KR20190100909A - Liquid crystal composition and liquid crystal display element - Google Patents

Abstract

The object of the present invention is at least one of properties such as high upper limit temperature, low lower limit temperature, small viscosity, suitable optical anisotropy, negatively large dielectric anisotropy, large specific resistance, high stability against UV light, high stability against heat. It is to provide a liquid crystal composition which satisfies characteristics or has a suitable balance between at least two of these characteristics. As a solution to this problem, an advantage of the present invention is a compound having a high solubility in a liquid crystal composition as a first additive and having an effect of suppressing display defects of a liquid crystal display element, and having negatively large dielectric anisotropy as a first component. It is a liquid crystal composition containing a specific compound and having negative dielectric anisotropy. This composition may contain the specific compound which has a high upper limit temperature or a small viscosity as a 2nd component, and the specific compound which has a polymeric group as a 2nd additive.

Description

Liquid crystal composition and liquid crystal display element

This invention relates to the liquid crystal composition containing a piperidine derivative, the liquid crystal display element containing this composition, etc. In particular, it relates to a liquid crystal composition having a negative dielectric anisotropy, and an element containing the composition and having modes such as IPS, VA, FFS, and FPA. The present invention also relates to a polymer-supported alignment device.

In the liquid crystal display device, the classification based on the operation mode of the liquid crystal molecules is divided into phase change (PC), twisted nematic (TN), super twisted nematic (STN), electrically controlled birefringence (ECB), optically compensated bend (OCB), and IPS. (in-plane switching), vertical alignment (VA), fringe field switching (FFS), and field-induced photo-reactive alignment (FPA). The classification based on the driving method of an element is a passive matrix (PM) and an active matrix (AM). PM is classified into static, multiplex, etc., and AM is classified into a thin film transistor (TFT), a metal insulator metal (MIM), and the like. The classification of TFTs is amorphous silicon and polycrystal silicon. The latter is classified into high temperature type and low temperature type according to the manufacturing process. The classification based on the light source is a reflection type using natural light, a transmission type using a backlight, and a semi-transmissive type using both natural light and a backlight.

The liquid crystal display element contains a liquid crystal composition having a nematic phase. This composition has appropriate properties. By improving the properties of this composition, an AM device having good properties can be obtained. The relevance in these properties is summarized in Table 1 below. The properties of the composition will be further described based on commercially available AM devices. The temperature range of the nemctic phase is related to the temperature range in which the device can be used. The preferable upper limit temperature of a nematic phase is about 70 degreeC or more, and the preferable minimum temperature of a nematic phase is about -10 degreeC or less. The viscosity of the composition is related to the response time of the device. Short response times are desirable for displaying moving images with the device. Shorter response times are preferred even at 1 millisecond. Therefore, small viscosities in the composition are preferred. Small viscosities at low temperatures are more preferred.

TABLE 1 Properties of composition and properties in AM device

Optical anisotropy of the composition is related to the contrast ratio of the device. Depending on the mode of the device, either large optical anisotropy or small optical anisotropy, i. The product (Δn × d) of the optical anisotropy (Δn) of the composition and the cell gap (d) of the device is designed to maximize the contrast ratio. The appropriate value of the product depends on the type of operating mode. This value is in the range of about 0.30 µm to about 0.40 µm in the VA mode element, and in the range of about 0.20 µm to about 0.30 µm in the IPS mode or FFS mode element. In these cases, the composition which has big optical anisotropy is preferable for the element of a small cell gap. Large dielectric anisotropy in the composition contributes to low threshold voltage, small power consumption and large contrast ratio in the device. Therefore, large dielectric anisotropy is desirable. The large specific resistance in the composition contributes to the large voltage retention and the large contrast ratio in the device. Therefore, a composition having a large specific resistance in the initial stage is preferable. After using for a long time, a composition having a large specific resistance is preferable. The stability of the composition against ultraviolet light or heat is related to the life of the device. When this stability is high, the lifetime of the device is long. Such a characteristic is suitable for an AM element used for a liquid crystal projector, a liquid crystal television, etc.

In the general-purpose liquid crystal display device, vertical alignment of liquid crystal molecules is achieved by a specific polyimide alignment film. In a polymer sustained alignment (PSA) type liquid crystal display device, a polymer is combined with an alignment film. First, a composition to which a small amount of the polymerizable compound is added is injected into the device. Next, an ultraviolet-ray is irradiated to a composition, applying a voltage between the board | substrates of this element. The polymerizable compound is polymerized to produce the mesh structure of the polymer in the composition. In this composition, since it becomes possible to control the orientation of the liquid crystal molecules by the polymer, the response time of the element is shortened and the baking of the image is improved. Such effects of polymers can be expected for devices having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.

In an AM device having a TN mode, a composition having positive dielectric anisotropy is used. In an AM device having a VA mode, a composition having negative dielectric anisotropy is used. In an AM device having the IPS mode or the FFS mode, a composition having positive or negative dielectric anisotropy is used. In the polymer-supported alignment type AM device, a composition having positive or negative dielectric anisotropy is used. The composition containing the compound similar to the compound (1) of this invention is disclosed by patent documents 1 and 2.

International Publication No. 2012/76105 Japanese Patent Application Laid-Open No. 2014-84460

One object of the present invention is a high upper temperature of the nematic phase, a low lower temperature of the nematic phase, a small viscosity, a suitable optical anisotropy, negatively large dielectric anisotropy, a large specific resistance, high stability against ultraviolet rays, high stability against heat, afterimage It is to provide a liquid crystal composition that satisfies at least one of characteristics such as suppression of display defects such as the like. Another object is to provide a liquid crystal composition having a suitable balance between at least two of these properties. Another object is to provide a liquid crystal display element containing such a composition. Another object is to provide an AM device having characteristics such as a short response time, a large voltage holding ratio, a low threshold voltage, a large contrast ratio and a long service life.

The present invention contains at least one compound selected from the group of compounds represented by formula (1) as the first additive and at least one compound selected from the group of compounds represented by formula (2) as the first component, It relates to a liquid crystal composition having a dielectric anisotropy of and a liquid crystal display element containing the composition.

In formulas (1) and (2), R ¹ and R ² are independently hydrogen, hydroxy, oxyradical, alkyl having 1 to 12 carbons, or alkoxy having 1 to 12 carbons; R ³ and R ⁴ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyloxy having 2 to 12 carbons; Ring A and Ring C are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen is fluorine or 1,4-phenylene, naphthalene-2,6-diyl substituted by chlorine, naphthalene-2,6-diyl, chroman-2,6-diyl, or at least 1 substituted with at least one hydrogen by fluorine or chlorine Hydrogens are Cromman-2,6-diyl substituted with fluorine or chlorine; Ring B is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4 -Phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, or 7,8-difluorochroman-2,6-diyl; Z ¹ is alkylene having 1 to 7 carbon atoms; Z ² and Z ³ are independently a single bond, ethylene, carbonyloxy, or methyleneoxy; a is 1, 2 or 3, b is 0 or 1, and the sum of a and b is 3 or less.

One advantage of the present invention is that the high upper temperature of the nematic phase, the low lower temperature of the nematic phase, small viscosity, suitable optical anisotropy, negatively large dielectric anisotropy, large specific resistance, high stability against ultraviolet rays, high stability against heat, afterimage It is to provide a liquid crystal composition that satisfies at least one of characteristics such as suppression of display defects such as the like. Another advantage is to provide a liquid crystal composition having a suitable balance between at least two of these properties. Another advantage is to provide a liquid crystal display element containing such a composition. Another advantage is to provide an AM device with characteristics such as short response time, large voltage retention, low threshold voltage, large contrast ratio and long lifetime.

Usage of the terms in the present specification are as follows. The terms "liquid crystal composition" and "liquid crystal display element" may be abbreviated as "composition" and "element", respectively. "Liquid crystal display element" is a generic term for a liquid crystal display panel and a liquid crystal display module. The term "liquid crystalline compound" is a compound having a liquid crystal phase such as a nematic phase, a smectic phase, and a liquid crystal phase, but the compound mixed in the composition for the purpose of adjusting characteristics such as temperature range, viscosity, and dielectric anisotropy of the nematic phase Collectively. This compound has 6-membered rings, such as 1, 4- cyclohexylene and 1, 4- phenylene, for example, and its molecular structure is rod-like. A "polymerizable compound" is a compound added for the purpose of producing a polymer in the composition. The liquid crystalline compound having alkenyl is not polymerizable in this sense.

The liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. Additives, such as an optically active compound, antioxidant, a ultraviolet absorber, a pigment | dye, an antifoamer, a polymeric compound, a polymerization initiator, a polymerization inhibitor, and a polar compound, are added to this liquid crystal composition as needed. The ratio of a liquid crystalline compound is represented by the mass percentage (mass%) based on the mass of the liquid crystal composition which does not contain an additive, even when an additive is added. The ratio of an additive is represented by the mass percentage (mass%) based on the mass of the liquid crystal composition which does not contain an additive. That is, the ratio of the liquid crystal compound and the additive is calculated based on the total mass of the liquid crystal compound. Mass parts per million (ppm) may be used. The proportion of the polymerization initiator and the polymerization inhibitor is exceptionally expressed based on the mass of the polymerizable compound.

"Upper limit temperature of a nematic phase" may be abbreviated as "upper limit temperature". The "lower limit temperature of a nematic phase" may be abbreviated as "lower limit temperature". "Large resistivity" means that a composition has a large specific resistance in an initial stage, and after using for a long time, it has a large specific resistance. "Large voltage retention" means that the device has a large voltage retention not only at room temperature but also near the upper limit temperature in the initial stage, and has a large voltage retention not only at room temperature but also close to the upper limit temperature after long time use. it means. The characteristic of a composition and an element may be examined by the time-dependent change test. The expression "increasing dielectric anisotropy" means that the value increases positive when the composition has a positive dielectric anisotropy, and that the value increases negative when the composition has a negative dielectric anisotropy.

The expression "at least one -CH ₂ -may be substituted with -O-" is used herein. In this case, -CH ₂ -CH ₂ -CH ₂ -may be converted to -O-CH ₂ -O- by replacing non-adjacent -CH ₂ -with -O-. However, adjacent -CH ₂ -is not substituted with -O-. This is because -OO-CH _2- (peroxide) is produced by this substitution. That is, this expression means 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 substitution with -O- but also substitution with a divalent group such as -CH = CH- or -COO-.

In the chemical formula of the component compound, the symbol of the terminal group R ¹ was used for a plurality of compounds. In these compounds, two groups represented by any two R ¹ may be the same. It may be different. For example, the R ¹ is ethyl of the compound (1-1), the R ¹ of the compound (1-2) in case there is ethyl. And the R ¹ of the compound 1-1 is ethyl, there are cases of R ¹ the profile of compound (1-2). This rule also applies to other symbols. In Formula (2), when the subscript 'a' is 2, two rings A exist. In this compound, two rings represented by two rings A may be the same. It may be different. This rule also applies to any two rings A when the subscript 'a' is greater than two. This rule also applies to other symbols. This rule applies also when a compound has a substituent represented by the same symbol.

Symbols such as A, B, C, and D enclosed in 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 compound (4), an oblique line across one side of the hexagon indicates that any hydrogen in a ring may be substituted with a group such as -Sp ¹ -P ¹ . Subscripts such as 'e' indicate the number of substituted groups. When the subscript 'e' is zero, there is no such substitution. When the subscript 'e' is 2 or more, a plurality of -Sp ¹ -P ¹ exists on the ring F. The plurality of groups represented by -Sp ¹ -P ¹ may be the same. In the expression of "ring A and ring B are independently X, Y, or Z", since a plurality of subjects are used, "independently" is used. When the subject is "ring A", do not use "independently" because the subject is singular.

 2-fluoro-1,4-phenylene means the following two divalent groups. In the chemical formula, fluorine may be leftward (L) or rightward (R). This rule also applies to bilaterally asymmetric divalent groups produced by removing two hydrogens from a ring, such as tetrahydropyran-2,5-diyl. This rule also applies to bivalent bonding groups such as carbonyloxy (-COO- or -OCO-).

Alkyl of a liquid crystalline compound is linear or branched, and does not contain cyclic alkyl. Linear alkyl is more preferable than branched alkyl. The same applies to terminal groups such as alkoxy and alkenyl. As for the three-dimensional arrangement regarding 1, 4- cyclohexylene, trans is more preferable than cis in order to raise an upper limit temperature.

The present invention is as follows.

Item 1. At least one compound selected from the group of compounds represented by formula (1) as a first additive and at least one compound selected from the group of compounds represented by formula (2) as a first component, wherein Liquid crystal composition having dielectric anisotropy.

In formulas (1) and (2), R ¹ and R ² are independently hydrogen, hydroxy, oxyradical, alkyl having 1 to 12 carbons, or alkoxy having 1 to 12 carbons; R ³ and R ⁴ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyloxy having 2 to 12 carbons; Ring A and Ring C are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen is fluorine or 1,4-phenylene, naphthalene-2,6-diyl substituted by chlorine, naphthalene-2,6-diyl, chroman-2,6-diyl, or at least 1 substituted with at least one hydrogen by fluorine or chlorine Hydrogens are Cromman-2,6-diyl substituted with fluorine or chlorine; Ring B is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4 -Phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, or 7,8-difluorochroman-2,6-diyl; Z ¹ is alkylene having 1 to 7 carbon atoms; Z ² and Z ³ are independently a single bond, ethylene, carbonyloxy, or methyleneoxy; a is 1, 2 or 3, b is 0 or 1, and the sum of a and b is 3 or less.

Item 2. The liquid crystal composition according to item 1, which contains at least one compound selected from the group of compounds represented by formulas (1-1) to (1-3) as the first additive.

In Formulas (1-1) to (1-3), R ¹ and R ² are independently hydrogen, hydroxy, oxyradical, alkyl having 1 to 12 carbons, or alkoxy having 1 to 12 carbons.

Item 3. The liquid crystal composition according to Item 1 or 2, wherein R ¹ is hydrogen and R ² is hydroxy, oxyradical, alkyl having 1 to 12 carbons, or alkoxy having 1 to 12 carbons.

Item 4. The liquid crystal composition according to any one of items 1 to 3, containing at least one compound selected from the group of compounds represented by formulas (2-1) to (2-22) as the first component.

In formulas (2-1) to (2-22), R ³ and R ⁴ are each independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or 2 carbon atoms. Alkenyloxy of -12.

Item 5. The liquid crystal composition according to any one of Items 1 to 4, wherein a ratio of the first additive is in a range of 0.005% by mass to 1% by mass.

Item 6. The liquid crystal composition according to any one of Items 1 to 5, wherein a proportion of the first component is in a range of 10% by mass to 90% by mass.

Item 7. The liquid crystal composition according to any one of items 1 to 6, containing at least one compound selected from the group of compounds represented by formula (3) as a second component.

In formula (3), R <^5> and R <^6> is independently C1-C12 alkyl, C1-C12 alkoxy, C2-C12 alkenyl, At least 1 hydrogen is substituted with fluorine or chlorine Alkyl of 1 to 12, or at least one hydrogen is alkenyl of 2 to 12 carbon atoms substituted with fluorine or chlorine; Ring D and Ring E are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenyl Ren; Z ⁴ is a single bond, ethylene or carbonyloxy; c is 1, 2, or 3.

Item 8. The liquid crystal composition according to any one of Items 1 to 7, which contains at least one compound selected from the group of compounds represented by formulas (3-1) to (3-13) as a second component.

In formulas (3-1) to (3-13), R ⁵ and R ⁶ are each independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, and at least one Alkyl having 1 to 12 carbons in which hydrogen is substituted with fluorine or chlorine, or alkenyl having 2 to 12 carbons in which at least one hydrogen is substituted with fluorine or chlorine.

Item 9. The liquid crystal composition according to item 7 or 8, wherein the ratio of the second component is in the range of 10% by mass to 90% by mass.

Item 10. The liquid crystal composition according to any one of items 1 to 9, containing at least one compound selected from the group of polymerizable compounds represented by formula (4) as a second additive.

In (4), ring F and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2 -Yl, pyrimidin-2-yl, or pyridin-2-yl, and in these rings, at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least 1 Hydrogens may be substituted with alkyl having 1 to 12 carbons substituted with fluorine or chlorine; Ring G is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4- Diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, Naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, In these rings, at least one hydrogen is substituted with fluorine, chlorine, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, or alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. May; Z ⁵ and Z ⁶ are independently a single bond or alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one -CH ₂ -is -O-, -CO-, -COO-, or- May be substituted with OCO-, and at least one -CH ₂ CH ₂ -is -CH = CH-, -C (CH ₃ ) = CH-, -CH = C (CH ₃ )-, or -C (CH ₃ ) = C (CH ₃ )-, and in these groups, at least one hydrogen may be substituted with fluorine or chlorine; P ¹ , P ² , and P ³ are independently a polymerizable group; Sp ¹ , Sp ² , and Sp ³ are independently a single bond or alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one -CH ₂ -is -O-, -COO-, -OCO Or may be substituted with -OCOO-, and at least one -CH ₂ -CH ₂ -may be substituted with -CH = CH- or -C≡C-, and in these groups, at least one hydrogen is May be substituted with fluorine or chlorine; d is 0, 1, or 2; e, f, and g are 0, 1, 2, 3, or 4 independently, and the sum of e, f, and g is 1 or more.

