KR102165665B1 - Liquid crystal composition and liquid crystal display device - Google Patents

Abstract

At least one of characteristics such as high upper limit temperature, low lower limit temperature, small viscosity, appropriate optical anisotropy, negatively large dielectric anisotropy, large specific resistance, high stability against ultraviolet rays, high stability against heat, suppression of display defects such as afterimages It provides a liquid crystal composition that satisfies one property or has an appropriate balance between at least two of these properties. An AM device having characteristics such as a short response time, a large voltage retention rate, a low threshold voltage, a large contrast ratio, and a long lifetime is provided. It is a liquid crystal composition having a compound having high solubility in a liquid crystal composition, containing a compound having an effect of suppressing display defects of a liquid crystal display device as a first additive, and having a positive dielectric anisotropy. A specific compound having positively large dielectric anisotropy as one component, a specific compound having a high upper limit temperature or small viscosity as the second component, and a specific compound having negative dielectric anisotropy as a third component may be contained.

Description

Liquid crystal composition and liquid crystal display device

The present invention relates to a liquid crystal composition, a liquid crystal display device containing the composition, and the like. In particular, it relates to a liquid crystal composition having positive dielectric anisotropy, and an AM (active matrix) device containing the composition and having a mode of TN, OCB, IPS, FFS, or FPA.

In a liquid crystal display device, classification based on the operation mode of the liquid crystal molecules is PC (phase change), TN (twisted nematic), STN (super twisted nematic), ECB (electrically controlled birefringence), OCB (optically compensated bend), and IPS. (in-plane switching), vertical alignment (VA), fringe field switching (FFS), and field-induced photo-reactive alignment (FPA) modes. Classification based on the driving method of the device is a passive matrix (PM) and an active matrix (AM). PM is classified into static, multiplex or the like, and AM is classified into TFT (thin film transistor), MIM (metal insulator metal), or the like. The classification of TFT is amorphous silicon and polycrystal 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 is a reflective type using natural light, a transmissive type using a backlight, and a transflective type using both natural light and backlight.

The liquid crystal display device contains a liquid crystal composition having a nematic phase. This composition has suitable properties. By improving the properties of this composition, an AM device having good properties can be obtained. The relationship between these properties is summarized in Table 1 below. The properties of the composition are further described based on commercially available AM devices. The temperature range of the nematic phase is related to the temperature range that the device fmf can use. The preferred upper limit temperature of the nematic phase is about 70°C or higher, and the preferred lower limit temperature of the nematic phase is about -10°C or lower. The viscosity of the composition is related to the response time of the device. A short response time is desirable in order to display a video with a device. Even 1 millisecond, a shorter response time is desirable. Therefore, a small viscosity in the composition is desirable. Small viscosity at low temperatures is more desirable.

[Table 1] Characteristics of the composition and characteristics of the AM device

The optical anisotropy of the composition is related to the contrast ratio of the device. Depending on the mode of the device, either a large optical anisotropy or a small optical anisotropy, i.e. an appropriate optical anisotropy is required. The product of the optical anisotropy (Δn) of the composition and the cell gap (d) of the device (Δn×d) is designed to maximize the contrast ratio. The appropriate product value depends on the type of operation mode. For devices in a mode such as TN, a suitable value is about 0.45 mu m. In this case, a composition having a large optical anisotropy is preferable for a device having a small cell gap. The large dielectric anisotropy in the composition contributes to a low threshold voltage, small power consumption and a large contrast ratio in the device. Therefore, large dielectric anisotropy is desirable. In particular, in the FFS mode, the arrangement of some liquid crystal molecules is not parallel to the panel substrate due to the oblique electric field, so the dielectric constant (ε⊥) in the short axis direction of the liquid crystal molecules is large to suppress the tilt-up of the liquid crystal molecules. It is desirable. By suppressing the tilt-up of the liquid crystal molecules, the transmittance of the device having the FFS mode can be increased, thereby contributing to a large contrast ratio. The large specific resistance in the composition contributes to a large voltage retention and a large contrast ratio in the device. Therefore, in the initial stage, 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 is preferable. After using for a long time, 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 is preferable. The stability of the composition against ultraviolet rays and heat is related to the life of the liquid crystal display device. When these stability are high, the life of this device is long. Such characteristics are suitable for AM elements used in liquid crystal projectors, liquid crystal TVs, and the like.

In an AM device having a TN mode, a composition having positive dielectric anisotropy can be used. In an AM device having a VA mode, a composition having negative dielectric anisotropy can be used. In the AM device having the IPS mode or the FFS mode, a composition having positive or negative dielectric anisotropy can be used. In a polymer sustained alignment (PSA) type AM device, a composition having positive or negative dielectric anisotropy can be 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, two polar groups are the same.

International Publication No. 2015/001916

One object of the present invention is a high upper limit temperature of a nematic phase, a low lower limit temperature of a nematic phase, a small viscosity, an appropriate optical anisotropy, a large dielectric anisotropy, a large specific resistance, a high stability against ultraviolet rays, a high stability against heat, an afterimage, etc. It is to provide a liquid crystal composition that satisfies at least one of characteristics such as suppression of display defects. 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 short response time, large voltage retention, low threshold voltage, large contrast ratio, and long lifespan.

The present invention, as an additive, formula has at least two or a monovalent group represented by (S), in groups of these monovalent, and tiling a group represented by R ¹ are represented by the other R ¹ contains a different compound, It relates to a liquid crystal composition having positive dielectric anisotropy, and a liquid crystal display device containing the composition.

