WO2018123184A1 - Liquid crystal composition and liquid crystal display element - Google Patents

Abstract

Provided is a liquid crystal composition which satisfies at least one of characteristics such as a high upper limit temperature, a low lower limit temperature, a low viscosity, an appropriate optical anisotropy, a high negative dielectric anisotropy, a high specific resistance, high stability against ultraviolet light, high stability against heat, and inhibition of display defects such as afterimages, or which has an appropriate balance between at least two of these characteristics. Provided is an AM element which 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. This liquid crystal composition has a compound having high solubility in the liquid crystal composition, contains, as a first additive, a compound having the effect of inhibiting display defects of a liquid crystal display element, and has a positive dielectric anisotropy. The composition may contain a specific compound having a high positive dielectric anisotropy as a first component, a specific compound having a high upper limit of temperature or a low viscosity as a second component, and a specific compound having a negative dielectric anisotropy as a third component.

Description

Liquid crystal composition 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 having a positive dielectric anisotropy, and an AM (active matrix) device containing this composition and having a TN, OCB, IPS, FFS, or FPA mode.

In the liquid crystal display element, the classification based on the operation mode of the liquid crystal molecules is as follows: PC (phase change), TN (twisted nematic), STN (super twisted nematic), ECB (electrically controlled birefringence), OCB (optically compensated bend), IPS. (In-plane switching), VA (vertical alignment), FFS (fringe field switching), FPA (field-induced photo-reactive alignment) mode. The classification based on the element drive system is PM (passive matrix) and AM (active matrix). PM is classified into static, multiplex, etc., and AM is classified into TFT (thin film insulator), MIM (metal film insulator), and the like. TFTs are classified into amorphous silicon and polycrystalline silicon. The latter is classified into a high temperature type and a low temperature type according to the manufacturing process. The classification based on the light source includes 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 suitable properties. By improving the characteristics of the composition, an AM device having good characteristics can be obtained. The relationships in these properties are 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 device can be used. A preferred upper limit temperature of the nematic phase is about 70 ° C. or more, and a preferred lower limit temperature of the nematic phase is about −10 ° C. or less. The viscosity of the composition is related to the response time of the device. A short response time is preferred for displaying moving images on the device. A shorter response time is desirable even at 1 millisecond. Therefore, a small viscosity in the composition is preferred. A small viscosity at low temperatures is even more preferred.

 

The optical anisotropy of the composition is related to the contrast ratio of the device. Depending on the mode of the device, a large optical anisotropy or a small optical anisotropy, ie an appropriate optical anisotropy is required. The product (Δn × d) of the optical anisotropy (Δn) of the composition and the cell gap (d) of the device is designed to maximize the contrast ratio. The appropriate product value depends on the type of operation mode. For a device with a mode such as TN, a suitable value is about 0.45 μm. In this case, a composition having a large optical anisotropy is preferable for a device having a small cell gap. A large dielectric anisotropy in 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 preferable. In particular, in the FFS mode, an alignment of some liquid crystal molecules is not parallel to the panel substrate due to an oblique electric field. Therefore, in order to suppress the tilt-up of these liquid crystal molecules, the dielectric constant (ε The larger i) is preferred. By suppressing the tilt-up of the liquid crystal molecules, the transmittance of the element having the FFS mode can be increased, which contributes to a large contrast ratio. A large specific resistance in the composition contributes to a large voltage holding ratio and a large contrast ratio in 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 preferable. 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 being used for a long time is preferable. The stability of the composition against ultraviolet rays and heat is related to the lifetime of the liquid crystal display device. When their stability is high, the lifetime of the device is long. Such characteristics are preferable for an AM device used in a liquid crystal projector, a liquid crystal television, and the like.

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 in an AM device having a VA mode. In an AM device having an IPS mode or an FFS mode, a composition having a positive or negative dielectric anisotropy is used. In a polymer-supported alignment (PSA) type AM device, a composition having a positive or negative dielectric anisotropy is used.

The following compound (A-1) is one of hindered amine light stabilizers (HALS). This compound has a polar group> N—CH ₃ . In this compound, the two polar groups are the same.

International Publication No. 2015/001916

One object of the present invention is to provide a high maximum temperature of the nematic phase, a low minimum temperature of the nematic phase, a small viscosity, a suitable optical anisotropy, a large dielectric anisotropy, a large specific resistance, a high stability against ultraviolet rays, a high heat It is an object to provide a liquid crystal composition satisfying at least one of the characteristics such as high stability against the above and suppression of display failure such as afterimage. Another object is to provide a liquid crystal composition having an appropriate balance between at least two of these properties. Another object is to provide a liquid crystal display device 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 lifetime.

The present invention has at least two monovalent groups represented by the formula (S) as an additive, and in these monovalent groups, a group represented by R ¹ is a group represented by another R ¹ . The present invention relates to a liquid crystal composition containing a compound different from the above and having a positive dielectric anisotropy, and a liquid crystal display device containing this composition.

In the formula (S), R ¹ is hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, hydroxy, or oxy radical; R is alkyl having 1 to 12 carbons.

One advantage of the present invention is that a high upper limit temperature of the nematic phase, a lower lower limit temperature of the nematic phase, a small viscosity, a suitable optical anisotropy, a large dielectric anisotropy, a large specific resistance, a high stability against ultraviolet rays, a high heat It is an object to provide a liquid crystal composition satisfying at least one of the characteristics such as high stability against the above and suppression of display failure such as afterimage. Another advantage is to provide a liquid crystal composition having an appropriate balance between at least two of these properties. Another advantage is to provide a liquid crystal display device containing such a composition. Another advantage 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 lifetime.

It is a photograph of the element which shows that expansibility is favorable. It is a photograph of the element which shows that expansibility is favorable. It is a photograph of the element which shows that the expansibility is poor.

用語 Terms used in this 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 general term for liquid crystal display panels and liquid crystal display modules. “Liquid crystal compound” is a compound having a liquid crystal phase such as a nematic phase and a smectic phase, and a liquid crystal phase, but has a composition for the purpose of adjusting characteristics such as temperature range, viscosity, and dielectric anisotropy of the nematic phase. It is a general term for compounds mixed with products. This compound has a six-membered ring such as 1,4-cyclohexylene and 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. A liquid crystalline compound having alkenyl is not polymerizable in that sense.

The liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. Additives such as optically active compounds, antioxidants, ultraviolet absorbers, dyes, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, and polar compounds are added to this liquid crystal composition as necessary. The The ratio of the liquid crystal compound is represented by a mass percentage (% by mass) based on the mass of the liquid crystal composition not containing the additive even when the additive is added. The ratio of the additive is expressed as a mass percentage (% by mass) based on the mass of the liquid crystal composition not containing the 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 ratio of the polymerization initiator and the polymerization inhibitor is exceptionally expressed based on the mass of the polymerizable compound.

“The upper limit temperature of the nematic phase” may be abbreviated as “the upper limit temperature”. “Lower limit temperature of nematic phase” may be abbreviated as “lower limit temperature”. “High specific resistance” means that the composition has a large specific resistance in the initial stage and a large specific resistance after long-term use. "High voltage holding ratio" means that the device has a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature in the initial stage, and a large voltage not only at room temperature but also at a temperature close to the upper limit temperature after long use. It means having a retention rate. The characteristics of the composition and the device may be examined by a aging test. The expression “increasing dielectric anisotropy” means that when the composition has a positive dielectric anisotropy, the value increases positively, and the composition having a negative dielectric anisotropy When it is a thing, it means that the value increases negatively.

Expressions such as “at least one —CH ₂ — may be replaced by —O—” are 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 replaced by —O—. This is because —O—O—CH ₂ — (peroxide) is formed by this replacement. That is, this expression includes both “one —CH ₂ — may be replaced with —O—” and “at least two non-adjacent —CH ₂ — may be replaced with —O—”. means. This rule applies not only to replacement with —O— but also to replacement with a divalent group such as —CH═CH— or —COO—.

In the chemical formulas of the component compounds, the symbol of the terminal group R ³ is used for a plurality of compounds. In these compounds, two groups represented by any two R ³ may be the same or different. For example, ^{R 3} of the compound (2-1) is ethyl, there are cases ^{R 3} is ethyl compound (2-2). In some cases, R ^{3 of} compound (2-1) is ethyl and R ³ of compound (2-2) is propyl. This rule also applies to other symbols. In the formula (2), when the subscript 'b' is 2, there are two rings B. In this compound, the two rings represented by the two rings B may be the same or different. This rule also applies to any two rings B when the subscript 'b' is greater than 2. This rule also applies to other symbols. This rule also applies when a compound has a substituent represented by the same symbol.

Symbols such as A, B, C, and D surrounded by hexagons correspond to rings such as ring A, ring B, ring C, and ring D, respectively, and represent rings such as a six-membered ring and a condensed ring. In the expression “ring A and ring B are independently X, Y, or Z”, since there are plural subjects, “independently” is used. When the subject is “ring A”, since the subject is singular, “independently” is not used.

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 groups produced by removing two hydrogens from the ring, such as tetrahydropyran-2,5-diyl. This rule also applies to divalent linking groups such as carbonyloxy (—COO— or —OCO—).

The alkyl of the liquid crystal compound is linear or branched and does not include cyclic alkyl. Linear alkyl is preferred over branched alkyl. The same applies to terminal groups such as alkoxy and alkenyl. As the configuration of 1,4-cyclohexylene, trans is preferable to cis for increasing the maximum temperature.

The present invention includes the following items.

Item 1. As an additive, has at least two monovalent radical of the formula (S), in these monovalent group, compound different from the group that the group represented by R ¹ is represented by the other of R ¹ And a liquid crystal composition having positive dielectric anisotropy.

In the formula (S), R ¹ is hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, hydroxy, or oxy radical; R is alkyl having 1 to 12 carbons.

Item 2. Item 2. The liquid crystal composition according to item 1, wherein R is methyl in the monovalent group represented by formula (S) according to item 1.

Item 3. Item 3. The liquid crystal composition according to item 1 or 2, containing at least one compound selected from the group of compounds represented by formula (1) as an additive.

In the formula (1) and the formula (S-1), R ¹ is hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, hydroxy, or an oxy radical, where R ¹ is represented by R ¹ The group represented is different from the group represented by R ¹ ; ring A 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- , 5-diyl, or pyridine-2,5-diyl, and in these rings, at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, at least one Hydrogen may be replaced by alkyl having 1 to 12 carbons replaced by fluorine or chlorine, or a group represented by formula (S-1); Z ¹ and Z ² are independently a single bond or carbon An alkylene having the number 1 to 20, in which at least one —CH ₂ — may be replaced by —O—, —COO—, —OCO—, or —OCOO—, At least one hydrogen may be replaced with fluorine, chlorine, or a group represented by the formula (S-1); Z ³ represents a single bond or an alkyl group having 1 to 20 carbon atoms. In the alkylene, at least one —CH ₂ — may be replaced by —O—, —COO—, —OCO—, or —OCOO—, in which at least one hydrogen is , Fluorine or chlorine; a is 0, 1, 2, or 3;

Item 4. Item 4. The liquid crystal composition according to any one of items 1 to 3, comprising at least one compound selected from the group of compounds represented by formulas (1-1) to (1-9) as an additive: object.