Item 11. The formula (4), wherein P ¹ , P ² , and P ³ are independently selected from the group of the polymerizable groups represented by formulas (P-1) to (P-5). Liquid crystal composition.

In formulas (P-1) to (P-5), M ¹ , M ² , and M ³ are independently hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or at least one hydrogen is fluorine or chlorine. Substituted alkyl having 1 to 5 carbon atoms.

Item 12. The liquid crystal composition according to any one of items 1 to 11, containing at least one compound selected from the group of polymerizable compounds represented by formulas (4-1) to (4-27) as a second additive. .

In formulas (4-1) to (4-27), P ⁴ , P ⁵ , and P ⁶ are independently selected from the group of polymerizable groups represented by formulas (P-1) to (P-3). Is the selected group,

Wherein M ¹ , M ² , and M ³ are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced with fluorine or chlorine; Sp ¹ , Sp ² , and Sp ³ are independently a single bond or alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one -CH ₂ -is -O-, -COO-, -OCO Or may be substituted with -OCOO- and at least one -CH ₂ CH ₂ -may be substituted with -CH = CH- or -C≡C-, and in these groups, at least one hydrogen is It may be substituted with fluorine or chlorine.

Item 13. The liquid crystal composition according to any one of Items 10 to 12, wherein the ratio of the second additive is in the range of 0.03% by mass to 10% by mass.

Item 14. A liquid crystal display device containing the liquid crystal composition according to any one of items 1 to 13.

Item 15. The liquid crystal display element according to item 14, wherein the operation mode of the liquid crystal display element is IPS mode, VA mode, FFS mode, or FPA mode, and the drive method of the liquid crystal display element is an active matrix system.

Item 16. The polymer-supported alignment type liquid crystal display device containing the liquid crystal composition according to any one of items 10 to 13, wherein the second additive contained in the liquid crystal composition is polymerized.

Item 17. Use of liquid crystal composition according to any one of items 1 to 13 in a liquid crystal display device.

Item 18. Use of the liquid crystal composition according to any one of items 1 to 13 in a polymer-supported alignment type liquid crystal display device.

The present invention also includes the following terms. (a) Said composition which further contains at least 1 of additives, such as an optically active compound, antioxidant, a ultraviolet absorber, a pigment | dye, an antifoamer, a polymeric compound, a polymerization initiator, a polymerization inhibitor, and a polar compound. (b) AM element containing said composition. (c) A polymer-supported orientation (PSA) type AM element containing the above-mentioned composition which further contains a polymeric compound. (d) A polymer-supported orientation (PSA) type AM element containing the composition mentioned above and to which the polymerizable compound in this composition is polymerized. (e) A device containing the composition described above and having a mode of PC, TN, STN, ECB, OCB, IPS, VA, FFS, or FPA. (f) A transmissive element containing the composition described above. (g) Use of said composition as a composition which has a nematic phase. (h) Use as an optically active composition by adding an optically active compound to said composition.

This compound was found to be effective for suppressing display defects of the device as shown in Comparative Examples and Examples. However, the cause of display defects is complicated and has not been sufficiently identified. In addition, the effect of this compound on poor display is not clear at this stage. In such a situation, the description as described in the following paragraphs will be possible.

When the element is used for a long time, the luminance may be partially lowered. One example is a line afterimage, which is a phenomenon in which the luminance between electrodes is reduced to a stripe shape by repeatedly applying different voltages to two adjacent electrodes. This phenomenon is attributable to the accumulation of ionic impurities contained in the liquid crystal composition on the alignment film near the electrode. Therefore, in order to suppress an afterimage, it is effective to prevent localization of an ion impurity on an alignment film. For this purpose, the surface of the alignment film is covered with an additive such as a polar compound, and ionic impurities are adsorbed to the additive. It is important that such additives have high solubility in the liquid crystal composition in order to obtain the desired effect.

The liquid crystal composition is injected from the injection port into the element under reduced pressure. Usually, the composition is filled into the device without changing the proportions of its components. However, additives such as polar compounds may be adsorbed onto the alignment film. When the adsorption rate is large, the additive may not reach the depth of the device in some cases. The addition remains because the adsorption rate is larger than the injection rate. In order to prevent this phenomenon, the additive which has suitable adsorption property with respect to an oriented film is preferable. Therefore, it is also important to select additives having the appropriate polarity. Compound (1) is suitable for this purpose.

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 properties of the component compounds and the main effects of these compounds on the composition or the device are described. Third, the combination of components in the composition, the preferred ratio of the components and the basis thereof will be described. Fourth, a preferred form of the component compound will be described. Fifth, preferred component compounds are shown. Sixth, the additive which may be added to a composition is demonstrated. Seventh, the synthesis method of the component compounds will be described. Finally, the use of the composition is described.

First, the composition of the composition will be described. This composition contains several liquid crystalline compounds. This composition may contain an additive. The additives are optically active compounds, antioxidants, ultraviolet absorbers, pigments, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds and the like. This composition is classified into composition A and composition B from a viewpoint of a liquid crystalline compound. The composition A may further contain other liquid crystalline compounds, additives and the like in addition to the liquid crystalline compounds selected from the compound (2) and the compound (3). "Other liquid crystalline compounds" are liquid crystalline compounds different from compound (2) and compound (3). Such a compound is mixed with a composition for the purpose of further adjusting a characteristic.

Composition B consists essentially of liquid crystal compounds selected from compound (2) and compound (3). "Substantially" means that although the composition B may contain an additive, it does not contain another liquid crystalline compound. Composition B has fewer components than composition A. From the viewpoint of lowering the cost, the composition B is preferable to the composition A. The composition A is more preferable than the composition B from a viewpoint which can further adjust a characteristic by mixing another liquid crystalline compound.

Second, the main properties of the component compounds and the main effects of these compounds on the composition or the device are described. The main characteristics of the component compounds are summarized in Table 2 based on the effects of the present invention. In the symbol of Table 2, L means big or high, M means medium, and S means small or low. The symbols L, M and S are classifications based on a qualitative comparison between the component compounds, and 0 (zero) means extremely small.

[Table 2] Characteristics of Liquid Crystal Compound

The main effects of the component compounds are as follows. Compound (1) contributes to suppression of poor display. Since compound (1) is extremely small in addition amount, in many cases, it does not affect characteristics, such as an upper limit temperature, optical anisotropy, and dielectric anisotropy. Compound (2) increases the dielectric anisotropy and lowers the lower limit temperature. Compound (3) lowers a viscosity or raises an upper limit temperature. Since compound (4) is polymerizable, a polymer is provided by polymerization. Since this polymer stabilizes the orientation of liquid crystal molecules, it shortens the response time of an element and improves the burn-out of an image.

Third, the combination of components in the composition, the preferred proportions of the component compounds and the basis thereof will be described. Preferred combinations of the components in the composition are Compound (1) + Compound (2), Compound (1) + Compound (3), Compound (1) + Compound (2) + Compound (3), Compound (1) + Compound (2) + Compound (4), Compound (1) + Compound (3) + Compound (4), or Compound (1) + Compound (2) + Compound (3) + Compound (4). A more preferable combination is compound (1) + compound (2) + compound (3) or compound (1) + compound (2) + compound (3) + compound (4).

The preferable ratio of compound (1) is about 0.005 mass% or more in order to suppress display defects, and is about 1 mass% or less in order to lower | hang minimum temperature. A more preferable ratio is the range of about 0.02 mass%-about 0.5 mass%. An especially preferable ratio is the range of about 0.12 mass%-about 0.3 mass%.

The preferable ratio of compound (2) is about 10 mass% or more in order to improve dielectric constant anisotropy, and about 90 mass% or less in order to lower | hang minimum temperature. A more preferable ratio is the range of about 20 mass%-about 80 mass%. An especially preferable ratio is the range of about 30 mass%-about 75 mass%.

A preferred ratio of the compound (3) is about 10% by mass or more for increasing the maximum temperature or decreasing the viscosity, and about 90% by mass or less for increasing the dielectric anisotropy. A more preferable ratio is the range of about 20 mass%-about 80 mass%. An especially preferable ratio is the range of about 30 mass%-about 70 mass%.