In formula (S), R ¹ is hydrogen, alkyl having 1 to 12 carbon atoms, alkoxy, hydroxy, or oxy radical having 1 to 12 carbon atoms; R is C1-C12 alkyl.

One advantage of the present invention is a high upper limit temperature of the nematic phase, a low lower limit temperature of the nematic phase, a small viscosity, an appropriate optical anisotropy, a large dielectric anisotropy, a large specific resistance, high stability against ultraviolet rays, high stability against heat, an afterimage, etc. It is to provide a liquid crystal composition that satisfies at least one of characteristics such as suppression of display defects. 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 retention rate, a low threshold voltage, a large contrast ratio, and a long lifetime.

1 is a photograph of a device showing good spreadability.
2 is a photograph of a device showing good spreadability.
3 is a photograph of a device showing poor spreadability.

The usage of terms in this specification is as follows. The terms "liquid crystal composition" and "liquid crystal display device" are sometimes referred to as "composition" and "element", respectively. "Liquid crystal display element" is a generic term for a liquid crystal display panel and a liquid crystal display module. The ``liquid crystal compound'' does not have a compound having a liquid crystal phase such as a nematic phase or a smectic phase, and does not have a liquid crystal phase, but is used in the composition for the purpose of controlling properties such as temperature range, viscosity, and dielectric anisotropy of the nematic phase. It is a generic term for a compound to be mixed. This compound has, for example, a 6-membered ring such as 1,4-cyclohexylene or 1,4-phenylene, and its molecular structure is rod-like. The "polymerizable compound" is a compound added for the purpose of forming a polymer in the composition. A liquid crystal compound having alkenyl is not polymerizable in that sense.

The liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. To this liquid crystal composition, additives such as an optically active compound, an antioxidant, an ultraviolet absorber, a dye, an antifoaming agent, a polymerizable compound, a polymerization initiator, a polymerization inhibitor, and a polar compound are added as needed. The proportion of the liquid crystal compound is expressed as a mass percentage (mass%) based on the mass of a liquid crystal composition containing no additive, even when an additive is added. The proportion of the additive is expressed as a mass percentage (mass%) based on the mass of the liquid crystal composition containing no additive. That is, the ratio of the liquid crystal compound or the additive is calculated based on the total mass of the liquid crystal compound. In some cases, parts per million by mass (ppm) are 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" is sometimes abbreviated as "the upper limit temperature". "Lower limit temperature of the nematic phase" is sometimes abbreviated as "lower limit temperature". "The specific resistance is large" means that the composition has a large specific resistance in the initial stage, and after using for a long time, it has a large specific resistance. ``High voltage retention'' means that the device has a large voltage retention rate not only at room temperature in the initial stage, but also at a temperature close to the upper limit temperature, and after using for a long time, it has a large voltage retention rate not only at room temperature but also at a temperature close to the upper limit temperature. it means. In some cases, the characteristics of a composition or device are examined by a change test over time. The expression "increasing dielectric anisotropy" means that the value increases positively when the composition has a positive dielectric anisotropy, and means that the value increases negatively when the composition has a negative dielectric anisotropy.

An expression such as "at least one -CH ₂ -may be substituted with -O-" is used in the present specification. In this case, -CH ₂ -CH ₂ -CH ₂ -may be converted into -O-CH ₂ -O- by replacing non-adjacent -CH ₂ -with -O-. However, adjacent -CH ₂ -is not substituted with -O-. This is because -OO-CH ₂ -(peroxide) is produced by this substitution. That is, this expression means both "one -CH ₂ -may be substituted with -O-" and "at least two non-adjacent -CH ₂ -may be substituted with -O-" . This rule applies not only to substitution with -O- but also to substitution with a divalent group such as -CH=CH- or -COO-.

In the chemical formula of the component compound, the symbol of the terminal group R ³ was used for a plurality of compounds. In these compounds, the two groups represented by any two R ³ may be the same or different. For example, R ³ is ethyl and the compound (2-1), the R ³ of the compound (2-2) in case there is ethyl. And the R ³ of the compound (2-1) ethyl, R ³ is also the case in a profile of the compound (2-2). This rule also applies to other symbols. In formula (2), when the subscript "b" is 2, two rings B exist. In this compound, the two rings represented by the two rings B may be the same or different. This rule is also applied 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 6-membered ring and a condensed ring. In the expression "ring A and ring B are independently X, Y, or Z", since the subject is plural, "independently" is used. When the subject is "Ring A", since the subject is singular, "independently" is not used.

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

The alkyl of the liquid crystal compound is linear or branched, and does not contain cyclic alkyl. Straight-chain alkyl is more preferable than branched alkyl. This is the same also for terminal groups such as alkoxy and alkenyl. For the configuration of 1,4-cyclohexylene, trans is preferable to cis in order to increase the upper limit temperature.

The present invention is the following items.

1. as an anti-additive formula has at least two monovalent group represented by (S), these monovalent groups in, a group represented by the group R ¹ R ¹ is represented by another containing different compounds, both A liquid crystal composition having a dielectric anisotropy of.

In formula (S), R ¹ is hydrogen, alkyl having 1 to 12 carbon atoms, alkoxy, hydroxy, or oxy radical having 1 to 12 carbon atoms; R is C1-C12 alkyl.