In formulas (1-1) to (1-9), R ² is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, hydroxy, or oxy radical; Z ⁴ is carbon 1 Z ⁵ and Z ⁶ are independently alkylene having 1 to 5 carbons; Z ⁷ and Z ⁸ are independently a single bond or alkylene having 1 to 20 carbons; In this alkylene, at least one —CH ₂ — may be replaced by —O—, —COO—, —OCO—, or —OCOO—, in which at least one hydrogen is fluorine or chlorine X ¹ is hydrogen or fluorine.

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

Item 6. Item 6. The liquid crystal composition according to any one of items 1 to 5, containing at least one compound selected from the group of compounds represented by formula (2) as a first component.

In the formula (2), R ³ is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons or alkenyl having 2 to 12 carbons; ring B is 1,4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyrimidine-2,5-diyl, 1,3- Dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl; Z ⁹ is a single bond, ethylene, carbonyloxy, or difluoromethyleneoxy; X ² and X ³ are independently hydrogen or is fluorine; Y ¹ is fluorine, chlorine, at least one hydrogen alkyl having 1 carbon is replaced by fluorine or chlorine 12, at least one hydrogen 1 to 12 carbon alkoxy substituted with fluorine or chlorine, or alkenyloxy having 2 to 12 carbon atoms with at least one hydrogen replaced with fluorine or chlorine; b is 1, 2, 3, or 4 It is.

Item 7. Item 7. The liquid crystal composition according to any one of items 1 to 6, comprising at least one compound selected from the group of compounds represented by formulas (2-1) to (2-35) as a first component: object.

In the formulas (2-1) to (2-35), R ³ is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons.

Item 8. Item 8. The liquid crystal composition according to item 6 or 7, wherein the ratio of the first component is in the range of 5% by mass to 90% by mass.

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

In Formula (3), R ⁴ and R ⁵ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or at least one hydrogen is fluorine or chlorine. Substituted alkenyl having 2 to 12 carbon atoms; ring C and ring D are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5 -Difluoro-1,4-phenylene; Z ¹⁰ is a single bond, ethylene, or carbonyloxy; c is 1, 2, or 3.

Item 10. Item 10. The liquid crystal composition according to any one of items 1 to 9, comprising at least one compound selected from the group of compounds represented by formulas (3-1) to (3-13) as a second component: object.

In the formulas (3-1) to (3-13), R ⁴ and R ⁵ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or C2-C12 alkenyl in which at least one hydrogen is replaced by fluorine or chlorine.

Item 11. Item 11. The liquid crystal composition according to item 9 or 10, wherein the ratio of the second component is in the range of 5% by mass to 90% by mass.

Item 12. Item 12. The liquid crystal composition according to any one of items 1 to 11, comprising at least one compound selected from the group of compounds represented by formula (4) as a third component.

In Formula (4), R ⁶ and R ⁷ 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. Yes; Ring E and Ring G are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine Or tetrahydropyran-2,5-diyl; ring F is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5 - methyl-1,4-phenylene, it is a 3,4,5-trifluoro-2,6-diyl or ^{7,8-difluoro-chroman-2,6-diyl,; Z 11} Contact Fine ^{Z 12} are independently a single bond, ethylene, carbonyloxy or methyleneoxy,; d is 1, 2, or 3,, e is 0 or 1; the sum of d and e 3 or less.

Item 13. 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 formulas (4-1) to (4-22) as a third component: object.

In the formulas (4-1) to (4-22), R ⁶ and R ⁷ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or It is alkenyloxy having 2 to 12 carbon atoms.

Item 14. Item 14. The liquid crystal composition according to item 12 or 13, wherein the ratio of the third component is in the range of 3% by mass to 25% by mass.

Item 15. The upper limit temperature of the nematic phase is 70 ° C. or higher, the optical anisotropy at a wavelength of 589 nm (measured at 25 ° C.) is 0.07 or higher, and the dielectric anisotropy at a frequency of 1 kHz (measured at 25 ° C.) is 2. Item 15. The liquid crystal composition according to any one of items 1 to 14, which is the above.

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

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

Item 18. Use of the liquid crystal composition according to any one of items 1 to 15 in a liquid crystal display device.

The present invention includes the following items. (A) The above composition further containing at least one additive such as an optically active compound, an antioxidant, an ultraviolet absorber, a dye, an antifoaming agent, a polymerizable compound, a polymerization initiator, a polymerization inhibitor, and a polar compound. object. (B) An AM device containing the above composition. (C) The above-mentioned composition further containing a polymerizable compound, and a polymer-supported orientation (PSA) type AM device containing this composition. (D) A polymer-supported orientation (PSA) type AM device comprising the above-described composition, wherein the polymerizable compound in the composition is polymerized. (E) A device containing the above composition and having a mode of PC, TN, STN, ECB, OCB, IPS, VA, FFS, or FPA. (F) A transmissive device containing the above composition. (G) Use of the above composition as a composition having a nematic phase. (H) Use as an optically active composition by adding an optically active compound to the above composition.

The liquid crystal composition of the present invention contains a compound having at least two monovalent groups represented by the formula (S).

In the formula (S), R ¹ is hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, hydroxy, or oxy radical. The four groups R are independently alkyl having 1 to 12 carbons.

The compound of the present invention has at least two monovalent groups represented by the formula (S). In these monovalent group, the group represented by R ¹ is different from the groups represented by the other R ^1. When this compound has two groups represented by the formula (S), the two groups represented by R ¹ are different from each other. Even when this compound has three groups represented by the formula (S), the two groups represented by R ¹ are different from each other. An example is when the three groups R ¹ are hydrogen, hydrogen, methyl. Another example is a combination of hydrogen, methyl and ethyl. That is, not all groups represented by R ¹ are the same.

This compound was found to be effective in suppressing display defects of the device as shown in Comparative Examples 1, 2, and 3. However, the causes of display defects are complex and have not been fully elucidated. Furthermore, the effect of this compound on display defects is not clear at this stage. Under such circumstances, explanations such as those described in the next paragraph may be possible.

If the device is used for a long time, the brightness may decrease partially. An example is a line afterimage, which is a phenomenon in which the luminance between the electrodes decreases in a streak-like manner when different voltages are repeatedly applied to two adjacent electrodes. This phenomenon is caused by accumulation of ionic impurities contained in the liquid crystal composition on the alignment film near the electrode. Therefore, in order to suppress the line afterimage, it is effective to prevent the ionic impurities from being localized on the alignment film. For this purpose, the surface of the alignment film is coated with an additive such as a polar compound, and ionic impurities are adsorbed on the additive. It is important that such an additive has 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 device under reduced pressure. Usually, the device is filled with the composition without changing the proportion of its components. However, additives such as polar compounds may be adsorbed on the alignment film. When the adsorption speed is high, the additive may not reach the back of the device. The additive is left behind because the rate of adsorption is greater than the rate of injection. In order to prevent this phenomenon, an additive having an appropriate adsorptivity to the alignment film is preferable. Therefore, it is also important to select an additive having an appropriate polarity. The compound described in item 1, particularly compound (1), is suitable for this purpose. Compound (1) has at least two groups R ¹ . Compound (1) is asymmetric because the groups represented by at least two groups R ¹ are different from each other. This asymmetry may contribute to the proper polarity. See comparative example. The composition of the present invention contains compound (1) as a first additive.

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 explained. 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, additives that may 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 explained. This composition contains a plurality of liquid crystal compounds. The composition may contain additives. Additives include optically active compounds, antioxidants, ultraviolet absorbers, dyes, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds and the like. This composition is classified into a composition A and a composition B from the viewpoint of a liquid crystal compound. The composition A may further contain other liquid crystal compounds, additives and the like in addition to the liquid crystal compounds selected from the compound (2), the compound (3), and the compound (4). The “other liquid crystal compound” is a liquid crystal compound different from the compound (2), the compound (3), and the compound (4). Such compounds are mixed into the composition for the purpose of further adjusting the properties.

Composition B consists essentially of a liquid crystalline compound selected from compound (2), compound (3), and compound (4). “Substantially” means that the composition may contain an additive but no other liquid crystal compound. Composition B has fewer components than composition A. From the viewpoint of reducing the cost, the composition B is preferable to the composition A. The composition A is preferable to the composition B from the viewpoint that the characteristics can be further adjusted by mixing other liquid crystal compounds.

Second, the main characteristics of the component compounds and the main effects of the compounds on the composition will be explained. The main characteristics of the component compounds are summarized in Table 2 based on the effects of the present invention. In the symbols in Table 2, L means large or high, M means moderate, and S means small or low. The symbols L, M, and S are classifications based on a qualitative comparison among the component compounds, and 0 (zero) means extremely small.

 

The main effects of the component compounds are as follows. Compound (1) contributes to suppression of display defects. Compound (2) increases the dielectric anisotropy. Compound (3) increases the maximum temperature or decreases the viscosity. Compound (4) increases the dielectric constant in the minor axis direction and decreases the minimum temperature.

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

A desirable ratio of compound (1) is approximately 0.005% by mass or more for suppressing poor display, and approximately 1% by mass or less for decreasing the minimum temperature. A more desirable ratio is in the range of approximately 0.02% by mass to approximately 0.5% by mass. A particularly desirable ratio is in the range of approximately 0.1% by mass to approximately 0.3% by mass.

A desirable ratio of the compound (2) is approximately 5% by mass or more for increasing the dielectric anisotropy, and approximately 90% by mass or less for decreasing the minimum temperature. A more desirable ratio is in the range of approximately 20% by mass to approximately 65% by mass. A particularly desirable ratio is in the range of approximately 25% by mass to approximately 60% by mass.

A desirable ratio of compound (3) is approximately 5% by mass or more for increasing the maximum temperature or decreasing the viscosity, and approximately 90% by mass or less for increasing the dielectric anisotropy. A more desirable ratio is in the range of approximately 15% by mass to approximately 65% by mass. A particularly desirable ratio is in the range of approximately 20% by mass to approximately 60% by mass.

A desirable ratio of compound (4) is approximately 3% by mass or more for increasing the dielectric constant in the minor axis direction of liquid crystal molecules, and approximately 25% by mass or less for decreasing the minimum temperature. A more desirable ratio is in the range of approximately 5% by mass to approximately 20% by mass. A particularly desirable ratio is in the range of approximately 5% by mass to approximately 15% by mass.

Fourth, a preferred form of the component compound will be described. In the formula (S), R ¹ is hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, hydroxy, or oxy radical, wherein the group represented by R ¹ is another R Different from the group represented by ¹ . R is alkyl having 1 to 12 carbons.

In formula (1) and formula (S-1), Z ¹ and Z ² are each independently a single bond or alkylene having 1 to 20 carbon atoms, and in this alkylene, at least one —CH ₂ — is — O—, —COO—, —OCO—, or —OCOO— may be substituted, and in these groups, at least one hydrogen is fluorine, chlorine, or a group represented by the formula (S-1) It may be replaced. Preferred Z ¹ or Z ² is a single bond or alkylene having 1 to 20 carbon atoms in which at least one —CH ₂ — is replaced by —COO— or —OCO—. Z ³ is a single bond or alkylene having 1 to 20 carbon atoms, in which at least one —CH ₂ — is replaced by —O—, —COO—, —OCO—, or —OCOO—. In these groups, at least one hydrogen may be replaced by fluorine or chlorine. Preferred Z ³ is a single bond or alkylene having 1 to 20 carbon atoms in which at least one —CH ₂ — is replaced by —COO— or —OCO—.

