TWI672332B - Liquid crystal composition, use thereof, and liquid crystal display device - Google Patents

Abstract

The present invention provides a liquid crystal composition containing a polymerizable compound (or a polymer thereof) and a polar compound, and achieving vertical alignment of liquid crystal molecules by the action of these compounds, and a liquid crystal display element containing the composition. The present invention is a nematic liquid crystal composition containing a polymerizable compound as a first additive and a polar compound as a second additive and having a negative dielectric anisotropy, and the composition may also contain a negative macromolecule. An anisotropic specific liquid crystal compound and a specific liquid crystal compound having a high upper limit temperature or a small viscosity, and a liquid crystal display element containing the composition.

Description

Liquid crystal composition and use thereof, and liquid crystal display element

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

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 electronically controlled birefringence (STN). electrically controlled birefringence (ECB), optically compensated bend (OCB), in-plane switching (IPS), vertical alignment (VA), fringe field switching (FFS), Field-induced photo-reactive alignment (FPA) and 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. TFT is classified as 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. A preferred upper limit temperature of the nematic phase is about 70 ° C or higher, and a preferred 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, large optical anisotropy or small optical anisotropy is required, ie Proper 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 is in the range of about 0.30 μm to about 0.40 μm, and in the IPS mode or FFS mode, the value is in the range of about 0.20 μm to about 0.30 μm. In these cases, a composition having a large optical anisotropy is 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 effectively using a polymer is obtained. 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. Polymerizable compounds are polymerized to form a polymer network in the composition 结构。 Structure. 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, a liquid crystal display element without an alignment film uses a liquid crystal composition containing a polymer and a polar compound. 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. With negative dielectric anisotropy Examples of the liquid crystal composition are disclosed in Patent Documents 1 to 3 below.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2003-307720

[Patent Document 2] Japanese Patent Laid-Open No. 2004-131704

[Patent Document 3] European Patent Application Publication No. 1889894

An object of the present invention is to provide a liquid crystal composition including a polymerizable compound (or a polymer thereof) and a polar compound, and achieving vertical alignment of liquid crystal molecules by the action of these compounds. Another object is a liquid crystal composition having a high upper limit temperature in the nematic phase, a low lower limit temperature in the nematic phase, a small viscosity, an appropriate optical anisotropy, a negative large dielectric anisotropy, a large Among the characteristics such as specific resistance, high stability to ultraviolet light, and high stability to heat, 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 such a composition. Still another object is an AM element having characteristics such as short response time, large voltage holding ratio, low threshold voltage, large contrast ratio, long life, and the like.

The present invention is a polymer containing at least one polymerizable compound selected from the group consisting of compounds represented by formula (1) as a first additive, and containing at least one polarizing compound. The compound serves as a second additive, and has a liquid crystal composition having negative dielectric anisotropy, and a liquid crystal display element containing the composition.

In formula (1), ring A and ring C 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 which at least one hydrogen may pass through fluorine, chlorine, alkyl having 1 to 12 carbons, and alkoxy having 1 to 12 carbons Group, or at least one hydrogen substituted with fluorine or chlorine, and an alkyl group having 1 to 12 carbons; ring B 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 , An alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or an alkyl group having 1 to 12 carbons in which at least one hydrogen is replaced with fluorine or chlorine; Z ¹ and Z ^{2 are} independently 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-, -CO-, -COO-, or -OCO-, and at least one -CH ₂ -CH ₂ -may be substituted with -CH = CH-, -C (CH ₃ ) = CH-, -CH = C (CH ₃ )-, or -C (CH ₃ ) = C (CH ₃ )-, these In the group, 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 a single bond or a carbon number of 1 to 10 Group, in the alkylene group, 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 through -CH = CH- or -C≡C- substitution, in these groups, at least one hydrogen may be substituted by fluorine or chlorine; a is 0, 1, or 2; b, c, and d are independently 0, 1, 2, 3 , Or 4; where ring A and ring C are phenyl, a is 1 or 2, and when a is 1, Sp ¹ and Sp ³ are single bonds.

The present invention is a polymer stable alignment type liquid crystal display device, which contains the liquid crystal composition, and polymerizable compounds in the liquid crystal composition are polymerized.

The present invention is a liquid crystal display element without an alignment film, which contains the liquid crystal composition, and a polymerizable compound in the liquid crystal composition is polymerized.

The present invention is a use of the liquid crystal composition, which is used in a liquid crystal display element.

The present invention is an application of the liquid crystal composition, and is used in a polymer-stable alignment type liquid crystal display element.

The present invention is a use of the liquid crystal composition, which is used in a liquid crystal display element without an alignment film.

An advantage of the present invention is a liquid crystal composition including a polymerizable compound (or a polymer thereof) and a polar compound, and the vertical alignment of liquid crystal molecules can be achieved by the action of these compounds. Another advantage is a liquid crystal composition, which is nematic High upper limit temperature of the phase, low lower limit temperature of the nematic phase, small viscosity, proper optical anisotropy, negative large dielectric anisotropy, large specific resistance, high stability to ultraviolet light, high heat resistance Among the characteristics such as high 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 such a composition. Yet another advantage is an AM element with characteristics such as short response time, large voltage retention, low threshold voltage, large contrast ratio, long life, and the like.

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 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 This sequence is mixed. 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 after a long-term use. It also has a large specific resistance at temperatures close to the upper limit temperature. "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 after long-term use, but also 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 a compound represented by formula (1) Compound, a mixture of two compounds, or a mixture of three or more compounds. 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'".

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 (2-1) is an ethyl group and R ¹ of the compound (2-2) is an ethyl group. In some cases, R ¹ of the compound (2-1) is an ethyl group, and R ¹ of the compound (2-2) is a propyl group. This rule also applies to other terminal group marks. In formula (2), when e is 2, two rings D exist. In this compound, the two rings represented by the two rings D may be the same or different. This rule also applies to any two rings D when e is greater than 2. This rule also applies to other tokens. This rule also applies to the case of two -Sp ² -P ² of compound (1-11).

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 (1), 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 'b' indicate the number of substituted groups. When the subscript 'b' is 0, it means that there is no such substitution. When the subscript 'b' is 2 or more, there are multiple -Sp ¹ -P ¹ on ring A. The multiple radicals represented by -Sp ¹ -P ¹ may be the same or different.

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 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 in this 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 group such as -CH = CH- or -COO-. In the formula (5), R ⁵ is an alkyl group having 4 to 20 carbon atoms, and at least one of -CH ₂ -in the alkyl group may be substituted with -CH = CH- or the like. By this substitution, the carbon number of the alkyl group increases. At this time, the maximum carbon number is 30. This rule also applies to alkylene, cycloalkylene, etc.

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. The stereo configuration associated with 1,4-cyclohexyl is usually trans The shape is better than the cis configuration. Halogen means fluorine, chlorine, bromine, and iodine. The preferred halogen is fluorine or chlorine. A particularly preferred halogen is fluorine.

The present invention includes the following items.

Item 1. A liquid crystal composition containing at least one polymerizable compound selected from the group of compounds represented by formula (1) as a first additive, at least one polar compound as a second additive, and Dielectric anisotropy,

In formula (1), ring A and ring C 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 which at least one hydrogen may pass through fluorine, chlorine, alkyl having 1 to 12 carbons, and alkoxy having 1 to 12 carbons Group, or at least one hydrogen substituted with fluorine or chlorine, and an alkyl group having 1 to 12 carbons; ring B 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 , An alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or an alkyl group having 1 to 12 carbons in which at least one hydrogen is replaced with fluorine or chlorine; Z ¹ and Z ^{2 are} independently 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-, -CO-, -COO-, or -OCO-, and at least one -CH ₂ -CH ₂ -may be substituted with -CH = CH-, -C (CH ₃ ) = CH-, -CH = C (CH ₃ )-, or -C (CH ₃ ) = C (CH ₃ )-, these In the group, 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 a single bond or a carbon number of 1 to 10 Group, in the alkylene group, 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 through -CH = CH- or -C≡C- substitution, in these groups, at least one hydrogen may be substituted by fluorine or chlorine; a is 0, 1, or 2; b, c, and d are independently 0, 1, 2, 3 , Or 4; where ring A and ring C are phenyl, a is 1 or 2, and when a is 1, Sp ¹ and Sp ³ are single bonds.

Item 2. The liquid crystal composition according to Item 1, wherein in Formula (1), P ¹ , P ² , and P ^{3 are} independently selected from the group consisting of Formulas (P-1) to (P-5) Polymerizable radicals in the group of radicals,

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 carbon atoms, or at least one hydrogen substituted by fluorine or chlorine. Alkyl having 1 to 5 carbons.

Item 3. The liquid crystal composition according to Item 1 or 2, wherein the first additive is at least one polymer selected from the group consisting of compounds represented by formula (1-1) to formula (1-12) Sex compounds,

In Formulas (1-1) to (1-12), P ¹ , P ² , and P ^{3 are} independently selected from the group consisting of the groups represented by Formulas (P-1) to (P-3) 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 by fluorine or chlorine. base;

Sp ¹ , Sp ² , and Sp ^{3 are} independently 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.

Item 4. The liquid crystal composition according to any one of Items 1 to 3, wherein the proportion of the first additive is in a range of 0.03% by weight to 10% by weight based on the weight of the liquid crystal composition.

Item 5. The liquid crystal composition according to any one of Items 1 to 4, which contains, as a first component, at least one compound selected from the group of compounds represented by Formula (2),

In formula (2), R ¹ and R ^{2 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, or an olefin having 2 to 12 carbons Oxygen; ring D and ring F are independently 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, 1,4- with at least one hydrogen substituted with fluorine or chlorine Phenylene, or tetrahydropyran-2,5-diyl; ring E is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene , 2,3-difluoro-5-methyl-1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, or 7,8-difluorochroman ) -2,6-diyl; Z ³ and Z ^{4 are} independently a single bond, -CH ₂ CH _2- , -CH ₂ O-, -OCH _2- , -COO-, or -OCO-; e is 1 , 2, or 3, f is 0 or 1, and the sum of e and f is 3 or less.

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 (2-21) as First ingredient,

In the formulae (2-1) to (2-21), 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. Or an alkenyloxy group having 2 to 12 carbon atoms.