Compound (4) is added to a composition for the purpose of making it suitable for a polymer support orientation element. The preferred ratio of the compound (4) is about 0.03% by mass or more in order to orient the liquid crystal molecules, and about 10% by mass or less in order to prevent display defects of the device. A more preferable ratio is the range of about 0.1 mass%-about 2 mass%. An especially preferable ratio is the range of about 0.2 mass%-about 1.0 mass%.

Fourth, a preferred form of the component compound will be described. In Formula (1), Formula (2), and Formula (3), R <^1> and R <^2> is hydrogen, hydroxy, oxy radical, C1-C12 alkyl, or C1-C12 alkoxy independently. Preferred combinations of R ¹ and R ² are both hydrogen in order to increase stability against ultraviolet rays and heat, and one side is hydrogen, the other side is hydroxy, oxyradical, in order to suppress poor display and lower the minimum temperature. Or alkyl having 1 to 12 carbons. R <^3> and R <^4> is independently C1-C12 alkyl, C1-C12 alkoxy, C2-C12 alkenyl, or C2-C12 alkenyloxy. Preferable R <^3> or R <^4> is C1-C12 alkyl in order to improve stability to an ultraviolet-ray or heat, and is C1-C12 alkoxy in order to improve dielectric constant anisotropy. R ⁵ and R ⁶ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkyl having 1 to 12 carbons in which at least one hydrogen is replaced with fluorine or chlorine, or At least one hydrogen is alkenyl having 2 to 12 carbon atoms substituted with fluorine or chlorine. Preferable R <^5> or R <^6> is C2-C12 alkenyl in order to reduce a viscosity, and in order to improve stability to an ultraviolet-ray or heat, it is C1-C12 alkyl.

Preferred alkyl is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl. More preferred alkyl is methyl, ethyl, propyl, butyl, or pentyl to lower the viscosity.

Preferred alkoxy is methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy or heptyloxy. In order to lower a viscosity, more preferable alkoxy is methoxy or ethoxy.

Preferred alkenyls are vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-phene Tenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl. More preferred alkenyl is vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl to lower the viscosity. Preferred steric configuration of -CH = CH- in this alkenyl depends on the position of the double bond. Trans is preferable in alkenyl, such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl, and 3-hexenyl, for the purpose of lowering the viscosity. For alkenyl such as 2-butenyl, 2-pentenyl, 2-hexenyl, cis is preferred.

Preferred alkenyloxy is vinyloxy, allyloxy, 3-butenyloxy, 3-pentenyloxy, or 4-pentenyloxy. In order to lower | hang a viscosity, more preferable alkenyloxy is allyl oxy or 3-butenyloxy.

Preferred examples of alkyl in which at least one hydrogen is substituted with fluorine or chlorine are fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl , 7-fluoroheptyl, or 8-fluorooctyl. More preferred examples are 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, or 5-fluoropentyl for increasing the dielectric anisotropy.

Preferred examples of alkenyl in which at least one hydrogen is substituted with fluorine include 2,2-difluorovinyl, 3,3-difluoro-2-propenyl and 4,4-difluoro-3-butenyl , 5,5-difluoro-4-pentenyl, or 6,6-difluoro-5-hexenyl. More preferred examples are 2,2-difluorovinyl or 4,4-difluoro-3-butenyl in order to lower the viscosity.

Ring A and Ring C are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen is fluorine or 1,4-phenylene, naphthalene-2,6-diyl substituted by chlorine, naphthalene-2,6-diyl, chroman-2,6-diyl, or at least 1 substituted with at least one hydrogen by fluorine or chlorine Hydrogens are Chroman-2,6-diyl substituted with fluorine or chlorine. Preferred ring A or ring C is 1,4-cyclohexylene for decreasing the viscosity, tetrahydropyran-2,5-diyl for increasing the dielectric anisotropy and 1,4-phenylene for increasing the optical anisotropy. Ring B is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4 -Phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, or 7,8-difluorochroman-2,6-diyl. Preferred ring B is 2,3-difluoro-1,4-phenylene for decreasing the viscosity, 2-chloro-3-fluoro-1,4-phenylene for decreasing the optical anisotropy, and the dielectric anisotropy 7,8-difluorochroman-2,6-diyl for height. Tetrahydropyran-2,5-diyl is,

or

, Preferably

to be.

Ring D and Ring E are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenyl Ren. Preferred ring D or ring E is 1,4-cyclohexylene for decreasing the viscosity or for increasing the maximum temperature, and 1,4-phenylene for decreasing the minimum temperature.

Z ¹ is alkylene having 1 to 7 carbon atoms. Preferred Z ¹ is alkylene having 2 carbon atoms in order to increase stability to ultraviolet rays and heat, and alkylene having 4 carbon atoms or 6 carbon atoms in order to lower the minimum temperature. Z ² and Z ³ are independently a single bond, ethylene, carbonyloxy, or methyleneoxy. Preferred Z ² or Z ³ is a single bond for decreasing the viscosity, ethylene for decreasing the minimum temperature, and methyleneoxy for increasing the dielectric anisotropy. Z ⁴ is a single bond, ethylene, or carbonyloxy. Preferred Z ⁴ is a single bond in order to increase stability to ultraviolet rays or heat.

a is 1, 2 or 3, b is 0 or 1, and the sum of a and b is 3 or less. Preferred a is 1 for decreasing the viscosity, and 2 or 3 for increasing the maximum temperature. Preferred b is 0 for decreasing the viscosity, and 1 for decreasing the minimum temperature. c is 1, 2, or 3. Preferred c is 1 for decreasing the viscosity, and 2 or 3 for increasing the maximum temperature.

In Formula (4), P <^1> , P <^2> and P <^3> are a polymeric group independently. Preferred P ¹ , P ² , or P ³ is a polymerizable group selected from the group of the groups represented by formulas (P-1) to (P-5). More preferable P ¹ , P ² , or P ³ is group (P-1) or group (P-2). A particularly preferred group (P-1) is a-CH = CH ₂ or -OCO _{-OCO-C (CH 3) =} CH 2. The broken line of group (P-1)-group (P-5) shows the site | part to couple.

In groups (P-1) to (P-5), M ¹ , M ² , and M ³ are independently hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or at least one hydrogen is fluorine or chlorine. Substituted alkyl having 1 to 5 carbon atoms. Preferred M ¹ , M ² , or M ³ is hydrogen or methyl in order to increase the reactivity. More preferred M ¹ is methyl and more preferred M ² or M ³ is hydrogen.

In formulas (4-1) to (4-27), P ⁴ , P ⁵ , and P ⁶ are groups represented by formulas (P-1) to (P-3) independently. Preferred P ⁴ , P ⁵ , or P ⁶ is group (P-1) or group (P-2). More preferable group (P-1) is -OCO-CH = CH ₂ or -OCO-C (CH ₃ ) = CH ₂ . The broken line of group (P-1)-group (P-3) shows the site | part to couple.

In the formula ^{(4), Sp 1, Sp} 2, Sp ^3, and are, each independently, a single bond or an alkylene group of 1 to 10 carbon atoms, in the alkylene group, at least one -CH ₂ - is, -O- , -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ CH ₂ -may be substituted with -CH = CH- or -C≡C-, At least one hydrogen may be substituted with fluorine or chlorine. Preferred 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-. More preferable Sp ¹ , Sp ² or Sp ³ is a single bond.

Ring F and Ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, pyrimidine- 2-yl or pyridin-2-yl, and in these rings, at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, or at least one hydrogen is fluorine or chlorine. It may be substituted with alkyl having 1 to 12 carbon atoms substituted with. Preferred ring F or ring I is phenyl. Ring G is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4- Diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, Naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, In these rings, at least one hydrogen is substituted with fluorine, chlorine, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, or alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. It may be. Preferred ring G is 1,4-phenylene or 2-fluoro-1,4-phenylene.

Z ⁵ and Z ⁶ are independently a single bond or alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one -CH ₂ -is -O-, -CO-, -COO-, or- May be substituted with OCO-, and at least one -CH ₂ CH ₂ -is -CH = CH-, -C (CH ₃ ) = CH-, -CH = C (CH ₃ )-, or -C (CH ₃ ) = C (CH ₃ )-, and in these groups, at least one hydrogen may be substituted with fluorine or chlorine. Preferred Z ⁵ or Z ⁶ is a single bond, -CH ₂ CH _2- , -CH ₂ O-, -OCH _2- , -COO-, or -OCO-. More preferable Z ⁵ or Z ⁶ is a single bond.

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

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

Preferred compound (2) is compound (2-1) to compound (2-22) described in item 4. In these compounds, at least 1 of a 1st component is a compound (2-1), a compound (2-3), a compound (2-4), a compound (2-6), a compound (2-8), or a compound It is preferable that it is (2-10). At least two of the first components include compound (2-1) and compound (2-6), compound (2-1) and compound (2-10), compound (2-3) and compound (2-6), It is preferable that it is a compound (2-3) and a compound (2-10), a compound (2-4) and a compound (2-6), or a combination of a compound (2-4) and a compound (2-8).