Ring A 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, At least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, at least one hydrogen is replaced by fluorine or chlorine Alkyl having 1 to 12 carbon atoms or may be substituted with a group represented by the formula (S-1),. Preferred ring A is 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, or naphthalene-2,7-diyl.

A is 0, 1, 2, or 3. Preferred a is 0 or 1. Further preferred a is 0.

In the formula (1-1) to the formula (1-9), R ² is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, hydroxy, or oxy radical. Preferred R ² is alkyl having 1 to 12 carbons.

Z ⁴ is alkylene having 1 to 15 carbons. Preferred Z ⁴ is alkylene having 2 to 8 carbon atoms. Z ⁵ and Z ⁶ are independently alkylene having 1 to 5 carbon atoms. Z ⁷ and Z ⁸ are each independently a single bond or alkylene having 1 to 20 carbon atoms, in which at least one —CH ₂ — is —O—, —COO—, —OCO—, or — OCOO— may be replaced, and in these groups at least one hydrogen may be replaced by fluorine or chlorine. Preferred Z ⁷ or Z ⁸ is a single bond.

X ¹ is hydrogen or fluorine. Preferred X ¹ is hydrogen.

In Formula (2), Formula (3), and Formula (4), R ³ is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons. Preferred R ³ is, in order to increase the stability to ultraviolet light or heat, is alkyl of 1 to 12 carbons. R ⁴ and R ⁵ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or carbon 2 having at least one hydrogen replaced with fluorine or chlorine. To 12 alkenyl. Desirable R ⁴ or R ⁵ is alkenyl having 2 to 12 carbons for decreasing the viscosity, and alkyl having 1 to 12 carbons for increasing the stability to ultraviolet light or heat. R ⁶ and R ⁷ 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. Desirable R ⁶ or R ⁷ is alkyl having 1 to 12 carbons for increasing the stability to ultraviolet light or heat, and alkoxy having 1 to 12 carbons for increasing the dielectric anisotropy.

Preferred alkyl is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl. More desirable alkyl is methyl, ethyl, propyl, butyl or pentyl for decreasing the viscosity.

Preferred alkoxy is methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, or heptyloxy. More desirable alkoxy is methoxy or ethoxy for decreasing the viscosity.

Preferred alkenyl is 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. More desirable alkenyl is vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl for decreasing the viscosity. The preferred configuration of —CH═CH— in these alkenyls 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 decreasing the viscosity. Cis is preferred for alkenyl such as 2-butenyl, 2-pentenyl, and 2-hexenyl.

Preferred alkenyloxy is vinyloxy, allyloxy, 3-butenyloxy, 3-pentenyloxy, or 4-pentenyloxy. More preferable alkenyloxy is allyloxy or 3-butenyloxy for decreasing the viscosity.

Preferred examples of alkyl in which at least one hydrogen is replaced by fluorine or chlorine are fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl, 7-fluoroheptyl. Or 8-fluorooctyl. Further 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 replaced by fluorine 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. Further preferred examples are 2,2-difluorovinyl or 4,4-difluoro-3-butenyl for decreasing the viscosity.

Ring B is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene Pyrimidine-2,5-diyl, 1,3-dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl. Preferred ring B is 1,4-cyclohexylene for increasing the maximum temperature, 1,4-phenylene for increasing the optical anisotropy, and 2,6-difluoro for increasing the dielectric anisotropy. -1,4-phenylene. Tetrahydropyran-2,5-diyl is

Or

And preferably

It is.

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

Ring E and Ring G are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, or Tetrahydropyran-2,5-diyl. Preferred ring E or ring G is 1,4-cyclohexylene for decreasing the viscosity, tetrahydropyran-2,5-diyl for increasing the dielectric anisotropy, and for increasing the optical anisotropy. 1,4-phenylene. Ring F 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 F is 2,3-difluoro-1,4-phenylene for decreasing the viscosity, and 2-chloro-3-fluoro-1,4-phenylene for decreasing the optical anisotropy, and the dielectric constant In order to increase the anisotropy, 7,8-difluorochroman-2,6-diyl.

Z ⁹ is a single bond, ethylene, carbonyloxy, or difluoromethyleneoxy. Desirable Z ⁹ is a single bond for decreasing the viscosity, and difluoromethyleneoxy for increasing the dielectric anisotropy. Z ¹⁰ is a single bond, ethylene or carbonyloxy. Desirable Z ¹⁰ is a single bond for decreasing the viscosity. Z ¹¹ and Z ¹² are independently a single bond, ethylene, carbonyloxy, or methyleneoxy. Desirable Z ¹¹ or Z ¹² is a single bond for decreasing the viscosity, ethylene for decreasing the minimum temperature, and methyleneoxy for increasing the dielectric anisotropy.

X ² and X ³ are independently hydrogen or fluorine. Desirable X ² or X ³ is fluorine for increasing the dielectric anisotropy.

Y ¹ is fluorine, chlorine, alkyl having 1 to 12 carbons in which at least one hydrogen is replaced with fluorine or chlorine, alkoxy having 1 to 12 carbons in which at least one hydrogen is replaced with fluorine or chlorine, or at least C2-C12 alkenyloxy in which one hydrogen is replaced by fluorine or chlorine. Desirable Y ¹ is fluorine for decreasing the minimum temperature. A preferred example of alkyl in which at least one hydrogen is replaced by fluorine or chlorine is trifluoromethyl. A preferred example of alkoxy in which at least one hydrogen is replaced by fluorine or chlorine is trifluoromethoxy. A preferred example of alkenyloxy in which at least one hydrogen has been replaced by fluorine or chlorine is trifluorovinyloxy.

B is 1, 2, 3, or 4. Preferred b is 2 or 3 for increasing the dielectric anisotropy. c is 1, 2 or 3. Preferred c is 1 for decreasing the viscosity, and 2 or 3 for increasing the maximum temperature. d is 1, 2, or 3, e is 0 or 1, and the sum of d and e is 3 or less. Preferred d is 1 for decreasing the viscosity, and 2 or 3 for increasing the maximum temperature. Preferred e is 0 for decreasing the viscosity, and 1 for decreasing the minimum temperature.

Fifth, preferred component compounds are shown. Desirable compounds (1) are the compounds (1-1) to (1-9) according to Item 4. More desirable compounds (1) are the compounds (1-1) to (1-3). Particularly preferred compound (1) is compound (1-1).

Desirable compound (2) is the compound (2-1) to the compound (2-35) according to item 7. In these compounds, at least one of the first components is compound (2-4), compound (2-12), compound (2-14), compound (2-15), compound (2-17), compound ( 2-18), compound (2-23), compound (2-24), compound (2-27), compound (2-29), or compound (2-30) is preferred. At least two of the first components are the compounds (2-12) and (2-15), the compounds (2-14) and (2-27), the compounds (2-18) and (2-24), The compound (2-18) and the compound (2-29), the compound (2-24) and the compound (2-29), or a combination of the compound (2-29) and the compound (2-30) is preferable.

Desirable compound (3) is the compound (3-1) to the compound (3-13) according to item 10. In these compounds, at least one of the third components is the compound (3-1), the compound (3-3), the compound (3-5), the compound (3-6), or the compound (3-7). It is preferable. At least two of the third components are compound (3-1) and compound (3-5), compound (3-1) and compound (3-6), compound (3-1) and compound (3-7), compound A combination of (3-3) and compound (3-5), compound (3-3) and compound (3-6), compound (3-3) and compound (3-7) is preferred.

Desirable compound (4) is the compound (4-1) to the compound (4-22) according to item 13. In these compounds, at least one of the fourth components is the compound (4-1), the compound (4-3), the compound (4-4), the compound (4-6), the compound (4-8), or the compound (4-10) is preferred. At least two of the fourth components are the compound (4-1) and the compound (4-6), the compound (4-3) and the compound (4-6), the compound (4-3) and the compound (4-10), A compound (4-4) and a compound (4-6), a compound (4-4) and a compound (4-8), or a combination of a compound (4-6) and a compound (4-10) is preferable.

Sixth, additives that may be added to the composition will be described. Such additives are optically active compounds, antioxidants, ultraviolet absorbers, dyes, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds and the like. An optically active compound is added to the composition for the purpose of inducing a helical structure of liquid crystal to give a twist angle. Examples of such compounds are compound (5-1) to compound (5-5). A desirable ratio of the optically active compound is approximately 5% by mass or less. A more desirable ratio is in the range of approximately 0.01% by mass to approximately 2% by mass.

 

In order to prevent a decrease in specific resistance due to 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 device for a long time, an antioxidant is composed. Added to the product. A preferred example of the antioxidant is a compound (6) in which t is an integer of 1 to 9.

In the compound (6), preferred t is 1, 3, 5, 7, or 9. Further preferred t is 7. Since the compound (6) in which t is 7 has low volatility, it is effective for maintaining a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature after using the device for a long time. A desirable ratio of the antioxidant is approximately 50 ppm or more for achieving its effect, and is approximately 600 ppm or less for avoiding a decrease in the maximum temperature or avoiding an increase in the minimum temperature. A more desirable ratio is in the range of approximately 100 ppm to approximately 300 ppm.

Preferred examples of the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Also preferred are light stabilizers such as sterically hindered amines. A desirable ratio of these absorbers and stabilizers is approximately 50 ppm or more for achieving the effect thereof, and approximately 10,000 ppm or less for avoiding a decrease in the maximum temperature or avoiding an increase in the minimum temperature. A more desirable ratio is in the range of approximately 100 ppm to approximately 10,000 ppm.

A dichroic dye such as an azo dye or an anthraquinone dye is added to the composition in order to adapt it to a GH (guest host) mode element. A preferred ratio of the dye is in the range of approximately 0.01% by mass to approximately 10% by mass. In order to prevent foaming, an antifoaming agent such as dimethyl silicone oil or methylphenyl silicone oil is added to the composition. A desirable ratio of the antifoaming agent is approximately 1 ppm or more for obtaining the effect thereof, and approximately 1000 ppm or less for preventing a display defect. A more desirable ratio is in the range of approximately 1 ppm to approximately 500 ppm.

A polymerizable compound is added to the composition in order to adapt it to a polymer support alignment (PSA) type device. Preferable examples of the polymerizable compound are compounds having a polymerizable group such as acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxirane, oxetane), vinyl ketone and the like. Further preferred examples are acrylate or methacrylate derivatives. A desirable ratio of the polymerizable compound is approximately 0.05% by mass or more for achieving the effect thereof, and approximately 10% by mass or less for preventing display defects. A more desirable ratio is in the range of approximately 0.1% by mass to approximately 2% by mass. The polymerizable compound is polymerized by irradiation with ultraviolet rays. The polymerization may be performed in the presence of an initiator such as a photopolymerization initiator. Appropriate conditions for polymerization, the appropriate type of initiator, and the appropriate amount 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), which are photoinitiators, are suitable for radical polymerization. A desirable ratio of the photopolymerization initiator is in the range of approximately 0.1% by mass to approximately 5% by mass based on the mass of the polymerizable compound. A more desirable ratio is in the range of approximately 1% by mass to approximately 3% by mass.

