in the liquid crystal composition. .

Item 23. The use of the liquid crystal composition according to any one of Items 1 to 18, which is used in a liquid crystal display element.

Item 24. The use of the liquid crystal composition according to any one of Items 1 to 18, which is used for a polymer-stable alignment type liquid crystal display element.

Item 25. The use of the liquid crystal composition according to any one of Items 1 to 18, which is used for a liquid crystal display element without an alignment film.

The present invention also includes the following items. (A) A method for manufacturing a liquid crystal display device, wherein the liquid crystal composition is arranged between two substrates, and light is irradiated in a state where a voltage is applied to the composition, so that polymerizable properties contained in the composition are provided. The compound of the group is polymerized to produce the liquid crystal display device. (B) The upper limit temperature of the nematic phase of the above liquid crystal composition is 70 ° C or higher, the optical anisotropy (measured at 25 ° C) at a wavelength of 589 nm is 0.08 or higher, and the dielectric anisotropy at a frequency of 1 kHz The anisotropy (measured at 25 ° C) is -2 or less.

The present invention also includes the following items. (C) The above-mentioned composition, although the compounds (5) to (7) described in Japanese Patent Laid-Open No. 2006-199941 are liquid crystal compounds having a positive dielectric anisotropy, the above-mentioned composition contains At least one compound from the group of compounds. (D) The above-mentioned composition containing at least two of the above-mentioned polar compounds. (E) The composition further containing a polar compound different from the polar compound. (F) The above composition contains one, two or at least three optically active compounds, antioxidants, ultraviolet absorbers, pigments, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds and the like Additives. The additive may be the same as the first additive or the second additive, or may be different. (G) An AM device containing the above composition. (H) An element containing the above composition and having a TN mode, ECB mode, OCB mode, IPS mode, FFS mode, VA mode, or FPA mode. (I) A transmissive element containing the above composition. (J) Use the above composition as a composition having a nematic phase. (K) Use of an optically active compound by adding an optically active compound to the composition.

The composition of the present invention will be described in the following order. First, the composition 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 components in the composition, the preferred ratio of the components, and the basis thereof will be described. Fourth, preferred embodiments of the component compounds will be described. Fifth, preferred component compounds are shown. Sixth, additives that can be added to the composition will be described. Seventh, a method for synthesizing the component compounds will be described. Finally, the use of the composition will be described.

First, the composition of the composition will be described. The composition of the present invention is classified into a composition A and a composition B. The composition A may contain other liquid crystal compounds, additives, etc. in addition to the liquid crystal compounds selected from the compounds (1) and (2). The "other liquid crystal compound" is a liquid crystal compound different from the compound (1) and the compound (2). Such a compound is mixed in the composition for the purpose of further adjusting the characteristics. The additives are optically active compounds, antioxidants, ultraviolet absorbers, pigments, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds, and the like.

The composition B contains substantially only a liquid crystal compound selected from the compound (1) and the compound (2). "Substantially" means that the composition may contain additives, but does not contain other liquid crystal compounds. Compared with the composition A, the number of components of the composition B is small. From the viewpoint of cost reduction, the composition B is superior to the composition A. From the viewpoint that the characteristics can be further adjusted by mixing other liquid crystal compounds, the composition A is superior to the composition B.

Second, the main characteristics of the component compounds and the main effects of the compounds on the characteristics of the composition will be described. Based on the effects of the present invention, the main characteristics of the component compounds are summarized in Table 2. In the symbols in Table 2, L is large or high, M is medium, and S is small or low. Symbols L, M, and S are classifications based on qualitative comparisons among component compounds, and symbol 0 means that the value is zero, or close to zero.

When the component compounds are mixed in the composition, the main effects of the component compounds on the characteristics of the composition are as follows. Compound (1) improves dielectric anisotropy. Compound (2) raises the upper limit temperature or decreases the viscosity. The compound (3) and the compound (4) are adsorbed on the substrate surface by the action of a polar group, and control the alignment of the liquid crystal molecules. In order to obtain a desired effect, these compounds must have high compatibility with a liquid crystal compound. These compounds have six-membered rings such as 1,4-cyclohexyl or 1,4-phenylene, and their molecular structures are rod-shaped, so they are most suitable for this purpose. The compound (5) is added to the composition for the purpose of further being suitable for a polymer-stabilized alignment device. The compound (3), the compound (4), and the compound (5) are polymerized to form a polymer. Since this polymer stabilizes the alignment of liquid crystal molecules, it shortens the response time of the device and improves the afterimage of the image.

Third, the combination of components in the composition, the preferred ratio of the components, and the basis thereof will be described. A preferred combination of the components in the composition is compound (1) + compound (2). The vertical alignment of liquid crystal molecules can be achieved by combining a polar compound (or the polymer) and a polymerizable compound (or the polymer) in the composition. If the "other liquid crystal compound" is a small amount, the same effect can be achieved even if it is added to the composition.

In order to improve the dielectric anisotropy, the preferred ratio of the compound (1) is about 10% by weight or more, and to reduce the viscosity, the preferred ratio of the compound (1) is about 90% by weight or less. A particularly preferred ratio is in the range of about 15% by weight to about 80% by weight. A particularly preferred ratio is in the range of about 20% by weight to about 70% by weight.

In order to increase the upper limit temperature or to reduce the viscosity, the preferred ratio of the compound (2) is about 10% by weight or more. In order to increase the dielectric anisotropy, the preferred ratio of the compound (2) is about 70% by weight or less. A particularly preferred ratio is in the range of about 10% by weight to about 65% by weight. A particularly preferred ratio is in the range of about 15% by weight to about 60% by weight.

The compound (3) and the compound (4) are added to the composition for the purpose of controlling the alignment of liquid crystal molecules. In order to align the liquid crystal molecules, the preferred ratio of compound (3) or compound (4) is about 0.05% by weight or more. In order to prevent poor display of the device, the preferred ratio of compound (3) or compound (4) is about 10 % By weight or less. A particularly preferred ratio is in the range of about 0.1% by weight to about 7% by weight. A particularly preferred ratio is in the range of about 0.5% by weight to about 5% by weight.

The compound (5) is added to the composition for the purpose of being suitable for a polymer-stable alignment device. In order to improve the long-term reliability of the device, the preferred ratio of the compound (5) is about 0.03% by weight or more. In order to prevent display failure of the device, the preferred ratio of the compound (5) is about 10% by weight or less. A particularly 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 embodiments of the component compounds will be described. In formulas (1) and (2), R ¹ and R ^{2 are} independently 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, and at least one hydrogen Alkenyl having 2 to 12 carbons or alkenyl having 2 to 12 carbons substituted with fluorine or chlorine. For increasing the stability to ultraviolet light or heat, preferably R ¹ or R ² is alkyl having 1 to 12, for increasing the dielectric anisotropy, the preferred R ¹ or R ² having 1 to 12 carbon atoms Alkoxy.

R ³ and R ^{4 are} independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, an alkenyl group having 2 to 12 carbons, at least one hydrogen having 1 to 12 carbon atoms substituted with fluorine or chlorine Alkyl, or at least one hydrogen alkenyl having 2 to 12 carbons substituted with fluorine or chlorine. In order to improve the stability to ultraviolet or heat, the preferred R ³ or R ⁴ is an alkyl group having 1 to 12 carbons. In order to reduce the lower limit temperature or the viscosity, the preferred R ³ or R ⁴ is 2 to carbon numbers. 12 alkenyl.

Preferred alkyl groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl. To reduce viscosity, particularly preferred alkyl groups are ethyl, propyl, butyl, pentyl or heptyl.

Preferred alkoxy groups are methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy or heptyloxy. To reduce viscosity, a particularly preferred alkoxy group is 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. To reduce viscosity, particularly preferred alkenyl is vinyl, 1-propenyl, 3-butenyl or 3-pentenyl. The preferred stereo configuration of -CH = CH- in these alkenyl groups depends on the position of the double bond. In order to reduce viscosity and the like, among alkenyl groups such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl, 3-hexenyl, etc. Trans configuration. Among alkenyl groups such as 2-butenyl, 2-pentenyl, and 2-hexenyl, the cis configuration is preferred.

Preferred alkenyloxy groups are vinyloxy, allyloxy, 3-butenyloxy, 3-pentenyloxy or 4-pentenyloxy. In order to reduce viscosity, particularly preferred allyloxy is allyloxy or 3-butenyloxy.

Preferred examples of the alkyl group in which at least one hydrogen is substituted by fluorine or chlorine are fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl, 7 -Fluoroheptyl or 8-fluorooctyl. To increase the dielectric anisotropy, particularly preferred 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 by fluorine or chlorine are 2,2-difluorovinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro-3-butenyl, 5,5-difluoro-4-pentenyl or 6,6-difluoro-5-hexenyl. In order to reduce the viscosity, a particularly preferred example is 2,2-difluorovinyl or 4,4-difluoro-3-butenyl.

或

，較佳為

。Ring A and ring C are independently 1,4-cyclohexyl, 1,4-cyclohexenyl, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen atom Fluorine or chlorine substituted 1,4-phenylene, naphthalene-2,6-diyl, at least one hydrogen substituted with fluorine or chlorine naphthalene-2,6-diyl, chromogen-2,6-diyl , Or at least one chromogen-2,6-diyl substituted with fluorine or chlorine. Preferred ring A or ring C is 1,4-cyclohexyl, 1,4-cyclohexenyl, tetrahydropyran-2,5-diyl, 1,4-phenylene, 2-fluoro -1,4-phenylene, 2,3-difluoro-1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl or 7,8-difluorochromogen -2,6-diyl. Particularly preferred ring A or ring C is 1,4-cyclohexyl or 1,4-phenylene. Among these rings, in order to reduce the viscosity, the preferred ring A or ring C is 1,4-cyclohexyl, and in order to improve the dielectric anisotropy, the preferred ring A or ring C is tetrahydropyran-2, In order to improve the optical anisotropy of the 5-diyl group, a preferable ring A or ring C is 1,4-phenylene. Tetrahydropyran-2,5-diyl is

or

, Preferably

.

Ring B 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 or 7,8-difluorochromogen-2,6-diyl. Preferred ring B is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene or 7,8-difluorochroman-2,6 -Two bases. Particularly preferred ring B is 2,3-difluoro-1,4-phenylene or 2-chloro-3-fluoro-1,4-phenylene. A particularly preferred ring B is 2,3-difluoro-1,4-phenylene. Among these rings, in order to reduce the viscosity, the preferred ring B is 2,3-difluoro-1,4-phenylene, and in order to reduce the optical anisotropy, the preferred ring B is 2-chloro-3-fluoro -1,4-phenylene. In order to improve the dielectric anisotropy, the preferred ring B is 7,8-difluorochroman-2,6-diyl.

Ring D and Ring E are independently 1,4-cyclohexyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene . In order to reduce the viscosity, or to increase the upper limit temperature, the preferred ring D or ring E is 1,4-cyclohexyl. In order to lower the lower limit temperature, the preferred ring D or ring E is 1,4-phenylene.

Z ¹ and Z ^{2 are} independently a single bond, -CH ₂ CH _2- , -CH ₂ O-, -OCH _2- , -COO-, or -OCO-. In order to reduce the viscosity, the preferred Z ¹ or Z ² is a single bond. In order to reduce the lower limit temperature, the preferred Z ¹ or Z ² is -CH ₂ CH _2- . In order to improve the dielectric anisotropy, the preferred Z ¹ Or Z ² is -CH ₂ O- or -OCH _2- . Z ³ is a single bond, -CH ₂ CH _2- , -CH ₂ O-, -OCH _2- , -COO-, or -OCO-. In order to reduce the viscosity, the preferred Z ³ is a single bond, to reduce the lower limit temperature, the preferred Z ³ is -CH ₂ CH _2- , and to increase the upper limit temperature, the preferred Z ³ is -COO- or -OCO-.