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

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 formulas (1) and (S-1), R ¹ is hydrogen, alkyl having 1 to 12 carbon atoms, alkoxy, hydroxy, or oxy radical having 1 to 12 carbon atoms, wherein R ¹ represents The group is different from the group represented by another 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-2,5-diyl, or pyridin-2,5-diyl, In these rings, at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkyl having 1 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine, or formula ( May be substituted with a group represented by S-1); Z ¹ and Z ² are independently a single bond or an alkylene having 1 to 20 carbon atoms, and in this alkylene, at least one of -CH ₂ -is -O-, -COO-, -OCO-, or- May be substituted with OCOO-, in these groups, at least one hydrogen may be substituted with fluorine, chlorine, or a group represented by formula (S-1); Z ³ is a single bond or an alkylene having 1 to 20 carbon atoms, and in this alkylene, at least one -CH ₂ -is substituted with -O-, -COO-, -OCO-, or -OCOO- Or, in these groups, at least one hydrogen may be substituted with fluorine or chlorine; a is 0, 1, 2, or 3.

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

In formulas (1-1) to (1-9), R ² is alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, hydroxy or oxy radical; Z ⁴ is alkylene having 1 to 15 carbon atoms; Z ⁵ and Z ⁶ are independently alkylene having 1 to 5 carbon atoms; Z ⁷ and Z ⁸ are independently a single bond or an alkylene having 1 to 20 carbon atoms, and in this alkylene, at least one of -CH ₂ -is -O-, -COO-, -OCO-, or- May be substituted with OCOO-, in these groups, at least one hydrogen may be substituted with fluorine or chlorine; X ¹ is hydrogen or fluorine.

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

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

In formula (2), R ³ is alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, or alkenyl having 2 to 12 carbon atoms; 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 fluorine; Y ¹ is fluorine, chlorine, alkyl having 1 to 12 carbons in which at least one hydrogen is substituted with fluorine or chlorine, alkoxy having 1 to 12 carbons in which at least one hydrogen is substituted with fluorine or chlorine, or at least one hydrogen Alkenyloxy having 2 to 12 carbon atoms substituted with fluorine or chlorine; b is 1, 2, 3, or 4.

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

In 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. 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. The liquid crystal composition according to any one of items 1 to 8, containing 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 substituted with fluorine or chlorine. 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-phenyl Is Len; Z ¹⁰ is a single bond, ethylene, or carbonyloxy; c is 1, 2, or 3.

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

In 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 at least 1 Hydrogens of each are alkenyl having 2 to 12 carbon atoms substituted with fluorine or chlorine.

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

In formula (4), R ⁶ and R ⁷ are independently alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, or alkenyloxy having 2 to 12 carbon atoms; 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 substituted with 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, 3,4,5-trifluoronaphthalene-2,6-diyl, or 7,8-difluorochroman-2,6-diyl; Z ¹¹ and Z ¹² are independently a single bond, ethylene, carbonyloxy, or methyleneoxy; d is 1, 2, or 3, and e is 0 or 1; The sum of d and e is 3 or less.

Item 13. The liquid crystal composition according to any one of items 1 to 12, containing at least one compound selected from the group of compounds represented by formulas (4-1) to (4-22) as the third component.

In 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 2 It is -12 alkenyloxy.

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

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

Item 17. The liquid crystal display element according to item 16, wherein the operation mode of the liquid crystal display element is 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 system. .

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 also includes the following terms.

(a) The above composition further contains at least one of additives 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. (b) AM device containing the above composition. (c) The above composition further containing a polymerizable compound, and a polymer sustained orientation (PSA) type AM device containing the composition. (d) A polymer sustained orientation (PSA) type AM device containing the above composition and in which a 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 formula (S).

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

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

As shown in Comparative Examples 1, 2, and 3, this compound was found to be effective in suppressing display defects of the device. However, the cause of the display failure is complicated, and thus, it has not been sufficiently investigated. Also, it is not clear at the present stage about the effect of this compound on poor display. Although this is the case, it is believed that the explanation described in the next paragraph is possible.

When the device is used for a long time, the luminance may be partially deteriorated. An example is a line afterimage, which is a phenomenon in which the luminance between the electrodes decreases in a stripe shape by repeatedly applying different voltages to two adjacent electrodes. This phenomenon is due to the 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 ionic impurities from localizing 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 to the additive. It is important that such an additive has high solubility in the liquid crystal composition in order to obtain a desired effect.

The liquid crystal composition is injected into the device from an injection port under reduced pressure. Usually, the composition is filled into the device without changing the proportion of its components. However, additives such as polar compounds may be adsorbed to the alignment film. When the rate of adsorption is high, there are cases where the additive does not reach the depths of the device. The reason the additive remains is because the adsorption rate is higher than the injection rate. In order to prevent this phenomenon, an additive having an appropriate adsorption property 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 . Since the groups represented by at least two groups R ¹ are different, compound (1) is asymmetric. This asymmetry may contribute to an appropriate polarity. See a 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 properties of the component compounds, and the main effects of these compounds on the composition, are described. Third, the combination of the 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, a preferred component compound is shown. Sixth, an additive 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 is described.

First, the composition of the composition will be described. This composition contains a plurality of liquid crystal compounds. This composition may contain an additive. The additives are 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. Composition A may further contain other liquid crystal compounds, additives, etc. in addition to the liquid crystal compounds selected from compound (2), compound (3), and compound (4). A "other liquid crystal compound" is a liquid crystal compound different from the compound (2), the compound (3), and the compound (4). Such a compound is mixed into the composition for the purpose of further adjusting the properties.