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

The polar compound is an organic compound having polarity. Here, a compound having an ionic bond is not included. Atoms such as oxygen, sulfur, and nitrogen are more electronegative and tend to have partial negative charges. Carbon and hydrogen tend to be neutral or have a partial positive charge. Polarity arises from the fact that partial charges are not evenly distributed among different types of atoms in a compound. For example, the polar compound has at least one of partial structures such as —OH, —COOH, —SH, —NH ₂ ,>NH,> N—.

Seventh, a method for synthesizing component compounds will be described. These compounds can be synthesized by known methods. The synthesis method is illustrated. Synthesis methods of Compound (1-1-1), Compound (1-1-2), Compound (1-1-7), and Compound (1-1-8) are described in the Examples section. Reference may be made to the synthesis method described in JP-A-2016-037605. Compound (2-4) is synthesized by the method described in JP-A-10-204016. Compound (3-1) is synthesized by the method described in JP-A-59-176221. Compound (4-1) is synthesized by the method described in JP-T-2-503441. Antioxidants are commercially available. A compound of formula (6) where t is 1 is available from Sigma-Aldrich® Corporation. Compound (6) etc. in which t is 7 are synthesized by the method described in US Pat. No. 3,660,505.

Compounds that have not been described as synthetic methods are Organic Synthesis (Organic Syntheses, John Wiley & Sons, Inc), Organic Reactions (Organic Reactions, John Wiley & Sons, Inc), Comprehensive Organic Synthesis (Comprehensive Organic) Synthesis, (Pergamon Press) and new experimental chemistry course (Maruzen). The composition is prepared from the compound thus obtained by known methods. For example, the component compounds are mixed and dissolved in each other by heating.

Finally, the use of the composition will be explained. Most compositions have a minimum temperature of about −10 ° C. or lower, a maximum temperature of about 70 ° C. or higher, and an optical anisotropy in the range of about 0.07 to about 0.20. A composition having an optical anisotropy in the range of about 0.08 to about 0.25 may be prepared by controlling the ratio of the component compounds or by mixing other liquid crystal compounds. Furthermore, a composition having optical anisotropy in the range of about 0.10 to about 0.30 may be prepared by trial and error. A 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 or can be used as an optically active composition by adding an optically active compound.

This composition can be used for an AM device. Further, it can be used for PM elements. This composition can be used for an AM device and a PM device having modes such as PC, TN, STN, ECB, OCB, IPS, FFS, VA, and FPA. Use for an AM device having a VA, OCB, IPS mode or FFS mode is particularly preferable. In an AM device having an IPS mode or an FFS mode, when no voltage is applied, the alignment of liquid crystal molecules may be parallel to or perpendicular to the glass substrate. These elements may be reflective, transmissive, or transflective. Use in a transmissive element is preferred. It can also be used for an amorphous silicon-TFT device or a polycrystalline silicon-TFT device. It can also be used for an NCAP (nematic-curvilinear-aligned-phase) type device produced by microencapsulating this composition, or a PD (polymer-dispersed) type device in which a three-dimensional network polymer is formed in the composition.

The present invention will be described in more detail with reference to examples. The 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. The present invention also includes a mixture in which at least two of the compositions of the composition examples are mixed. The synthesized compound was identified by a method such as NMR analysis. The characteristics of the compound, composition and device were measured by the methods described below.

NMR analysis: DRX-500 manufactured by Bruker BioSpin Corporation was used for measurement. ^{In the 1} H-NMR measurement, the sample was dissolved in a deuterated solvent such as CDCl _3, and the measurement was performed at room temperature, 500 MHz, and 16 times of integration. Tetramethylsilane was used as an internal standard. ^{For 19} F-NMR measurement, CFCl ₃ was used as an internal standard and the number of integrations was 24. In the description of the nuclear magnetic resonance spectrum, s is a singlet, d is a doublet, t is a triplet, q is a quartet, quint is a quintet, sex is a sextet, m is a multiplet, and br is broad.

Gas chromatographic analysis: GC-14B gas chromatograph manufactured by Shimadzu Corporation was used for measurement. The carrier gas is helium (2 mL / min). The sample vaporization chamber was set at 280 ° C, and the detector (FID) was set at 300 ° C. For separation of the component compounds, capillary column DB-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm; stationary liquid phase is dimethylpolysiloxane; nonpolar) manufactured by Agilent Technologies Inc. was used. The column was held at 200 ° C. for 2 minutes and then heated to 280 ° C. at a rate of 5 ° C./min. A sample was prepared in an acetone solution (0.1% by mass), and 1 μL thereof was injected into the sample vaporization chamber. The recorder is a C-R5A Chromatopac manufactured by Shimadzu Corporation, or an equivalent product. The obtained gas chromatogram showed the peak retention time and peak area corresponding to the component compounds.

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

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

Measurement sample: When measuring the characteristics of the composition or the device, the composition was used as it was as a sample. When measuring the characteristics of the compound, a sample for measurement was prepared by mixing this compound (15% by mass) with the mother liquid crystal (85% by mass). The characteristic value of the compound was calculated from the value obtained by the measurement by extrapolation. (Extrapolated 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. at 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, and 1% by mass: 99% by mass in this order. changed. By this extrapolation method, the maximum temperature, optical anisotropy, viscosity, and dielectric anisotropy values for the compound were determined.

The following mother liquid crystals were used. The ratio of the component compound is indicated by mass%.

Measurement method: The characteristics were measured by the following method. Many of these are the methods described in the JEITA standard (JEITA ED-2521B) deliberated and established by the Japan Electronics and Information Industry Association (JEITA), or a modified method thereof. Met. No thin film transistor (TFT) was attached to the TN device used for the measurement.

(1) Maximum temperature of nematic phase (NI; ° C.): A sample was placed on a hot plate of a melting point measuring apparatus equipped with a polarizing microscope and heated at a rate of 1 ° C./min. The temperature was measured when a part of the sample changed from a nematic phase to an isotropic liquid. The upper limit temperature of the nematic phase may be abbreviated as “upper limit temperature”.

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

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

(4) Viscosity (Rotational Viscosity; γ1; 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). I followed. A sample was put in a TN device having a twist angle of 0 ° and a distance (cell gap) between two glass substrates of 5 μm. A voltage was applied to this device in steps of 0.5 V in the range of 16 V to 19.5 V. After no application for 0.2 seconds, the application was repeated under the condition of only one rectangular wave (rectangular pulse; 0.2 seconds) and no application (2 seconds). The peak current (peak current) and peak time (peak time) of the transient current (transient current) generated by this application were measured. The value of rotational viscosity was obtained from these measured values and the calculation formula (8) described on page 40 in the paper by M. Imai et al. The value of dielectric anisotropy necessary for this calculation was determined by the method described below using the element whose rotational viscosity was measured.

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

(6) Dielectric anisotropy (Δε; measured at 25 ° C.): A sample was put in a TN device in which the distance between two glass substrates (cell gap) was 9 μm and the twist angle was 80 degrees. Sine waves (10 V, 1 kHz) were applied to the device, and after 2 seconds, the dielectric constant (ε∥) in the major axis direction of the liquid crystal molecules was measured. Sine waves (0.5 V, 1 kHz) were applied to the device, and after 2 seconds, the dielectric constant (ε⊥) in the minor axis direction of the liquid crystal molecules was measured. The value of dielectric anisotropy was calculated from the equation: Δε = ε∥−ε⊥.

(7) Threshold voltage (Vth; measured at 25 ° C .; V): An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source was a halogen lamp. A sample was put in a normally white mode TN device in which the distance between two glass substrates (cell gap) was 0.45 / Δn (μm) and the twist angle was 80 degrees. The voltage (32 Hz, rectangular wave) applied to this element was increased stepwise from 0V to 10V by 0.02V. 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 was created in which the transmittance was 100% when the light amount reached the maximum and the transmittance was 0% when the light amount was the minimum. The threshold voltage was expressed as a voltage when the transmittance reached 90%.

(8) Voltage holding ratio (VHR-1; measured at 25 ° C .;%): The TN device used for the measurement had a polyimide alignment film, and the distance between two glass substrates (cell gap) was 5 μm. . This element was sealed with an adhesive that was cured with ultraviolet rays after the sample was placed. The TN device was charged by applying a pulse voltage (60 microseconds at 5 V). The decaying voltage was measured for 16.7 milliseconds with a high-speed voltmeter, and the area A between the voltage curve and the horizontal axis in a unit cycle was determined. Area B was the area when it was not attenuated. The voltage holding ratio was expressed as a percentage of area A with respect to 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 it was measured at 80 ° C. instead of 25 ° C. The obtained value was expressed as VHR-2.

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

(11) Voltage holding ratio (VHR-4; measured at 25 ° C .;%): The TN device injected with the sample was heated in a constant temperature bath at 80 ° C. for 500 hours, and then the voltage holding ratio was measured to determine the stability against heat. Evaluated. In the measurement of VHR-4, a voltage decaying for 16.7 milliseconds was measured. A composition having a large VHR-4 has a large stability to heat.

(12) Response time (τ; measured at 25 ° C .; ms): An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement. The light source was a halogen lamp. The low-pass filter was set to 5 kHz. A sample was placed in a normally white mode TN device in which the distance between two glass substrates (cell gap) was 5.0 μm and the twist angle was 80 degrees. A rectangular wave (60 Hz, 5 V, 0.5 seconds) was applied to this 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. It was considered that the transmittance was 100% when the light amount was the maximum, and the transmittance was 0% when the light amount was the minimum. The rise time (τr: rise time; millisecond) is the time required for the transmittance to change from 90% to 10%. The fall time (τf: fall time; millisecond) is the time required to change the transmittance from 10% to 90%. The response time was expressed as the sum of the rise time and the fall time thus obtained.

(13) Elastic constant (K; measured at 25 ° C .; pN): An HP4284A LCR meter manufactured by Yokogawa-Hewlett-Packard Co., Ltd. was used for the measurement. A sample was put in a horizontal alignment element in which the distance between two glass substrates (cell gap) was 20 μm. A charge of 0 to 20 volts was applied to the device, and the capacitance and applied voltage were measured. Fitting the measured values of capacitance (C) and applied voltage (V) using “Liquid Crystal Device Handbook” (Nikkan Kogyo Shimbun), page 75, formula (2.98), formula (2.101) Thus, the values of K11 and K33 were obtained from the formula (2.99). Next, K22 was calculated from the equation (3.18) on page 171 using the values of K11 and K33 obtained earlier. The elastic constant was expressed as an average value of K11, K22, and K33 thus determined.

(14) Specific resistance (ρ; measured at 25 ° C .; Ωcm): A sample (1.0 mL) was poured into a container equipped with electrodes. A DC voltage (10 V) was applied to the container, and the DC current after 10 seconds was measured. The specific resistance was calculated from the following equation. (Resistivity) = {(Voltage) × (Capacity of container)} / {(DC current) × (Dielectric constant of vacuum)}.

(15) Dielectric constant in the minor axis direction (ε⊥; measured at 25 ° C.): A sample was put in a TN device in which the distance between two glass substrates (cell gap) was 9 μm and the twist angle was 80 degrees. . Sine waves (0.5 V, 1 kHz) were applied to the device, and after 2 seconds, the dielectric constant (ε⊥) in the minor axis direction of the liquid crystal molecules was measured.