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

In formula (3), R ⁸ is a polar group. In formula (4), R ¹⁰ is a polar group. The compound (3) or the compound (4) is preferably stable to ultraviolet rays or heat. When compound (3) or compound (4) is added to the composition, it is preferred that the compound does not reduce the voltage retention of the device. The compound (3) or the compound (4) preferably has low volatility. The preferred molar mass is 130 g / mol or more. A particularly preferred molar mass is in the range of 150 g / mol to 500 g / mol. Preferred compound (3) or compound (4) has polymerization such as propylene alkoxy group (-OCO-CH = CH ₂ ), methacryl methoxy group (-OCO- (CH ₃ ) C = CH ₂ ) and the like Sex-based.

The polar group has a non-covalent bonding interaction with the surface of a glass substrate or a metal oxide film. Preferred polar groups have heteroatoms selected from the group of nitrogen, oxygen, sulfur, and phosphorus. Preferred polar groups have at least one or at least two such heteroatoms. A particularly preferred polar group is by removing hydrogen from a compound selected from the group consisting of alcohols, primary, secondary, and tertiary amines, ketones, carboxylic acids, thiols, esters, ethers, thioethers, and combinations thereof. And derived monovalent base. The structures of these groups may be linear, branched, cyclic, or a combination of these. A particularly preferred polar group has at least one oxygen atom of an OH structure or at least one of nitrogen atoms of a primary, secondary or tertiary amine structure. The most preferred polar group is hydroxyl (carbon-OH).

Examples of the polar group R ⁸ are the groups represented by Formula (A1) to Formula (A4).

In the formulae (A1) to (A4), Sp ⁶ , Sp ⁸ and Sp ^{9 are} independently a single bond or an alkylene group having 1 to 12 carbon atoms. In the alkylene group, at least one of -CH ₂ -may pass through- O-, -S-, -NH-, -N (R ⁰ )-, -CO-, -CO-O-, -O-CO, -O-CO-O-, -S-CO-, -CO -S-, -N (R ⁰ ) -CO-O-, -O-CO-N (R ⁰ )-, -N (R ⁰ ) -CO-N (R ⁰ )-, -CH = CH- or -C≡C- substitution. Among these groups, at least one hydrogen may be substituted with fluorine or chlorine. Here, R ⁰ is hydrogen or an alkyl group having 1 to 12 carbons. Sp ⁷ is>CH-,> CR ⁰ -,> N-, or> C <, where R ⁰ is hydrogen or an alkyl group having 1 to 12 carbon atoms. That is, it means that Sp ⁷ in formula (A2) is>CH-,> CR ^0- , or> N-, and Sp ⁷ in formula (A3) is> C <.

Preferred Sp ⁶ , Sp ⁸ or Sp ⁹ are single bonds,-(CH ₂ ) _p1 -,-(CH ₂ ) _p1 -O-,-(CH ₂ CH ₂ O) _q1 -CH ₂ CH ₂ -,- (CH ₂ ) _p1 -O-CO-,-(CH ₂ ) _p1 -O-CO-O-, -CH ₂ CH ₂ -S-CH ₂ CH ₂ -or -CH ₂ CH ₂ -NHCH ₂ CH _2- Here, p1 is an integer from 1 to 12, and q1 is an integer from 1 to 3. Particularly preferred Sp ⁶ , Sp ⁸ or Sp ⁹ are ethylene, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and eleven Alkyl, dodecyl, octadecyl, vinyloxyalkylene, methyleneoxybutylene, ethylenethioalkylene, ethylene-N-methylimidoethylene, 1- Methylalkylene, vinylene, propenyl, and butenyl.

， 此處，R⁰ 為氫或碳數1至12的烷基。In formulae (A1) to (A4), X ¹⁷ is -OH, -OR ⁰ , -COOH, -NH ₂ , -NHR ⁰ , -N (R ⁰ ) ₂ , -SH, -SR ⁰ ,

Here, R ⁰ is hydrogen or an alkyl group having 1 to 12 carbon atoms.

In formula (A1), X ¹⁸ is -O-, -CO-, -NH-, -NR ^0- , -S- or a single bond, and R ⁰ is hydrogen or an alkyl group having 1 to 12 carbons. Z ¹⁰ is a single bond or an alkylene group having 1 to 15 carbon atoms, at least one of -CH ₂ -may pass through -C≡C-, -CH = CH-, -COO-, -OCO-, -CO- or -O-, in which at least one hydrogen may be substituted with fluorine or chlorine. Ring P is an aryl group having 6 to 25 carbons, in which one to three hydrogens may be passed through -OH,-(CH ₂ ) _q -OH, fluorine, chlorine, an alkyl group having 1 to 5 carbons, or at least One hydrogen is substituted with an alkyl group having 1 to 5 carbon atoms substituted with fluorine or chlorine, where q is 1, 2, 3, or 4. n is 0, 1, 2 or 3, and m is 1, 2, 3, 4 or 5.

Aryl is a monovalent radical derived by removing one hydrogen from an aromatic hydrocarbon and does not contain heteroatoms. The aryl group may be any of monocyclic or polycyclic. That is, the aryl group has at least one ring, and the ring may be condensed (for example, naphthyl), and the two rings may be connected by a covalent bond (for example, biphenyl). The aryl group may have a combination of a condensed ring and a linked ring. Aryl may also be substituted. Examples of the substituent are -OH,-(CH ₂ ) _q -OH, fluorine, chlorine, 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 replaced with fluorine or chlorine. Where q is 1, 2, 3, or 4.

、苝、稠四苯、稠五苯、苯并芘、茀、茚、茚并茀、螺二茀中去除一個氫而衍生的一價基。The preferred aryl groups are those derived from

, Fluorene, fused tetrabenzene, fused pentabenzene, benzofluorene, fluorene, indene, indenofluorene, spirobifluorene, and a monovalent group derived by removing one hydrogen.

In formula (3), R ⁸ is a polar group of at least one of an oxygen atom having an OH structure, a sulfur atom having an SH structure, and a nitrogen atom having a primary, secondary, or tertiary amine structure. Preferred R ⁸ is -OH,-(CH ₂ ) _n -OH, -O- (CH ₂ ) _n -OH,-[O- (CH ₂ ) _n1- ] _n2 -OH, -COOH,-(CH ₂ ) _n -COOH, -O- (CH ₂ ) _n -COOH or-[O- (CH ₂ ) _n1- ] _n2 -COOH. Here, n, n1, and n2 are each independently an integer of 1 to 12, preferably 1, 2, 3, or 4.

Preferred R ⁸ may also be -NH ₂ , -NH- (CH ₂ ) _n3 H,-(CH ₂ ) _n -NH ₂ ,-(CH ₂ ) _n -NH- (CH ₂ ) _n3 H, -NH -(CH ₂ ) _n -NH ₂ , -NH- (CH ₂ ) _n -NH- (CH ₂ ) _n3 H,-(CH ₂ ) _n1 -NH- (CH ₂ ) _n2 -NH ₂ ,-(CH ₂ ) _n1 -NH- (CH ₂ ) _n2 -NH- (CH ₂ ) _n3 H, -O- (CH ₂ ) _n -NH ₂ ,-(CH ₂ ) _n1 -O- (CH ₂ ) _n -NH ₂ , -(CH ₂ ) _n1 -NH- (CH ₂ ) _n2 -OH, -O- (CH ₂ ) _n1 -NH- (CH ₂ ) _n2 -NH ₂ , -O- (CH ₂ ) _n1 -NH- (CH ₂ ) _n2 -OH or-(CH ₂ ) _n1 -NH- (CH ₂ ) _n2 -NH- (CH ₂ ) _n3 H. Here, n, n1, n2, and n3 are independently integers of 1 to 12, preferably 1, 2, 3, or 4.

From the viewpoint of high solubility in the liquid crystal composition, R ^{8 is} particularly preferably -OH or -NH ₂ . -OH is superior to -O-, -CO- or -COO- because of its high anchoring force. Particularly preferred is a group having multiple heteroatoms (nitrogen, oxygen). A compound having such a polar group is effective even at a low concentration.

In the formula (3), R ⁷ is hydrogen, fluorine, chlorine, or an alkyl group having 1 to 25 carbon atoms. In the alkyl group, at least one -CH ₂ -may pass through -NR ^0- , -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- or a cycloalkyl group having 3 to 8 carbon atoms, and at least one tertiary carbon (> CH-) may be substituted with nitrogen (> N-) substitution. Among these groups, at least one hydrogen may be substituted with fluorine or chlorine. Here, R ⁰ is hydrogen or an alkyl group having 1 to 12 carbons. Preferred R ⁷ is an alkyl group having 1 to 25 carbon atoms.

In Formula (3), P ¹ , P ^2, and P ^{3 are} independently a polymerizable group. Preferably, P ¹ , P ² or P ³ is a group selected from the group of polymerizable groups represented by formula (P-1) to formula (P-5). Particularly preferred P ¹ , P ² or P ³ is a group represented by Formula (P-1), Formula (P-2) or Formula (P-3). Particularly preferred P ¹ , P ² or P ³ is a group represented by formula (P-1) or formula (P-2). The most preferable P ¹ , P ² or P ³ is a group represented by the formula (P-1). A preferred group represented by the formula (P-1) is -OCO-CH = CH ₂ or -OCO-C (CH ₃ ) = CH ₂ . The wavy lines in the formula (P-1) to the formula (P-5) indicate the bonding sites.

In the formulae (P-1) to (P-5), M ¹ , M ² and M ^{3 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbons, or a carbon in which at least one hydrogen is replaced by fluorine or chlorine. Number 1 to 5 alkyl. To increase reactivity, preferred M ¹ , M ² or M ³ is hydrogen or methyl. Particularly preferred M ¹ is hydrogen or methyl, and particularly preferred M ² or M ³ is hydrogen.

In the formula (3), 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 of -CH ₂ -may pass through -O-, -COO. -, -OCO- or -OCOO-, and at least one -CH ₂ CH ₂ -may be substituted with -CH = CH- or -C≡C-. Among these groups, at least one hydrogen may be substituted with 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-. Particularly preferred Sp ¹ , Sp ² or Sp ³ are single bonds. However, when ring J and ring L are phenyl groups, Sp ¹ and Sp ³ are single bonds.

In formula (3), ring J, ring K, and ring L are independently 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, and naphthalene-1,2-di Naphthalene, 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-diyl Oxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, at least one hydrogen of these rings may pass fluorine, chlorine, alkyl group having 1 to 12 carbons , An alkoxy group having 1 to 12 carbons, or at least one hydrogen substituted with an alkyl group having 1 to 12 carbons substituted with fluorine or chlorine. Preferred ring J, ring K or ring L is 1,4-phenylene or 2-fluoro-1,4-phenylene.

In the formula (3), Z ⁷ and Z ^{8 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms. In the alkylene group, at least one -CH ₂ -may pass through -O-, -CO-,- COO- or -OCO- substituted, and at least one -CH ₂ CH ₂ -can be via -CH = CH-, -C (CH ₃ ) = CH-, -CH = C (CH ₃ )-or -C (CH ₃ ) = C (CH ₃ ) -substitution. Among these groups, at least one hydrogen may be substituted by fluorine or chlorine. Preferably, Z ⁷ or Z ⁸ is a single bond, -CH ₂ CH _2- , -CH ₂ O-, -OCH _2- , -COO-, or -OCO-. A particularly preferred Z ⁷ or Z ⁸ is a single bond.

In the formula (3), g and h are independently 0, 1, 2, 3, or 4, and the sum of g and h is 0, 1, 2, 3, or 4. The preferred g or h is 0, 1 or 2. k and p are independently 0, 1, 2, 3, or 4. The preferred k or p is 1 or 2. o is 1, 2, 3, or 4. The preferred o is 1 or 2.