Composition B consists essentially of only a liquid crystal compound selected from compound (2), compound (3), and compound (4). "Substantially" means that the composition may contain an additive, but does not contain other liquid crystal compounds. Composition B has fewer components compared to Composition A. From the viewpoint of lowering the cost, Composition B is more preferable than Composition A. Composition A is more preferable than composition B from the viewpoint of further adjusting properties by mixing other liquid crystal compounds.

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

[Table 2] Properties of the compound

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

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

The preferable ratio of compound (1) is about 0.005 mass% or more for suppressing display defects, and about 1 mass% or less for lowering the lower limit temperature. A more preferable ratio is in the range of about 0.02% by mass to about 0.5% by mass. A particularly preferable ratio is in the range of about 0.1% by mass to about 0.3% by mass.

The preferable proportion of compound (2) is about 5% by mass or more in order to increase the dielectric anisotropy, and about 90% by mass or less in order to lower the lower limit temperature. A more preferable ratio is in the range of about 20% by mass to about 65% by mass. A particularly preferable ratio is in the range of about 25% by mass to about 60% by mass.

The preferable proportion of compound (3) is about 5% by mass or more for increasing the upper limit temperature or decreasing the viscosity, and about 90% by mass or less for increasing the dielectric anisotropy. A more preferable ratio is in the range of about 15% by mass to about 65% by mass. A particularly preferable ratio is in the range of about 20% by mass to about 60% by mass.

The preferable proportion of compound (4) is about 3% by mass or more in order to increase the dielectric constant in the short axis direction of the liquid crystal molecules, and about 25% by mass or less in order to lower the lower limit temperature. A more preferable ratio is in the range of about 5% by mass to about 20% by mass. A particularly preferable ratio is in the range of about 5% by mass to about 15% by mass.

Fourth, a preferred form of the component compound will be described. In formula (S), R ¹ is hydrogen, alkyl having 1 to 12 carbon atoms, alkoxy, hydroxy, or oxy radical having 1 to 12 carbon atoms, wherein the group represented by R ¹ is represented by another R ¹ The tile that is used is different. R is C1-C12 alkyl.

In formulas (1) and (S-1), Z ¹ and Z ² are independently a single bond or alkylene having 1 to 20 carbon atoms, and in this alkylene, at least one -CH ₂ -is, May be substituted with -O-, -COO-, -OCO-, or -OCOO-, in these groups, at least one hydrogen may be substituted with fluorine, chlorine, or a group represented by formula (S-1) have. Preferred Z ¹ or Z ² is a single bond or alkylene having 1 to 20 carbon atoms in which at least one of -CH ₂ -is substituted by -COO- or -OCO-. Z ³ is a single bond or an alkylene having 1 to 20 carbon atoms, and in this alkylene, at least one -CH ₂ -is substituted with -O-, -COO-, -OCO-, or -OCOO- In addition, in these groups, at least one hydrogen may be substituted with fluorine or chlorine. Preferred Z ³ is an alkylene having 1 to 20 carbon atoms in which a single bond or at least one -CH ₂ -is substituted with -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 pyridin-2,5-diyl, In these rings, at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkyl having 1 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine, or formula ( It may be substituted with a group represented by 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. More preferable a is 0.

In formulas (1-1) to (1-9), R ² is a C1-C12 alkyl, a C1-C12 alkoxy, a hydroxy, or an oxy radical. Preferred R ² is alkyl having 1 to 12 carbon atoms.

Z ⁴ is alkylene having 1 to 15 carbon atoms. 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 independently a single bond or an alkylene having 1 to 20 carbon atoms, and in this alkylene, at least one of -CH ₂ -is -O-, -COO-, -OCO-, or- OCOO- may be substituted, and in these groups, at least one hydrogen may be substituted with fluorine or chlorine. Preferred Z ⁵ or Z ⁶ is a single bond.

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

In formulas (2), (3), and (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 alkyl having 1 to 12 carbon atoms in order to increase stability against ultraviolet rays or heat. 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 alkenyl having 2 to 12 carbons in which at least one hydrogen is substituted with fluorine or chlorine. to be. Preferred R ⁴ or R ⁵ is alkenyl having 2 to 12 carbon atoms in order to lower the viscosity, and alkyl having 1 to 12 carbon atoms in order to increase stability against ultraviolet rays 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. Preferred R ⁶ or R ⁷ is alkyl having 1 to 12 carbon atoms in order to increase stability against ultraviolet rays or heat, and alkoxy having 1 to 12 carbon atoms in order to increase dielectric anisotropy.

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

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

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

Preferred alkenyloxy is vinyloxy, allyloxy, 3-butenyloxy, 3-pentenyloxy, or 4-pentenyloxy. In order to lower the viscosity, more preferable alkenyloxy is allyloxy or 3-butenyloxy.

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

Preferred examples of alkenyl in which at least one hydrogen is substituted with 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. A more preferred example is 2,2-difluorovinyl or 4,4-difluoro-3-butenyl in order to lower 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 to increase the upper limit temperature, 1,4-phenylene to increase optical anisotropy, and 2,6-difluoro-1,4-phenyl to increase dielectric anisotropy. It's Len. Tetrahydropyran-2,5-diyl,

or

And, preferably

to be.