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

(16a) Measurement of luminance: An image of the element was taken using an imaging color luminance meter (manufactured by RadiantianZemax, PM-1433F-0). The luminance of each region of the element was calculated by analyzing this image using software (Prometric 9.1, manufactured by Radiant Imaging).

(16b) Setting of stress voltage: A cell gap is 3.5 μm, a sample is put in an FFS element (16 cells of 4 vertical cells × 4 horizontal cells) having a matrix structure, and an adhesive that cures the element with ultraviolet rays is used. And sealed. Polarizers were arranged on the upper and lower surfaces of the element so that the polarization axes were orthogonal. The device was irradiated with light and a voltage (rectangular wave, 60 Hz) was applied. The voltage was increased stepwise by 0.1V in the range of 0V to 7.5V, and the brightness of transmitted light at each voltage was measured. The voltage when the luminance reached the maximum was abbreviated as V255. The voltage when the luminance was 21.6% of V255 (that is, 127 gradations) was abbreviated as V127.

(16c) Stress conditions: V255 (rectangular wave, 30 Hz) and 0.5 V (rectangular wave, 30 Hz) were applied to the element under the conditions of 60 ° C. and 23 hours to display a checker pattern. Next, V127 (rectangular wave, 0.25 Hz) was applied, and the luminance was measured under an exposure time of 4000 milliseconds.

(16d) Calculation of line afterimage: Among 16 cells, 4 cells in the center (2 vertical cells × 2 horizontal cells) were used for the calculation. These 4 cells were divided into 25 regions (5 vertical cells × 5 horizontal cells). The average luminance of four regions at the four corners (vertical 2 cells × horizontal 2 cells) was abbreviated as luminance A. The area excluding the four corner areas from the 25 area was a cross. In the four areas excluding the central intersection area from the cross-shaped area, the minimum luminance value is abbreviated as luminance B. The line afterimage was calculated from the following equation. (Line afterimage) = (luminance A−luminance B) / luminance A × 100.

(17) Spreadability: The spreadability of the additive was qualitatively evaluated by applying a voltage to the device and measuring the luminance. The measurement of luminance was performed in the same manner as (16a) above. The voltage (V127) was set in the same manner as (16b) above. However, a VA element was used instead of the FFS element. The luminance was measured as follows. First, a DC voltage (2 V) was applied to the device for 2 minutes. Next, V127 (rectangular wave, 0.05 Hz) was applied, and the luminance was measured under the condition of an exposure time of 4000 milliseconds. The spreadability was evaluated from this result.

1 to 3 are photographs of the element, showing the state of brightness. In FIG. 1 and FIG. 2, the brightness is different from each other, but the brightness is uniform as a whole. These indicate that the spreadability is good. In FIG. 3, a convex curve is observed at the upper corner, and the luminance is not uniform. This is because the liquid crystal composition was injected into the entire device from the injection port (not shown) on the lower side of the photograph, but the additive contained in the composition did not reach the entire device. It shows that the spreadability is poor.

Synthesis example 1
Compound (1-1-1) was synthesized by the following route.

First step:
Under a nitrogen atmosphere, sebacoyl chloride (532.0 g, 2.225 mol) and diethyl ether (1500 ml) were placed in a reactor and cooled to -70 ° C. Benzyl alcohol (158.8 g, 1.468 mol) was added dropwise thereto over 1.5 hours, and then triethylamine (225.1 g, 2.225 mol) was added dropwise over 1 hour. The mixture was warmed to room temperature and stirred for 18 hours. The reaction mixture was cooled to 0 ° C. and 1N hydrochloric acid (500 ml) was added dropwise. The organic layer was separated and the aqueous layer was extracted with diethyl ether. The combined organic layers were washed with saturated brine and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography. As the developing solvent, first, toluene was used, and then a mixed solvent of toluene / ethyl acetate = 9/1 (volume ratio) was used. Recrystallization from a mixed solvent of heptane / toluene = 1/1 (volume ratio) gave Compound (T-1) (206.5 g, yield 31.7%).

Second step:
Under a nitrogen atmosphere, compound (T-1) (60.00 g, 204.8 mmol), 4-hydroxy-1,2,2,6,6-pentamethylpiperidine (36.83 g, 215.1 mmol), and dichloromethane ( 600 ml) was placed in a reactor and cooled to 0 ° C. DMAP (4-dimethylaminopyridine) (7.51 g, 61.44 mmol) was added thereto, and then DCC (N, N′-dicyclohexylcarbodiimide) (46.48 g, 225.3 mmol) was added. The mixture was warmed to room temperature and stirred for 24 hours. The precipitated colorless solid was removed, and the filtrate was washed with a saturated aqueous sodium hydrogen carbonate solution and water in that order, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (toluene / ethyl acetate = 8/2 to 0/10 (volume ratio)) to obtain compound (T-2) (69.44 g, yield). Rate 75.9%).

Third step:
Compound (T-2) (69.44 g, 155.5 mmol), 20% palladium hydroxide on carbon (3.47 g), IPA (2-propanol) (700 ml) was placed in a reactor, and the reaction was carried out at room temperature under a hydrogen atmosphere at room temperature. Stir for hours. 20% Palladium hydroxide carbon was removed, the filtrate was concentrated, and the residue was purified by silica gel column chromatography (acetone) to obtain compound (T-3) (55.01 g, yield 99.5%). It was.

Fourth step:
Under nitrogen atmosphere, compound (T-3) (56.43 g, 158.7 mmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine (26.21 g, 166.7 mmol), and dichloromethane (600 ml) Was placed in a reactor and cooled to 0 ° C. DMAP (5.82 g, 47.62 mmol) was added thereto, and then DCC (36.03 g, 174.6 mmol) was added. The mixture was warmed to room temperature and stirred for 16 hours. The precipitated colorless solid was removed, and the filtrate was washed with a saturated aqueous sodium hydrogen carbonate solution and water in that order, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (acetone). Recrystallization from heptane gave compound (1-1-1) (25.51 g, yield 32.4%).

¹ H-NMR (ppm; CDCl ₃ ): δ 5.19 (tt, J = 11.5 Hz, J = 4.2 Hz, 1H), 5.09 (tt, J = 11.7 Hz, J = 4.2 Hz, 1H), 2.27 (t, J = 7.5 Hz, 2H), 2.26 (t, J = 7.4 Hz, 2H), 2.24 (s, 3H), 1.91 (ddd, J = 10.9 Hz, J = 4.2 Hz, J = 1.4 Hz, 2H), 1.83 (ddd, J = 11.0 Hz, J = 4.2 Hz, J = 1.4 Hz, 2H), 1.59 ( quin, J = 6.9 Hz, 4H), 1.47 (dd, J = 11.6 Hz, J = 11.6 Hz, 2H), 1.36-1.28 (m, 8H), 1.24 (s , 6H), 1.16 (s, 6H), 1.15 (s, 6H), 1.13 (dd, J = 11.7 Hz, J = 11.7 Hz, 2H), .07 (s, 6H), 0.88-0.50 (br, 1H).

Synthesis example 2
Compound (1-1-2) was synthesized by the following route.

First step:
4-Hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical (25.00 g, 145.1 mmol) and t-butyl alcohol (50 ml) / water (25 ml) were placed in the reactor. To the solution, nonanal (72.26 g, 508.0 mmol) and copper (I) chloride (0.36 g, 3.63 mmol) were added. Further, hydrogen peroxide (30% aqueous solution; 49.37 g, 435.4 mmol) was added dropwise over 1.5 hours, and the mixture was stirred at room temperature for 18 hours. The reaction mixture was extracted with heptane, and the extract was washed with 10% ascorbic acid aqueous solution, 10% sodium hydrogensulfite aqueous solution, 1N sodium hydroxide aqueous solution, water and saturated brine in that order, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (heptane / acetone = 8/1 (volume ratio)) to obtain compound (T-4) (25.00 g, yield 60.3%). )

Second step:
In a nitrogen atmosphere, the compound (T-4) (2.56 g, 8.98 mmol), the compound (T-1) obtained in Synthesis Example 1 (2.63 g, 8.98 mmol), and dichloromethane (250 ml) were reacted. Placed in a vessel and cooled to 0 ° C. DMAP (0.33 g, 2.69 mmol) was added thereto, and then DCC (2.04 g, 9.88 mmol) was added. The mixture was warmed to room temperature and stirred for 22 hours. The precipitated colorless solid was removed, and the filtrate was washed with a saturated aqueous sodium hydrogen carbonate solution and water in that order, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (heptane / ethyl acetate = 4/1 (volume ratio)) to obtain compound (T-5) (3.64 g, yield 72.4). %).

Third step:
Compound (T-5) (3.64 g, 6.50 mmol), 20% palladium hydroxide on carbon (0.18 g), and toluene (35 ml) / IPA (35 ml) were placed in a reactor and at room temperature under a hydrogen atmosphere. Stir for 18 hours. 20% Palladium hydroxide carbon was removed, the filtrate was concentrated, the residue was purified by silica gel column chromatography (heptane / ethyl acetate = 4/1 (volume ratio)), and compound (T-6) (2. 40 g, yield 78.6%).

Fourth step:
Under nitrogen atmosphere, compound (T-6) (2.83 g, 6.03 mmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine (0.99 g, 6.33 mmol), and dichloromethane (50 ml) Was placed in a reactor and cooled to 0 ° C. DMAP (0.22 g, 1.81 mmol) was added thereto, and then DCC (1.37 g, 6.63 mmol) was added. The mixture was warmed to room temperature and stirred for 24 hours. The precipitated colorless solid was removed, and the filtrate was washed with a saturated aqueous sodium hydrogen carbonate solution and water in that order, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (ethyl acetate) to obtain compound (1-1-2) (1.62 g, yield 44.2%).

¹ H-NMR (ppm; CDCl ₃ ): δ 5.19 (tt, J = 11.4 Hz, J = 4.2 Hz, 1H), 5.01 (tt, J = 11.5 Hz, J = 4.4 Hz, 1H), 3.72 (t, J = 6.7 Hz, 2H), 2.27 (t, J = 7.5 Hz, 2H), 2.25 (t, J = 7.7 Hz, 2H), 91 (dd, J = 12.5 Hz, J = 4.2 Hz, 2H), 1.80 (dd, J = 11.1 Hz, J = 3.7 Hz, 2H), 1.61 (quin, J = 7. 2Hz, 4H), 1.56-1.48 (m, 4H), 1.37-1.28 (m, 18H), 1.24 (s, 6H), 1.18 (s, 12H), 1 .15 (s, 6H), 1.14 (dd, J = 11.9 Hz, J = 11.9 Hz, 2H), 0.88 (t, J = 6.9 Hz, 3H), 0.8 -0.65 (br, 1H).

Synthesis example 3
Compound (1-1-7) was synthesized by the following route.

First step:
In a nitrogen atmosphere, compound (T-1) (10.00 g, 34.20 mmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine (6.03 g, 38.8 mmol), DMAP · TFA (4 -Dimethylaminopyridine trifluoroacetate salt (2.42 g, 10.2 mmol) and dichloromethane (100 ml) were charged to the reactor and cooled to 0 ° C. EDC.HCl (1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride) (8.51 g, 44.4 mmol) was added thereto. The mixture was warmed to room temperature and stirred for 24 hours. The reaction mixture was washed with a saturated aqueous sodium hydrogen carbonate solution and water in that order, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (acetone) to obtain compound (T-7) (12.88 g, yield 87.1%).