In the formulae (3-1) to (3-15), Sp ¹⁰ is a single bond or an alkylene group having 1 to 10 carbon atoms. At least one of the alkylene groups may be -CH ₂ -via -O-,- COO-, -OCO-, or -OCOO-, and at least one -CH ₂ CH ₂ -may be substituted with -CH = CH- or -C≡C-. Among these groups, at least one hydrogen may be substituted with fluorine or chlorine. . L ¹ , L ² , L ³ and L ^{4 are} independently hydrogen, fluorine, methyl or ethyl. R ¹¹ and R ^{12 are} independently hydrogen or methyl.

In formula (4), R ¹⁰ is a group represented by -OH, -OR ⁰ , -NH ₂ , -NHR ^0, or -N (R ⁰ ) _2. Here, R ⁰ is hydrogen or a group having 1 to 12 carbons. alkyl. From the viewpoint of high solubility in the liquid crystal composition, R ^{2 is} particularly preferably -OH or -NH ₂ . -OH is superior to -O-, -CO- or -COO- because of its high anchoring force. Particularly preferred is a group having multiple heteroatoms (nitrogen, oxygen). A compound having such a polar group is effective even at a low concentration.

In formula (4), R ⁹ is hydrogen, fluorine, chlorine, 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, and at least one hydrogen is subjected to fluorine or chlorine. A substituted alkyl group having 1 to 12 carbons, or an alkenyl group having 2 to 12 carbons in which at least one hydrogen is replaced with fluorine or chlorine. Preferred R ⁹ is an alkyl group having 1 to 12 carbon atoms.

In formula (4), ring M and ring N are independently 1,4-cyclohexyl, 1,4-cyclohexenyl, 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, pyridine-2,5-diyl, pyrene-2,7-diyl, phenanthrene-2,7-diyl, or anthracene-2,6-di In these rings, at least one hydrogen may be substituted by fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen substituted by fluorine or chlorine. Alkyl substitution. Preferred ring M or ring N is 1,4-cyclohexyl, 1,4-phenylene or 2-fluoro-1,4-phenylene.

In formula (4), Z ⁹ is a single bond, -CH ₂ CH _2- , -CH = CH-, -C≡C-, -COO-, -OCO-, -CF ₂ O-, -OCF _2- , -CH ₂ O-, -OCH _2- , or -CF = CF-. Preferred Z ⁹ is a single bond, -CH ₂ CH _2- , -CH ₂ O-, -OCH _2- , -COO-, or -OCO-. The particularly preferred Z ⁹ is a single bond.

In formula (4), Sp ⁴ and Sp ^{5 are} independently a single bond or an alkylene group having 1 to 7 carbon atoms. In the alkylene group, at least one -CH ₂ -may pass through -O-, -COO-, or- OCO- substituted, at least one -CH ₂ CH ₂ -may be substituted with -CH = CH-, and among these groups, at least one hydrogen may be substituted with fluorine. The preferred Sp ⁴ or Sp ⁵ is a single bond.

In the formula (4), j is 0, 1, 2, 3, or 4. The preferred j is 0, 1, or 2.

In formulas (4-1) to (4-9), L ⁵ , L ⁶ , L ⁷ , L ⁸ , L ⁹ , L ¹⁰ , L ¹¹ , L ¹² , L ¹³ , L ¹⁴ , L ¹⁵ and L ¹⁶ Independently is hydrogen, fluorine, methyl or ethyl. Preferred L ⁵ to L ¹⁶ are hydrogen or fluorine.

In Formula (5), P ⁴ , P ⁵ and P ^{6 are} independently a polymerizable group. P ⁴ , P ⁵ or P ⁶ is preferably a group selected from the group of polymerizable groups represented by formula (P-1) to formula (P-5). Particularly preferred P ⁴ , P ⁵ or P ⁶ is a group represented by formula (P-1), formula (P-2) or formula (P-3). Particularly preferred P ⁴ , P ⁵ or P ⁶ is a group represented by formula (P-1) or formula (P-2). The most preferable P ⁴ , P ⁵ or P ⁶ is a group represented by the formula (P-1). A preferred group represented by the formula (P-1) is -OCO-CH = CH ₂ or -OCO-C (CH ₃ ) = CH ₂ . The wavy lines in the formula (P-1) to the formula (P-5) indicate the bonding sites.

In the formulae (P-1) to (P-5), M ¹ , M ² and M ^{3 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbons, or a carbon in which at least one hydrogen is replaced by fluorine or chlorine. Number 1 to 5 alkyl. To increase reactivity, preferred M ¹ , M ² or M ³ is hydrogen or methyl. Particularly preferred M ¹ is hydrogen or methyl, and particularly preferred M ² or M ³ is hydrogen.

In Formula (5), Sp ¹⁰ , Sp ^11, and Sp ^{12 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms. In the alkylene group, at least one -CH ₂ -may be substituted by -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ CH ₂ -may be -CH = CH- or -C. ≡C-substitution. Among these groups, at least one hydrogen may be substituted by fluorine or chlorine. Preferred Sp ¹⁰ , Sp ¹¹ or Sp ¹² are single bonds, -CH ₂ CH _2- , -CH ₂ O-, -OCH _2- , -COO-, -OCO-, -CO-CH = CH- or- CH = CH-CO-. Particularly preferred Sp ¹⁰ , Sp ¹¹ or Sp ¹² are single bonds.

In formula (5), ring T and ring V are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane Alk-2-yl, pyrimidin-2-yl or pyridin-2-yl, in these rings, at least one hydrogen may pass through fluorine, chlorine, alkyl having 1 to 12 carbons, and alkoxy having 1 to 12 carbons Or at least one hydrogen is substituted with fluorine or chlorine substituted alkyl having 1 to 12 carbon atoms. Preferred ring T or ring V is phenyl. Ring U is 1,4-cyclohexyl, 1,4-cyclohexenyl, 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 may be passed through fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one Hydrogen is substituted by a C1-C12 alkyl group substituted by fluorine or chlorine. The preferred ring U is 1,4-phenylene or 2-fluoro-1,4-phenylene.

In the formula (5), Z ¹¹ and Z ^{12 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms. In the alkylene group, at least one -CH ₂ -may pass through -O-, -CO-,- COO- or -OCO- substituted, and at least one -CH ₂ CH ₂ -can be via -CH = CH-, -C (CH ₃ ) = CH-, -CH = C (CH ₃ )-or -C (CH ₃ ) = C (CH ₃ ) -substitution. Among these groups, at least one hydrogen may be substituted by fluorine or chlorine. Preferably, Z ¹¹ or Z ¹² is a single bond, -CH ₂ CH _2- , -CH ₂ O-, -OCH _2- , -COO-, or -OCO-. Particularly preferred Z ¹¹ or Z ¹² are single bonds.

In Formula (5), t is 0, 1 or 2. The preferred t is 0 or 1. u, v, and w are independently 0, 1, 2, 3, or 4, and the sum of u, v, and w is 3 or more.

Fifth, preferred component compounds are shown. Preferred compound (1) is the compound (1-1) to compound (1-22) according to item 3. Among these compounds, it is preferred that at least one of the first components is compound (1-1), compound (1-3), compound (1-4), compound (1-6), compound (1-8) or Compound (1-10). It is preferable that at least two of the first components are compound (1-1) and compound (1-6), compound (1-1) and compound (1-10), compound (1-3) and compound (1- 6) Compound (1-3) and compound (1-10), compound (1-4) and compound (1-6), or a combination of compound (1-4) and compound (1-8).

Preferred compound (2) is the compound (2-1) to compound (2-13) according to item 6. Among these compounds, it is preferred that at least one of the second components is compound (2-1), compound (2-3), compound (2-5), compound (2-6), compound (2-8) or Compound (2-9). It is preferable that at least two of the second component are the compound (2-1) and the compound (2-3), the compound (2-1) and the compound (2-5) or the compound (2-1) and the compound (2- 6) The combination.

Preferred compound (3) is the compound (3-1) to compound (3-15) according to item 12. Among these compounds, it is preferred that at least one of the first additives is compound (3-6), compound (3-8), compound (3-10), compound (3-11), compound (3-13) Or compound (3-15). Preferably, at least two of the first additives are a compound (3-1) and a compound (3-11) or a combination of a compound (3-3) and a compound (3-8).

Preferred compound (4) is the compound (4-1) to compound (4-9) according to item 13. Among these compounds, it is preferred that at least one of the first additives is compound (4-1), compound (4-2), compound (4-3), compound (4-5) or compound (4-6) . It is preferable that at least two of the first additives are a compound (4-1) and a compound (4-2) or a combination of a compound (4-1) and a compound (4-4).

Preferred compound (5) is the compound (5-1) to compound (5-7) according to item 17. Among these compounds, it is preferred that at least one of the second additives is compound (5-2), compound (5-5) or compound (5-7). It is preferred that at least two of the second additives are compound (5-1) and compound (5-2), compound (5-2) and compound (5-5), or compound (5-2) and compound (5 -7).

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

In order to prevent the 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 the composition. Preferable examples of the antioxidant are a compound (7) in which n is an integer of 1 to 9, and the like.

In compound (7), preferred n is 1, 3, 5, 7, or 9. A particularly preferred n is 7. The compound (7) in which n is 7 is small in volatility, and is therefore 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 a long-term use of the device. In order to obtain the above effect, a preferred ratio of the antioxidant is about 50 ppm or more, and in order not to lower the upper limit temperature, or not to raise the lower limit temperature, the preferred ratio of the antioxidant is about 600 ppm or less. A particularly preferred ratio is in the range of about 100 ppm to about 300 ppm.

Preferred examples of the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, and triazole derivatives. In addition, a light stabilizer such as an amine having a steric hindrance is also preferable. In order to obtain the above effect, the preferred ratio of these absorbers or stabilizers is about 50 ppm or more. In order not to lower the upper limit temperature or to not raise the lower limit temperature, the preferred ratio of these absorbers or stabilizers is about 10,000 ppm. the following. A particularly preferred ratio is in the range of about 100 ppm to about 10,000 ppm.

In order to be suitable for a device in a guest host (GH) mode, a dichroic dye such as an azo pigment, an anthraquinone pigment, or the like is added to the composition. A preferred ratio of the pigment is in the range of about 0.01% by weight to about 10% by weight. To prevent foaming, antifoaming agents such as dimethyl silicone oil and methylphenyl silicone oil are added to the composition. In order to obtain the above effect, the preferred ratio of the defoaming agent is about 1 ppm or more, and the preferred ratio of the defoaming agent is about 1,000 ppm or less in order to prevent display failure. A particularly preferred ratio is in the range of about 1 ppm to about 500 ppm.

In order to be suitable for a polymer stabilized alignment (PSA) type device, a polymerizable compound is used. Compound (3), compound (4) and compound (5) are suitable for this purpose. The compound (3), the compound (4), and the compound (5) and a polymerizable compound different from the compound (3), the compound (4), and the compound (5) may be added to the composition together. Preferred examples of such polymerizable compounds are acrylates, methacrylates, vinyl compounds, vinyloxy compounds, propenyl ethers, epoxy compounds (oxetane, oxetane), and vinyl ketones. And other compounds. A particularly preferred example is acrylate or methacrylate. A preferable ratio of the compound (3), the compound (4), and the compound (5) is about 10% by weight or more based on the total weight of the polymerizable compound. A particularly preferred ratio is about 50% by weight or more. A particularly preferred ratio is about 80% by weight or more. A particularly good ratio is also 100% by weight. By changing the types of the compound (3), the compound (4), and the compound (5), or by combining other polymerizable compounds with the compound (3), the compound (4), and the compound (5) at an appropriate ratio, it is possible to Adjust the reactivity of the polymerizable compound or the pretilt angle of the liquid crystal molecules. 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 irradiation with ultraviolet rays. Polymerization may be performed in the presence of a suitable initiator such as a photopolymerization initiator. Appropriate conditions for carrying out the polymerization, an appropriate type of the initiator, and an appropriate amount are known to those having ordinary knowledge in the technical field to which the present invention pertains, and are described in the literature. For example, Irgacure 651 (registered trademark; BASF), Irgacure 184 (registered trademark; BASF) or Darocur 1173 (registered trademark; BASF) as photoinitiators ) Suitable for free radical polymerization. The preferred ratio of the photopolymerization initiator is in the range of about 0.1% by weight to about 5% by weight based on the total weight of the polymerizable compound. A particularly preferred ratio is in the range of about 1% to about 3% by weight.