Ring C and ring D are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenyl It's Len. Preferred ring C or ring D is 1,4-cyclohexylene for lowering the viscosity or increasing the upper limit temperature, and 1,4-phenylene for lowering the lower limit 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 substituted with 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 dielectric anisotropy, and 1,4-phenylene for increasing optical anisotropy. 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 to lower the viscosity, 2-chloro-3-fluoro-1,4-phenylene to lower optical anisotropy, and dielectric anisotropy To increase, it is 7,8-difluorochroman-2,6-diyl.

Z ⁹ is a single bond, ethylene, carbonyloxy, or difluoromethyleneoxy. Preferred Z ⁹ is a single bond for lowering the viscosity and difluoromethyleneoxy for increasing the dielectric anisotropy. Z ¹⁰ is a single bond, ethylene or carbonyloxy. Preferred Z ¹⁰ is a single bond in order to lower the viscosity. Z ¹¹ and Z ¹² are independently a single bond, ethylene, carbonyloxy, or methyleneoxy. Preferred Z ¹¹ or Z ¹² is a single bond to lower the viscosity, ethylene to lower the lower limit temperature, and methyleneoxy to increase the dielectric anisotropy.

X ² and X ³ are independently hydrogen or fluorine. Preferred X ² or X ³ is fluorine in order to increase dielectric anisotropy.

Y ¹ is fluorine, chlorine, alkyl having 1 to 12 carbons in which at least one hydrogen is substituted with fluorine or chlorine, alkoxy having 1 to 12 carbons in which at least one hydrogen is substituted with fluorine or chlorine, or at least one hydrogen Alkenyloxy having 2 to 12 carbon atoms substituted with fluorine or chlorine. Preferred Y ¹ is fluorine in order to lower the lower limit temperature. A preferred example of alkyl in which at least one hydrogen is substituted with fluorine or chlorine is trifluoromethyl. A preferred example of alkoxy in which at least one hydrogen is substituted with fluorine or chlorine is trifluoromethoxy. A preferred example of alkenyloxy in which at least one hydrogen is substituted with fluorine or chlorine is trifluorovinyloxy.

b is 1, 2, 3, or 4. Preferred b is 2 or 3 in order to increase dielectric anisotropy. c is 1, 2, or 3. Preferred c is 1 for lowering the viscosity and 2 or 3 for increasing the upper limit 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 lowering the viscosity and 2 or 3 for increasing the upper limit temperature. Preferred e is 0 to lower the viscosity and 1 to lower the lower limit temperature.

Fifth, a preferred component compound is shown. Preferred compound (1) is compound (1-1) to compound (1-9) described in item 4. Further preferred compound (1) is compound (1-1) to compound (1-3). A particularly preferred compound (1) is compound (1-1).

Preferred compound (2) is compound (2-1) to compound (2-35) described in 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 preferable. At least two of the first components are compound (2-12) and compound (2-15), compound (2-14) and compound (2-27), compound (2-18) and compound (2-24), It is preferably a combination of compound (2-18) and compound (2-29), compound (2-24) and compound (2-29), or compound (2-29) and compound (2-30).

Preferred compounds (3) are compounds (3-1) to (3-13) described in item 10. In these compounds, at least one of the second components is compound (3-1), compound (3-3), compound (3-5), compound (3-6), or compound (3-7). desirable. At least two of the second components are compound (3-1) and compound (3-5), compound (3-1) and compound (3-6), compound (3-1) and compound (3-7), and compound It is preferably a combination of (3-3) and compound (3-5), compound (3-3) and compound (3-6), compound (3-3), and compound (3-7).

A preferable compound (4) is a compound (4-1) to a compound (4-22) described in item 13. In these compounds, at least one of the third components is compound (4-1), compound (4-3), compound (4-4), compound (4-6), compound (4-8), or compound It is preferably (4-10). At least two of the third components are compound (4-1) and compound (4-6), compound (4-3) and compound (4-6), compound (4-3) and compound (4-10), It is preferably a combination of compound (4-4) and compound (4-6), compound (4-4) and compound (4-8), or compound (4-6) and compound (4-10).

Sixth, an additive that may be added to the composition will be described. Such additives are optically active compounds, antioxidants, ultraviolet absorbers, pigments, defoaming 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 the liquid crystal to give a twist angle. Examples of such a compound are compound (5-1) to compound (5-5). The preferred ratio of the optically active compound is about 5% by mass or less. A more preferable ratio is in the range of about 0.01% by mass to about 2% by mass.

In order to prevent a decrease in the specific resistance due to heating in the air, or to maintain a large voltage retention rate 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 added to the composition. A preferable example of an antioxidant is compound (6) etc. in which t is an integer of 1-9.

In compound (6), preferred t is 1, 3, 5, 7, or 9. A more preferred t is 7. Since the compound (6) having t of 7 has low volatility, it is effective for maintaining a large voltage retention rate 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 preferred proportion of the antioxidant is about 50 ppm or more in order to obtain the effect, and about 600 ppm or less so as not to lower the upper limit temperature or increase the lower limit temperature. A more preferable ratio is in the range of about 100 ppm to about 300 ppm.

Preferred examples of the ultraviolet absorber are benzophenone derivatives, benzoate derivatives, triazole derivatives, and the like. Light stabilizers such as sterically hindered amines are also preferred. In order to obtain the effect, the preferable ratio of the absorbent or stabilizer is about 50 ppm or more, and is 10000 ppm or less so as not to lower the upper limit temperature or increase the lower limit temperature. A more preferred ratio is in the range of about 100 ppm to about 10000 ppm.