Second step:
Compound (T-7) (12.38 g, 28.68 mmol), 20% palladium hydroxide on carbon (0.62 g) and IPA (120 ml) were placed in a reactor and stirred at room temperature for 24 hours under a hydrogen atmosphere. 20% Palladium hydroxide carbon was removed, the filtrate was concentrated, and the residue was purified by silica gel column chromatography (acetone) to obtain compound (T-8) (8.58 g, yield 87.4%). It was.

Third step:
Compound (T-8) (4.30 g, 12.6 mmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical (2.43 g, 14.1 mmol) under nitrogen atmosphere , DMAP · TFA (0.89 g, 3.8 mmol), and dichloromethane (40 ml) were charged to the reactor and cooled to 0 ° C. EDC.HCl (3.14 g, 16.4 mmol) was added thereto. The mixture was warmed to room temperature and stirred for 21 hours. The reaction mixture was washed with a saturated aqueous sodium hydrogen carbonate solution and water in that order, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (ethyl acetate to acetone). Recrystallization from a mixed solvent of heptane / ethyl acetate = 4/1 (volume ratio) gave compound (1-1-7) (5.46 g, yield 87.5%).

Melting point: 74.0 ° C.

Synthesis example 4
Compound (1-1-8) was synthesized by the following route.

First step:
Under a nitrogen atmosphere, succinic anhydride (20.05 g, 200.4 mmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine (30.00 g, 190.8 mmol), DMAP (2.33 g, 19. 1 mmol) and toluene (500 ml) were added to the reactor and stirred at reflux for 5 hours. After cooling to room temperature, the precipitate was collected by filtration and washed thoroughly with tetrahydrofuran to obtain Compound (T-9) (47.26 g, yield 96.3%).

Second step:
Compound (T-9) (4.00 g, 15.5 mmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical (3.01 g, 17.5 mmol) under nitrogen atmosphere , DMAP.TFA (1.10 g, 4.66 mmol), and dichloromethane (40 ml) were charged to the reactor and cooled to 0 ° C. EDC · HCl (3.87 g, 20.21 mmol) was added thereto. The mixture was warmed to room temperature and stirred for 17 hours. The reaction mixture was washed with a saturated aqueous sodium hydrogen carbonate solution and water in that order, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (ethyl acetate to acetone). Recrystallization from a mixed solvent of heptane / ethyl acetate = 2/1 (volume ratio) gave Compound (1-1-8) (3.46 g, yield 54.1%).

Melting point: 105.2 ° C.

Examples of the composition are shown below. The component compounds were represented by symbols based on the definitions in Table 3 below. In Table 3, the configuration regarding 1,4-cyclohexylene is trans. The number in parentheses after the symbolized compound represents the chemical formula to which the compound belongs. The symbol (−) means other liquid crystal compounds. The ratio (percentage) of the liquid crystal compound is a mass percentage (% by mass) based on the mass of the liquid crystal composition containing no additive. Finally, the characteristic values of the composition are summarized.

 

[Example 1]
3-HHXB (F, F) -CF3 (2-5) 12%
3-GB (F, F) XB (F, F) -F (2-14) 8%
3-GBB (F) B (F, F) -F (2-22) 3%
4-GBB (F) B (F, F) -F (2-22) 2%
3-HBBBXB (F, F) -F (2-23) 3%
4-GB (F) B (F, F) XB (F, F) -F
(2-27) 5%
5-GB (F) B (F, F) XB (F, F) -F
(2-27) 5%
5-BB (F) B (F, F) XB (F, F) -F
(2-29) 12%
3-HH-V (3-1) 23%
3-HH-V1 (3-1) 10%
1V2-HH-3 (3-1) 9%
V2-HHB-1 (3-5) 8%
The above composition (1) was prepared. To the composition (1), the compound (1-1-1) was added at a ratio of 0.15% by mass. When a line afterimage (LISP) was measured according to the method described in Measurement (16), it was 2.3%.

NI = 88.8 ° C .; Tc <−20 ° C .; Δn = 0.101; Δε = 13.4; Vth = 1.34 V; η = 20.6 mPa · s;

[Comparative Example 1]
The comparative compound (A-1) was added to the composition (1) described in Example 1 at a ratio of 0.15% by mass. The line afterimage (LISP) by the method described in measurement (16) was 3.0%. The results are shown in Table 4 together with the results of Example 1. From Table 4, it can be seen that the effect of suppressing the line afterimage is higher in the compound (1-1-1) than in the comparative compound (A-1) because the value of the line afterimage is lower. The characteristic that the effect of suppressing the line afterimage is high is a characteristic required for using the element for a long time. Therefore, it can be seen that the composition of the present invention is superior.

 

[Example 2]
Compound (1-1-2) was added to the composition (1) described in Example 1 at a ratio of 0.15% by mass. The lower limit temperature (Tc) was <−20 ° C. This result was the same as in Example 1.

[Comparative Example 2]
The following comparative compound (A-2) was added to the composition (1) described in Example 1 at a ratio of 0.15% by mass. The lower limit temperature (Tc) was <0 ° C. The results are summarized in Table 5 together with the results of Examples 1 and 2. If the solubility of the additive in the composition is good, it is easy to maintain the nematic phase. When the solubility is inferior, it tends to transition to a crystal (or a smectic phase). By this method, solubility at low temperatures can be compared. From Table 5, it can be seen that the compound (1) is superior in solubility compared to the comparative compound.

[Example 3]
3-HHXB (F, F) -CF3 (2-5) 12%
3-GB (F, F) XB (F, F) -F (2-14) 8%
3-GBB (F) B (F, F) -F (2-22) 3%
4-GBB (F) B (F, F) -F (2-22) 2%
3-HBBBXB (F, F) -F (2-23) 3%
4-GB (F) B (F, F) XB (F, F) -F
(2-27) 5%
5-GB (F) B (F, F) XB (F, F) -F
(2-27) 5%
5-BB (F) B (F, F) XB (F, F) -F
(2-29) 12%
3-HH-V (3-1) 23%
3-HH-V1 (3-1) 10%
1V2-HH-3 (3-1) 9%
V2-HHB-1 (3-5) 8%
To this composition, the compound (1-1-3) was added at a ratio of 0.15% by mass.

NI = 88.8 ° C .; Tc <−20 ° C .; Δn = 0.101; Δε = 13.4; Vth = 1.34 V; η = 20.6 mPa · s; γ1 = 1123.7 mPa · s; LISP = 2 4%.

[Example 4]
3-HHB (F, F) -F (2-2) 10%
3-HHXB (F, F) -F (2-4) 2%
3-GHB (F, F) -F (2-7) 4%
3-BB (F) B (F, F) -F (2-15) 7%
3-BB (F, F) XB (F, F) -F (2-18) 14%
4-BB (F) B (F, F) XB (F, F) -F
(2-29) 10%
5-BB (F) B (F, F) XB (F, F) -F
(2-29) 6%
3-HH-V (3-1) 18%
3-HH-4 (3-1) 11%
5-HB-O2 (3-2) 2%
3-HHB-1 (3-5) 5%
3-HHB-3 (3-5) 5%
3-HHB-O1 (3-5) 6%
To this composition, the compound (1-1-1) was added at a ratio of 0.10% by mass.

NI = 78.2 ° C .; Tc <−20 ° C .; Δn = 0.108; Δε = 10.4; Vth = 1.35V; η = 17.8 mPa · s; γ1 = 79.9 mPa · s; LISP = 2 4%.

[Example 5]
3-HHB (F, F) -F (2-2) 10%
3-HHXB (F, F) -F (2-4) 2%
3-GHB (F, F) -F (2-7) 4%
3-BB (F) B (F, F) -F (2-15) 7%
3-BB (F, F) XB (F, F) -F (2-18) 14%
4-BB (F) B (F, F) XB (F, F) -F
(2-29) 10%
5-BB (F) B (F, F) XB (F, F) -F
(2-29) 6%
3-HH-V (3-1) 18%
3-HH-4 (3-1) 11%
5-HB-O2 (3-2) 2%
3-HHB-1 (3-5) 5%
3-HHB-3 (3-5) 5%
3-HHB-O1 (3-5) 6%
The compound (1-1-3) was added to this composition at a ratio of 0.10% by mass.

NI = 78.1 ° C .; Tc <−20 ° C .; Δn = 0.108; Δε = 10.4; Vth = 1.35V; η = 17.8 mPa · s; γ1 = 79.9 mPa · s; LISP = 2 .5%.

[Example 6]
3-HHXB (F, F) -F (2-4) 6%
3-BB (F, F) XB (F, F) -F (2-18) 13%
3-HHBB (F, F) -F (2-19) 4%
4-HHBB (F, F) -F (2-19) 5%
3-HBBBXB (F, F) -F (2-23) 3%
3-BB (F) B (F, F) XB (F) -F (2-28) 2%
4-BB (F) B (F, F) XB (F, F) -F
(2-29) 8%
5-BB (F) B (F, F) XB (F, F) -F
(2-29) 7%
3-HH-V (3-1) 44%
V-HHB-1 (3-5) 6%
2-BB (F) B-3 (3-8) 2%
To this composition, the compound (1-1-1) was added at a ratio of 0.10% by mass.

NI = 79.6 ° C .; Tc <−20 ° C .; Δn = 0.106; Δε = 8.5; Vth = 1.45 V; η = 11.6 mPa · s; γ1 = 60.0 mPa · s; LISP = 2 .3%

[Example 7]
5-HXB (F, F) -F (2-1) 3%
3-HHXB (F, F) -F (2-4) 3%
3-HHXB (F, F) -CF3 (2-5) 3%
3-HGB (F, F) -F (2-6) 3%
3-HB (F) B (F, F) -F (2-9) 5%
3-BB (F, F) XB (F, F) -F (2-18) 6%
3-HHBB (F, F) -F (2-19) 6%
5-BB (F) B (F, F) XB (F) B (F, F) -F
(2-31) 2%
3-BB (2F, 3F) XB (F, F) -F (2-32) 4%
3-B (2F, 3F) BXB (F, F) -F (2-33) 5%
3-HHB (F, F) XB (F, F) -F (2) 4%
3-HB-CL (2) 3%
3-HHB-OCF3 (2) 3%
3-HH-V (3-1) 22%
3-HH-V1 (3-1) 10%
5-HB-O2 (3-2) 5%
3-HHEH-3 (3-4) 3%
3-HBB-2 (3-6) 7%
5-B (F) BB-3 (3-7) 3%
To this composition, the compound (1-1-1) was added at a ratio of 0.10% by mass.

NI = 71.2 ° C .; Tc <−20 ° C .; Δn = 0.099; Δε = 6.1; Vth = 1.74 V; η = 13.2 mPa · s; γ1 = 59.3 mPa · s; LISP = 2 .5%.