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

A polar compound is a polar organic compound. Here, a compound having an ionic bond is not included. Atoms such as oxygen, sulfur, and nitrogen are electrically negative and tend to have a partial negative charge. Carbon and hydrogen are neutral or tend to have a partially positive charge. Polarity is caused by the uneven distribution of partial charges among different kinds of atoms in a compound. For example, the polar compound has at least one of a partial structure such as -OH, -COOH, -SH, -NH ₂ ,>NH,> N-.

Seventh, a method for synthesizing the component compounds will be described. These compounds can be synthesized by known methods. Illustrative synthesis methods. Compound (1-1) was synthesized by a method described in Japanese Patent Application Publication No. Hei 2-503441. Compound (2-1) is synthesized by a method described in Japanese Patent Laid-Open No. 59-176221. A method for synthesizing the compound (3-1) and the compound (4-1) is described in the item of Examples. Compound (5-1) is synthesized by a method described in International Publication No. 2013-161576. A part of the compound (7) is commercially available. The compound of formula (7) where n is 1 is available from Sigma-Aldrich Corporation. Compound (7) and the like in which n is 7 are synthesized by a method described in US Pat. No. 3,660,505.

Compounds without a synthetic method can be synthesized by methods described in the following books: "Organic Syntheses" (John Wiley & Sons, Inc.), "Organic Reactions" , John Wiley & Sons Publishing Company), Comprehensive Organic Synthesis (Pergamon Press), New Experimental Chemistry Lecture (Maruzen), etc. The composition is prepared from the compound obtained in the above manner by a known method. For example, the component compounds are mixed and then dissolved in each other by heating.

Finally, the use of the composition will be described. Most compositions have a lower limit temperature of about -10 ° C or lower, an upper limit temperature of about 70 ° C or higher, and optical anisotropy in a range of about 0.07 to about 0.20. A composition having an optical anisotropy in a range of about 0.08 to about 0.25 can be prepared by controlling the ratio of the component compounds or by mixing other liquid crystal compounds. Furthermore, a composition having an optical anisotropy in a range of about 0.10 to about 0.30 can be prepared by trial and error. The device containing this composition has a large voltage holding ratio. This composition is suitable for an AM device. This composition is particularly suitable for a transmissive AM device. This 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.

This composition can be used for an AM device. It can also be used for PM devices. This composition can be used for AM devices and PM devices with PC, TN, STN, ECB, OCB, IPS, FFS, VA, FPA and other modes. Particularly good is for AM devices with TN, OCB, IPS, FFS and other modes. In an AM device having an IPS mode or an FFS mode, when no voltage is applied, the alignment of the liquid crystal molecules may be parallel to the glass substrate, or may be vertical. These elements can be reflective, transmissive, or transflective. It is preferably used for a transmissive element. It can also be used for amorphous silicon-TFT elements or polycrystalline silicon-TFT elements. The composition can also be used in a nematic curvilinear aligned phase (NCAP) device made by microencapsulation or a polymer formed by forming a three-dimensional network polymer in the composition. A polymer dispersed (PD) type device.

An example of a method for manufacturing a conventional polymer-stabilized alignment element is described below. Assemble an element that includes two substrates, which are called an array substrate and a color filter substrate. The substrate has an alignment film. At least one of the substrates has an electrode layer. Liquid crystal compounds are mixed to prepare a liquid crystal composition. A polymerizable compound is added to this composition. Additives can be added if necessary. This composition is injected into a device. Light irradiation is performed in a state where a voltage is applied to the element. Preferred is ultraviolet light. The polymerizable compound is polymerized by light irradiation. A polymer-containing composition is produced by this polymerization. The polymer stabilized alignment type element is manufactured in the order described above.

In this sequence, when a voltage is applied, the liquid crystal molecules are aligned by the action of an alignment film and an electric field. According to this alignment, the molecules of the polymerizable compound are also aligned. Since the polymerizable compound is polymerized by ultraviolet rays in this state, a polymer that maintains the alignment is produced. The effect of this polymer shortens the response time of the device. Since the residual image of the image is a poor operation of the liquid crystal molecules, the effect of the polymer also improves the residual image. 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.

When a polar compound having a polymerizable group such as the compound (3) and the compound (4) is used as the polymerizable compound, the substrate of the device does not require an alignment film. An element without an alignment film is manufactured from a substrate without an alignment film in the order described in the paragraphs preceding two paragraphs.

In this order, the compound (3) or the compound (4) is aligned on the substrate due to the interaction between the polar group and the surface of the substrate. The liquid crystal molecules are aligned according to the arrangement. When a voltage is applied, the alignment of liquid crystal molecules is further promoted. Since the polymerizable group is polymerized by ultraviolet rays in this state, a polymer that maintains the alignment is produced. By the effect of this polymer, the alignment of liquid crystal molecules is additionally stabilized, and the response time of the device is shortened. Since the residual image of the image is a poor operation of the liquid crystal molecules, the effect of the polymer also improves the residual image. [Example]

The present invention will be further described in detail through examples. The invention is not limited by these examples. The present invention includes a mixture of the composition M1 and the composition M2. The present invention also includes a mixture 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 following methods.

NMR analysis: DRX-500 manufactured by Bruker BioSpin was used for measurement. ^In the measurement of ¹ H-NMR, a sample was dissolved in a deuterated solvent such as CDCl _3, and the measurement was performed at room temperature under conditions of 500 MHz and a cumulative number of 16 times. Tetramethylsilane was used as the internal standard. ^{In the 19} F-NMR measurement, CFCl _{3 was} used as an internal standard, and the total number of measurements was performed 24 times. In the description of nuclear magnetic resonance spectrum, s refers to singlet, d refers to doublet, t refers to triplet, q refers to quartet, and quin refers to quintet. (Quintet), sex means sixt (sextet), m means multiplet, and br means broad.

Gas chromatographic analysis: The GC-14B gas chromatograph manufactured by Shimadzu Corporation was used for the measurement. The carrier gas was helium (2 mL / min). The sample gasification chamber was set to 280 ° C, and the detector (flame ionization detector (FID)) was set to 300 ° C. For separation of constituent compounds, a capillary column DB-1 (30 m in length, 0.32 mm in inner diameter, and 0.25 μm in thickness) manufactured by Agilent Technologies Inc. was used; the fixed liquid phase was dimethylpolysiloxane ; Non-polar). 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 sample was injected into the sample gasification chamber. The recorder is a C-R5A Chromatopac manufactured by Shimadzu Corporation or its equivalent. The obtained gas chromatogram showed the retention time of the peak corresponding to the component compounds and the area of the peak.

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

The ratio of the liquid crystal compound contained in the composition can be calculated by the method described below. A gas chromatograph (FID) was used to analyze a mixture of liquid crystal compounds. The area ratio of the peaks in the gas chromatogram corresponds to the ratio of the liquid crystal compound. When the capillary column described above is used, the correction coefficient of various liquid crystal compounds can be regarded as one. Therefore, the ratio (% by weight) of the liquid crystalline compound can be calculated from the peak area ratio.

Measurement sample: When measuring the characteristics of the composition and the device, the composition is directly used as a sample. When measuring the characteristics of a compound, a sample for measurement was prepared by mixing the compound (15% by weight) with a mother liquid crystal (85% by weight). Based on the value obtained by the measurement, the characteristic value of the compound is calculated by an extrapolation method. (Extrapolated value) = ｛(measured value of the sample)-0.85 × (measured value of the mother liquid crystal)｝ /0.15. When the smectic phase (or crystal) is precipitated at 25 ° C at this ratio, the ratio of the compound to the mother liquid crystal is 10% by weight: 90% by weight, 5% by weight: 95% by weight, and 1% by weight: 99% % Order change. This extrapolation method was used to find the values of the compound-dependent upper temperature, optical anisotropy, viscosity, and dielectric anisotropy.

The following mother liquid crystals were used. The proportion of the component compounds is expressed in% by weight.

Measurement method: The characteristics were measured by the following method. Most of these methods are methods described or modified by the Japan Electronics and Information Technology Industries Association (referred to as JEITA) as specified in the JEITA standard (JEITA · ED-2521B). The thin-film transistor (TFT) was not mounted on the TN element used for the measurement.

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

(2) Lower limit temperature of nematic phase (TC; ℃): Put the sample with nematic phase into a glass bottle and freeze it at 0 ℃, -10 ℃, -20 ℃, -30 ℃ and -40 ℃. After storing in the container for 10 days, the liquid crystal phase was observed. For example, when the sample maintains a nematic phase state at -20 ° C and changes to a crystal or a smectic phase at -30 ° C, the T _{C is} described as <-20 ° C. The lower limit temperature of the nematic phase may be simply referred to as "lower limit temperature".

(3) Viscosity (volume viscosity; η; measured at 20 ° C; mPa · s): For measurement, an E-type rotary viscometer manufactured by Tokyo Keiki Co., Ltd. was used.

(4) Viscosity (rotational viscosity; γ1; measured at 25 ° C; mPa · s): According to "Molecular Crystals and Liquid Crystals" by M. Imai et al. The measurement was performed by the method described in page 37 (1995). A sample was injected into a VA device having a distance (cell gap) between two glass substrates of 20 μm. A voltage is applied to the device in a range of 39 volts to 50 volts in steps of 1 volt. After 0.2 seconds without applying voltage, the voltage was repeatedly applied under the conditions of applying only 1 rectangular wave (rectangular pulse; 0.2 seconds) and not applying (2 seconds). The peak current and the peak time of the transient current generated by the application were measured. From these measured values and the calculation formula (8) on page 40 of the paper by M. Imai et al., The value of the rotational viscosity is obtained. The dielectric anisotropy required for this calculation is measured by the method described in Measurement (6).

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

(6) Dielectric anisotropy (Δε; measured at 25 ° C): The value of the dielectric anisotropy is 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∥): Apply a solution of octadecyl triethoxysilane (0.16 mL) in ethanol (20 mL) on a fully cleaned glass substrate. After the glass substrate was rotated by a spinner, it was heated at 150 ° C for 1 hour. A sample was placed in a VA device having a distance (cell gap) between two glass substrates of 4 μm, and the device was sealed with an adhesive hardened with ultraviolet rays. A sine wave (0.5 V, 1 kHz) was applied to the device, 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 is coated on a sufficiently cleaned glass substrate. After the glass substrate is fired, the obtained alignment film is subjected to a rubbing treatment. A sample was injected into a TN device having a distance (cell gap) between 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 device, and the dielectric constant (ε⊥) of the minor axis direction of the liquid crystal molecules was measured after 2 seconds.

(7) Threshold voltage (Vth; measured at 25 ° C; V): The LCD5100 brightness 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 device with a gap (cell gap) of two glass substrates of 4 μm and a rubbing direction in antiparallel, and the adhesive was cured with an ultraviolet-curing adhesive. Component sealed. The voltage (60 Hz, rectangular wave) applied to the device was increased stepwise from 0 V to 20 V in units of 0.02 V. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. A voltage-transmittance curve having a transmittance of 100% when the amount of light reaches the maximum and a transmittance of 0% when the amount of light reaches the minimum is made. The threshold voltage is expressed as a voltage when the transmittance reaches 10%.