Item 7. The liquid crystal composition according to Item 5 or 6, wherein the proportion of the first component is in a range of 10% by weight to 90% 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, which contains, as a second component, at least one compound selected from the group of compounds represented by formula (3),

In the formula (3), 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 G and ring I are independently 1,4-cyclohexyl, 1,4-cyclohexyl Phenyl, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene; Z ⁵ is a single bond, -CH ₂ CH _2- , -CH ₂ O-, -OCH _2- , -COO-, or -OCO-; g is 1, 2, or 3.

Item 9. The liquid crystal composition according to any one of Items 1 to 8, which contains at least one compound selected from the group of compounds represented by formula (3-1) to formula (3-13) as The second component,

In the formulae (3-1) to (3-13), 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 10. The liquid crystal composition according to Item 8 or 9, wherein the proportion of the second component is in the range of 10% by weight to 90% by weight based on the weight of the liquid crystal composition.

Item 11. The liquid crystal composition according to any one of Items 1 to 10, wherein the second additive is a polar compound containing a polar group having a hetero atom selected from nitrogen, oxygen, sulfur, and phosphorus.

Item 12. The liquid crystal composition according to any one of Items 1 to 11, which contains as a second addition at least one polar compound selected from the group of compounds represented by Formula (4) and Formula (5) Property, MES-R ⁶ (4)

(R ⁵ ) _h -R ⁶ (5)

In the formula (4), MES is a mesogen having at least one ring; in the formula (5), R ⁵ is an alkyl group having 4 to 20 carbon atoms. In the alkyl group, at least one -CH ₂ -can pass through -CH = CH-, -CF = CH-, -CH = CF-, -C≡C-, or a cycloalkylene group having 3 to 8 carbon atoms, in which at least one hydrogen may be substituted by fluorine or chlorine; In formulae (4) and (5), R ⁶ is a polar group of at least one of an oxygen atom having an OH structure, a sulfur atom of an SH structure, and a nitrogen atom of a primary, secondary, or tertiary amine structure; h is 1 or 2.

Item 13. The liquid crystal composition according to any one of Items 1 to 12, comprising at least one compound selected from the group of compounds represented by formula (4-1) as a second additive,

In formula (4-1), ring J and ring K are independently an aromatic group having 6 to 25 carbon atoms, a heteroaromatic group having 5 to 25 carbon atoms, an alicyclic group having 3 to 25 carbon atoms, or carbon Heteroalicyclic groups of 4 to 25. These groups may be condensed rings. Among these groups, at least one hydrogen may be substituted by a group T. Here, the group T is -OH,-(CH ₂ ) _j -OH. , Halogen, -CN, -NO ₂ , -NCO, -NCS, -OCN, -SCN, -C (= O) N (R ⁰ ) ₂ , -C (= O) R ⁰ , -N (R ⁰ ) ₂ ,-(CH ₂ ) _j -N (R ⁰ ) ₂ , aryl having 6 to 20 carbons, heteroaryl having 6 to 20 carbons, alkyl having 1 to 25 carbons, and 1 to 25 carbons Alkoxy, alkylcarbonyl with 2 to 25 carbons, alkoxycarbonyl with 2 to 25 carbons, alkylcarbonyloxy with 2 to 25 carbons, or alkoxycarbonyloxy with 2 to 25 carbons 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, j is 1, 2, 3, or 4; Z ⁶ is -O- , -S-, -CO-, -CO-O-, -OCO-, -O-CO-O-, -OCH _2- , -CH ₂ O-, -SCH _2- , -CH ₂ S-,- CF ₂ O-, -OCF _2- , -CF ₂ S-, -SCF ₂ -,-(CH ₂ ) _j- , -CF ₂ CH _2- , -CH ₂ CF ₂ -,-(CF ₂ ) _j- , -CH = CH-, -CF = CF-, -C≡C-, -CH = CH -COO-, -OCO-CH = CH-, -C (R ⁰ ) ₂ , or a single bond, where R ⁰ is hydrogen or an alkyl group having 1 to 12 carbon atoms, and j is 1, 2, 3, or 4; R ⁶ is an alkyl group having 1 to 25 carbon atoms, in which at least one -CH ₂ -may pass through -NR ^0- , -O-, -S-, -CO-, -COO-, -OCO -, -OCOO-, or a cycloalkyl group having 3 to 8 carbon atoms, where R ⁰ is hydrogen or an alkyl group having 1 to 12 carbon atoms, and at least one tertiary carbon (> CH-) may be replaced by nitrogen ( > N-) substitution, and at least one hydrogen may be substituted with fluorine or chlorine, wherein R ⁶ has an oxygen atom of OH structure, a sulfur atom of SH structure, or a nitrogen atom of primary, secondary or tertiary amine structure. At least one; R ⁷ is hydrogen, halogen, alkyl having 1 to 25 carbons, at least one of -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; i is 0, 1, 2, 3, 4, or 5 .

Item 14. The liquid crystal composition according to any one of Items 1 to 12, which contains, as a second additive, at least one polar compound selected from the group of compounds represented by formula (5-1), R ⁵ -R ⁶ (5-1)

In the formula (5-1), R ⁵ is an alkyl group having 4 to 20 carbon atoms. In the alkyl group, at least one of -CH ₂ -may pass through -CH = CH-, -CF = CH-, -CH = CF- , -C≡C-, or a cycloalkyl group having 3 to 8 carbon atoms, at least one hydrogen of which may be substituted by fluorine or chlorine; R ⁶ is an alkyl group having 1 to 25 carbon atoms, and the alkyl group In which at least one -CH ₂ -may pass through -NR ^0- , -O-, -S-, -CO-, -COO-, -OCO-, -OCOO-, or a cycloalkyl group having 3 to 8 carbon atoms Substitution, where R ⁰ is hydrogen or an alkyl group having 1 to 12 carbons, at least one tertiary carbon (> CH-) may be substituted with nitrogen (> N-), and at least one hydrogen may also be substituted with fluorine or chlorine Substitution, wherein R ⁶ has at least one of an oxygen atom of an OH structure, a sulfur atom of an SH structure, or a nitrogen atom of a primary, secondary, or tertiary amine structure.

Item 15. The liquid crystal composition according to any one of items 12 to 14, wherein in formulas (4) and (5) according to item 12, R ⁶ is a compound of formula (A1) to formula (A4) Any of the bases represented,

In formulas (A1) to (A4), Sp ⁴ , Sp ⁶ , and Sp ^{7 are} independently a single bond or a radical (-Sp "-X"-), where Sp "is a carbon number of 1 to 20 Group, at least one of -CH ₂ -in the alkylene group 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-, at least one of these groups may be substituted with fluorine, chlorine, or -CN, and X "is- O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CO-N (R ⁰ )-, -N (R ⁰ ) -CO- , -N (R ⁰ ) -CO-N (R ⁰ )-, -OCH _2- , -CH ₂ O-, -SCH _2- , -CH ₂ S-, -CF ₂ O-, -OCF _2- , -CF ₂ S-, -SCF _2- , -CF ₂ CH _2- , -CH ₂ CF _2- , -CF ₂ CF _2- , -CH = N-, -N = CH-, -N = N-, -CH = CR ^0- , -CY ² = CY ^3- , -C≡C-, -CH = CH-CO-O-, -O-CO-CH = CH-, or single bond, here, R ⁰ Is hydrogen or an alkyl group having 1 to 12 carbons, and Y ² and Y ^{3 are} independently hydrogen, fluorine, chlorine, or -CN; Sp ⁵ is>CH-,> CR ¹¹ -,> N-, or> C < X ¹ is -OH, -OR ¹¹ , -COOH, -NH ₂ , -NHR ¹¹ , -N (R ¹¹ ) ₂ , -SH, -SR ¹¹ , Here, R ⁰ is hydrogen or alkyl having 1 to 12 carbons; X ² is -O-, -CO-, -NH-, -NR ^11- , -S-, or single bond; Z ⁷ is carbon number 1 to 15 alkylene groups, 5 or 6 carbon alicyclic groups, or a combination of these, at least one of these groups may be -OH, -OR ¹¹ , -COOH, -NH ₂ ,- NHR ¹¹ , -N (R ¹¹ ) ₂ , fluorine, or chlorine substitution; R ¹¹ is an alkyl group having 1 to 15 carbon atoms. In the alkyl group, at least one -CH ₂ -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 L is an aromatic group having 6 to 25 carbon atoms or Alicyclic groups with 3 to 25 carbon atoms, these groups may be condensed rings, in these groups, 1 to 3 hydrogens may be substituted by R ^L ; R ^L is -OH,-(CH ₂ ) _j -OH , Fluorine, chlorine, -CN, -NO ₂ , -NCO, -NCS, -OCN, -SCN, -C (= O) N (R ⁰ ) ₂ , -C (= O) R ⁰ , -N (R ⁰ ) ₂ ,-(CH ₂ ) _j -N (R ⁰ ) ₂ , -SH, -SR ⁰ , aryl having 6 to 20 carbons, heteroaryl having 6 to 20 carbons, 1 to 25 carbons Alkyl, alkoxy having 1 to 25 carbons, alkylcarbonyl having 2 to 25 carbons, alkoxycarbonyl having 2 to 25 carbons, alkylcarbonyloxy having 2 to 25 carbons, or carbon An alkoxycarbonyl group having 2 to 25, the plurality of groups, at least one hydrogen may be replaced by fluorine or chlorine, where, R ⁰ is hydrogen or alkyl of 1 to 12 carbon atoms, j is 1, 2, , Or 4; k is 0, 1, 2, or 3; m is 2, 3, 4, or 5.