In order to be suitable for a device in a GH (guest host) mode, a dichroic pigment such as an azo pigment, an anthraquinone pigment, or the like is added to the composition. A preferable proportion of the dye is in the range of about 0.01% by mass to about 10% by mass. In order to prevent foaming, antifoaming agents such as dimethyl silicone oil and methylphenyl silicone oil are added to the composition. The preferred proportion of the antifoaming agent is about 1 ppm or more to obtain the effect, and about 1000 ppm or less to prevent display defects. A more preferable ratio is in the range of about 1 ppm to about 500 ppm.

A polymerizable compound is added to the composition to make it suitable for a polymer sustained orientation (PSA) type device. Preferred 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), and vinyl ketone. A more preferable example is a derivative of acrylate or methacrylate. The preferable proportion of the polymerizable compound is about 0.05% by mass or more in order to obtain the effect, and about 10% by mass or less in order to prevent display defects. A more preferable ratio is in the range of about 0.1% by mass to about 2% by mass. The polymerizable compound is polymerized by ultraviolet irradiation. It can also be superimposed in the presence of an initiator such as a photopolymerization initiator. Appropriate conditions for polymerization, an appropriate type of initiator, and an appropriate amount are known to those skilled in the art and are described in the literature. For example, photoinitiators Irgacure651 (registered trademark; BASF), Irgacure184 (registered trademark; BASF), or Darocur1173 (registered trademark; BASF) are suitable for radical polymerization. A preferred ratio of the photopolymerization initiator is in the range of about 0.1% by mass to about 5% by mass based on the mass of the polymerizable compound. A more preferable ratio is in the range of about 1% by mass to about 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 are hydroquinone, hydroquinone derivatives such as 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 electrically negative and tend to have a partial negative charge. Carbon and hydrogen tend to be neutral or have a partial static charge. The polarity arises because partial charges are not evenly distributed between different kinds of atoms in the compound. For example, the polar compound has at least one of partial structures such as -OH, -COOH, -SH, -NH ₂ , >NH, >N-.

Seventh, a method for synthesizing the component compounds will be described. These compounds can be synthesized by known methods. The synthesis method is illustrated. The method for synthesizing compound (1-1-1), compound (1-1-2), compound (1-1-7), and compound (1-1-8) is described in the section of Examples. The synthesis method described in Japanese Laid-Open Patent No. 2016-037605 can also be referred. Compound (2-4) is synthesized by the method described in Japanese Patent Application Laid-Open No. 10-204016. Compound (3-1) is synthesized by the method described in Japanese Laid-Open Patent Publication No. 59-176221. Compound (4-1) is synthesized by the method published in Japanese Patent Application Laid-Open No. 2-503441. Antioxidants are commercially available. The compound in which t in formula (6) is 1 can be obtained from Aldrich (Sigma-Aldrich Corporation). Compound (6) and the like in which t is 7 are synthesized by the method described in US Patent No. 3660505.

Compounds for which no synthesis method is described are Organic Syntheses (John Wiley & Sons, Inc), Organic Reactions (John Wiley & Sons, Inc), Comprehensive Organic Synthesis, Pergamon Press), New Experimental Chemistry Course (Maruzen), etc. can be synthesized by the method described in books. The composition is prepared from the compound thus obtained by a known method. For example, the component compounds are mixed and dissolved with each other by heating.

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

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

[Example]

The present invention will be described in more detail by examples. The present invention is not limited by these examples. The present invention includes a mixture of the composition of Example 1 and the composition of Example 2. 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 confirmed by methods such as NMR analysis. The properties of the compound, composition, and device were measured by the following method.

NMR analysis: For the measurement, DRX-500 manufactured by Bruker BioSpin was used. ^{In the 1} H-NMR measurement, a sample was dissolved in a deuterated solvent such as CDCl ₃ , and the measurement was performed at room temperature under conditions of 500 MHz and 16 times of integration. Tetramethylsilane was used as an internal standard. ^In the measurement of ¹⁹ F-NMR, CFCl ₃ was used as an internal standard, and the number of times of integration was 24 times. 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, quin is a quintet, sex means sextet, m means multiplet, br means broad.

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

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

The proportion of the liquid crystalline compound contained in the composition can also be calculated by the following method. [0035] The mixture of the liquid crystalline compound is analyzed by gas chromatography (FID). The area ratio of the peak in the gas chromatogram corresponds to the ratio (mass ratio) of the liquid crystal compound. When the above-described capillary column is used, the correction factor of each liquid crystal compound may be regarded as 1. Therefore, the ratio (mass%) of the liquid crystal compound can be calculated from the area ratio of the peak.

Measurement sample: When measuring the properties of the composition or device, the composition was used as a sample as it is. When measuring the properties 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 by extrapolation from the value obtained by the measurement. (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 in this ratio, the ratio of the compound and the mother liquid crystal is 10% by mass: 90% by mass, 5% by mass: 95% by mass, 1% by mass: 99% by mass Changed in the order of. The values of the upper limit temperature, optical anisotropy, viscosity, and dielectric anisotropy for the compound were determined by this extrapolation method.

The following mother liquid crystal was used. The proportion of component compounds is expressed in mass%.