(8) Voltage holding ratio (VHR-1; measured at 25 ° C;%): The TN device used for the measurement has a polyimide alignment film, and the distance (cell gap) between two glass substrates is 5 μm. This device was sealed with a UV-curable adhesive after the sample was injected. A pulse voltage (5 V, 60 microseconds) was applied to the TN device to charge it. The decaying voltage was measured with a high-speed voltmeter over a period of 16.7 milliseconds, and the area A between the voltage curve per unit cycle and the horizontal axis was obtained. Area B is the area when the voltage is not attenuated. The voltage holding ratio is expressed as a percentage of the area A to the area B.

(9) Voltage holding ratio (VHR-2; measured at 80 ° C;%): The voltage holding ratio was measured in the same procedure as 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 to evaluate the stability to ultraviolet rays. The TN device used for the measurement has a polyimide alignment film, and the cell gap is 5 μm. A sample was injected into the device, and the device was irradiated with light for 20 minutes. The light source is an ultra-high-pressure mercury lamp USH-500D (made by Ushio Motor), and the distance between the component and the light source is 20 cm. In the measurement of VHR-3, the attenuated voltage was measured during 16.7 milliseconds. A composition having a large VHR-3 has a large stability to ultraviolet rays. VHR-3 is preferably 90% or more, particularly preferably 95% or more.

(11) Voltage holding ratio (VHR-4; measured at 25 ° C;%): After heating the TN element filled with the sample in a constant temperature bath at 80 ° C for 500 hours, measure the voltage holding ratio and evaluate the stability to heat . In the measurement of VHR-4, the attenuated voltage was measured during 16.7 milliseconds. A composition having a large VHR-4 has a large stability to heat.

(12) Response time (τ; measured at 25 ° C; ms): LCD5100 type brightness meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement. The light source is a halogen lamp. The low-pass filter is set to 5 kHz. A sample was placed in a VA device having a distance (cell gap) between two glass substrates of 3.5 μm without an alignment film. This element was sealed with an adhesive hardened with ultraviolet rays. While applying a voltage of 30 V to this device, it was irradiated with ultraviolet light of 78 mW / cm ² (405 nm) for 449 seconds (35 J). For ultraviolet irradiation, a UV-curable polymetal lamp M04-L41 manufactured by Eye Grapics Co., Ltd. was used. A rectangular wave (120 Hz) was applied to the element. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. When the amount of light reaches the maximum, the transmittance is considered to be 100%, and when the amount of light is the smallest, the transmittance is considered to be 0%. The maximum voltage of the rectangular wave is set so that the transmittance becomes 90%. The minimum voltage of the rectangular wave is set to 2.5 V with a transmittance of 0%. The response time is expressed by the time (rise time; milliseconds) required for the transmittance to change from 10% to 90%.

(13) Elastic constant (K11: spray elastic constant, K33: bend elastic constant; measured at 25 ° C; pN): EC-manufactured by TOYO Corporation is used for measurement Type 1 elastic constant tester. A sample was injected into a vertical alignment element having a distance (cell gap) between two glass substrates of 20 μm. A charge of 20 volts to 0 volts was applied to the device, and the capacitance and the applied voltage were measured. Use equations (2.98) and (2.101) on page 75 of "Liquid Crystal Device Handbook" (Nikkan Kogyo Shimbun) to fit the measured values of electrostatic capacitance (C) and applied voltage (V). Equation (2.100) obtains the value of the elastic constant.

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

(15) Pretilt angle (degrees): A spectroscopic ellipsometer M-2000U (manufactured by J. A. Woollam Co., Inc.) was used for the measurement of the pretilt angle.

(16) Alignment stability (stability of liquid crystal alignment axis): Changes in the liquid crystal alignment axis on the electrode side of the liquid crystal display element were evaluated. Measure the orientation angle f (before) of the liquid crystal on the electrode side before applying stress. Then, apply rectangular wave 4.5 V, 60 Hz to the device for 20 minutes, buffer for 1 second, and measure the electrode side again after 1 second and 5 minutes. LCD alignment angle f (after). From these values, the change Δf (deg.) Of the liquid crystal alignment angle after 1 second and after 5 minutes was calculated using the following formula. Δf (deg.) = F (after) -f (before) (Equation 2) Take J. Hilfik, B. Jensen, C. Hessinger, JF Elman, E. Montebach, D. Bryant and PJ Boss (J. Hilfiker, B. Johs, C. Herzinger, JF Elman, E. Montbach, D. Bryant, and PJ Bos), Thin Solid Films, 455-456 (2004) 596-600 for reference. It can be said that the smaller the Δf, the smaller the rate of change of the liquid crystal alignment axis, and the better the stability of the liquid crystal alignment axis.

Synthesis Example 1 Compound (3-1) was synthesized by the following method.

In the first step, compound (T-1) (4.98 g), compound (T-2) (5.00 g), potassium carbonate (6.88 g), tetrakis (triphenylphosphine) palladium (0.289 g), and isopropanol ( IPA (isopropyl alcohol; 100 ml) was added to the reactor, and heated to reflux at 80 ° C for 2 hours. The reaction mixture was poured into water, neutralized with 1 N hydrochloric acid, and then extracted with ethyl acetate. The organic layers generated together were washed with brine, and dried over anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene) to obtain compound (T-3) (6.38 g; 99%).

Step 2 Add sodium borohydride (1.88 g) and methanol (90 ml) to the reactor and cool to 0 ° C. A tetrahydrofuran (THF) (40 ml) solution of the compound (T-3) (6.38 g) was slowly added dropwise thereto, and the mixture was stirred for 8 hours while returning to room temperature. The reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The organic layers produced together were washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene: ethyl acetate = 3: 1). Further, purification was performed by recrystallization from a mixed solvent (volume ratio, 1: 1) of heptane and toluene to obtain a compound (T-4) (5.50 g; 85%).

In the third step, compound (T-4) (0.600 g), potassium carbonate (0.637 g), and dimethylformamide (DMF) (6 ml) were added to the reactor, and stirred at 80 ° C for 1 hour. After the reaction mixture was cooled to room temperature, a DMF (6 ml) solution of the compound (T-5) (0.983 g) synthesized according to the method described in Japanese Patent Laid-Open No. 2013-177561 was slowly added dropwise at 80 ° C. Stir for 8 hours. The reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The organic layers produced together were washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene: ethyl acetate = 7: 1) to obtain compound (3-1) (0.350 g; 40%).

¹ H-NMR: chemical shift δ (ppm; CDCl ₃ ): 7.35-7.29 (m, 2H), 7.15-7.10 (m, 1H), 7.07-6.94 (m, 3H), 6.14 (s, 1H), 5.60 (s, 1H), 4.71 (d, 6.6 Hz, 2H), 4.58 (t, J = 4.5 Hz, 2H), 4.32 (t, J = 4.5 Hz, 2H), 2.65-2.58 (m, 3H), 1.95 (s, 3H), 1.72-1.63 (m, 2H), 0.98 (t, J = 7.5 Hz, 3H).

Synthesis Example 2 Compound (4-1) was synthesized by the following method.

Step 1 Add compound (T-11) (25.0 g), acrylic acid (7.14 g), 4-dimethylaminopyridine (DMAP (4-dimethylaminopyridine); 1.21 g) and dichloromethane (300 ml) to In the reactor, it was cooled to 0 ° C. A solution of 1,3-dicyclohexylcarbodiimide (DCC (1,3-dicyclohexyl carbodiimide; 24.5 g) in dichloromethane (125 ml) was slowly added dropwise thereto, and stirred while returning to room temperature for 12 hour. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with dichloromethane. The organic layers produced together were washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, heptane: toluene = 2: 1). Further, it was purified by recrystallization from Solmix (registered trademark) A-11 to obtain a compound (T-12) (11.6 g; 38%). Furthermore, Solmix (registered trademark) A-11 is a mixture of ethanol (85.5%), methanol (13.4%), and isopropanol (1.1%), which was obtained from the Japanese alcohol sales (stock) .

In the second step, paraformaldehyde (2.75 g), 1,4-diazabicyclo [2.2.2] octane (DABCO (1,4-diazabicyclo [2.2.2] octane); 4.62 g) and Water (40 ml) was added to the reactor and stirred at room temperature for 15 minutes. A solution of the compound (T-12) (6.31 g) in THF (90 ml) was added dropwise thereto, and the mixture was stirred at room temperature for 72 hours. The reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The organic layers produced together were washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene: ethyl acetate = 5: 1). Further, it was purified by recrystallization (volume ratio, heptane: toluene = 1: 1) to obtain compound (4-1) (1.97 g; 29%).

¹ H-NMR of compound (6-1): chemical shift δ (ppm; CDCl ₃ ): 6.23 (s, 1H), 5.79 (d, J = 1.2 Hz, 1H), 4.79-4.70 (m, 1H), 4.32 (d, J = 6.7 Hz, 2H), 2.29 (t, J = 6.7 Hz, 1H), 2.07-2.00 (m, 2H), 1.83-1.67 (m, 6H), 1.42-1.18 (m, 8H) , 1.18-0.91 (m, 9H), 0.91-0.79 (m, 5H).

Examples of the composition are shown below. The component compounds are represented by symbols based on the definitions in Table 3 below. In Table 3, the stereo configuration related to 1,4-cyclohexyl is a trans configuration. The number in parentheses after the marked compound indicates the chemical formula to which the compound belongs. The symbol (-) refers to another liquid crystal compound. The ratio (percentage) of the liquid crystalline compound is a weight percentage (% by weight) based on the weight of the liquid crystal composition containing no additives. Finally, the characteristic values of the composition are summarized.

Example of device 1. Raw material A component to which a polar compound is added is injected into a device having no alignment film. After irradiating ultraviolet rays, the vertical alignment of liquid crystal molecules in the device was investigated. First, the raw materials will be described. The raw materials are appropriately selected from the composition M1 to the composition M18, the polar compound (PC-1) to the polar compound (PC-22), and the polymerizable compound (RM-1) to the polymerizable compound (RM-7). The composition is as follows.

[Composition M1] 3-HB (2F, 3F) -O2 (1-1) 10% 5-HB (2F, 3F) -O2 (1-1) 7% 2-BB (2F, 3F) -O2 ( 1-4) 7% 3-BB (2F, 3F) -O2 (1-4) 7% 3-B (2F, 3F) B (2F, 3F) -O2 (1-5) 3% 2-HHB ( 2F, 3F) -O2 (1-6) 5% 3-HHB (2F, 3F) -O2 (1-6) 10% 2-HBB (2F, 3F) -O2 (1-10) 8% 3-HBB (2F, 3F) -O2 (1-10) 10% 2-HH-3 (2-1) 14% 3-HB-O1 (2-2) 5% 3-HHB-1 (2-5) 3% 3-HHB-O1 (2-5) 3% 3-HHB-3 (2-5) 4% 2-BB (F) B-3 (2-8) 4% NI = 73.2 ℃; Tc <-20 ℃; Δn = 0.113; Δε = -4.0; Vth = 2.18 V; η = 22.6 mPa × s.

[Composition M2] 3-HB (2F, 3F) -O4 (1-1) 6% 3-H2B (2F, 3F) -O2 (1-2) 8% 3-H1OB (2F, 3F) -O2 ( 1-3) 4% 3-BB (2F, 3F) -O2 (1-4) 7% 2-HHB (2F, 3F) -O2 (1-6) 7% 3-HHB (2F, 3F) -O2 (1-6) 7% 3-HH2B (2F, 3F) -O2 (1-7) 7% 5-HH2B (2F, 3F) -O2 (1-7) 4% 2-HBB (2F, 3F)- O2 (1-10) 5% 3-HBB (2F, 3F) -O2 (1-10) 5% 4-HBB (2F, 3F) -O2 (1-10) 6% 2-HH-3 (2- 1) 12% 1-BB-5 (2-3) 12% 3-HHB-1 (2-5) 4% 3-HHB-O1 (2-5 3% 3-HBB-2 (2-6) 3% NI = 82.8 ℃; Tc <-30 ℃; Δn = 0.118; Δε = -4.4; Vth = 2.13 V; η = 22.5 mPa × s.