[Example 8]
5-HXB (F, F) -F (2-1) 6%
3-HHXB (F, F) -F (2-4) 6%
V-HB (F) B (F, F) -F (2-9) 5%
3-HHB (F) B (F, F) -F (2-20) 7%
2-BB (F) B (F, F) XB (F) -F (2-29) 3%
3-BB (F) B (F, F) XB (F) -F (2-29) 3%
4-BB (F) B (F, F) XB (F) -F (2-29) 4%
5-HB-CL (2) 5%
2-HH-5 (3-1) 8%
3-HH-V (3-1) 10%
3-HH-V1 (3-1) 7%
4-HH-V (3-1) 10%
4-HH-V1 (3-1) 8%
5-HB-O2 (3-2) 7%
4-HHEH-3 (3-4) 3%
1-BB (F) B-2V (3-8) 3%
1O1-HBBH-3 (-) 5%
Compound (1-1-4) was added to this composition at a ratio of 0.10% by mass.

NI = 78.5 ° C .; Tc <−20 ° C .; Δn = 0.095; Δε = 3.4; Vth = 1.50 V; η = 8.4 mPa · s; γ1 = 54.2 mPa · s; LISP = 2 .5%.

[Example 9]
3-HHXB (F, F) -F (2-4) 3%
3-BBXB (F, F) -F (2-17) 3%
3-BB (F, F) XB (F, F) -F (2-18) 8%
3-HHBB (F, F) -F (2-19) 5%
4-HHBB (F, F) -F (2-19) 4%
3-BB (F) B (F, F) XB (F, F) -F
(2-29) 3%
4-BB (F) B (F, F) XB (F, F) -F
(2-29) 6%
5-BB (F) B (F, F) XB (F, F) -F
(2-29) 5%
3-HH-V (3-1) 30%
3-HH-V1 (3-1) 5%
3-HHB-O1 (3-5) 2%
V-HHB-1 (3-5) 5%
2-BB (F) B-3 (3-8) 6%
F3-HH-V (-) 15%
To this composition, the compound (1-1-1) was added at a ratio of 0.10% by mass.

NI = 80.2 ° C .; Tc <−20 ° C .; Δn = 0.106; Δε = 5.8; Vth = 1.40 V; η = 11.6 mPa · s; γ1 = 61.0 mPa · s; LISP = 2 .3%

[Example 10]
3-HGB (F, F) -F (2-6) 3%
5-GHB (F, F) -F (2-7) 4%
3-GB (F, F) XB (F, F) -F (2-14) 5%
3-BB (F) B (F, F) -CF3 (2-16) 2%
3-HHBB (F, F) -F (2-19) 4%
3-GBB (F) B (F, F) -F (2-22) 2%
2-dhBB (F, F) XB (F, F) -F (2-25) 4%
3-GB (F) B (F, F) XB (F, F) -F
(2-27) 3%
3-HGB (F, F) XB (F, F) -F (2) 5%
7-HB (F, F) -F (2) 3%
2-HH-3 (3-1) 14%
2-HH-5 (3-1) 4%
3-HH-V (3-1) 26%
1V2-HH-3 (3-1) 5%
1V2-BB-1 (3-3) 3%
2-BB (F) B-3 (3-8) 3%
3-HB (F) HH-2 (3-10) 4%
5-HBB (F) B-2 (3-13) 6%
Compound (1-1-1) was added to the composition at a ratio of 0.12% by mass.

NI = 78.2 ° C .; Tc <−20 ° C .; Δn = 0.094; Δε = 5.6; Vth = 1.45 V; η = 11.5 mPa · s; γ1 = 61.7 mPa · s; LISP = 2 .3%

[Example 11]
3-HBB (F, F) -F (2-8) 5%
5-HBB (F, F) -F (2-8) 4%
3-BB (F) B (F, F) -F (2-15) 3%
3-BB (F) B (F, F) XB (F, F) -F
(2-29) 3%
4-BB (F) B (F, F) XB (F, F) -F
(2-29) 5%
3-BB (F, F) XB (F) B (F, F) -F
(2-30) 3%
5-BB (F) B (F, F) XB (F) B (F, F) -F
(2-31) 4%
3-HH2BB (F, F) -F (2) 3%
4-HH2BB (F, F) -F (2) 3%
2-HH-5 (3-1) 8%
3-HH-V (3-1) 25%
3-HH-V1 (3-1) 7%
4-HH-V1 (3-1) 6%
5-HB-O2 (3-2) 5%
7-HB-1 (3-2) 5%
VFF-HHB-O1 (3-5) 8%
VFF-HHB-1 (3-5) 3%
Compound (1-1-1) was added to the composition at a ratio of 0.15% by mass.

NI = 79.8 ° C .; Tc <−20 ° C .; Δn = 0.101; Δε = 4.6; Vth = 1.71 V; η = 11.0 mPa · s; γ1 = 47.2 mPa · s; LISP = 2 .3%

[Example 12]
3-HHB (F, F) -F (2-2) 8%
3-GB (F) B (F) -F (2-11) 2%
3-GB (F) B (F, F) -F (2-12) 3%
3-BB (F, F) XB (F, F) -F (2-18) 8%
3-GB (F) B (F, F) XB (F, F) -F
(2-27) 6%
5-GB (F) B (F, F) XB (F, F) -F
(2-27) 5%
3-HH-V (3-1) 30%
3-HH-V1 (3-1) 10%
1V2-HH-3 (3-1) 8%
3-HH-VFF (3-1) 8%
V2-BB-1 (3-3) 2%
5-HB (F) BH-3 (3-12) 5%
5-HBBH-3 (3) 5%
To this composition, the compound (1-1-1) was added at a ratio of 0.10% by mass.

NI = 78.4 ° C .; Tc <−20 ° C .; Δn = 0.088; Δε = 5.6; Vth = 1.85 V; η = 13.9 mPa · s; γ1 = 66.9 mPa · s; LISP = 2 .3%

[Example 13]
3-HHEB (F, F) -F (2-3) 4%
5-HHEB (F, F) -F (2-3) 3%
3-HBEB (F, F) -F (2-10) 3%
5-HBEB (F, F) -F (2-10) 3%
3-BB (F) B (F, F) -F (2-15) 3%
3-GB (F) B (F, F) XB (F, F) -F
(2-27) 5%
4-GB (F) B (F, F) XB (F, F) -F
(2-27) 5%
5-HB-CL (2) 5%
3-HHB-OCF3 (2) 4%
3-HHB (F, F) XB (F, F) -F (2) 5%
5-HHB (F, F) XB (F, F) -F (2) 3%
3-HGB (F, F) XB (F, F) -F (2) 5%
2-HH-5 (3-1) 3%
3-HH-5 (3-1) 5%
3-HH-V (3-1) 24%
4-HH-V (3-1) 5%
1V2-HH-3 (3-1) 5%
3-HHEH-3 (3-4) 5%
5-B (F) BB-2 (3-7) 3%
5-B (F) BB-3 (3-7) 2%
To this composition, the compound (1-1-1) was added at a ratio of 0.10% by mass.

NI = 82.7 ° C .; Tc <−20 ° C .; Δn = 0.093; Δε = 6.9; Vth = 1.50 V; η = 16.3 mPa · s; γ1 = 65.2 mPa · s; LISP = 2 .3%

[Example 14]
3-HHXB (F, F) -F (2-4) 9%
3-HBB (F, F) -F (2-8) 3%
3-BB (F) B (F, F) -F (2-15) 4%
3-BB (F) B (F, F) -CF3 (2-16) 4%
3-BB (F, F) XB (F, F) -F (2-18) 5%
3-GBB (F) B (F, F) -F (2-22) 3%
4-GBB (F) B (F, F) -F (2-22) 4%
3-HH-V (3-1) 25%
3-HH-V1 (3-1) 10%
5-HB-O2 (3-2) 10%
7-HB-1 (3-2) 5%
V2-BB-1 (3-3) 3%
3-HHB-1 (3-5) 4%
1V-HBB-2 (3-6) 5%
5-HBB (F) B-2 (3-13) 6%
To this composition, the compound (1-1-5) was added at a ratio of 0.10% by mass.

NI = 79.4 ° C .; Tc <−20 ° C .; Δn = 0.111; Δε = 4.7; Vth = 1.86 V; η = 9.7 mPa · s; γ1 = 49.9 mPa · s; LISP = 2 .6%.

[Example 15]
3-BB (F, F) XB (F, F) -F (2-18) 14%
5-BB (F) B (F, F) XB (F, F) -F
(2-29) 7%
7-HB (F, F) -F (2) 6%
2-HH-5 (3-1) 5%
3-HH-V (3-1) 30%
3-HH-V1 (3-1) 3%
3-HH-VFF (3-1) 10%
3-HHB-1 (3-5) 4%
3-HHB-3 (3-5) 5%
3-HHB-O1 (3-5) 3%
1-BB (F) B-2V (3-8) 3%
3-HHEBH-3 (3-11) 3%
3-HHEBH-4 (3-11) 4%
3-HHEBH-5 (3-11) 3%
Compound (1-1-1) was added to the composition at a ratio of 0.15% by mass.

NI = 82.8 ° C .; Tc <−20 ° C .; Δn = 0.086; Δε = 3.8; Vth = 1.94 V; η = 7.5 mPa · s; γ1 = 51.5 mPa · s; LISP = 2 4%.

[Example 16]
3-HBB (F, F) -F (2-8) 5%
5-HBB (F, F) -F (2-8) 4%
3-BB (F) B (F, F) -F (2-15) 3%
3-BB (F) B (F, F) XB (F, F) -F
(2-29) 3%
4-BB (F) B (F, F) XB (F, F) -F
(2-29) 5%
3-BB (F, F) XB (F) B (F, F) -F
(2-30) 3%
5-BB (F) B (F, F) XB (F) B (F, F) -F
(2-31) 4%
3-HH2BB (F, F) -F (2) 3%
4-HH2BB (F, F) -F (2) 3%
2-HH-5 (3-1) 8%
3-HH-V (3-1) 28%
4-HH-V1 (3-1) 7%
5-HB-O2 (3-2) 2%
7-HB-1 (3-2) 5%
VFF-HHB-O1 (3-5) 8%
VFF-HHB-1 (3-5) 3%
2-BB (2F, 3F) B-3 (4-9) 4%
3-HBB (2F, 3F) -O2 (4-10) 2%
The compound (1-1-3) was added to this composition at a ratio of 0.10% by mass.

NI = 81.7 ° C .; Tc <−20 ° C .; Δn = 0.109; Δε = 4.8; Vth = 1.75 V; η = 13.3 mPa · s; γ1 = 57.4 mPa · s; LISP = 2 4%.

[Example 17]
3-HHEB (F, F) -F (2-3) 4%
3-HBEB (F, F) -F (2-10) 3%
5-HBEB (F, F) -F (2-10) 3%
3-BB (F) B (F, F) -F (2-15) 3%
3-HBBBXB (F, F) -F (2-23) 6%
4-GBB (F, F) XB (F, F) -F (2-26) 2%
5-GBB (F, F) XB (F, F) -F (2-26) 2%
3-GB (F) B (F, F) XB (F, F) -F
(2-27) 5%
4-GB (F) B (F, F) XB (F, F) -F
(2-27) 5%
5-HHB (F, F) XB (F, F) -F (2) 3%
5-HEB (F, F) -F (2) 3%
5-HB-CL (2) 2%
3-HHB-OCF3 (2) 4%
3-HH-5 (3-1) 4%
3-HH-V (3-1) 21%
3-HH-V1 (3-1) 3%
4-HH-V (3-1) 4%
1V2-HH-3 (3-1) 6%
5-B (F) BB-2 (3-7) 3%
5-B (F) BB-3 (3-7) 2%
3-HB (2F, 3F) -O2 (4-1) 3%
3-BB (2F, 3F) -O2 (4-4) 2%
3-HHB (2F, 3F) -O2 (4-6) 4%
F3-HH-V (-) 3%
Compound (1-1-1) was added to the composition at a ratio of 0.15% by mass.