Preferred compound (3) is compound (3-1) to compound (3-13) described in item 8. In these compounds, at least 1 of a 2nd component is a compound (3-1), a compound (3-3), a compound (3-5), a compound (3-6), a compound (3-8), or a compound It is preferable that it is (3-9). At least two of the second components include compound (3-1) and compound (3-3), compound (3-1) and compound (3-5), or compound (3-1) and compound (3-6). It is preferable that it is a combination of.

Preferred compound (4) is compound (4-1) to compound (4-27) described in item 12. In these compounds, at least one of the second additives is compound (4-1), compound (4-2), compound (4-24), compound (4-25), compound (4-26), or compound It is preferable that it is (4-27). At least two of the second additives include compound (4-1) and compound (4-2), compound (4-1) and compound (4-18), compound (4-2) and compound (4-24), Compound (4-2) and compound (4-25), compound (4-2) and compound (4-26), compound (4-25) and compound (4-26), or compound (4-18) and It is preferable that it is a combination of compound (4-24).

Sixth, the additive which may be added to a composition is demonstrated. Such additives are optically active compounds, antioxidants, ultraviolet absorbers, pigments, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds and the like. An optically active compound is added to the composition for the purpose of inducing the helical structure of the liquid crystal to impart a twist angle. Examples of such a compound include compound (5-1) to compound (5-5). The preferable ratio of an optically active compound is about 5 mass% or less. A more preferable ratio is the range of about 0.01 mass%-about 2 mass%.

An antioxidant is added to the composition in order to prevent a decrease in specific resistance due to heating in the atmosphere or to maintain a large voltage retention not only at room temperature but also at a temperature close to an upper limit temperature after using the device for a long time. Preferable examples of the antioxidant are compounds (6) and the like in which n is an integer of 1 to 9.

In compound (6), preferable n is 1, 3, 5, 7, or 9. More preferred n is 7. Since compound (6) of n is 7 has low volatility, it is effective in maintaining a large voltage retention not only at room temperature but also at a temperature close to an upper limit temperature after using an element for a long time. The preferable ratio of antioxidant is about 50 ppm or more in order to acquire the effect, and is about 600 ppm or less so that an upper limit temperature may not be lowered or a lower limit temperature may not be raised. A further preferred ratio is in the range of about 100 ppm to about 300 ppm.

Preferable examples of the ultraviolet absorber are benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Light stabilizers such as sterically hindered amines are also preferred. The preferable ratio in these absorbents and stabilizers is about 50 ppm or more in order to acquire the effect, and is about 10000 ppm or less so that an upper limit temperature may not be lowered or a lower limit temperature may not be raised. A more preferred ratio is in the range of about 100 ppm to about 10000 ppm.

In order to make it suitable for the device of a GH (guest host) mode, dichroic dye, such as an azo dye, an anthraquinone pigment, etc., is added to a composition. The preferable ratio of a pigment is the range of about 0.01 mass%-about 10 mass%. In order to prevent foaming, antifoaming agents such as dimethylsilicone oil and methylphenylsilicone oil are added to the composition. A preferred ratio of the antifoaming agent is about 1 ppm or more for obtaining the effect, and about 1000 ppm or less for preventing display defects. A further preferred ratio is in the range of about 1 ppm to about 500 ppm.

Polymeric compounds are used to make them suitable for polymeric support orientation (PSA) devices. Compound (4) is suitable for this purpose. Along with compound (4), a polymerizable compound different from compound (4) may be added to the composition. Instead of compound (4), a polymerizable compound different from compound (4) may be added to the composition. Preferable examples of such a polymerizable compound are compounds such as acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxirane, oxetane), vinyl ketone and the like. More preferred examples are derivatives of acrylates or methacrylates. By changing the type of the compound (4) or by combining the polymerizable compound different from the compound (4) with the compound (4) in an appropriate ratio, the reactivity of the polymerization and the pretilt angle of the liquid crystal molecules can be adjusted. have. By optimizing the pretilt angle, short response times of the device can be achieved. Since the orientation of liquid crystal molecules is stabilized, a large contrast ratio and a long lifetime can be achieved.

The polymerizable compound is polymerized by ultraviolet irradiation. It can also superpose | polymerize in presence of initiators, such as a photoinitiator. Appropriate conditions for polymerization and the appropriate type and amount of initiator are known to those skilled in the art and are described in the literature. For example, the photoinitiator Irgacure651® (BASF), Irgacure184 (BASF), or Darocur1173® (BASF) are suitable for radical polymerization. The preferable ratio of a photoinitiator is the range of about 0.1 mass%-about 5 mass% based on the mass of a polymeric compound. A more preferable ratio is the range of about 1 mass%-about 3 mass%.

When storing the polymerizable compound, a polymerization inhibitor may be added to prevent the 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 methylhydroquinone, 4-tert-butylcatechol, 4-methoxyphenol, phenothiazine and the like.

A polar compound is an organic compound which has polarity. Here, the compound which has an ionic bond is not contained. Atoms such as oxygen, sulfur, and nitrogen are more electrically negative and tend to have partial negative charges. Carbon and hydrogen tend to be neutral or have partial positive charges. Polarity is caused by the partial charge being not evenly distributed between different kinds of atoms in the compound. For example, the polar compound has at least one of partial structures such as -OH, -COOH, -SH, -NH ₂ ,> NH, and> N-.

Seventh, the synthesis method of the component compounds will be described. These compounds can be synthesized by a known method. Synthesis method is illustrated. Compound (1-1-2) is synthesize | combined by the method of Unexamined-Japanese-Patent No. 1987-260842. Compound (2-6) is synthesize | combined by the method of Unexamined-Japanese-Patent No. 2000-53602. Compound (3-1) is synthesize | combined by the method of Unexamined-Japanese-Patent No. 59-176221. Compound (4-18) is synthesized by the method described in JP-A-7-101900. The compound whose n of Formula (6) is 1 can be obtained from Aldrich (Sigma-Aldrich Corporation). Compound (6) etc. whose n is 7 is synthesize | combined by the method as described in US Patent 3660505.

Compounds which do not describe the synthesis method are Organic Syntheses (John Wiley & Sons, Inc.), Organic Reactions (Organic Reactions, John Wiley & Sons, Inc.), Comprehensive Organic Synthesis ( Comprehensive Organic Synthesis, Pergamon Press), a new experimental chemical lecture (Maruzen), etc. can be synthesize | combined by the method as described in books. A composition is prepared by a well-known method from the compound obtained in this way. For example, the component compounds are mixed and dissolved in each other by heating.

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

This composition can be used as an AM device. It can also be used as a PM element. This composition can be used for AM elements and PM elements having modes such as PC, TN, STN, ECB, OCB, IPS, FFS, VA, and FPA. Particular preference is given to use as an AM element having a VA, OCB, IPS mode or FFS mode. In the AM element having the IPS mode or the FFS mode, when the voltage is not applied, the arrangement of the liquid crystal molecules may be parallel to the glass substrate or perpendicular to the glass substrate. These elements may be reflective, transmissive, or transflective. Use as a transmissive element is preferred. Use as an amorphous silicon-TFT device or a polycrystalline silicon-TFT device is also possible. The composition can also be used for NCAP (nematic curvilinear aligned phase) devices produced by microencapsulating the composition, or PD (polymer dispersed) devices in which a three-dimensional mesh polymer is formed in the composition.

An example of the method of manufacturing a polymer support orientation element is as follows. An element having two substrates called an array substrate and a color filter substrate is assembled. This substrate has an alignment film. At least one of these substrates has an electrode layer. A liquid crystal compound is mixed to prepare a liquid crystal composition. A polymerizable compound is added to this composition. If necessary, additives may be further added. This composition is injected into the device. Light irradiation is performed while a voltage is applied to this element. Ultraviolet light is preferred. The polymerizable compound is polymerized by light irradiation. By this polymerization, the composition containing a polymer is produced. A polymeric support orientation element is manufactured by such a procedure.

In this procedure, when a voltage is applied, the liquid crystal molecules are aligned by the action of the alignment film and the electric field. Along the orientation, molecules of the polymerizable compound are also oriented. In this state, since the polymerizable compound polymerizes with ultraviolet rays, a polymer having this orientation is produced. By the effect of this polymer, the response time of an element is shortened. Since baking of an image is a malfunction of liquid crystal molecules, baking is also improved simultaneously by the effect of this polymer. 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 device.