Item 16. The liquid crystal composition according to Item 13, wherein the second additive is at least one selected from the group of compounds represented by the formulas (4-1-1) to (4-1-4) Compounds,

In formula (4-1-1) and formula (4-1-4), ring J and ring K are independently 1,4-cyclohexyl, 1,4-phenylene, 2-fluoro-1,4 -Phenylene, 2-fluoro-1,3-phenylene, 2-ethyl-1,4-phenylene, 2,6-diethyl-1,4-phenylene, 2-trifluoro Methyl-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1, 4-phenylene, or 2,3,5,6-tetrafluoro-1,4-phenylene; ring L is cyclohexyl or phenyl; Z ⁶ is a single bond, ethylidene, or carbonyloxy; Z ⁷ is a single bond, an alkylene group having 1 to 15 carbon atoms, an alicyclic group having 5 or 6 carbon atoms, or a combination of these groups. Among these groups, at least one hydrogen may pass through -OH, -OR ¹¹ , -COOH, -NH ₂ , -NHR ¹¹ , -N (R ¹¹ ) ₂ , or halogen substitution, R ¹¹ is an alkyl group having 1 to 15 carbon atoms, in which at least one -CH ₂ -may pass -C≡ C-, -CH = CH-, -COO-, -OCO-, -CO-, -O-, or -NH- substituted; Sp ⁴ is a single bond, ethylene, propyl, or methylene oxide Sp ⁷ is a single bond or an alkylene group having 1 to 5 carbon atoms. In this alkylene group, -CH ₂ -may be substituted by -O- or -NH-; R ⁷ is an alkyl group having 1 to 8 carbon atoms. or fluoro group; I is 0,1,2,3,4, or 5; X ¹ is _{-OH, -COOH, -SH, -OCH 3} , -NH ^_2; X ₂ is a single bond or -O-.

Item 17. The liquid crystal composition according to Item 14, wherein the second additive is at least one selected from the group of compounds represented by formula (5-1-1) to formula (5-1-29) Compounds,

In the formulae (5-1-1) to (5-1-29), R ⁵ is an alkyl group having 4 to 20 carbon atoms. In the alkyl group, at least one of -CH ₂ -may pass through -CH = CH-, -CF = CH-, -CH = CF-, -C≡C-, or a cycloalkylene group having 3 to 8 carbon atoms. 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 1 to 17, wherein the proportion of the second additive is less than 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 an operation mode of the liquid crystal display element is an IPS mode, a VA mode, an FFS mode, or an FPA mode, and a driving method of the liquid crystal display element is an active matrix method.

Item 21. A polymer stabilized alignment type liquid crystal display element comprising The liquid crystal composition according to any one of items 1 to 18, and the polymerizable compound in the liquid crystal composition is polymerized.

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 a polymerizable compound 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, which comprises disposing the liquid crystal composition between two substrates and irradiating light with a voltage applied to the composition to cause a polymerizable compound contained in the composition. Polymerization was performed to manufacture the above-mentioned liquid crystal display element. (b) The liquid crystal composition has an upper limit temperature of a nematic phase of 70 ° C or higher, an optical anisotropy (measured at 25 ° C) at a wavelength of 589nm of 0.08 or higher, and a dielectric anisotropy at a frequency of 1kHz (Measured at 25 ° C) was -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 composition containing at least two of the polymerizable compounds (1). (e) The above-mentioned composition further containing a polymerizable compound different from the polymerizable compound (1). (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 Of additives. (g) An AM device containing the above composition. (h) A device containing the above composition and having a TN, ECB, OCB, IPS, FFS, VA, or FPA mode. (i) A transmissive element containing the 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 compound selected from the compound (2) and the compound (3). "Other liquid crystalline compound" is the same as compound (2) and compound (3) Different liquid crystal compounds. This compound is for further tuning It is mixed in the composition for the purpose. 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 (2) and the compound (3). "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 near 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) is 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. The compound (2) increases the dielectric anisotropy and lowers the lower limit temperature. Compound (3) reduces viscosity. The compound (4) and the compound (5) are adsorbed on the substrate surface by the action of a polar group, and control the alignment of the liquid crystal molecules. From the viewpoint of alignment of liquid crystal molecules, the polymer of the compound (1) is effective. The compound (4) or the compound (5) is also effective. Compound (1) and compound (4), or a combination of compound (1) and compound (5) are more effective. By this combination, a multiplication effect can be expected. This combination can be expected to have better long-term stability than the case where only the compound (4) or only the compound (5) is used.

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) + compound (3) + compound (4), compound (1) + compound (2) + compound (3) + compound (5), Or compound (1) + compound (2) + compound (3) + compound (4) + compound (5). A particularly preferred combination is compound (1) + compound (2) + compound (3) + compound (4).

The compound (1) is added to the composition for the purpose of being suitable for a polymer-stabilized alignment device. In order to improve the long-term reliability of the device, the preferred ratio of the compound (1) is about 0.03% by weight or more. In order to prevent display failure of the device, the preferred ratio of the compound (1) is about 10% by weight or less. A particularly preferred ratio is about 0.1 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.

In order to improve the dielectric anisotropy, the preferred ratio of the compound (2) is about 10% by weight or more, and in order to lower the lower limit temperature, the preferred ratio of the compound (2) is about 90% by weight or less. A particularly preferred ratio is in the range of about 20% by weight to about 85% by weight. A particularly preferred ratio is in the range of about 30% by weight to about 85% by weight.

In order to increase the upper limit temperature or lower the lower limit temperature, the preferred ratio of the compound (3) is about 10% by weight or more, and the preferred ratio of the compound (3) is about 90% by weight or less in order to improve the dielectric anisotropy. A particularly preferred ratio is in the range of about 15% by weight to about 75% by weight. A particularly preferred ratio is in the range of about 15% by weight to about 60% by weight.

The compound (4) or the compound (5) is 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 (4) or compound (5) is about 0.05% by weight or more. In order to prevent poor display of the device, the preferred ratio of compound (4) or 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 7% by weight. A particularly preferred ratio is in the range of about 0.5% by weight to about 5% by weight.

Fourth, preferred embodiments of the component compounds will be described. In formula (1), P ¹ , P ² , and P ^{3 are} independently a polymerizable group. Preferably, P ¹ , P ² , or P ³ is a polymerizable group selected from the group of groups represented by formula (P-1) to formula (P-5). Particularly preferably, 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 of 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 carbon atoms, or at least one hydrogen substituted by fluorine or chlorine. Alkyl having 1 to 5 carbons. In order to improve 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.

Sp ¹ , Sp ² , and Sp ^{3 are} independently 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. Preferably, Sp ¹ , Sp ² , or Sp ³ is a single bond, -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 A and ring C are phenyl groups, Sp ¹ and Sp ³ are single bonds.

Ring A and ring C are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, Pyrimidin-2-yl, or pyridin-2-yl, in these rings, at least one hydrogen may be passed through fluorine, chlorine, an alkyl group having 1 to 12 carbons, carbon An alkoxy group having 1 to 12 or at least one hydrogen is substituted with an alkyl group having 1 to 12 carbons substituted with fluorine or chlorine. Preferred ring A or ring C is phenyl. Ring B 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. Preferred ring B is 1,4-phenylene or 2-fluoro-1,4-phenylene.

Z ¹ and Z ^{2 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-, -CO-, -COO-, or -OCO -Substitution, and at least one -CH ₂ -CH ₂ -may be via -CH = CH-, -C (CH ₃ ) = CH-, -CH = C (CH ₃ )-, or -C (CH ₃ ) = C (CH ₃ ) -substituted, in which at least one hydrogen may be substituted with fluorine or chlorine. Preferably, Z ¹ or Z ² is a single bond, -CH ₂ CH _2- , -CH ₂ O-, -OCH _2- , -COO-, or -OCO-. Particularly preferred Z ¹ or Z ² are single bonds.

a is 0, 1, or 2. The preferred a is 0 or 1. b, c, and d are independently 0, 1, 2, 3, or 4, and the sum of b, c, and d is 1 or more. Preferred b, c, and d are 1 or 2. However, when ring A and ring C are phenyl, a is 1 or 2. Therefore, polymerizable compounds having a biphenyl skeleton are excluded.

In Formula (2) and Formula (3), 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, or a carbon number 2 to 12 alkenyloxy. 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 reduce the viscosity, preferred R ³ or R ⁴ is an alkenyl group having 2 to 12 carbons. In order to improve the stability to ultraviolet rays or heat, preferred R ³ or R ⁴ is an alkyl group having 1 to 12 carbon numbers. 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.

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 is 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 For reasons such as viscosity reduction, it is preferred to use alkenyl groups such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl, and 3-hexenyl. Style configuration. Among alkenyl groups such as 2-butenyl, 2-pentenyl, and 2-hexenyl, the cis configuration is preferred.

The preferred alkenyloxy group is 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. In order 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.

Ring D and Ring F are independently 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, 1,4-phenylene with at least one hydrogen substituted by fluorine or chlorine , Or tetrahydropyran-2,5-diyl. Preferred examples of "the 1,4-phenylene substituted with at least one hydrogen by fluorine or chlorine" are 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, Or 2-chloro-3-fluoro-1,4-phenylene. In order to reduce the viscosity, the preferred ring D or ring F is 1,4-cyclohexyl. In order to improve the dielectric anisotropy, the preferred ring D or ring F is tetrahydropyran-2,5-diyl. In order to improve the optical anisotropy, the preferred ring D or ring F is 1,4-phenylene. 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. Tetrahydropyran-2,5-diyl is or , Preferably

Ring E is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4- Phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, or 7,8-difluorochroman-2,6-diyl. To reduce viscosity, the preferred ring E is 2,3-difluoro-1,4-phenylene. To reduce the optical anisotropy, the preferred ring E is 2-chloro-3-fluoro-1,4- In order to increase the dielectric anisotropy of phenylene, the preferred ring E is 7,8-difluorochroman-2,6-diyl.

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

Z ³ , Z ⁴ , and Z ^{5 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 ³ or Z ⁴ is a single bond. In order to reduce the lower limit temperature, the preferred Z ³ or Z ⁴ is -CH ₂ CH _2- . In order to improve the dielectric anisotropy, the preferred Z ³ Or Z ⁴ is -CH ₂ O- or -OCH _2- . In order to reduce the viscosity, the preferred Z ⁵ is a single bond, to reduce the lower limit temperature, the preferred Z ⁵ is -CH ₂ CH _2- , and to increase the upper limit temperature, the preferred Z ⁵ is -COO- or -OCO-.

e is 1, 2, or 3, f is 0 or 1, and the sum of e and f is 3 or less. In order to reduce the viscosity, the preferred e is 1, and in order to increase the upper limit temperature, the preferred e is 2 or 3. In order to reduce the viscosity, the preferred f is 0, and to lower the lower limit temperature, the preferred f is 1. g is 1, 2, or 3. In order to reduce the viscosity, the preferred g is 1, and in order to increase the upper limit temperature, the preferred g is 2 or 3.