[Composition M3] 3-HB (2F, 3F) -O2 (1-1) 7% 5-HB (2F, 3F) -O2 (1-1) 7% 3-BB (2F, 3F) -O2 ( 1-4) 8% 3-HHB (2F, 3F) -O2 (1-6) 5% 5-HHB (2F, 3F) -O2 (1-6) 4% 3-HH1OB (2F, 3F) -O2 (1-8) 4% 2-BB (2F, 3F) B-3 (1-9) 5% 2-HBB (2F, 3F) -O2 (1-10) 3% 3-HBB (2F, 3F) -O2 (1-10) 8% 4-HBB (2F, 3F) -O2 (1-10) 5% 5-HBB (2F, 3F) -O2 (1-10) 8% 3-HH-V (2 -1) 27% 3-HH-V1 (2-1) 6% V-HHB-1 (2-5) 3% NI = 78.1 ℃; Tc <-30 ℃; Δn = 0.107; Δε = -3. 2; Vth = 2.02 V; η = 15.9 mPa × s.

[Composition M4] 3-HB (2F, 3F) -O2 (1-1) 10% 5-HB (2F, 3F) -O2 (1-1) 10% 3-H2B (2F, 3F) -O2 ( 1-2) 8% 5-H2B (2F, 3F) -O2 (1-2) 8% 2-HBB (2F, 3F) -O2 (1-10) 6% 3-HBB (2F, 3F) -O2 (1-10) 8% 4-HBB (2F, 3F) -O2 (1-10) 7% 5-HBB (2F, 3F) -O2 (1-10) 7% 3-HDhB (2F, 3F)- O2 (1-16) 5% 3-HH-4 (2-1) 14% V-HHB-1 (2-5) 10% 3-HBB-2 (2-6) 7% NI = 88.5 ℃; Tc <-30 ° C; Δn = 0.108; Δε = -3.8; Vth = 2.25 V; η = 24.6 mPa × s; VHR-1 = 99.1%; VHR-2 = 98.2%; VHR-3 = 97.8%.

[Composition M5] 3-HB (2F, 3F) -O2 (1-1) 7% 3-HB (2F, 3F) -O4 (1-1) 8% 3-H2B (2F, 3F) -O2 ( 1-2) 8% 3-BB (2F, 3F) -O2 (1-4) 10% 2-HHB (2F, 3F) -O2 (1-6) 4% 3-HHB (2F, 3F) -O2 (1-6) 7% 3-HHB (2F, 3F) -1 (1-6) 6% 2-HBB (2F, 3F) -O2 (1-10) 6% 3-HBB (2F, 3F)- O2 (1-10) 6% 4-HBB (2F, 3F) -O2 (1-10) 5% 5-HBB (2F, 3F) -O2 (1-10) 4% 3-HEB (2F, 3F) B (2F, 3F) -O2 (1-11) 3% 3-H1OCro (7F, 8F) -5 (1-14) 3% 3-HDhB (2F, 3F) -O2 (1-16) 5% 3 -HH-O1 (2-1) 5% 1-BB-5 (2-3) 4% V-HHB-1 (2-5) 4% 5-HB (F) BH-3 (2-12) 5% NI = 81.1 ℃; Tc <-30 ℃ Δn = 0.119; Δε = -4.5; Vth = 1.69 V; η = 31.4 mPa × s.

[Composition M6] 3-HB (2F, 3F) -O4 (1-1) 15% 3-HBB (2F, 3F) -O2 (1-10) 8% 4-HBB (2F, 3F) -O2 ( 1-10) 5% 5-HBB (2F, 3F) -O2 (1-10) 7% 3-dhBB (2F, 3F) -O2 (1-17) 5% 3-chB (2F, 3F) -O2 (1-18) 7% 2-HchB (2F, 3F) -O2 (1-19) 8% 5-HH-V (2-1) 18% 7-HB-1 (2-2) 5% V- HHB-1 (2-5) 7% V2-HHB-1 (2-5) 7% 3-HBB (F) B-3 (2-13) 8% NI = 98.8 ℃; Tc <-30 ℃; Δn = 0.111; Δε = -3.2; Vth = 2.47 V; η = 23.9 mPa × s.

[Composition M7] 3-H2B (2F, 3F) -O2 (1-2) 18% 5-H2B (2F, 3F) -O2 (1-2) 17% 3-HHB (2F, 3Cl) -O2 ( 1-12) 5% 3-HBB (2F, 3Cl) -O2 (1-13) 8% 5-HBB (2F, 3Cl) -O2 (1-13) 7% 3-HDhB (2F, 3F) -O2 (1-16) 5% 3-HH-V (2-1) 11% 3-HH-VFF (2-1) 7% F3-HH-V (2-1) 10% 3-HHEH-3 (2 -4) 4% 3-HB (F) HH-2 (2-10) 4% 3-HHEBH-3 (2-11) 4% NI = 77.5 ℃; Tc <-30 ℃; Δn = 0.084; Δε = -2.6; Vth = 2.43 V; η = 22.8 mPa × s.

[Composition M8] 3-HB (2F, 3F) -O2 (1-1) 8% 3-H2B (2F, 3F) -O2 (1-2) 10% 3-BB (2F, 3F) -O2 ( 1-4) 10% 2O-BB (2F, 3F) -O2 (1-4) 3% 2-HHB (2F, 3F) -O2 (1-6) 4% 3-HHB (2F, 3F) -O2 (1-6) 7% 2-HHB (2F, 3F) -1 (1-6) 5% 2-BB (2F, 3F) B-3 (1-9) 6% 2-BB (2F, 3F) B-4 (1-9) 6% 2-HBB (2F, 3F) -O2 (1-10) 4% 3-HBB (2F, 3F) -O2 (1-10) 7% 3-HH1OCro (7F, 8F) -5 (1-15) 4% 3-HDhB (2F, 3F) -O2 (1-16) 6% 3-dhBB (2F, 3F) -O2 (1-17) 4% 3-HH-V (2-1) 11% 1-BB-5 (2-3) 5% NI = 70.6 ℃; Tc <-20 ℃; Δn = 0.129; Δε = -4.3; Vth = 1.69 V; η = 27.0 mPa × s.

[Composition M9] 3-HB (2F, 3F) -O4 (1-1) 14% 3-H1OB (2F, 3F) -O2 (1-3) 3% 3-BB (2F, 3F) -O2 ( 1-4) 10% 2-HHB (2F, 3F) -O2 (1-6) 7% 3-HHB (2F, 3F) -O2 (1-6) 7% 3-HH1OB (2F, 3F) -O2 (1-8) 6% 2-HBB (2F, 3F) -O2 (1-10) 4% 3-HBB (2F, 3F) -O2 (1-10) 6% 4-HBB (2F, 3F)- O2 (1-10) 4% 3-HH-V (2-1) 14% 1-BB-3 (2-3) 3% 3-HHB-1 (2-5) 4% 3-HHB-O1 ( 2-5) 4% V-HBB-2 (2-6) 4% 1-BB (F) B-2V (2-8) 6% 5-HBBH-1O1 (-) 4% NI = 93.0 ℃; Tc <-30 ℃; Δn = 0.123; Δε = -4.0; Vth = 2.27 V; η = 29.6 mPa × s.

[Composition M10] 3-HB (2F, 3F) -O4 (1-1) 6% 3-H2B (2F, 3F) -O2 (1-2) 8% 3-H1OB (2F, 3F) -O2 ( 1-3) 5% 3-BB (2F, 3F) -O2 (1-4) 10% 2-HHB (2F, 3F) -O2 (1-6) 7% 3-HHB (2F, 3F) -O2 (1-6) 7% 5-HHB (2F, 3F) -O2 (1-6) 7% 2-HBB (2F, 3F) -O2 (1-10) 4% 3-HBB (2F, 3F)- O2 (1-10) 7% 5-HBB (2F, 3F) -O2 (1-10) 6% 3-HH-V (2-1) 11% 1-BB-3 (2-3) 6% 3 -HHB-1 (2-5) 4% 3-HHB-O1 (2-5) 4% 3-HBB-2 (2-6) 4% 3-B (F) BB-2 (2-7) 4% NI = 87.6 ℃; Tc <-30 ℃; Δn = 0.126; Δε = -4.5; Vth = 2.21 V; η = 25.3 mPa × s.

[Composition M11] 3-HB (2F, 3F) -O4 (1-1) 6% 3-H2B (2F, 3F) -O2 (1-2) 8% 3-H1OB (2F, 3F) -O2 ( 1-3) 4% 3-BB (2F, 3F) -O2 (1-4) 7% 2-HHB (2F, 3F) -O2 (1-6) 6% 3-HHB (2F, 3F) -O2 (1-6) 10% 5-HHB (2F, 3F) -O2 (1-6) 8% 2-HBB (2F, 3F) -O2 (1-10) 5% 3-HBB (2F, 3F)- O2 (1-10) 7% 5-HBB (2F, 3F) -O2 (1-10) 5% 2-HH-3 (2-1) 12% 1-BB-3 (2-3) 6% 3 -HHB-1 (2-5) 3% 3-HHB-O1 (2-5) 4% 3-HBB-2 (2-6) 6% 3-B (F) BB-2 (2-7) 3% NI = 93.0 ℃; Tc <-20 ℃; Δn = 0.124; Δε = -4.5; Vth = 2.22 V; η = 25.0 mPa × s.

[Composition M12] 3-HB (2F, 3F) -O2 (1-1) 7% 5-HB (2F, 3F) -O2 (1-1) 7% 3-BB (2F, 3F) -O2 ( 1-4) 8% 3-HHB (2F, 3F) -O2 (1-6) 4% 5-HHB (2F, 3F) -O2 (1-6) 5% 3-HH1OB (2F, 3F) -O2 (1-8) 5% 2-BB (2F, 3F) B-3 (1-9) 4% 2-HBB (2F, 3F) -O2 (1-10) 3% 3-HBB (2F, 3F) -O2 (1-10) 8% 4-HBB (2F, 3F) -O2 (1-10) 5% 5-HBB (2F, 3F) -O2 (1-10) 8% 3-HH-V (2 -1) 33% V-HHB-1 (2-5) 3% NI = 76.4 ℃; Tc <-30 ℃; Δn = 0.104; Δε = -3.2; Vth = 2.06 V; η = 15.6 mPa × s.

[Composition M13] 2-H1OB (2F, 3F) -O2 (1-3) 6% 3-H1OB (2F, 3F) -O2 (1-3) 4% 3-BB (2F, 3F) -O2 ( 1-4) 3% 2-HH1OB (2F, 3F) -O2 (1-8) 14% 2-HBB (2F, 3F) -O2 (1-10) 7% 3-HBB (2F, 3F) -O2 (1-10) 11% 5-HBB (2F, 3F) -O2 (1-10) 9% 2-HH-3 (2-1) 5% 3-HH-VFF (2-1) 30% 1- BB-3 (2-3) 5% 3-HHB-1 (2-5) 3% 3-HBB-2 (2-6) 3% NI = 78.3 ℃; Tc <-20 ℃; Δn = 0.103; Δε = -3.2; Vth = 2.17 V; η = 17.7 mPa × s.