EXAMPLE

The present invention will be described in more detail by way of examples. The present invention is not limited by these examples. The present invention includes a mixture of the composition of Example 1 and the composition of Example 2. This invention also includes the mixture which mixed at least two of the compositions of a composition example. The synthesized compound was confirmed by a method such as NMR analysis. The characteristic of a compound, a composition, and an element was measured by the following method.

NMR analysis: In the 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 carried out under conditions of 500 MHz and 16 times of integration times at room temperature. Tetramethylsilane was used as internal standard. ^{In 19} F-NMR measurement, CFCl ₃ was used as an internal standard, and the integration was performed 24 times. In the description of the nuclear magnetic resonance spectrum, s is a singlelet, d is a doublet, t is a triplet, q is a quartet, quin is a quintet, and sex is a sext (sextet), m means multiplet, br means broad.

Gas chromatographic analysis: GC-14B type gas chromatography manufactured by Shimadzu Corporation was used for the measurement. Carrier gas is helium (2 mL / min). The sample vaporization chamber was set to 280 degreeC, and the detector (FID) was set to 300 degreeC. At the time of separation of the component compounds, Capillary Column DB-1 manufactured by Agilent Technologies Inc. (30 m in length, 0.32 mm in inner diameter, 0.25 µm thick; dimethylpolysiloxane in fixed liquid phase; nonpolar) Was used. This column was hold | maintained at 200 degreeC for 2 minutes, and it heated up to 280 degreeC at the ratio of 5 degreeC / min. The sample was prepared with an acetone solution (0.1 mass%), and then injected into the 1 μL sample vaporization chamber. The recorder is a C-R5A type Chromatopac manufactured by Shimadzu Corporation, or an equivalent thereof. The obtained gas chromatogram shows the retention time of the peak corresponding to a component compound, and the area of a peak.

Chloroform, hexane, etc. can also be used as a solvent for diluting a sample. In order to separate the component compounds, the following capillary columns may be used. HP-1 manufactured by Agilent Technologies Inc. (30 m long, 0.32 mm inner diameter, 0.25 µm thick), Rtx-1 manufactured by Restek Corporation (30 m long, 0.32 mm inner diameter, 0.25 µm thick), SGE International Pty. BP-1 (length 30m, inner diameter 0.32mm, film thickness 0.25㎛) manufactured by Ltd. The capillary column CBP1-M50-025 (length 50m, inner diameter 0.25mm, film thickness 0.25micrometer) manufactured by Shimadzu Corporation may be used for the purpose of preventing the superposition of a compound peak.

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

Measurement sample: When measuring the characteristic of a composition or an element, the composition was used as a sample as it was. When measuring the characteristic of a compound, the sample for a measurement was prepared by mixing this compound (15 mass%) with a mother liquid crystal (85 mass%). The characteristic value of the compound was computed by the extrapolation method from the value obtained by the measurement. (Extrapolation value) = {(measured value of sample) -0.85 × (measured value of mother liquid crystal)} / 0.15. When the smectic phase (or crystal) precipitates at 25 ° C in this ratio, the ratio of the compound and the mother liquid crystal is 10% by mass: 90% by mass, 5% by mass: 95% by mass, 1% by mass: 99% by mass. Was changed in order. By this extrapolation, the upper limit temperature, optical anisotropy, viscosity, and dielectric anisotropy of the compound were determined.

The following mother liquid crystal was used. The ratio of a component compound is shown by the mass%.

Measurement method: The measurement of the characteristic was performed by the following method. Most of these methods are methods described in the JEITA standard (JEITA / ED-2521B) that are deliberated by the Japan Electronics and Information Technology Industries Association (Jeita), or methods thereof. The thin film transistor (TFT) was not attached to the TN element used for the measurement.

(1) Upper limit temperature (NI; degreeC) of a nematic phase: The sample was put into the hot plate of the melting-point measuring apparatus provided with the polarizing microscope, and it heated at the speed of 1 degree-C / min. The temperature when a part of the sample changed from the nematic phase to the isotropic liquid was measured. The upper limit temperature of a nematic phase may be abbreviated as "upper limit temperature."

(2) Lower limit temperature of nematic phase (T _C ; ° C): A sample having a nematic phase is placed in a glass bottle, and a freezer of 0 ° C, -10 ° C, -20 ° C, -30 ° C, and -40 ° C. After storing for 10 days, the liquid crystal phase was observed. For example, when the sample remained nematic at -20 ° C and changed to crystal or smectic at -30 ° _C , T _C was described as <-20 ° C. The lower limit temperature of a nematic phase may be abbreviated as "lower limit temperature."

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

(4) Viscosity (rotational viscosity; γ 1; measured at 25 ° C .; mPa · s): The measurement was performed according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). It was. The sample was put into the VA element whose spacing (cell gap) of two glass substrates is 20 micrometers. This element was applied in steps of 1 volt in the range of 39 to 50 volts. After 0.2 seconds of no application, application was repeated under conditions of only one rectangular wave (square pulse; 0.2 seconds) and no application (2 seconds). The peak current and peak time of the transient current generated by this application were measured. The value of the rotational viscosity was obtained from these measured values and the paper of M. Imai et al. And 40-page formula (8). The dielectric anisotropy required for this calculation was measured in (6).

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

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

1) Measurement of permittivity (ε ∥ ): A ethanol (20 mL) solution of octadecyltriethoxysilane (0.16 mL) was applied to a glass substrate that was well cleaned. After rotating a glass substrate with a spinner, it heated at 150 degreeC for 1 hour. The sample was put into the VA element whose interval (cell gap) of two glass substrates is 4 micrometers, and it sealed with the adhesive agent which hardens with an ultraviolet-ray. A sine wave (0.5 V, 1 kHz) was applied to this element, and after 2 seconds, the dielectric constant (ε ∥ ) in the long axis direction of the liquid crystal molecules was measured.

2) Measurement of dielectric constant (ε⊥): The polyimide solution was apply | coated to the glass substrate wash | cleaned favorably. After baking this glass substrate, the rubbing process was performed to the obtained orientation film. The sample was put into the TN element of 9 micrometers of space | interval (cell gap) of two glass substrates, and twist angle of 80 degree | times. A sine wave (0.5 V, 1 kHz) was applied to this element, and after 2 seconds, the dielectric constant (ε⊥) in the minor axis direction of the liquid crystal molecules was measured.

(7) Threshold voltage (Vth; measured at 25 ° C; V): An LCD5100 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source is a halogen lamp. Samples are placed in a VA device in a normally black mode in which the spacing (cell gap) of two glass substrates is 4 μm and the rubbing direction is antiparallel, and the sample is sealed using an adhesive that cures the device with ultraviolet rays. did. The voltage (60 Hz, square wave) applied to this element was increased in steps of 0.02V from 0V to 20V. At this time, light was irradiated to the device from the vertical direction, and the amount of light transmitted through the device was measured. When this light amount became maximum, the transmittance | permeability curve which created 100% of transmittance and 0% transmittance was created when this light amount was minimum. The threshold voltage is represented by the voltage when the transmittance reaches 10%.

(8) Voltage retention (VHR-1; measured at 60 ° C;%): The TN element used for the measurement had a polyimide alignment film, and the interval (cell gap) of two glass substrates was 5 µm. This element was sealed with the adhesive which hardens with ultraviolet-ray after putting a sample. The TN element was charged by applying a pulse voltage (60 microseconds at 1 V). The decaying voltage was measured with a high speed voltmeter for 166.7 milliseconds, and the area A between the voltage curve and the horizontal axis in the unit period was obtained. Area B is the area without attenuation. The voltage retention is expressed as a percentage of area A to area B.

(9) Voltage retention (VHR-2; measured at 80 ° C;%): The voltage retention 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 retention (VHR-3; measured at 60 ° C;%): After irradiating ultraviolet rays, the voltage retention was measured, and the stability to ultraviolet rays was evaluated. The TN element used for the measurement had a polyimide oriented film, and the cell gap was 5 micrometers. The sample was inject | poured into this element, and light was irradiated for 167 minutes. The light source is black light (peak wavelength 369 nm), and the distance between the element and the light source is 5 mm. In the measurement of VHR-3, the voltage decaying for 166.7 milliseconds was measured. Compositions with large VHR-3 have great stability against ultraviolet radiation.

(11) Voltage retention (VHR-4; measured at 60 ° C;%): After heating the TN element into which the sample was injected in a thermostat at 120 ° C for 20 hours, voltage retention was measured and stability to heat was evaluated. In the measurement of VHR-4, the voltage decaying for 166.7 milliseconds was measured. Compositions with large VHR-4 have great stability against heat.