In Formula (4) and Formula (5), R ⁶ is a polar group. Since a polar compound having a polar group is added to the composition, it is preferably stable. When a polar compound is added to the composition, it is preferred that the compound does not reduce the voltage retention of the device. The polar compound 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. The preferred polar compound does not have a polymerizable group such as acryloxy (-OCO-CH = CH ₂ ) and methacryloxy (-OCO- (CH ₃ ) C = CH ₂ ).

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 removal 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. A monovalent radical derived from hydrogen. The structure of these groups may be linear, branched, cyclic, or a combination of these. A particularly preferred polar group has at least one of an oxygen atom of an OH structure or a nitrogen atom of a primary, secondary or tertiary amine structure. The most preferred polar group is hydroxyl (carbon-OH).

Examples of the polar group R ⁶ are the groups represented by the formula (A1) to the formula (A4).

In the formulae (A1) to (A4), Sp ⁴ , Sp ⁶ , and Sp ^{7 are} independently a single bond or a group (-Sp "-X"-), and X "is bonded to a MES group or R ⁵ . Sp "is an alkylene group having 1 to 20 carbon atoms, preferably an alkylene group having 1 to 12 carbon atoms. At least one -CH ₂ -in this alkylene group may be passed 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- Among these groups, at least one hydrogen may be substituted by fluorine, chlorine, or -CN, and X "is -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO- O-, -CO-N (R ⁰ )-, -N (R ⁰ ) -CO-, -N (R ⁰ ) -CO-N (R ⁰ )-, -OCH _2- , -CH ₂ O-, -SCH _2- , -CH ₂ S-, -CF ₂ O-, -OCF _2- , -CF ₂ S-, -SCF _2- , -CF ₂ CH _2- , -CH ₂ CF _2- , -CF ₂ CF _2- , -CH = N-, -N = CH-, -N = N-, -CH = CR ^0- , -CY ² = CY ^3- , -C≡C-, -CH = CH-CO- O-, -O-CO-CH = CH-, or a single bond, where R ⁰ is hydrogen or an alkyl group having 1 to 12 carbons, and Y ² and Y ^{3 are} independently hydrogen, fluorine, chlorine, or- CN. The preferred X "is -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR ^0- , -NR ⁰ -CO-, -NR ⁰ -CO-N R ^0- , or a single bond. Sp ⁵ is>CH-,> CR ¹¹ -,> N-, or> C <. That is, Sp ⁵ in the formula (A2) is>CH-,> CR ^11- , or> N-, and Sp ⁵ in the formula (A3) means> C <.

The preferred Sp "is-(CH ₂ ) _p1 -,-(CH ₂ CH ₂ O) _q1 -CH ₂ CH _2- , -CH ₂ CH ₂ -S-CH ₂ CH _2- , or -CH ₂ CH ₂ -NHCH ₂ CH _2- , where p1 is an integer from 1 to 12, and q1 is an integer from 1 to 3. Preferred bases (-Sp "-X"-) are-(CH ₂ ) _p1 -,-( CH ₂ ) _p1 -O-,-(CH ₂ ) _p1 -O-CO-,-(CH ₂ ) _p1 -O-CO-O-, where p1 and q1 have the meanings shown above. Particularly preferred "Sp" is ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl , Octadecyl, vinyloxyethylene, methylenedioxybutylene, ethylenethioethylene, ethylene-N-methyliminoethylene, 1-methylalkylene, vinylene , Propenyl, and butenyl.

X ¹ is -NH ₂ , -NHR ¹¹ , -N (R ¹¹ ) ₂ , -OR ¹¹ , -OH, -COOH, -SH, -SR ¹¹ ,

Here, R ¹¹ is an alkyl group having 1 to 15 carbons. Among the alkyl groups, at least one -CH ₂ -may pass through -C≡C-, -CH = CH-, -COO-, -OCO-,- CO-, or -O- substitution. Among these groups, at least one hydrogen may be substituted by fluorine or chlorine, and R ⁰ is hydrogen or an alkyl group having 1 to 12 carbon atoms.

X ² is -O-, -CO-, -NH-, -NR ^11- , -S-, or a single bond, Z ⁷ represents an alkylene group having 1 to 15 carbon atoms, and an alicyclic system having 5 to 6 carbon atoms Group, or a combination of at least one ring and an alkylene group, in these groups, at least one hydrogen may pass through -OH, -OR ¹¹ , -COOH, -NH ₂ , -NHR ¹¹ , -N (R ¹¹ ) ₂ , fluorine Or chloro, R ¹¹ has the meaning shown above. k is 0, 1, 2, or 3.

Particularly preferred nitrogen-containing groups R ⁶ are -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, where n, n1, n2, and n3 are independently 1 to 12 An integer, preferably 1, 2, 3, or 4.

Particularly preferred non-nitrogen-containing groups R ⁶ are -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, where n, n1, and n2 are independently 1 An integer of 12 is preferably 1, 2, 3, or 4.

From the viewpoint of high solubility in the liquid crystal composition, R ^{6 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 a plurality of heteroatoms (nitrogen, oxygen). A compound having such a polar group is effective even at a low concentration.

In the formula (4), the MES is a mesogenic group having at least one ring. Liquid crystal primitives are well known to those skilled in the art. The mesogen is a portion that contributes to the formation of a liquid crystal phase when the compound has a liquid crystal phase (mesophase). A preferable example of the compound (4) is the compound (4-1).

In formula (4-1), ring J and ring K are independently an aromatic group having 6 to 25 carbon atoms, a heteroaromatic group having 5 to 25 carbon atoms, an alicyclic group having 3 to 25 carbon atoms, or carbon Heteroalicyclic groups of 4 to 25. These groups may be condensed rings. Among these groups, at least one hydrogen may be substituted by a group T. Among these groups, preferred carbon numbers are 4 to 25. These groups It may be a condensed ring, and among these groups, at least one hydrogen may be substituted by a group T. The meaning of the base T is described at the end of this paragraph. Preferred ring J or ring K is 1,4-phenylene, naphthalene-1,4-diyl, or naphthalene-2,6-diyl (of these 3 groups, at least one tertiary carbon (> CH-) can be substituted with nitrogen (> N-)), 1,4-cyclohexyl (in which at least one -CH ₂ -can be substituted with -O- or -S-), 3,3'-bicyclic Butylene, 1,4-cyclohexenyl, bicyclo [1.1.1] pentane-1,3-diyl, bicyclo [2.2.2] octane-1,4-diyl, spiro [3.3] Heptane-2,6-diyl, piperidine-1,4-diyl, decalin-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, Indane-2,5-diyl, octahydro-4,7-methyleneindane-2,5-diyl, or perhydrocyclopentene [a] phenanthrene-3,17-diyl (in particular Is sterane-3,17-diyl). Among these groups, at least one hydrogen may be substituted by a group T. Here, the group T is -OH-,-(CH ₂ ) _j -OH, halogen, -CN, -NO ₂ , -NCO, -NCS, -OCN, -SCN, -C (= O) N (R ⁰ ) ₂ , -C (= O) R ⁰ , -N (R ⁰ ) ₂ ,-(CH ₂ ) _j -N (R ⁰ ) ₂ , aryl or heteroaryl with 6 to 20 carbons, alkyl with 1 to 25 carbons, alkoxy, alkyl with 2 to 25 carbons, alkoxycarbonyl , Alkylcarbonyloxy, or alkoxycarbonyloxy, in which at least one hydrogen may be substituted with fluorine or chlorine, here R ⁰ is hydrogen or an alkyl group having 1 to 12 carbon atoms, j is 2, 3, or 4.

Z ⁶ is a single bond, -O-, -S-, -CO-, -CO-O-, -OCO-, -O-CO-O-, -OCH _2- , -CH ₂ O-, -SCH ₂ -, -CH ₂ S-, -CF ₂ O-, -OCF _2- , -CF ₂ S-, -SCF ₂ -,-(CH ₂ ) _j- , -CF ₂ CH _2- , -CH ₂ CF ₂ -,-(CF ₂ ) _j- , -CH = CH-, -CF = CF-, -C≡C-, -CH = CH-COO-, -OCO-CH = CH-, or -C (R ⁰ ) _2- . R ⁰ is hydrogen or an alkyl group having 1 to 12 carbons, and j is 1, 2, 3, or 4. The preferred Z ⁶ is a single bond.

R ⁶ is 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-, -COO-, -OCO- , -OCOO-, or a cycloalkyl group having 3 to 8 carbon atoms, where R ⁰ is hydrogen or an alkyl group having 1 to 12 carbon atoms, and at least one tertiary carbon (> CH-) may be replaced by nitrogen (> N-), and at least one hydrogen may be substituted with fluorine or chlorine, wherein R ⁶ has at least one of an oxygen atom of an OH structure, a sulfur atom of an SH structure, and a nitrogen atom of a primary, secondary or tertiary amine structure One. Preferred R ⁶ has at least one> NH, -OH, or -SH. R ⁷ is hydrogen, halogen, or an alkyl group having 1 to 25 carbon atoms. Among the alkyl groups, at least one of -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-) 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. Preferred R ⁷ is alkyl.

The aromatic group refers to an aryl group or a substituted aryl group. Heteroaromatic means heteroaryl or substituted heteroaryl. Heteroaryl refers to an aromatic group having at least one heteroatom. Aryl and heteroaryl may be either monocyclic or polycyclic. That is, the groups have at least one ring, and the rings may be condensed (for example, naphthyl), two rings may be connected by a covalent bond (for example, biphenyl), or may have a combination of a condensed ring and a linked ring . Preferred heteroaryl groups have at least one heteroatom selected from the group of nitrogen, oxygen, sulfur, and phosphorus.

The preferred aryl or heteroaryl group has 6 to 25 carbon atoms, and may be a five-membered ring, a six-membered ring, or a seven-membered ring. The preferred aryl or heteroaryl group may be monocyclic or bicyclic or tricyclic. These groups may be condensed rings or substituted.

Preferred aryl groups are benzene, biphenyl, terphenyl, [1,1 ': 3,1 "] terphenyl, naphthalene, anthracene, binaphthyl, phenanthrene, fluorene, dihydrofluorene, , Fluorene, fused tetrabenzene, fused pentabenzene, benzofluorene, fluorene, indene, indenofluorene, spirobifluorene, and a monovalent group derived by removing one hydrogen.