[Composition M14] 3-HB (2F, 3F) -O2 (1-1) 5% 5-HB (2F, 3F) -O2 (1-1) 7% 3-BB (2F, 3F) -O2 ( 1-4) 8% 3-HHB (2F, 3F) -O2 (1-6) 5% 5-HHB (2F, 3F) -O2 (1-6) 4% 3-HH1OB (2F, 3F) -O2 (1-8) 5% 2-BB (2F, 3F) B-3 (1-9) 4% 2-HBB (2F, 3F) -O2 (1-10) 3% 3-HBB (2F, 3F) -O2 (1-10) 9% 4-HBB (2F, 3F) -O2 (1-10) 4% 5-HBB (2F, 3F) -O2 (1-10) 8% 3-HH-V (2 -1) 27% 3-HH-V1 (2-1) 6% V-HHB-1 (2-5) 5% NI = 81.2 ℃; Tc <-20 ℃; Δn = 0.107; Δε = -3 .2; Vth = 2.11 V; η = 15.5 mPa × s.

[Composition M15] 3-H2B (2F, 3F) -O2 (1-2) 7% 3-HHB (2F, 3F) -O2 (1-6) 8% 3-HH1OB (2F, 3F) -O2 ( 1-8) 5% 2-BB (2F, 3F) B-3 (1-9) 7% 2-BB (2F, 3F) B-4 (1-9) 7% 3-HDhB (2F, 3F) -O2 (1-16) 3% 5-HDhB (2F, 3F) -O2 (1-16) 4% 2-HchB (2F, 3F) -O2 (1-19) 8% 4-HH-V (2 -1) 15% 3-HH-V1 (2-1) 6% 1-HH-2V1 (2-1) 6% 3-HH-2V1 (2-1) 4% V2-BB-1 (2-3 ) 5% 1V2-BB-1 (2-3) 5% 3-HHB-1 (2-5) 6% 3-HB (F) BH-3 (2-12) 4% NI = 88.7 ℃; Tc <-30 ℃; Δn = 0.115; Δε = -1.9; Vth = 2.82 V; η = 17.3 mPa × s.

[Composition M16] V2-H2B (2F, 3F) -O2 (1-2) 8% V2-H1OB (2F, 3F) -O4 (1-3) 4% 3-BB (2F, 3F) -O2 ( 1-4) 7% 2-HHB (2F, 3F) -O2 (1-6) 7% 3-HHB (2F, 3F) -O2 (1-6) 7% 3-HH2B (2F, 3F) -O2 (1-7) 7% 5-HH2B (2F, 3F) -O2 (1-7) 4% V-HH2B (2F, 3F) -O2 (1-7) 6% V2-HBB (2F, 3F)- O2 (1-10) 5% V-HBB (2F, 3F) -O2 (1-10) 5% V-HBB (2F, 3F) -O4 (1-10) 6% 2-HH-3 (2- 1) 12% 1-BB-5 (2-3) 12% 3-HHB-1 (2-5) 4% 3-HHB-O1 (2-5) 3% 3-HBB-2 (2-6) 3% NI = 89.9 ℃; Tc <-20 ℃; Δn = 0.122; Δε = -4.2; Vth = 2.16 V; η = 23.4 mPa × s.

[Composition M17] 3-HB (2F, 3F) -O2 (1-1) 3% V-HB (2F, 3F) -O2 (1-1) 3% V2-HB (2F, 3F) -O2 ( 1-1) 5% 5-H2B (2F, 3F) -O2 (1-2) 5% V2-BB (2F, 3F) -O2 (1-4) 3% 1V2-BB (2F, 3F) -O2 (1-4) 3% 3-HHB (2F, 3F) -O2 (1-6) 6% V-HHB (2F, 3F) -O2 (1-6) 6% V-HHB (2F, 3F)- O4 (1-6) 5% V2-HHB (2F, 3F) -O2 (1-6) 4% V2-BB (2F, 3F) B-1 (1-9) 4% V2-HBB (2F, 3F ) -O2 (1-10) 5% V-HBB (2F, 3F) -O2 (1-10) 4% V-HBB (2F, 3F) -O4 (1-10) 5% V-HHB (2F, 3Cl) -O2 (1-12) 3% 3-HH- V (2-1) 27% 3-HH-V1 (2-1) 6% V-HHB-1 (2-5) 3% NI = 77.1 ℃; Tc <-20 ℃; Δn = 0.101; Δε =- 3.0; Vth = 2.04 V; η = 13.9 mPa × s.

[Composition M18] V-HB (2F, 3F) -O2 (1-1) 10% V2-HB (2F, 3F) -O2 (1-1) 10% 2-H1OB (2F, 3F) -O2 ( 1-3) 3% 3-H1OB (2F, 3F) -O2 (1-3) 3% 2O-BB (2F, 3F) -O2 (1-4) 3% V2-BB (2F, 3F) -O2 (1-4) 8% V2-HHB (2F, 3F) -O2 (1-6) 5% 2-HBB (2F, 3F) -O2 (1-10) 3% 3-HBB (2F, 3F)- O2 (1-10) 3% V-HBB (2F, 3F) -O2 (1-10) 6% V-HBB (2F, 3F) -O4 (1-10) 8% V-HHB (2F, 3Cl) -O2 (1-12) 7% 3-HH-4 (2-1) 14% V-HHB-1 (2-5) 10% 3-HBB-2 (2-6) 7% NI = 75.9 ℃; Tc <-20 ℃; Δn = 0.114; Δε = -3.9; Vth = 2.20 V; η = 24.7 mPa × s.

The first additive is a polar compound (PC-1) to a polar compound (PC-22).

The second additive is a polymerizable compound (RM-1) to a polymerizable compound (RM-7).

2. Vertical alignment of liquid crystal molecules Example 1 A polar compound (PC-1) was added to the composition M1 at a ratio of 5% by weight, and a polymerizable compound (RM-1) was further added to the composition at a ratio of 0.5% by weight.物 M1。 Object M1. This mixture was injected on a hot stage at 100 ° C. into a device having an interval (cell gap) between two glass substrates of 4.0 μm without an alignment film. The device was polymerized with a polar compound (PC-1) and a polymerizable compound (RM-1) by irradiating the device with ultraviolet rays (28 J) using an ultrahigh-pressure mercury lamp USH-250-BY (made by Ushio Electric). This element was placed in a polarizing microscope in which a polarizing element and an analyzer were orthogonally arranged, and the element was irradiated with light from below to observe the presence or absence of light leakage. When light does not pass through the element, the vertical alignment is judged to be "good". This is because the liquid crystal molecules are presumed to be sufficiently aligned. When the light transmitted through the device was observed, it was expressed as "defective".

Examples 2 to 22 and Comparative Example 1 A device without an alignment film was produced using a mixture of a composition, a polar compound, and a polymerizable compound. The presence or absence of light leakage was observed in the same manner as in Example 1. The results are summarized in Table 4. In Comparative Example 1, for comparison, a polar compound having a polymerizable group was not added.

Table 4. Vertical alignment of liquid crystal molecules

As is clear from Table 4, although the types of the composition, the polar compound, or the polymerizable compound were changed in Examples 1 to 22, no light leakage was observed. This result indicates that even if there is no alignment film in the device, the vertical alignment is good, and the liquid crystal molecules are stably aligned. On the other hand, in Comparative Example 1, light leakage was observed. This result indicates that the vertical alignment is not good. Therefore, it is understood that the polymer produced from the polar compound having a polymerizable group and the polymerizable compound plays an important role in the vertical alignment of the liquid crystal molecules. [Industrial availability]

The liquid crystal composition of the present invention can be used in a liquid crystal projector, a liquid crystal television, and the like.

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Claims (20)

A liquid crystal composition includes a polar compound having at least one polymerizable group as a first additive and a polymerizable compound having at least three polymerizable groups as a second additive, and has negative dielectric anisotropy. The liquid crystal composition according to item 1 of the scope of patent application, which contains, as a first component, at least one compound selected from the group of compounds represented by formula (1),

In formula (1), R ¹ and R ^{2 are} independently 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, and at least one hydrogen is substituted with fluorine or chlorine Alkenyl having 2 to 12 carbon atoms, or alkenyloxy having 2 to 12 carbon atoms; ring A and ring C are independently 1,4-cyclohexyl, 1,4-cyclohexenyl, tetrahydropyridine Ran-2,5-diyl, 1,4-phenylene, at least one hydrogen substituted by fluorine or chlorine, 1,4-phenylene, naphthalene-2,6-diyl, at least one hydrogen substituted by fluorine or chlorine Substituted naphthalene-2,6-diyl, chromogen-2,6-diyl, or chromogen-2,6-diyl with at least one hydrogen substituted by fluorine or chlorine; ring B 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 or 7,8-difluorochromogen-2,6-diyl; Z ¹ and Z ^{2 are} independently a single bond, -CH ₂ CH ₂ -,- CH ₂ O-, -OCH _2- , -COO-, or -OCO-; a is 1, 2 or 3, b is 0 or 1, and the sum of a and b is 3 or less. The liquid crystal composition according to item 2 of the scope of patent application, which contains at least one compound selected from the group of compounds represented by formula (1-1) to formula (1-22) as the first component,

In formulae (1-1) to (1-22), R ¹ and R ^{2 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. , At least one hydrogen substituted with fluorine or chlorine, an alkenyl group having 2 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms. The liquid crystal composition according to item 2 of the scope of patent application, wherein the proportion of the first component is in a range of 10% by weight to 90% by weight based on the weight of the liquid crystal composition. The liquid crystal composition according to item 1 of the scope of patent application, which contains at least one compound selected from the group of compounds represented by formula (2) as a second component,

In formula (2), R ³ and R ^{4 are} independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, an alkenyl group having 2 to 12 carbons, and at least one hydrogen is substituted with fluorine or chlorine Alkyl group having 1 to 12 carbon atoms, or alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine; ring D and ring E are independently 1,4-cyclohexyl, 1,4-cyclohexyl Phenyl, 2-fluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene; Z ³ is a single bond, -CH ₂ CH _2- , -CH ₂ O-,- OCH _2- , -COO- or -OCO-; c is 1, 2 or 3. The liquid crystal composition according to item 5 of the scope of patent application, which contains at least one compound selected from the group of compounds represented by formula (2-1) to formula (2-13) as the second component,

In the formulae (2-1) to (2-13), R ³ and R ^{4 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. , At least one hydrogen having 1 to 12 carbons substituted with fluorine or chlorine, or at least one hydrogen having 2 to 12 carbons substituted with fluorine or chlorine. The liquid crystal composition according to item 5 of the scope of patent application, wherein the proportion of the second component is in the range of 10% by weight to 70% by weight based on the weight of the liquid crystal composition. The liquid crystal composition according to item 1 of the scope of patent application, wherein the first additive is a polar compound having a hetero atom selected from nitrogen, oxygen, sulfur, and phosphorus. The liquid crystal composition according to item 1 of the scope of patent application, which contains at least one compound selected from the group of polar compounds represented by formula (3) and formula (4) as the first additive,