(12) Response time (τ; measured at 25 ° C; ms): An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source is a halogen lamp. The low-pass filter was set at 5kHz. The sample was put into the VA element of the normally black mode whose spacing (cell gap) of two glass substrates is 4 micrometers, and a rubbing direction is anti-parallel. This element was sealed using the adhesive agent which hardens with an ultraviolet-ray. Rectangular waves (60 Hz, 10 V, 0.5 seconds) were applied to this device. At this time, light was irradiated to the device from the vertical direction, and the amount of light transmitted through the device was measured. The maximum amount of light was considered to be 100% transmittance, and the minimum amount of light was considered to be 0% transmittance. The response time is expressed as the time required to change from 90% of transmittance to 10% (fall time; milliseconds).

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

(14) Line Image Sticking Parameter (LISP;%): An afterimage was generated by applying electrical stress to the liquid crystal display element. The luminance of the area with residual afterimages and the luminance of the remaining areas were measured. The rate at which the luminance decreased due to the afterimage was calculated, and the size of the afterimage was represented by this ratio.

14a) Measurement of luminance: The image of the element was imaged using an imaging color luminance meter (manufactured by Radiant Zemax, PM-1433F-0). The brightness of each area of the device was calculated by analyzing the image using software (Prometric 9.1, manufactured by Radiant Imaging).

14b) Setting the stress voltage: The sample was placed in an FFS element (16 cells of 4 cells in length x 4 cells in width) having a cell gap of 3.5 占 퐉 and a matrix structure, and the device was sealed by using an ultraviolet curing adhesive. . The polarizing plate was arrange | positioned in the upper surface and lower surface of this element so that a polarization axis might orthogonally cross. Light was irradiated to this element, and the voltage (rectangle wave, 60 Hz) was applied. The voltage was gradually increased every 0.1 V in the range of 0 V to 7.5 V, and the luminance of the transmitted light at each voltage was measured. The voltage when the luminance becomes maximum is abbreviated as V255. When the luminance reaches 21.6% of V255 (that is, 127 gradations), the voltage is abbreviated as V127.

14c) Conditions of stress: V255 (rectangle wave, 30 Hz) and 0.5 V (rectangular wave, 30 Hz) were applied to the device under conditions of 60 ° C and 23 hours, and a checker pattern was displayed. Next, V127 (rectangle wave, 0.25 Hz) was applied, and luminance was measured under the conditions of an exposure time of 4000 milliseconds.

14d) Calculation of an afterimage: Four cells (two vertical cells × two horizontal cells) were used for calculation in the center part among 16 cells. These four cells were divided into 25 areas (5 cells in height × 5 cells in width). The average luminance of four areas (two vertical cells × two horizontal cells) at four corners is abbreviated as luminance A. FIG. The area | region except the area | region of four corner | corners from 25 area | regions is a cross shape. In the four regions excluding the cross region in the center from the cross region, the minimum value of luminance is abbreviated as luminance B. FIG. An afterimage was computed from the following formula. (Afterimage) = (luminance A-luminance B) / luminance A * 100.

(15) Spreadability: The spreadability of the additives was qualitatively evaluated by applying a voltage to the device and measuring the brightness. The luminance was measured in the same manner as in the above item 14a. The voltage V127 was set in the same manner as in the above item 14b. However, VA devices were used instead of FFS devices. Luminance was measured as follows. First, a DC voltage (2V) was applied to the device for 2 minutes. Next, V127 (square wave, 0.05 Hz) was applied, and luminance was measured on the conditions of 4000 milliseconds of exposure time. The spreadability was evaluated from this result.

Examples of the composition are shown below. A component compound is represented by a symbol based on the definition of following Table 3. In Table 3, the steric configuration for 1,4-cyclohexylene is trans. The numbers in parentheses following the symbolized compound indicate the chemical formula to which the compound belongs. The sign of (-) means other liquid crystalline compound. The ratio (percentage) of the liquid crystal compound is a mass percentage (mass%) based on the mass of the liquid crystal composition containing no additives. Finally, the characteristic values of the composition are shown collectively.

TABLE 3

Comparative Example 1

The composition which does not contain compound (1) was made into the comparative example (1).

NI = 87.5 ° C .; Tc <-20 ° C; Δn = 0.107; Δε = -3.7; Vth = 2.25V; eta = 23.3 mPa · s; LISP = 6.5%.

Example 1

Compound (1-1-1) was added to this composition in the ratio of 0.10 mass%, and linear afterimage (LISP) was measured. LISP = 3.0%.

Example 2

Compound (1-1-2) was added to this composition in 0.10 mass%, and the after-image (LISP) was measured. LISP = 2.1%.

Comparative Example 2

The composition containing compound (A) similar to compound (1) was referred to as Comparative Example 2.

Compound (A) was added to this composition in 0.10 mass%, and voltage retention (VHR-3) was measured. VHR-3 = 75.4%.

Example 3

Compound (1-1-1) was added to this composition in 0.10 mass%, and voltage retention (VHR-3) was measured. VHR-3 = 84.2%.

Example 4

Compound (1-1-1) was added to this composition in the ratio of 0.15 mass%. NI = 74.8 ° C .; Tc <-20 ° C; Δn = 0.104; Δε = -3.2; Vth = 2.06V; eta = 15.5 mPa · s; LISP = 3.2%.

Example 5

Compound (1-1-2) was added to this composition in 0.10 mass%. NI = 80.5 ° C .; Δn = 0.101; Δε = -3.2; Vth = 2.17V; η = 21.1 mPa · s; LISP = 2.2%.

Example 6

Compound (1-1-1) was added to this composition in the ratio of 0.12 mass%. NI = 81.5 ° C .; Tc <-20 ° C; Δn = 0.106; Δε = -3.1; Vth = 2.11 V; η = 14.3 mPa · s; LISP = 3.0%.

Example 7

Compound (1-2-1) was added to this composition in 0.15 mass%. NI = 81.7 ° C .; Tc <-20 ° C; Δn = 0.111; Δε = -2.0; Vth = 2.82V; η = 17.2 mPa · s; LISP = 3.1%.

Example 8

Compound (1-1-1) was added to this composition in the ratio of 0.10 mass%. NI = 84.8 ° C .; Tc <-20 ° C; Δn = 0.105; Δε = -3.1; Vth = 2.47V; eta = 19.0 mPa · s; LISP = 2.9%.

Example 9

Compound (1-3-1) was added to this composition in the ratio of 0.12 mass%. NI = 79.0 ° C .; Tc <-20 ° C; Δn = 0.087; Δε = -2.6; Vth = 2.43V; η = 20.1 mPa · s; LISP = 3.2%.

Example 10

Compound (1-1-1) was added to this composition in the ratio of 0.10 mass%. NI = 70.2 ° C .; Tc <-20 ° C; Δn = 0.119; Δε = -3.4; Vth = 2.08V; eta = 18.4 mPa · s; LISP = 3.0%.

Example 11

Compound (1-1-2) was added to this composition in 0.10 mass%. NI = 77.6 ° C .; Δn = 0.097; Δε = -3.3; Vth = 2.01V; η = 20.3 mPa · s; LISP = 2.1%.

Example 12

Compound (1-1-1) was added to this composition in the ratio of 0.15 mass%. NI = 83.0 ° C .; Tc <-20 ° C; Δn = 0.113; Δε = -4.0; Vth = 1.93V; η = 19.9 mPa · s; LISP = 2.8%.

Example 13

Compound (1-1-1) was added to this composition in the ratio of 0.15 mass%. NI = 74.4 ° C .; Tc <-20 ° C; Δn = 0.114; Δε = -3.9; Vth = 2.18V; eta = 21.2 mPa · s; LISP = 3.3%.

Example 14

Compound (1-2-1) was added to this composition in 0.10 mass%. NI = 88.7 ° C .; Tc <-20 ° C; Δn = 0.110; Δε = -4.4; Vth = 2.13V; η = 20.8 mPa · s; LISP = 3.4%.

Example 15

Compound (1-1-1) was added to this composition in the ratio of 0.15 mass%. NI = 73.9 ° C .; Tc <-20 ° C; Δn = 0.104; Δε = -3.2; Vth = 2.02V; eta = 15.4 mPa · s; LISP = 2.9%.

Example 16

Compound (1-3-1) was added to this composition in the ratio of 0.15 mass%. NI = 83.5 ° C .; Tc <-20 ° C; Δn = 0.116; Δε = -4.0; Vth = 1.95V; η = 21.0 mPa · s; LISP = 3.1%.