Preferred heteroaryl groups are via pyrrole, pyrazole, imidazole, 1,2,3-triazole, 1,2,4-triazole, tetrazole, furan, thiophene, selenophene, oxazole, isoxazole Azole, 1,2-thiazole, 1,3-thiazole, 1, 2,3-oxadiazole, 1, 2, 4-oxadiazole, 1, 2, 5-oxadiazole, 1, 3, 4- Oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole and other five-membered ring compounds, or Pyridine, pyridazine, pyrimidine, pyrazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, 1,2,4,5-tetrazine, 1, A monovalent group derived by removing one hydrogen from six-membered ring compounds such as 2,3,4-tetrazine, 1,2,3,5-tetrazine.

Preferred heteroaryl groups are also those obtained from Benzimidazole, quinoxaline imidazole, benzoxazole, naphthoxazole, anthraxazole, phenanthrazole, isoxazole, benzothiazole, benzofuran, isobenzofuran, dibenzofuran , Quinoline, isoquinoline, pyridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, benzoisoquinoline, acridine, Phenothiazine, phenoxazine, benzopyridazine, benzopyrimidine, quinoxaline, phenazine, naphthyridine, azacarbazole, benzocarboline, morphine, morpholine, thieno [2,3b] A monovalent group derived by removing one hydrogen from condensed ring compounds such as thiophene, thieno [3,2b] thiophene, dithienothiophene, isobenzothiophene, dibenzothiophene, and benzothiadiazolethiophene. The preferred heteroaryl group is also a monovalent group derived by removing one hydrogen from a ring formed by combining two groups selected from the five-membered ring, the six-membered ring, and the condensed ring. These heteroaryl groups may be substituted with alkyl, alkoxy, thioalkyl, fluorine, fluoroalkyl, aryl, or heteroaryl.

The alicyclic group and the heteroalicyclic group may be saturated or unsaturated. That is, these groups may have only a single bond or a combination of a single bond and multiple bonds. A saturated ring is better than an unsaturated ring. A preferred heteroalicyclic group has at least one heteroatom selected from nitrogen, oxygen, sulfur, and phosphorus.

The alicyclic group and the heteroalicyclic group may be one ring or multiple rings. Preferred examples of these groups are monocyclic, bicyclic, or tricyclic carbons having 3 to 25 carbon atoms. These groups may be condensed rings or substituted. Preferred examples of these groups are a five-membered ring, a six-membered ring, a seven-membered ring, or an eight-membered ring. In these groups, at least one carbon may be substituted by silicon, and at least one> CH- may be substituted by> N-. Moreover, at least one -CH ₂ -may be substituted by -O- or -S-.

Preferred alicyclic and heteroalicyclic groups are five-membered rings such as cyclopentane, tetrahydrofuran, tetrahydrothiofuran, and pyrrolidine, cyclohexane, cyclohexene, tetrahydropyran, Six-membered rings such as hydrothiopyran, 1,3-dioxane, 1,3-dithiane, piperidine, seven-membered rings such as cycloheptane, tetrahydronaphthalene, decalin, indan, bicyclic [ 1.1.1] Divalent group derived by removing two hydrogens from condensed rings such as pentane, bicyclo [2.2.2] octane, spiro [3.3] heptane, octahydro-4,7-methyleneindane .

i is 0, 1, 2, 3, 4, or 5.

In the formula (5), R ⁵ is an alkyl group having 4 to 20 carbon atoms. Among the alkyl groups, at least one of -CH ₂ -can pass through -CH = CH-, -CF = CH-, -CH = CF-, -C≡C-, or a cycloalkylene group having 3 to 8 carbon atoms, and at least one hydrogen may be substituted with fluorine or chlorine. h is 1 or 2, preferably 1.

Preferred R ⁵ is an alkyl group having 4 to 20 carbon atoms. Particularly preferred R ⁵ is an alkyl group having 6 to 18 carbon atoms. At least one -CH ₂ -may be substituted with -CH = CH-, -CF = CH-, -CH = CF-, -C≡C-, or -O-, and at least one hydrogen may be substituted with fluorine or chlorine.

Particularly preferred compound (4-1) is selected from the following compounds.

In the formulae (4-1-1-1) to (4-1-4-4), R ⁷ is an alkyl group having 1 to 8 carbon atoms or fluorine.

Particularly preferred compound (5-1) is selected from compound (5-1-1-1) to compound (5-1-29-1) below.

Fifth, preferred component compounds are shown. Preferred compound (1) is the compound (1-1) to compound (1-12) according to item 3. Among these compounds, it is preferred that at least one of the first additives is compound (1-7), compound (1-8), compound (1-9), or compound (1-10). It is preferred that at least two of the first additives are a compound (1-8) and a compound (1-9), or a combination of a compound (1-2) and a compound (1-7).

Preferred compound (2) is the compound (2-1) to compound (2-21) according to item 6. Among these compounds, it is preferred that at least one of the first components is compound (2-1), compound (2-4), compound (2-5), compound (2-7), compound (2-10), Or compound (2-15). It is preferable that at least two of the first components are compound (2-1) and compound (2-7), compound (2-1) and compound (2-15), compound (2-4) and compound (2- 7), compound (2-4) and compound (2-15), or compound (2-5) And compound (2-10).

Preferred compound (3) is the compound (3-1) to compound (3-13) according to item 9. Among these compounds, it is preferred that at least one of the second components is compound (3-1), compound (3-3), compound (3-5), compound (3-6), compound (3-7), Or compound (3-8). It is preferable that at least two of the second component are the compound (3-1) and the compound (3-3), the compound (3-1) and the compound (3-5), or the compound (3-1) and the compound (3 -6).

A preferred compound (4) is the compound (4-1) according to item 13. Particularly preferred compound (4) is the compound (4-1-1) to compound (4-1-4) according to item 16. A preferred compound (5) is the compound (5-1) according to item 14. Particularly preferred compound (5) is the compound (5-1-1) to compound (5-1-29) according to item 17. In general, compound (4) is superior to compound (5).

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. Preferred examples of the antioxidant are the compound (7) and the like in which n is an integer of 1 to 9.

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 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 effects, the preferred ratio of these absorbers or stabilizers is about 50 ppm or more. In order not to lower the upper limit temperature, or not to increase the lower limit temperature, the preferred ratio of these absorbers or stabilizers is about 10,000 ppm or less. A particularly preferred ratio is in the range of about 100 ppm to about 10,000 ppm.

A dichroic dye such as an azo-based pigment, an anthraquinone-based pigment, or the like is added to the composition in order to be suitable for an element in a guest host (GH) mode. 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 defoamer is about 1 At least ppm, in order to prevent poor display, the preferred ratio of the defoamer is about 1,000 ppm or less. A particularly preferred ratio is in the range of about 1 ppm to about 500 ppm.

In order to be suitable for a polymer stable alignment (PSA) type device, a polymerizable compound is used. Compound (1) is suitable for this purpose. The compound (1) and other polymerizable compounds different from the compound (1) may be added to the composition together. Preferable examples of the other polymerizable compound are acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxetane, oxetane), vinyl ketone, etc. Compound. A particularly preferred example is acrylate or methacrylate. A preferable ratio of the compound (1) 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 kind of the compound (1), or by combining other polymerizable compounds with the compound (1) at an appropriate ratio, the reactivity of the polymerizable compound or the pretilt angle of the liquid crystal molecules can be adjusted. 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.

A polymerizable compound such as the compound (1) is polymerized by irradiation with ultraviolet rays. Polymerization may be performed in the presence of a suitable initiator such as a photopolymerization initiator. Suitable conditions for carrying out the polymerization, suitable types of initiators, and appropriate amounts are known to those skilled in the art 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 are suitable for 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 a polymerizable compound such as the compound (1) is stored, 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.

Seventh, a method for synthesizing the component compounds will be described. These compounds can be synthesized by known methods. Illustrative synthesis methods. Compound (1-2) was synthesized by the method described in Japanese Patent Laid-Open No. 7-101900. Compound (2-1) was synthesized by a method described in Japanese Patent Application Publication No. Hei 2-503441. Compound (3-5) is synthesized by a method described in Japanese Patent Laid-Open No. 57-165328. Compound (4-1) is synthesized by a method described in International Publication No. 2012-038026. A part of the compound (5) is commercially available. The compound of formula (7) wherein n is 1 is available from Sigma-Aldrich Corporation. Compound (7) and the like where 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" ,approximately Hewlett-Packard & 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 of the 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 preferred is for AM elements with TN, OCB, IPS mode or FFS mode. 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. Compare Ideal for transmissive components. 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. 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 the 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.

An example of a method of manufacturing an element without an alignment film is described below. An element including two substrates is prepared, which are called an array substrate and a color filter substrate. The substrate does not have 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 and a polar compound are added to the 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. By this polymerization, a layer containing a composition of a polymer and a polar compound is formed on a substrate.

In this sequence, polar compounds are aligned on the substrate due to interaction between the polar groups and the surface of the substrate. According to this arrangement, the liquid crystal molecules are aligned. When a voltage is applied, the alignment of the liquid crystal molecules is further promoted, and the polymerizable compound is also aligned according to the alignment. Since the polymerizable compound 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 the 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 compound was synthesized by nuclear magnetic resonance (nuclear magnetic resonance, NMR) analysis. The properties of compounds, compositions, and devices were measured by the following methods.

NMR analysis: For measurement, DRX-500 manufactured by Bruker BioSpin was used. ^In the measurement of ¹ H-NMR, the sample was dissolved in a deuterated solvent such as CDCl _3, and the measurement was performed at room temperature under the conditions of 500 MHz and 16 times of accumulation. 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 refers to a sextet, (sextet), m refers to a multiplet, and br refers to a broad peak.

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 component compounds, a capillary column DB-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by Agilent Technologies Inc. was used; the 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 preparing a sample as an acetone solution (0.1% by weight), 1 μL of the sample was injected into the sample gasification chamber. The recorder is C-R5A Chromatopac manufactured by Shimadzu Corporation or its equivalent. The resulting gas chromatogram shows a combination with the ingredients The peak holding time and the area of the peak corresponding to the object.