NI = 78.0 ° C .; Tc <−20 ° C .; Δn = 0.101; Δε = 6.7; Vth = 1.45 V; η = 17.8 mPa · s; γ1 = 67.8 mPa · s; LISP = 2 .3%

[Example 18]
3-HHB (F, F) -F (2-2) 10%
3-HHXB (F, F) -F (2-4) 2%
3-GHB (F, F) -F (2-7) 4%
3-BB (F) B (F, F) -F (2-15) 7%
3-BB (F, F) XB (F, F) -F (2-18) 14%
4-BB (F) B (F, F) XB (F, F) -F
(2-29) 10%
5-BB (F) B (F, F) XB (F, F) -F
(2-29) 6%
3-HH-V (3-1) 18%
3-HH-4 (3-1) 11%
5-HB-O2 (3-2) 2%
3-HHB-1 (3-5) 5%
3-HHB-3 (3-5) 5%
3-HHB-O1 (3-5) 6%
To this composition, the compound (1-1-7) was added at a ratio of 0.10% by mass.

NI = 77.8 ° C .; Tc <−20 ° C .; Δn = 0.108; Δε = 10.4; Vth = 1.35 V; η = 17.8 mPa · s; γ1 = 79.9 mPa · s; LISP = 1 9%.

[Example 19]
3-HHB (F, F) -F (2-2) 10%
3-HHXB (F, F) -F (2-4) 2%
3-GHB (F, F) -F (2-7) 4%
3-BB (F) B (F, F) -F (2-15) 7%
3-BB (F, F) XB (F, F) -F (2-18) 14%
4-BB (F) B (F, F) XB (F, F) -F
(2-29) 10%
5-BB (F) B (F, F) XB (F, F) -F
(2-29) 6%
3-HH-V (3-1) 18%
3-HH-4 (3-1) 11%
5-HB-O2 (3-2) 2%
3-HHB-1 (3-5) 5%
3-HHB-3 (3-5) 5%
3-HHB-O1 (3-5) 6%
To this composition, the compound (1-1-8) was added at a ratio of 0.10% by mass.

NI = 77.8 ° C .; Tc <−20 ° C .; Δn = 0.108; Δε = 10.4; Vth = 1.35 V; η = 17.8 mPa · s; γ1 = 79.9 mPa · s; LISP = 2 .2%.

[Example 20]
Finally, the spreadability was evaluated. The compound (1-1-1) was added to the composition (1) described in Example 1 in a proportion of 0.005% by mass. The luminance was measured by the method described in Measurement (17), and the expansibility of this compound was qualitatively evaluated from FIG. 1 which is the measurement result (Table 6).

[Example 21]
Compound (1-1-2) was added to the composition (1) described in Example 1 at a ratio of 0.005% by mass. The luminance was measured by the method described in Measurement (17), and the expansibility of this compound was qualitatively evaluated from FIG. 2 which is the measurement result (Table 6).

[Comparative Example 3]
The comparative compound (A-2) was added to the composition (1) described in Example 1 in a proportion of 0.005% by mass. The luminance was measured by the method described in Measurement (17), and the expansibility of this compound was qualitatively evaluated from FIG. 3 which is the measurement result. The results are shown in Table 6 together with the results of Examples 18 and 19.

1 to 3 are photographs of the element. The inlet was located on the lower side of the photograph (not shown), from which the composition containing the additive was injected. In FIG. 1 and FIG. 2, although the magnitudes of the brightness are different from each other, the brightness is uniform throughout. These indicate that the spreadability is good. In FIG. 3, a convex curve was observed at the upper corner, and the luminance was not uniform. This indicates that the device was filled with the liquid crystal composition, but the additive contained in the composition did not reach the entire device. From these results, it was found that in Examples 18 and 19, the expansibility was good, and in Comparative Example 3, the expansibility was poor.

Comparative experiments of line afterimage, lower limit temperature (solubility at low temperature), and spreadability were conducted, and the results are summarized in Tables 4, 5, and 6. In any case, compound (1) gave superior results compared to the comparative compound. Therefore, it is concluded that the composition of the present invention has excellent properties.

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

Claims (18)

1. As an additive, has at least two monovalent radical of the formula (S), in these monovalent group, compound different from the group that the group represented by R ¹ is represented by the other of R ¹ And a liquid crystal composition having positive dielectric anisotropy.
   

   

   
   In the formula (S), R ¹ is hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, hydroxy, or oxy radical; R is alkyl having 1 to 12 carbons.
2. The liquid crystal composition according to claim 1, wherein R is methyl in the monovalent group represented by the formula (S) according to claim 1.
3. The liquid crystal composition according to claim 1 or 2, comprising at least one compound selected from the group of compounds represented by formula (1) as an additive.
   

   

   
   In the formula (1) and the formula (S-1), R ¹ is hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, hydroxy, or an oxy radical, where R ¹ is represented by R ¹ The group represented is different from the group represented by R ¹ ; ring A 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- , 5-diyl, or pyridine-2,5-diyl, and in these rings, at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, at least one Hydrogen may be replaced by alkyl having 1 to 12 carbons replaced by fluorine or chlorine, or a group represented by formula (S-1); Z ¹ and Z ² are independently a single bond or carbon An alkylene having the number 1 to 20, in which at least one —CH ₂ — may be replaced by —O—, —COO—, —OCO—, or —OCOO—, At least one hydrogen may be replaced with fluorine, chlorine, or a group represented by the formula (S-1); Z ³ represents a single bond or an alkyl group having 1 to 20 carbon atoms. In the alkylene, at least one —CH ₂ — may be replaced by —O—, —COO—, —OCO—, or —OCOO—, in which at least one hydrogen is , Fluorine or chlorine; a is 0, 1, 2, or 3;
4. 4. The liquid crystal according to claim 1, comprising at least one compound selected from the group of compounds represented by formula (1-1) to formula (1-9) as an additive. 5. Composition.
   

   

   
   

   

   
   In formulas (1-1) to (1-9), R ² is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, hydroxy, or oxy radical; Z ⁴ is carbon 1 Z ⁵ and Z ⁶ are independently alkylene having 1 to 5 carbons; Z ⁷ and Z ⁸ are independently a single bond or alkylene having 1 to 20 carbons; In this alkylene, at least one —CH ₂ — may be replaced by —O—, —COO—, —OCO—, or —OCOO—, in which at least one hydrogen is fluorine or chlorine X ¹ is hydrogen or fluorine.
5. The liquid crystal composition according to any one of claims 1 to 4, wherein a ratio of the additive is in a range of 0.005% by mass to 1% by mass.
6. The liquid crystal composition according to any one of claims 1 to 5, comprising at least one compound selected from the group of compounds represented by formula (2) as a first component.
   

   

   
   In the formula (2), R ³ is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons or alkenyl having 2 to 12 carbons; ring B is 1,4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyrimidine-2,5-diyl, 1,3- Dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl; Z ⁹ is a single bond, ethylene, carbonyloxy, or difluoromethyleneoxy; X ² and X ³ are independently hydrogen or is fluorine; Y ¹ is fluorine, chlorine, at least one hydrogen alkyl having 1 carbon is replaced by fluorine or chlorine 12, at least one hydrogen 1 to 12 carbon alkoxy substituted with fluorine or chlorine, or alkenyloxy having 2 to 12 carbon atoms with at least one hydrogen replaced with fluorine or chlorine; b is 1, 2, 3, or 4 It is.
7. The liquid crystal according to any one of claims 1 to 6, comprising at least one compound selected from the group of compounds represented by formula (2-1) to formula (2-35) as a first component. Composition.
   

   

   
   

   

   
   

   

   
   

   

   
   In the formulas (2-1) to (2-35), R ³ is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons.
8. The liquid crystal composition according to claim 6 or 7, wherein the ratio of the first component is in the range of 5% by mass to 90% by mass.
9. The liquid crystal composition according to any one of claims 1 to 8, comprising at least one compound selected from the group of compounds represented by formula (3) as the second component.
   

   

   
   In Formula (3), R ⁴ and R ⁵ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or at least one hydrogen is fluorine or chlorine. Substituted alkenyl having 2 to 12 carbon atoms; ring C and ring D are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5 -Difluoro-1,4-phenylene; Z ¹⁰ is a single bond, ethylene, or carbonyloxy; c is 1, 2, or 3.
10. The liquid crystal according to any one of claims 1 to 9, comprising at least one compound selected from the group of compounds represented by formulas (3-1) to (3-13) as a second component: Composition.
    

    

    
    In the formulas (3-1) to (3-13), R ⁴ and R ⁵ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or C2-C12 alkenyl in which at least one hydrogen is replaced by fluorine or chlorine.
11. The liquid crystal composition according to claim 9 or 10, wherein the ratio of the second component is in the range of 5% by mass to 90% by mass.
12. The liquid crystal composition according to any one of claims 1 to 11, comprising at least one compound selected from the group of compounds represented by formula (4) as a third component.
    

    

    
    In Formula (4), R ⁶ and R ⁷ 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. Yes; Ring E and Ring G are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine Or tetrahydropyran-2,5-diyl; ring F is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5 - methyl-1,4-phenylene, it is a 3,4,5-trifluoro-2,6-diyl or ^{7,8-difluoro-chroman-2,6-diyl,; Z 11} Contact Fine ^{Z 12} are independently a single bond, ethylene, carbonyloxy or methyleneoxy,; d is 1, 2, or 3,, e is 0 or 1; the sum of d and e 3 or less.
13. The liquid crystal according to any one of claims 1 to 12, comprising at least one compound selected from the group of compounds represented by formulas (4-1) to (4-22) as a third component: Composition.
    
    

    

    
    

    

    
    In the formulas (4-1) to (4-22), R ⁶ and R ⁷ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or It is alkenyloxy having 2 to 12 carbon atoms.
14. The liquid crystal composition according to claim 12 or 13, wherein the ratio of the third component is in the range of 3% by mass to 25% by mass.
15. The upper limit temperature of the nematic phase is 70 ° C. or higher, the optical anisotropy at a wavelength of 589 nm (measured at 25 ° C.) is 0.07 or higher, and the dielectric anisotropy at a frequency of 1 kHz (measured at 25 ° C.) is 2. The liquid crystal composition according to claim 1, which is as described above.
16. A liquid crystal display element comprising the liquid crystal composition according to claim 1.
17. The liquid crystal display according to claim 16, wherein an operation mode of the liquid crystal display element is a TN mode, an ECB mode, an OCB mode, an IPS mode, an FFS mode, or an FPA mode, and the driving method of the liquid crystal display element is an active matrix method. element.
18. Use of the liquid crystal composition according to any one of claims 1 to 15 in a liquid crystal display device.

Images