Example 17

Compound (1-1-1) was added to this composition in the ratio of 0.15 mass%. NI = 71.0 ° C .; Tc <-20 ° C; Δn = 0.097; Δε = -3.3; Vth = 2.35V; eta = 18.2 mPa · s; LISP = 3.0%.

Example 18

Compound (1-1-1) was added to this composition in the ratio of 0.15 mass%. NI = 83.1 ° C .; Tc <-20 ° C; Δn = 0.107; Δε = -3.7; Vth = 2.25V; eta = 23.3 mPa · s; LISP = 2.8%.

Example 19

Compound (1-1-3) was added to this composition in the ratio of 0.10 mass%. NI = 74.8 ° C .; Tc <-20 ° C; Δn = 0.104; Δε = -3.2; Vth = 2.06V; eta = 15.5 mPa · s; LISP = 3.2%.

The composition residual image of Comparative Example 1 was 6.5%. On the other hand, the composition residual image of Example 1 and Example 2 was 3.0% and 2.1%, respectively. From this fact, it turns out that the composition of this invention has a high effect of suppressing an afterimage. In addition, the composition voltage retention of Comparative Example 2 was 75.4%. On the other hand, the composition voltage retention of Example 3 was 84.2%. The characteristic which has a high effect of suppressing an afterimage, and the characteristic with large voltage retention are the characteristics calculated | required for the use of element for a long time. Thus, it can be concluded that the composition of the present invention has excellent properties.

[Industry availability]

The liquid crystal composition of this invention can be used for a liquid crystal monitor, a liquid crystal TV, etc.

Claims (18)

At least one compound selected from the group of compounds represented by the following formula (1) as the first additive, and at least one compound selected from the group of compounds represented by the following formula (2) as the first component, is negative (- Liquid crystal composition having dielectric anisotropy of:

In the formulas (1) and (2), R ¹ and R ² are independently hydrogen, hydroxy, oxy radicals, alkyl having 1 to 12 carbons or alkoxy having 1 to 12 carbons; R ³ and R ⁴ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons or alkenyloxy having 2 to 12 carbons; Ring A and Ring C are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen is fluorine or 1,4-phenylene, naphthalene-2,6-diyl substituted by chlorine, naphthalene-2,6-diyl, chroman-2,6-diyl, or at least 1 substituted with at least one hydrogen by fluorine or chlorine Hydrogens are Cromman-2,6-diyl substituted with fluorine or chlorine; Ring B is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4 -Phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, or 7,8-difluorochroman-2,6-diyl; Z ¹ is alkylene having 1 to 7 carbon atoms; Z ² and Z ³ are independently a single bond, ethylene, carbonyloxy or methyleneoxy; a is 1, 2 or 3, b is 0 or 1 and the sum of a and b is 3 or less. The method of claim 1,
A liquid crystal composition containing at least one compound selected from the group of compounds represented by the following formulas (1-1) to (1-3) as the first additive:

In the formulas (1-1) to (1-3), R ¹ and R ² are independently hydrogen, hydroxy, oxyradical, alkyl having 1 to 12 carbons or alkoxy having 1 to 12 carbons. The method according to claim 1 or 2,
R <^1> is hydrogen and R <^2> is hydroxy, oxyradical, C1-C12 alkyl, or C1-C12 alkoxy. The method according to any one of claims 1 to 3,
A liquid crystal composition containing at least one compound selected from the group of the compounds represented by the following formulas (2-1) to (2-22) as the first component:

In said Formula (2-1)-Formula (2-22), R <^3> and R <^4> is independently C1-C12 alkyl, C1-C12 alkoxy, C2-C12 alkenyl, or C2 Alkenyloxy of -12. The method according to any one of claims 1 to 4,
Liquid crystal composition whose ratio of a 1st additive is the range of 0.005 mass%-1 mass%. The method according to any one of claims 1 to 5,
Liquid crystal composition whose ratio of a 1st component is 10 mass%-90 mass%. The method according to any one of claims 1 to 6,
A liquid crystal composition containing at least one compound selected from the group of compounds represented by the following formula (3) as a second component:

In formula (3), R <^5> and R <^6> is independently C1-C12 alkyl, C1-C12 alkoxy, C2-C12 alkenyl, At least 1 hydrogen is substituted by fluorine or chlorine. Alkyl having 1 to 12 carbons or at least one hydrogen is alkenyl having 2 to 12 carbons substituted with fluorine or chlorine; Ring D and Ring E are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene Is; Z ⁴ is a single bond, ethylene or carbonyloxy; c is 1, 2 or 3. The method according to any one of claims 1 to 7,
A liquid crystal composition containing at least one compound selected from the group of the compounds represented by the following formulas (3-1) to (3-13) as the second component:

In said Formula (3-1)-Formula (3-13), R <^5> and R <^6> is independently C1-C12 alkyl, C1-C12 alkoxy, C2-C12 alkenyl, at least 1 Alkyl having 1 to 12 carbons substituted with fluorine or chlorine, or alkenyl having 2 to 12 carbons with at least one hydrogen substituted with fluorine or chlorine. The method according to claim 7 or 8,
Liquid crystal composition whose ratio of a 2nd component is 10 mass%-90 mass%. The method according to any one of claims 1 to 9,
A liquid crystal composition containing at least one compound selected from the group of polymerizable compounds represented by the following formula (4) as a second additive:

In the above (4), ring F and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane- 2-yl, pyrimidin-2-yl or pyridin-2-yl, and in these rings, at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least 1 Hydrogens may be substituted with alkyl having 1 to 12 carbons substituted with fluorine or chlorine; Ring G is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4- Diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, Naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl, these In the ring, at least one hydrogen may be substituted with fluorine, chlorine, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, or alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. There is; Z ⁵ and Z ⁶ are independently a single bond or alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one -CH ₂ -is -O-, -CO-, -COO- or -OCO-. At least one -CH ₂ CH ₂ -may be substituted -CH = CH-, -C (CH ₃ ) = CH-, -CH = C (CH ₃ )-or -C (CH ₃ ) = C ( CH ₃ )-, and in these groups, at least one hydrogen may be substituted with fluorine or chlorine; P ¹ , P ² and P ³ are independently a polymerizable group; Sp ¹ Sp ² and Sp ³ are independently a single bond or alkylene having 1 to 10 carbon atoms, in which at least one -CH ₂ -is -O-, -COO-, -OCO- or -OCOO May be substituted with at least one —CH ₂ —CH ₂ — may be substituted with —CH═CH— or —C, C—, in which at least one hydrogen is substituted with fluorine or chlorine May; d is 0, 1 or 2; e, f and g are independently 0, 1, 2, 3 or 4 and the sum of e, f and g is 1 or more. The method of claim 10,
In said formula (4), P <^1> , P <^2> and P <^3> are group chosen independently from the group of the polymeric group represented by following formula (P-1)-formula (P-5):

In the formulas (P-1) to (P-5), M ¹ , M ^2, and M ³ are independently hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or at least one hydrogen is fluorine or chlorine. Substituted alkyl having 1 to 5 carbon atoms. The method according to any one of claims 1 to 11,
A liquid crystal composition containing at least one compound selected from the group of polymerizable compounds represented by the following formulas (4-1) to (4-27) as a second additive:

In the formula (4-1) ~ Formula (4-27), P ^4, P ⁵ and P ⁶ are, each independently, a group of the formula polymerizable group represented by (P-1) ~ formula (P-3) Is a group selected from

Wherein M ¹ , M ² and M ³ are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced with fluorine or chlorine; Sp ¹ , Sp ² and Sp ³ are independently a single bond or alkylene having 1 to 10 carbon atoms, in which at least one -CH ₂ -is -O-, -COO-, -OCO- or- May be substituted with OCOO-, and at least one -CH ₂ CH ₂ -may be substituted with -CH = CH- or -C≡C-, in which at least one hydrogen is replaced with fluorine or chlorine May be. The method according to any one of claims 10 to 12,
Liquid crystal composition whose ratio of a 2nd additive is a range of 0.03 mass%-10 mass%. The liquid crystal display element containing the liquid crystal composition of any one of Claims 1-13. The method of claim 14,
The operation mode of a liquid crystal display element is IPS mode, VA mode, FFS mode, or FPA mode, The liquid crystal display element whose drive system of a liquid crystal display element is an active matrix system. The polymer support orientation liquid crystal display element which contains the liquid crystal composition as described in any one of Claims 10-13, and the 2nd additive contained in this liquid crystal composition superposed | polymerized. Use of the liquid crystal composition according to any one of claims 1 to 13 in a liquid crystal display device. Use of the liquid crystal composition according to any one of claims 1 to 13 in a polymer-supported alignment type liquid crystal display device.