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 manufactured by Agilent Technologies Co., Ltd. (length 30m, inner diameter 0.32mm, film thickness 0.25μm), Rtx-1 manufactured by Restek Corporation (length 30m, inner diameter 0.32mm, film thickness 0.25μm ), BP-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by SGE International Pty. Ltd. of Australia. To prevent the 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 was calculated by an extrapolation method. (Extrapolated value) = {(measured value of sample) -0.85 × (measured value of mother liquid crystal)} / 0.15. When the smectic phase (or crystal) is precipitated at 25 ° C at this ratio, The ratio of the compound to the mother liquid crystal was changed in the order of 10% by weight: 90% by weight, 5% by weight: 95% by weight, and 1% by weight: 99% by weight. 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 in the JEITA specification (JEITA.ED-2521B) reviewed and designated by the Japan Electronics and Information Technology Industries Association (JEITA), or modified methods. The thin-film transistor (TFT) was not mounted on the TN device used for the measurement.

(1) Maximum temperature of nematic phase (NI; ° C): in a polarizing microscope A sample was placed on a hot plate of a melting point measuring device 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; ° C): Put the sample with nematic phase into a glass bottle at 0 ° C, -10 ° C, -20 ° C, -30 ° C, and -40 ° C. After storing in a freezer 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, TC 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): The E-type rotary viscometer manufactured by Tokyo Keiki Co., Ltd. was used for measurement.

(4) Viscosity (rotational viscosity; γ1; measured at 25 ° C; mPa.s): According to "Molecular Crystals and Liquid Crystals" by M. Imai et al. The measurement is 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 the voltage was applied for 0.2 seconds, the voltage was repeatedly applied under the conditions of applying only one 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 attached to 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 was calculated according to the formula of Δε = ε∥-ε⊥. The dielectric constants (ε∥ and ε⊥) were measured as follows.

1) Measurement of dielectric constant (ε∥): A solution of octadecyltriethoxysilane (0.16 mL) in ethanol (20 mL) was coated on a sufficiently 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 gap (cell gap) of 4 μm between two glass substrates, and the device was sealed with an adhesive hardened by 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 2 seconds later.

2) Measurement of dielectric constant ε⊥: A polyimide solution is coated on a sufficiently cleaned glass substrate. After the glass substrate was fired, the obtained alignment film was 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): used during measurement LCD5100 brightness meter manufactured by Otsuka Electronics Co., Ltd. The light source is a halogen lamp. A sample was placed in a normally black mode VA device with a gap (cell gap) of 2 glass substrates of 4 μm and an anti-parallel rubbing direction, and the device was cured with an ultraviolet-curing adhesive. seal. The voltage (60 Hz, rectangular wave) applied to the device was gradually increased 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 the 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;%): irradiation After ultraviolet rays, the voltage holding ratio was measured, and the stability to ultraviolet rays was evaluated. The TN element used for the measurement had a polyimide alignment film, and the cell gap was 5 μm. A sample was injected into the 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 element 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 device filled with the sample in a 80 ° C thermostat 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): The LCD5100 brightness meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source is a halogen lamp. The low-pass filter is set to 5 kHz. A sample was placed in a VA device having a distance (cell gap) between two glass substrates of 3.5 μm and no alignment film. This element was sealed with an adhesive hardened with ultraviolet rays. This device was irradiated with ultraviolet light of 78 mW / cm ² (405 nm) for 449 seconds (35 J) while applying a voltage of 30 V. For ultraviolet irradiation, an ultraviolet curing 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 was 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 Type 1 elastic constant tester. A sample was injected into a vertical alignment element having a gap (cell gap) of 20 μm between two glass substrates. 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): 1.0 mL of a sample was placed 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) × (electrical capacity of the container)} / {(DC current) × (dielectric constant of vacuum)}.

(15) Pretilt angle (degrees): A spectroscopic ellipticometer 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 liquid crystal alignment angle Φ (before) on the electrode side before applying stress. Then, apply rectangular wave 4.5V, 60Hz to the device for 20 minutes, buffer for 1 second, and measure the liquid crystal on the electrode side again after 1 second and 5 minutes. Alignment angle Φ (after). From these values, the change ΔΦ (deg.) Of the liquid crystal alignment angle after 1 second and after 5 minutes was calculated using the following formula.

ΔΦ (deg.) = Φ (after) -Φ (before) (Eq. 2)

Taking J. Hilfiker, 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 PJBos), "Thin Solid Films", 455-456, (2004) 596-600 for reference to perform these measurements. It can be said that the smaller the ΔΦ, the smaller the rate of change of the liquid crystal alignment axis, and the better the stability of the liquid crystal alignment axis.

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 (-) means another liquid crystal compound. The ratio (percentage) of the liquid crystal compound is a weight percentage (% by weight) based on the weight of the liquid crystal composition. Finally, the characteristic values of the composition are summarized.

Examples of components

Raw material

A device without an alignment film was fabricated to study the vertical alignment of liquid crystal molecules, the conversion rate of a polymerizable compound, and the response time. First, the raw materials will be described. The raw materials are liquid crystal composition (M1) to liquid crystal composition (M15), polymerizable compound (RM-1) to polymerizable compound (RM-8), polar compound (PC-1) to polar compound (PC-33), And listed in sequence.

[Composition M1]

NI = 73.2 ℃; Tc <-20 ℃; Δn = 0.113; Δε = -4.0; Vth = 2.18V; η = 22.6mPa. s.

[Composition M2]

NI = 82.8 ℃; Tc <-30 ℃; Δn = 0.118; Δε = -4.4; Vth = 2.13V; η = 22.5mPa. s.

[Composition M3]

NI = 78.1 ℃; Tc <-30 ℃; Δn = 0.107; Δε = -3.2; Vth = 2.02V; η = 15.9mPa. s.

[Composition M4]

NI = 88.5 ℃; Tc <-30 ℃; Δn = 0.108; Δε = -3.8; Vth = 2.25V; η = 24.6mPa. s; VHR-1 = 99.1%; VHR-2 = 98.2%; VHR-3 = 97.8%.

[Composition M5]

NI = 81.5 ℃; Tc <-30 ℃; Δn = 0.119; Δε = -4.5; Vth = 1.70V; η = 31.8mPa. s.

[Composition M6]

NI = 98.8 ℃; Tc <-30 ℃; Δn = 0.111; Δε = -3.2; Vth = 2.47V; η = 23.9mPa. s.

[Composition M7]

NI = 77.5 ℃; Tc <-30 ℃; Δn = 0.084; Δε = -2.6; Vth = 2.43V; η = 22.8mPa. s.

[Composition M8]

NI = 70.6 ℃; Tc <-20 ℃; Δn = 0.129; Δε = -4.3; Vth = 1.69V; η = 27.0mPa. s.

[Composition M9]

NI = 93.0 ℃; Tc <-30 ℃; Δn = 0.123; Δε = -4.0; Vth = 2.27V; η = 29.6mPa. s.

[Composition M10]

NI = 87.6 ℃; Tc <-30 ℃; Δn = 0.126; Δε = -4.5; Vth = 2.21V; η = 25.3mPa. s.

[Composition M11]

NI = 93.0 ℃; Tc <-20 ℃; Δn = 0.124; Δε = -4.5; Vth = 2.22V; η = 25.0mPa. s.

[Composition M12]

NI = 76.4 ℃; Tc <-30 ℃; Δn = 0.104; Δε = -3.2; Vth = 2.06V; η = 15.6mPa. s.

[Composition M13]

NI = 78.3 ℃; Tc <-20 ℃; Δn = 0.103; Δε = -3.2; Vth = 2.17V; η = 17.7 mPa. s.

[Composition M14]

NI = 81.2 ℃; Tc <-20 ℃; Δn = 0.107; Δε = -3.2; Vth = 2.11V; η = 15.5mPa. s.

[Composition M15]

NI = 88.3 ℃; Tc <-30 ℃; Δn = 0.115; Δε = -2.0; Vth = 2.80V; η = 17.8mPa. s.

The following polymerizable compound (RM-1) to polymerizable compound (RM-8) were used as the first additive.

Use the following polar compounds (PC-1) to polar compounds (PC-33) As a second additive.

2. Vertical alignment of liquid crystal molecules

Test number 1

A polymerizable compound (RM-1) was added to the composition (M1) at a ratio of 0.5% by weight and a polar compound (PC-1) was added at a ratio of 5% by weight. 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 and having no alignment film. The element was irradiated with ultraviolet light (28 by using an ultra-high pressure mercury lamp USH-250-BY (made by Ushio Motor) J) to polymerize a polymerizable compound. This element was placed in a polarizing microscope in which a polarizing element and an analyzer were arranged in parallel, and the element was irradiated with light from below to observe the presence or absence of light leakage. When the liquid crystal molecules are sufficiently aligned and light does not pass through the device, it is judged that the vertical alignment is "good". When the light transmitted through the device was observed, it was expressed as "defective".

Test number 2 to test number 33

An element without an alignment film was produced using a mixture of a composition, a polymerizable compound, and a polar compound. The presence or absence of light leakage was observed in the same manner as in Test No. 1. The results are summarized in Table 4.

3. Conversion rate of polymerizable compounds

A polar compound is added to the composition together with a polymerizable compound. This polymerizable compound is consumed by polymerization to form a polymer. The conversion of this reaction is preferably large. This is because from the viewpoint of the afterimage of the image, the residual amount of the polymerizable compound (the amount of the unreacted polymerizable compound) is preferably small. When manufacturing a polymer-stable alignment device, ultraviolet rays are usually radiated in two stages for the purpose of optimizing the pretilt angle of liquid crystal molecules. In the next test, after irradiating the ultraviolet rays in the first stage, the remaining amount of the polymerizable compound was measured and the conversion rate was calculated. For comparison, the following polymerizable compound (RM-9) was selected. This compound is excluded from compound (1) due to the definition of the symbol.