In the formula (3), R ⁷ is hydrogen, fluorine, chlorine, or an alkyl group having 1 to 25 carbon atoms. Among the alkyl groups, at least one -CH ₂ -may pass through -NR ^0- , -O-, -S- , -CO-, -CO-O-, -O-CO-, -O-CO-O-, or a cycloalkyl group with 3 to 8 carbon atoms, and at least one tertiary carbon (> CH-) can be replaced by Nitrogen (> N-) substitution. Among these groups, at least one hydrogen may be substituted by fluorine or chlorine. Here, R ⁰ is hydrogen or an alkyl group having 1 to 12 carbons; R ⁸ is an oxygen atom having an OH structure, Polar group of at least one of sulfur atom of SH structure and nitrogen atom of primary, secondary or tertiary amine structure; ring J, ring K and ring L are independently 1,4-cyclohexyl, 1,4- Cyclohexenyl, 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, the In these rings, at least one hydrogen may be substituted with fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or carbon in which at least one hydrogen is substituted with fluorine or chlorine 1 to 12 alkyl groups are substituted; Z ⁷ and Z ^{8 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, at least one of -CH ₂ -may be -O-,- CO-, -COO-, or -OCO-, and at least one -CH ₂ CH ₂ -can be via -CH = CH-, -C (CH ₃ ) = CH-, -CH = C (CH ₃ )-or- C (CH ₃ ) = C (CH ₃ ) -substitution. Among these groups, at least one hydrogen may be substituted by fluorine or chlorine; P ¹ , P ² and P ³ are polymerizable groups; Sp ¹ , Sp ² and Sp ³ Independently a single bond or an alkylene group having 1 to 10 carbons, at least one of -CH ₂ -of which may be substituted with -O-, -COO-, -OCO-, or -OCOO-, and at least One -CH ₂ CH ₂ -may be substituted by -CH = CH- or -C≡C-. Among these groups, at least one hydrogen may be substituted by fluorine or chlorine; g and h are independently 0, 1, 2, 3 Or 4, and the sum of g and h is 0, 1, 2, 3, or 4; k and p are independently 0, 1, 2, 3, or 4, and o is 1, 2, 3, or 4; Formula (4) In the formula, R ⁹ is hydrogen, fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or a carbon number in which at least one hydrogen is replaced by fluorine or chlorine 1 to 12 alkyl groups, or at least one hydrogen alkenyl group having 2 to 12 carbon atoms substituted with fluorine or chlorine R ¹⁰ is _{^{-OH, -OR 0, -NH 2,}} -NHR 0 , or -N (R ⁰⁾ ₂ group represented by where, R ⁰ is hydrogen or an alkyl group having 1 to 12 carbon atoms; the ring M and Ring N is independently 1,4-cyclohexyl, 1,4-cyclohexenyl, 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, pyridine-2,5-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, or anthracene-2,6-diyl, at least one of these rings Hydrogen may be substituted with fluorine, chlorine, an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or at least one hydrogen substituted with an alkyl group having 1 to 12 carbons with fluorine or chlorine; Z ⁹ is mono Bond, -CH ₂ CH _2- , -CH = CH-, -C≡C-, -COO-, -OCO-, -CF ₂ O-, -OCF _2- , -CH ₂ O-, -OCH _2- Or -CF = CF-; Sp ⁴ and Sp ^{5 are} independently a single bond or an alkylene group having 1 to 7 carbon atoms. Among the alkylene groups, at least one -CH ₂ -can pass through -O-, -COO- or -OCO-, at least one -CH ₂ CH ₂ - may be replaced by -CH = CH-, the plurality of groups, at least Hydrogen may be replaced by fluorine; J 3, or 4. The liquid crystal composition according to item 9 of the scope of patent application, wherein in formula (3) as described in item 9 of the scope of patent application, R ⁸ is a polar group selected from the group consisting of formula (A1) to formula (A4) Base in group,

In formulas (A1) to (A4), Sp ⁶ , Sp ^8, and Sp ^{9 are} independently a single bond or an alkylene group having 1 to 12 carbon atoms. Among the alkylene groups, at least one of -CH ₂ -may pass through -O-, -S-, -NH-, -N (R ⁰ )-, -CO-, -CO-O-, -O-CO, -O-CO-O-, -S-CO-,- CO-S-, -N (R ⁰ ) -CO-O-, -O-CO-N (R ⁰ )-, -N (R ⁰ ) -CO-N (R ⁰ )-, -CH = CH- Or -C≡C- substitution. Among these groups, at least one hydrogen may be substituted by fluorine or chlorine. Here, R ⁰ is hydrogen or an alkyl group having 1 to 12 carbon atoms; Sp ⁷ is>CH-,> CR ⁰ -,> N- or> C <, where R ⁰ is hydrogen or an alkyl group having 1 to 12 carbons; X ¹⁷ is -OH, -OR ⁰ , -COOH, -NH ₂ , -NHR ⁰ , -N (R ⁰ ) ₂ , -SH, -SR ⁰ ,

Here, R ⁰ is hydrogen or an alkyl group having 1 to 12 carbons; X ¹⁸ is -O-, -CO-, -NH-, -NR ^0- , -S-, or a single bond; here, R ⁰ Is hydrogen or an alkyl group having 1 to 12 carbons; Z ¹⁰ is a single bond or an alkylene group having 1 to 15 carbons, and at least one -CH ₂ -in the alkylene group may pass through -C≡C-,- CH = CH-, -COO-, -OCO-, -CO- or -O-, at least one of these groups may be substituted with fluorine or chlorine; ring P is an aryl group having 6 to 25 carbon atoms, so In the aryl group, one to three hydrogens may be substituted with -OH,-(CH ₂ ) _q -OH, fluorine, chlorine, an alkyl group having 1 to 5 carbon atoms, or at least one hydrogen substituted with fluorine or chlorine having a carbon number 1 Alkyl substitution to 5, where q is 1, 2, 3 or 4; n is 0, 1, 2 or 3; m is 1, 2, 3, 4 or 5. The liquid crystal composition according to item 9 of the scope of patent application, wherein in the formula (3) described in item 9 of the scope of patent application, P ¹ , P ² and P ^{3 are} independently selected from the formula (P-1) To a group in the group of polymerizable groups represented by formula (P-5),

In the formulae (P-1) to (P-5), M ¹ , M ² and M ^{3 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbons, or a carbon in which at least one hydrogen is replaced by fluorine or chlorine. Number 1 to 5 alkyl. The liquid crystal composition according to item 9 of the scope of patent application, wherein the first additive is at least one compound selected from the group of polar compounds represented by formula (3-1) to formula (3-15) ,

In the formulae (3-1) to (3-15), R ⁷ is hydrogen, fluorine, chlorine, or an alkyl group having 1 to 25 carbon atoms. At least one of the alkyl groups may be -CH ₂ -via -NR ⁰ -, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, or a cycloalkylene group having 3 to 8 carbon atoms, and at least one of three The higher carbon (> CH-) may be substituted by nitrogen (> N-). Among these groups, at least one hydrogen may be substituted by fluorine or chlorine. Here, R ⁰ is hydrogen or an alkyl group having 1 to 12 carbons; Sp ² is a single bond or an alkylene group having 1 to 10 carbon atoms, at least one -CH ₂ -of which may be substituted with -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ CH ₂ -may be substituted by -CH = CH- or -C≡C-, in these groups, at least one hydrogen may be substituted by fluorine or chlorine; Sp ¹⁰ is a single bond or an alkylene having 1 to 10 carbon atoms Group, in the alkylene group, at least one -CH ₂ -may be substituted by -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ CH ₂ -may be -CH = CH- Or -C≡C- substitution, in these groups, at least one hydrogen may be substituted by fluorine or chlorine; L ¹ , L ² , L ³ and L ^{4 are} independently hydrogen, fluorine, methyl or ethyl; R ¹¹ and R ^{12 is} independently hydrogen or methyl. The liquid crystal composition according to item 9 of the scope of patent application, wherein the first additive is at least one compound selected from the group of polar compounds represented by formula (4-1) to formula (4-9) ,

In the formulae (4-1) to (4-9), R ⁹ is hydrogen, fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an olefin having 2 to 12 carbon atoms. Group, at least one hydrogen group having 1 to 12 carbon atoms substituted with fluorine or chlorine, or at least one hydrogen group having 2 to 12 carbon atoms substituted with fluorine or chlorine; Z ⁹ is a single bond, -CH ₂ CH ₂ -, -CH = CH-, -C≡C-, -COO-, -OCO-, -CF ₂ O-, -OCF _2- , -CH ₂ O-, -OCH _2- , or -CF = CF-; Sp ⁴ and Sp ^{5 are} independently a single bond or an alkylene group having 1 to 7 carbon atoms, and at least one of -CH ₂ -may be substituted with -O-, -COO-, or -OCO-, at least One -CH ₂ CH ₂ -may be substituted by -CH = CH-. Among these groups, at least one hydrogen may be substituted by fluorine; L ⁵ , L ⁶ , L ⁷ , L ⁸ , L ⁹ , L ¹⁰ , L ¹¹ , L ¹² , L ¹³ , L ¹⁴ , L ¹⁵ and L ^{16 are} independently hydrogen, fluorine, methyl or ethyl. The liquid crystal composition according to item 1 of the scope of patent application, wherein the proportion of the first additive is in the range of 0.05% by weight to 10% by weight based on the weight of the liquid crystal composition. The liquid crystal composition according to item 1 of the scope of patent application, which contains at least one compound selected from the group of polymerizable compounds represented by formula (5) as the second additive,

In formula (5), ring T and ring V are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane Alk-2-yl, pyrimidin-2-yl or pyridin-2-yl, in these rings, at least one hydrogen may pass through fluorine, chlorine, alkyl having 1 to 12 carbons, and alkoxy having 1 to 12 carbons Or at least one hydrogen is substituted by fluorine or chlorine alkyl group having 1 to 12 carbons; ring U is 1,4-cyclohexyl, 1,4-cyclohexenyl, 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-di Group, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, at least one of these rings may be fluorine, chlorine, carbon 1 to 12 alkyl groups, 1 to 12 carbon alkoxy groups, or at least one hydrogen substituted with fluorine or chlorine 1 to 12 alkyl groups; Z ¹¹ and Z ^{12 are} independently a single bond or carbon 1 to 10 alkylene groups, at least one -CH ₂ -of which may be substituted with -O-, -CO-, -COO-, or -OCO-, and at least one -CH ₂ CH ₂ -may be substituted by -CH = CH-, -C (CH ₃ ) = CH-, -CH = C (CH ₃ )-, or -C (CH ₃ ) = C (CH ₃ )-, these groups At least one hydrogen may be substituted by fluorine or chlorine; P ⁴ , P ⁵ and P ⁶ are polymerizable groups; Sp ¹⁰ , Sp ¹¹ and Sp ^{12 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, so In the alkylene group, at least one -CH ₂ -may be substituted by -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ CH ₂ -may be substituted by -CH = CH- or -C. ≡C- substitution, in these groups, at least one hydrogen may be substituted by fluorine or chlorine; t is 0, 1 or 2; u, v, and w are independently 0, 1, 2, 3, or 4, and u, v And the sum of w is 3 or more. The liquid crystal composition according to item 15 of the scope of patent application, wherein in the formula (5) as described in item 15 of the scope of patent application, P ⁴ , P ⁵ and P ^{6 are} independently selected from the formula (P-1) To a group in the group of polymerizable groups represented by formula (P-5),

In the formulae (P-1) to (P-5), M ¹ , M ² and M ^{3 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbons, or a carbon in which at least one hydrogen is replaced by fluorine or chlorine. Number 1 to 5 alkyl. The liquid crystal composition according to item 15 of the scope of patent application, which contains at least one compound selected from the group of polymerizable compounds represented by formula (5-1) to formula (5-7) as the second Additives,

In Formulas (5-1) to (5-7), P ⁴ , P ^5, and P ^{6 are} independently selected from the group of polymerizable groups represented by Formulas (P-1) to (P-3) In the base,

Here, M ¹ , M ² and M ^{3 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbons, or an alkyl group having 1 to 5 carbons in which at least one hydrogen is replaced with fluorine or chlorine; Sp ¹⁰ , Sp ¹¹ and Sp ^{12 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, at least one of -CH ₂ -may pass through -O-, -COO-, -OCO-, or -OCOO- And at least one -CH ₂ CH ₂ -may be substituted with -CH = CH- or -C≡C-, and among these groups, at least one hydrogen may be substituted with fluorine or chlorine. The liquid crystal composition according to item 15 of the scope of patent application, wherein the proportion of the second additive is in the range of 0.03% by weight to 10% by weight based on the weight of the liquid crystal composition. A liquid crystal display element includes the liquid crystal composition according to item 1 of the scope of patent application. A liquid crystal display element without an alignment film, comprising the liquid crystal composition according to any one of claims 1 to 18 of the scope of patent application, and the first additive and the first additive in the liquid crystal composition. The second additive is polymerized.