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

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

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

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

(4) Viscosity (rotational viscosity; γ1; measured at 25°C; mPa·s): Measurement was performed according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). I did. A sample was placed in a TN element having a twist angle of 0° and an interval (cell gap) between two glass substrates of 5 μm. The device was applied step by step every 0.5V in the range of 16V to 19.5V. After 0.2 seconds of no application, the application was repeated under the conditions of only one rectangular wave (square pulse; 0.2 seconds) and no application (2 seconds). The peak current and peak time of the transient current generated by this application were measured. The value of the rotational viscosity was obtained by this measured value and the calculation formula (8) described on page 40 in the paper of M. Imai et al. The value of the dielectric anisotropy required for this calculation was determined by the following method using an element in which this rotational viscosity was measured.

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

(6) Dielectric anisotropy (Δε; measured at 25° C.): A sample was placed in a TN element having a gap (cell gap) of 9 μm between two glass substrates and a twist angle of 80°. A sine wave (10 V, 1 kHz) was applied to this device, and after 2 seconds, the dielectric constant (ε ∥ ) in the long axis direction of the liquid crystal molecules was measured. A sine wave (0.5 V, 1 kHz) was applied to this device, and after 2 seconds, the dielectric constant (ε⊥) in the short axis direction of the liquid crystal molecules was measured. The value of dielectric anisotropy is, Δε = ε ∥ was calculated from the formula -ε⊥.

(7) Threshold voltage (Vth; measured at 25°C; V): For the measurement, an LCD5100 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used. The light source was a halogen lamp. A sample was placed in a normally white mode TN element with a gap (cell gap) of 0.45/Δn (µm) between the two glass substrates and a twist angle of 80 degrees. The voltage applied to this device (32Hz, square wave) was increased in steps of 0.02V from 0V to 10V. At this time, the device was irradiated with light from a direction perpendicular to the device, 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 amount of light reached the maximum, and the transmittance was 0% when the amount of light was minimum. The threshold voltage is expressed as the voltage when the transmittance reaches 90%.

(8) Voltage retention (VHR-1; measured at 25°C; %): The TN element used for the measurement had a polyimide alignment film, and the interval (cell gap) between the two glass substrates was 5 μm. The device was sealed with an adhesive curing by ultraviolet rays after the sample was placed. The TN element 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 in a unit period and the horizontal axis was obtained. Area B was the area without attenuation. Voltage retention is expressed as a percentage of area A to area B.

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

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

(11) Voltage retention (VHR-4; measured at 25°C; %): The TN element in which the sample was injected was heated in a thermostat at 80°C for 500 hours, and then the voltage retention was measured and stability against heat was evaluated. In the measurement of VHR-4, the voltage decaying for 16.7 milliseconds was measured. Compositions with a large VHR-4 have great stability against heat.

(12) Response time (τ; measured at 25°C; ms): For the measurement, an LCD5100 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used. The light source was a halogen lamp. The low-pass filter was set to 5 kHz. The sample was placed in a normally white mode TN element with a distance (cell gap) of 5.0 µm and a twist angle of 80 degrees between the two glass substrates. A rectangular wave (60 Hz, 5 V, 0.5 seconds) was applied to this device. At this time, the device was irradiated with light from a direction perpendicular to the device, and the amount of light transmitted through the device was measured. When the amount of light reached the maximum, the transmittance was 100%, and when the amount of light was the minimum, the transmittance was considered to be 0%. The rise time (τr) is the time required for the transmittance to change from 90% to 10%. The fall time (τf: milliseconds) is the time required to change the transmittance from 10% to 90%. The response time is expressed by the sum of the rise time and fall time determined in this way.

(13) Elasticity constant (K; measured at 25°C; pN): For the measurement, an HP4284A type LCR meter manufactured by Yokogawa Hewlett-Packard Co., Ltd. was used. A sample was placed in a horizontal alignment element having an interval (cell gap) of 20 µm between two glass substrates. Charges of 0 volts to 20 volts were applied to this device, and the capacitance and applied voltage were measured. The values of the measured capacitance (C) and applied voltage (V) were fitted using the equations (2.98) and (2.101) in the 「Liquid Crystal Device Handbook」 (Daily Industrial Newspaper), page 75, and the equation (2.99). The values of K11 and K33 were obtained from. Next, K22 was calculated by using the values of K11 and K33 just obtained in equation (3.18) on page 171 of the above book. The elastic constant is represented by the average value of K11, K22, and K33 obtained in this way.

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

(15) Dielectric constant in the minor axis direction (ε⊥; measured at 25°C): A sample was placed in a TN element having a gap (cell gap) of 9 μm between two glass substrates and a twist angle of 80°. A sine wave (0.5 V, 1 kHz) was applied to this device, and after 2 seconds, the dielectric constant (ε⊥) in the short axis direction of the liquid crystal molecules was measured.

(16) Line Image Sticking Parameter (LISP; %): Line image sticking was generated by applying electrical stress to the liquid crystal display device. The luminance of the region with the line afterimage and the luminance of the remaining region were measured. The ratio at which the luminance decreases due to the line afterimage is calculated, and the size of the line afterimage is indicated by this ratio.

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

(16b) Setting of the stress voltage: Put the sample in an FFS element (4 cells in length x 16 cells in width 4 cells) with a cell gap of 3.5 μm and a matrix structure, and seal this element with an adhesive curing with ultraviolet rays. did. Polarizing plates were disposed on the upper and lower surfaces of the device 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 incrementally increased every 0.1 V in the range of 0 V to 7.5 V, and the luminance of transmitted light at each voltage was measured. The voltage when the luminance reached its maximum was abbreviated as V255. The voltage at the time when the luminance became 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 device at 60° C. for 23 hours, and a checker pattern was displayed. Next, V127 (rectangular wave, 0.25 Hz) was applied, and luminance was measured under conditions of an exposure time of 4000 milliseconds.