The polymerization was performed as follows. The method described in the paragraph "Vertical alignment of liquid crystal molecules" was used to produce an element without an alignment film. The device was irradiated with ultraviolet light of 78 mW / cm ² (405 nm) for 359 seconds (28 J) while a voltage of 30 V was applied to the device. For ultraviolet irradiation, an ultraviolet curing polymetal lamp M04-L41 manufactured by Eye Grapics Co., Ltd. was used. Then, the residual amount of the polymerizable compound was measured by HPLC, and the conversion rate was calculated. The results are summarized in Table 5. The conversions from test number 1 to test number 8 ranged from 34% to 44%. In Comparative Example 1, the polymerizable compound (RM-1) used in Test No. 1 was replaced with a polymerizable compound (RM-9) to perform polymerization. In this case, the conversion rate was 16%. From this comparison, it can be concluded that the composition of the present invention is excellent from the viewpoint of conversion.

4. Response time

As described in Table 6, a mixture prepared by combining various compositions, polymerizable compounds, and polar compounds was injected into a device having no alignment film. According to the item (12), after the polymerizable compound is polymerized by irradiating ultraviolet rays, the response time of the device is measured. For comparison, a device was prepared from the composition (M5) or the composition (M9) in a state where the polymerizable compound and the polar compound were not added, and the response time was measured by the same method. As is known from Table 6, in Test No. 1 to Test No. 33, the response time is in the range of 5.2 ms to 10.4 ms. On the other hand, the response times of Comparative Examples 1 and 2 were 21.8 ms and 21.7 ms, respectively. That is, when a polymerizable compound and a polar compound are not added, the response time is about twice. Therefore, it can be concluded that the combination of the polymer derived from the polymerizable compound (1) and the polar compound (4) or the polar compound (5) is effective in shortening the response time.

In a liquid crystal display element, a short response time is preferred. The response time of the embodiment shown in Table 6 is in the range of 5.2 milliseconds to 10.4 milliseconds, which is shorter than that of the comparative example. As a result, since a liquid crystal composition containing a polymerizable compound and a polar compound was used, Regarding the different types of components, the devices without alignment films all achieve short response times. This is because the liquid crystal molecules are stably aligned even without an alignment film, which is a feature of the present invention that should be specifically explained.

[Industrial availability]

The liquid crystal composition of the present invention can control the alignment of liquid crystal molecules in an element without an alignment film. The composition has a high upper limit temperature, a low lower limit temperature, a small viscosity, an appropriate optical anisotropy, a negative large dielectric anisotropy, a large specific resistance, high stability to ultraviolet rays, and high thermal resistance. Among characteristics such as high stability, at least one characteristic is satisfied, or there is an appropriate balance regarding at least two characteristics. The liquid crystal display element containing the composition has characteristics such as a short response time, a large voltage holding ratio, a low threshold voltage, a large contrast ratio, and a long life. Therefore, it can be used in a liquid crystal projector, a liquid crystal television, and the like.

Claims (25)

A liquid crystal composition containing at least one polymerizable compound selected from the group of compounds represented by formula (1) as a first additive and at least one polar compound as a second additive and having a negative dielectric Anisotropy,

In formula (1), ring A and ring C are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan Alkan-2-yl, pyrimidin-2-yl, or pyrid-2-yl, in these rings, at least one hydrogen can be through fluorine, chlorine, C 1-12 alkyl, C 1-12 alkoxy Group, or at least one hydrogen is substituted by fluorine or chlorine, a C 1-12 alkyl group; ring B 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 can be fluorine, chlorine , A C 1-12 alkyl group, a C 1-12 alkoxy group, or a C 1-12 alkyl group substituted with at least one hydrogen by fluorine or chlorine; Z ¹ and Z ^{2 are} independently single bonds Or an alkylene group having 1 to 10 carbon atoms, in which at least one -CH ₂ -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 )-, the In 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 a single bond or an extension of carbon numbers 1 to 10 Alkyl 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 substituted by- CH = CH- or -C≡C- substitution, in these groups, at least one hydrogen may be substituted by fluorine or chlorine; a is 0, 1, or 2; b, c, and d are independently 0, 1, 2 , 3, or 4; wherein, when ring A and ring C are phenyl, a is 1 or 2, and when a is 1, Sp ¹ and Sp ³ are single bonds. The liquid crystal composition according to item 1 of the patent application range, wherein, in formula (1), P ¹ , P ² , and P ^{3 are} independently selected from formula (P-1) to formula (P-5) The polymerizable group in the group of groups represented,

In formula (P-1) to formula (P-5), M ¹ , M ² , and M ^{3 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or at least one hydrogen is substituted with fluorine or chlorine C1-C5 alkyl. The liquid crystal composition according to item 1 of the patent application range, wherein the first additive is at least one polymerizable compound selected from the group of compounds represented by formula (1-1) to formula (1-12) ,

In formula (1-1) to formula (1-12), P ¹ , P ² , and P ^{3 are} independently selected from the group of groups represented by formula (P-1) to formula (P-3) The polymerizable group of here, M ¹ , M ² , and M ^{3 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine base;

Sp ¹ , Sp ² , and Sp ^{3 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one -CH ₂ -may be passed through -O-, -COO-, -OCO -, Or -OCOO- substitution, 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. The liquid crystal composition according to item 1 of the patent application range, wherein the proportion of the first additive is in the range of 0.03% 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 patent application scope, which contains at least one compound selected from the group of compounds represented by formula (2) as the first component,

In formula (2), R ¹ and R ^{2 are} independently a C 1-12 alkyl group, a C 1-12 alkoxy group, a C 2-12 alkenyl group, or a C 2-12 alkenyl group Oxygen; Ring D and Ring F are independently 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, 1,4-hydrogen substituted with fluorine or chlorine Phenylene, or tetrahydropyran-2,5-diyl; ring E is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene , 2,3-difluoro-5-methyl-1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, or 7,8-difluorochroman-2 , 6-diyl; Z ³ and Z ^{4 are} independently a single bond, -CH ₂ CH _2- , -CH ₂ O-, -OCH _2- , -COO-, or -OCO-; e is 1, 2, Or 3, f is 0 or 1, and the sum of e and f is 3 or less. The liquid crystal composition according to item 5 of the patent application scope, which contains at least one compound selected from the group of compounds represented by formula (2-1) to formula (2-21) as the first component,

In formula (2-1) to formula (2-21), R ¹ and R ^{2 are} independently C 1-12 alkyl, C 1-12 alkoxy, C 2-12 alkenyl , Or an alkoxy group having 2 to 12 carbon atoms. The liquid crystal composition according to item 5 of the patent application range, wherein the proportion of the first component is in the 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 patent application scope, which contains at least one compound selected from the group of compounds represented by formula (3) as the second component,

In formula (3), R ³ and R ^{4 are} independently C 1-12 alkyl, C 1-12 alkoxy, C 2-12 alkenyl, and at least one hydrogen is substituted by fluorine or chlorine Alkyl having 1 to 12 carbons, or alkenyl having 2 to 12 carbons in which at least one hydrogen is substituted with fluorine or chlorine; ring G and ring I are independently 1,4-cyclohexyl, 1,4-extend Phenyl, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene; Z ⁵ is a single bond, -CH ₂ CH _2- , -CH ₂ O-, -OCH _2- , -COO-, or -OCO-; g is 1, 2, or 3. The liquid crystal composition according to item 8 of the patent application scope, which contains at least one compound selected from the group of compounds represented by formula (3-1) to formula (3-13) as the second component,

In formula (3-1) to formula (3-13), R ³ and R ^{4 are} independently C 1-12 alkyl, C 1-12 alkoxy, C 2-12 alkenyl , At least one hydrogen substituted with fluorine or chlorine, a C 1-12 alkyl group, or at least one hydrogen substituted with fluorine or chlorine, a C 2-12 alkenyl group. The liquid crystal composition according to item 8 of the patent application range, wherein the proportion of the second component is in the 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 patent application range, wherein the second additive is a polar compound containing a polar group having a hetero atom selected from nitrogen, oxygen, sulfur, and phosphorus. The liquid crystal composition according to item 11 of the patent application scope, which contains at least one polar compound selected from the group of compounds represented by formula (4) and formula (5) as a second additive, MES-R ⁶ (4) (R ⁵ ) _h -R ⁶ (5) In formula (4), MES is a liquid crystal original group having at least one ring; in formula (5), R ⁵ is an alkyl group having 4 to 20 carbon atoms, so In the alkyl group, at least one -CH ₂ -may be substituted with -CH = CH-, -CF = CH-, -CH = CF-, -C≡C-, or a cycloalkylene group having 3 to 8 carbon atoms, In these groups, at least one hydrogen may be substituted by fluorine or chlorine; in formulas (4) and (5), R ⁶ is an oxygen atom having an OH structure, a sulfur atom having an SH structure, and a first-, second-, or third-order A polar group of at least one of the nitrogen atoms of the amine structure; h is 1 or 2. The liquid crystal composition according to item 12 of the patent application scope, which contains at least one compound selected from the group of compounds represented by formula (4-1) as a second additive,

In formula (4-1), ring J and ring K are independently an aromatic group having 6 to 25 carbon atoms, a heteroaromatic group having 5 to 25 carbon atoms, an alicyclic group having 3 to 25 carbon atoms, or carbon Heteroalicyclic groups of 4 to 25. These groups may be condensed rings. In these groups, at least one hydrogen may be substituted with a group T. Here, the group T is -OH,-(CH ₂ ) _j -OH , Halogen, -CN, -NO ₂ , -NCO, -NCS, -OCN, -SCN, -C (= O) N (R ⁰ ) ₂ , -C (= O) R ⁰ , -N (R ⁰ ) ₂ ,-(CH ₂ ) _j -N (R ⁰ ) ₂ , aryl group having 6 to 20 carbon atoms, heteroaryl group having 6 to 20 carbon atoms, alkyl group having 1 to 25 carbon atoms, and 1 to 25 carbon atoms Alkoxy, C2-C25 alkylcarbonyl, C2-C25 alkoxycarbonyl, C2-C25 alkylcarbonyloxy, or C2-C25 alkoxycarbonyloxy In these groups, at least one hydrogen may be substituted by fluorine or chlorine, where R ⁰ is hydrogen or an alkyl group having 1 to 12 carbons, j is 1, 2, 3, or 4; Z ⁶ is -O- , -S-, -CO-, -CO-O-, -OCO-, -O-CO-O-, -OCH _2- , -CH ₂ O-, -SCH _2- , -CH ₂ S-,- CF ₂ O-, -OCF _2- , -CF ₂ S-, -SCF ₂ -,-(CH ₂ ) _j- , -CF ₂ CH _2- , -CH ₂ CF ₂ -,-(CF ₂ ) _j- , -CH = CH-, -CF = CF-, -C≡C-, -CH = CH-COO-, -OCO-CH = CH-, -C (R ⁰ ) ₂ , or single bond, here, R ⁰ is hydrogen or an alkyl group having 1 to 12 carbons, and j is 1, 2, 3, or 4; R ⁶ is an alkyl group having 1 to 25 carbons, and at least one of the alkyl groups may be -CH _2- by ^{-NR 0 -, - O -,} - S -, - CO -, - COO -, - OCO -, - OCOO-, a cycloalkyl group or a C 3-8 extending substituted, where, R ⁰ is hydrogen Or an alkyl group having 1 to 12 carbons, at least one tertiary carbon (> CH-) may be substituted with nitrogen (> N-), and at least one hydrogen may be substituted with fluorine or chlorine, wherein R ⁶ has an OH structure At least one of an oxygen atom, a sulfur atom in an SH structure, or a nitrogen atom in a primary, secondary, or tertiary amine structure; R ⁷ is hydrogen, halogen, or an alkyl group having 1 to 25 carbon atoms. In the alkyl group, at least One -CH ₂ -can pass -NR ^0- , -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, or carbon number 3 to 8 Cycloalkylene is substituted, and at least one tertiary carbon (> CH-) can be substituted by nitrogen (> N-). In these radicals, at least one hydrogen can be substituted by fluorine or chlorine. Here, R ⁰ is Hydrogen or alkyl having 1 to 12 carbons; i is 0, 1, 2, 3, 4, or 5. The liquid crystal composition according to item 12 of the patent application scope, which contains at least one polar compound selected from the group of compounds represented by formula (5-1) as a second additive, R ⁵ -R ⁶ (5 -1) In the formula (5-1), R ⁵ is an alkyl group having 4 to 20 carbon atoms. In the alkyl group, at least one -CH ₂ -may be substituted by -CH = CH-, -CF = CH-,- CH = CF-, -C≡C-, or a C3 to C8 ring-extended alkyl group, in these groups, at least one hydrogen may be substituted by fluorine or chlorine; R ⁶ is a C 1-25 alkyl group group in which at least one -CH ₂ - may be ^{-NR 0 -, - O -,} - S -, - CO -, - COO -, - OCO -, - OCOO-, from 3 to 8 carbon atoms, or Cycloalkylene substitution, where R ⁰ is hydrogen or an alkyl group having 1 to 12 carbons, at least one tertiary carbon (> CH-) can be substituted by nitrogen (> N-), and at least one hydrogen is also It may be substituted with fluorine or chlorine, wherein R ⁶ has at least one of an oxygen atom of an OH structure, a sulfur atom of an SH structure, or a nitrogen atom of a primary, secondary, or tertiary amine structure. The liquid crystal composition according to item 12 of the patent application scope, wherein, in formulas (4) and (5) according to item 12 of the patent application scope, R ⁶ is from formula (A1) to formula (A4) Any of the bases represented,

In formula (A1) to formula (A4), Sp ⁴ , Sp ⁶ , and Sp ^{7 are} independently a single bond or group (-Sp "-X"-), where Sp "is an extension of carbon numbers 1 to 20 Alkyl group, in the alkylene group, at least one -CH ₂ -may be passed 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, in these groups, at least one hydrogen may be substituted by fluorine, chlorine, or -CN, and X " -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CO-N (R ⁰ )-, -N (R ⁰ )- CO-, -N (R ⁰ ) -CO-N (R ⁰ )-, -OCH _2- , -CH ₂ O-, -SCH _2- , -CH ₂ S-, -CF ₂ O-, -OCF ₂ -, -CF ₂ S-, -SCF _2- , -CF ₂ CH _2- , -CH ₂ CF _2- , -CF ₂ CF _2- , -CH = N-, -N = CH-, -N = N -, -CH = CR ^0- , -CY ² = CY ^3- , -C≡C-, -CH = CH-CO-O-, -O-CO-CH = CH-, or single bond, here, R ⁰ is hydrogen or an alkyl group having 1 to 12 carbons, Y ² and Y ^{3 are} independently hydrogen, fluorine, chlorine, or -CN; Sp ⁵ is>CH-,> CR ¹¹ -,> N-, or> C <; X ¹ is -OH, -OR ¹¹ , -COOH, -NH ₂ , -NHR ¹¹ , -N (R ¹¹ ) ₂ , -SH, -SR ¹¹ ,

Here, R ⁰ is hydrogen or an alkyl group having 1 to 12 carbon atoms; X ² is -O-, -CO-, -NH-, -NR ^11- , -S-, or a single bond; Z ⁷ is a carbon number 1 to 15 alkylene groups, alicyclic groups having 5 or 6 carbon atoms, or a combination of these groups, at least one hydrogen in these groups may be passed through -OH, -OR ¹¹ , -COOH, -NH ₂ ,- NHR ¹¹ , -N (R ¹¹ ) ₂ , fluorine, or chlorine substitution; R ¹¹ is an alkyl group having 1 to 15 carbon atoms, in which at least one -CH ₂ -may be substituted by -C≡C-,- CH = CH-, -COO-, -OCO-, -CO-, or -O-, in these groups, at least one hydrogen may be substituted by fluorine or chlorine; ring L is an aromatic group having 6 to 25 carbon atoms Or an alicyclic group having 3 to 25 carbon atoms, these groups may be condensed rings, and in these groups, 1 to 3 hydrogens may be substituted by R ^L ; R ^L is -OH,-(CH ₂ ) _j- OH, fluorine, chlorine, -CN, -NO ₂ , -NCO, -NCS, -OCN, -SCN, -C (= O) N (R ⁰ ) ₂ , -C (= O) R ⁰ , -N ( R ⁰ ) ₂ ,-(CH ₂ ) _j -N (R ⁰ ) ₂ , -SH, -SR ⁰ , C 6-20 aryl, C 6-20 heteroaryl, C 1-25 Alkyl group, alkoxy group having 1 to 25 carbon atoms, alkylcarbonyl group having 2 to 25 carbon atoms, alkoxycarbonyl group having 2 to 25 carbon atoms, alkylcarbonyloxy group having 2 to 25 carbon atoms, or carbon number The alkoxycarbonyloxy group of 2 to 25, in these groups, at least one hydrogen may be substituted by fluorine or chlorine, where R ⁰ is hydrogen or an alkyl group having 1 to 12 carbons, and j is 1, 2, or 3 , Or 4; k is 0, 1, 2, or 3; m is 2, 3, 4, or 5. The liquid crystal composition according to item 13 of the patent application range, wherein the second additive is at least one selected from the group of compounds represented by formula (4-1-1) to formula (4-1-4) A compound,

In formula (4-1-1) and formula (4-1-4), ring J and ring K are independently 1,4-cyclohexyl, 1,4-phenylene, 2-fluoro-1,4 -Phenylene, 2-fluoro-1,3-phenylene, 2-ethyl-1,4-phenylene, 2,6-diethyl-1,4-phenylene, 2-trifluoro Methyl-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1, 4-phenylene, or 2,3,5,6-tetrafluoro-1,4-phenylene; ring L is cyclohexyl or phenyl; Z ⁶ is a single bond, ethylidene, or carbonyloxy; Z ⁷ is a single bond, an alkylene group having 1 to 15 carbon atoms, an alicyclic group having 5 or 6 carbon atoms, or a combination of these, in which at least one hydrogen can pass through -OH, -OR ¹¹ , -COOH, -NH ₂ , -NHR ¹¹ , -N (R ¹¹ ) ₂ , or halogen substitution, R ¹¹ is an alkyl group having 1 to 15 carbon atoms or a halogenated alkyl group, among these groups, at least one -CH ₂ -Can be substituted by -C≡C-, -CH = CH-, -COO-, -OCO-, -CO-, -O-, or -NH-; Sp ⁴ is a single bond, ethyl, propyl Group, or methyleneoxy group, Sp ⁷ is a single bond, or an alkylene group having 1 to 5 carbon atoms, in which alkyl group, -CH ₂ -may be substituted with -O- or -NH-; R ⁷ C1-C8 alkyl or fluorine; i is 0, ¹ , 2, 3, 4, or 5; X ¹ is -OH, -COOH, -SH, -OCH ₃ , or -NH ₂ ; X ² It is a single bond or -O-. The liquid crystal composition according to item 14 of the patent application range, wherein the second additive is at least one selected from the group of compounds represented by formula (5-1-1) to formula (5-1-29) A compound,

In formula (5-1-1) to formula (5-1-29), R ⁵ is an alkyl group having 4 to 20 carbon atoms, and at least one of the alkyl groups -CH ₂ -may be substituted by -CH = CH- , -CF = CH-, -CH = CF-, -C≡C-, or a cycloalkylene group having 3 to 8 carbon atoms, and in these groups, at least one hydrogen may be substituted by fluorine or chlorine. The liquid crystal composition according to item 11 of the patent application scope, wherein the proportion of the second additive is less than 10% by weight based on the weight of the liquid crystal composition. A liquid crystal display element containing the liquid crystal composition as described in item 1 of the patent application. The liquid crystal display element of claim 19, wherein the operation mode of the liquid crystal display element is a coplanar switching mode, a vertical alignment mode, a fringe field switching mode, or an electric field induced light reaction alignment mode, and the liquid crystal display element The driving method is active matrix method. A polymer-stabilized alignment type liquid crystal display element, which contains the liquid crystal composition as described in item 1 of the patent application range, and the polymerizable compound in the liquid crystal composition is polymerized. A liquid crystal display element without an alignment film contains the liquid crystal composition as described in item 1 of the patent application scope, and the polymerizable compound in the liquid crystal composition is polymerized. Use of a liquid crystal composition, which is the liquid crystal composition as described in item 1 of the patent application scope, which is used in a liquid crystal display element. Use of a liquid crystal composition, which is the liquid crystal composition as described in item 1 of the patent application range, which is used in a polymer-stabilized alignment type liquid crystal display element. Use of a liquid crystal composition, which is the liquid crystal composition as described in item 1 of the patent application range, which is used in a liquid crystal display element without an alignment film.