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

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

1 to 3 are photographs of the device and show a state of luminance. In Figs. 1 and 2, the magnitude of luminance is different, but the luminance is uniform as a whole. These show that the spreadability is good. In Fig. 3, a convex curve is observed at the upper corner, and the luminance is not uniform. This indicates that the liquid crystal composition was injected into the entire element from an injection port (not shown) in the lower part of the photograph, but the additives contained in the composition did not reach the entire element, indicating poor spreadability.

Synthesis Example 1

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

Step 1:

In a nitrogen atmosphere, sebacoyl chloride (532.0 g, 2.225 mol) and diethyl ether (1500 ml) were put into 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. It heated up 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 layer was washed with saturated brine, and dried over anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography. As a developing solvent, toluene was used first, and a mixed solvent of toluene/ethyl acetate = 9/1 (volume ratio) was used next. Recrystallized from a mixed solvent of heptane/toluene=1/1 (volume ratio) to obtain compound (T-1) (206.5 g, yield 31.7%).

Second process:

In 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 ( 600ml) was put into the reactor and cooled to 0°C. DMAP (4-dimethylaminopyridine) (7.51 g, 61.44 mmol) was added thereto, followed by DCC (N,N'-dicyclohexylcarbodiimide) (46.48 g, 225.3 mmol). It heated up 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 chloride 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 75.9%). Got it.

Step 3:

Compound (T-2) (69.44 g, 155.5 mmol), 20% palladium hydroxide carbon (3.47 g), and IPA (2-propanol) (700 ml) were put into a reactor, followed by stirring at room temperature for 18 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-3) (55.01 g, yield 99.5%).

Step 4:

In a nitrogen atmosphere, compound (T-3) (56.43g, 158.7mmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine (26.21g, 166.7mmol), and dichloromethane (600ml) Was put into the reactor, and cooled to 0°C. DMAP (5.82 g, 47.62 mmol) was added thereto, followed by DCC (36.03 g, 174.6 mmol). The temperature was raised 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 chloride solution and water in that order, and dried over anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (acetone). It was recrystallized from heptane to obtain compound (1-1-1) (25.51 g, yield 32.4%).

¹ H-NMR (ppm; CDCl ₃ ): δ 5.19 (tt, J=11.5Hz, J=4.2Hz, 1H), 5.09 (tt, J=11.7Hz, J=4.2Hz, 1H), 2.27 (t, J=7.5Hz, 2H), 2.26(t, J=7.4Hz, 2H), 2.24(s, 3H), 1.91(ddd, J=10.9Hz, J=4.2Hz, J=1.4Hz, 2H), 1.83 (ddd, J=11.0Hz, J=4.2Hz, J=1.4Hz, 2H), 1.59(quin, J=6.9Hz, 4H), 1.47(dd, J=11.6Hz, J=11.6Hz, 2H), 1.36-1.28(m, 8H), 1.24(s, 6H), 1.16(s, 6H), 1.15(s, 6H), 1.13(dd, J=11.7Hz, J=11.7Hz, 2H), 1.07(s , 6H), 0.88-0.50 (br, 1H).

Synthesis Example 2

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

Step 1:

4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical (25.00 g, 145.1 mmol), and tert-butyl alcohol (50 ml)/water (25 ml) were added to the reactor, Thereto, nonananal (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, followed by stirring at room temperature for 18 hours. The reaction mixture was extracted with heptane, and the extract was washed sequentially with a 10% ascorbic acid aqueous solution, 10% sodium hydrogen sulfite aqueous solution, 1N sodium hydroxide aqueous solution, water and saturated brine, and dried over anhydrous magnesium sulfate. This 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 process:

In a nitrogen atmosphere, compound (T-4) (2.56g, 8.98mmol), compound (T-1) (2.63g, 8.98mmol) obtained in Synthesis Example 1, and dichloromethane (250ml) were put into a reactor, and 0°C Cooled to. DMAP (0.33 g, 2.69 mmol) was added thereto, followed by DCC (2.04 g, 9.88 mmol). It heated up 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 chloride solution and water in that order, and dried over anhydrous magnesium sulfate. This 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%).

Step 3:

Compound (T-5) (3.64 g, 6.50 mmol), 20% palladium hydroxide carbon (0.18 g), and toluene (35 ml)/IPA (35 ml) were put into a reactor, followed by stirring at room temperature under a hydrogen atmosphere for 18 hours. 20% palladium hydroxide carbon was removed, the filtrate was concentrated, and 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) %).

Step 4:

In a nitrogen atmosphere, compound (T-6) (2.83g, 6.03mmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine (0.99g, 6.33mmol), and dichloromethane (50ml) Was put into the reactor, and cooled to 0°C. DMAP (0.22 g, 1.81 mmol) was added thereto, followed by DCC (1.37 g, 6.63 mmol). It heated up 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 chloride solution and water in that order, and dried over anhydrous magnesium sulfate. This 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=11.4Hz, J=4.2Hz, 1H), 5.01 (tt, J=11.5Hz, J=4.4Hz, 1H), 3.72 (t, J=6.7Hz, 2H), 2.27(t, J=7.5Hz, 2H), 2.25(t, J=7.7Hz, 2H), 1.91(dd, J=12.5Hz, J=4.2Hz, 2H), 1.80 (dd, J=11.1Hz, J=3.7Hz, 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=11.9Hz, J=11.9Hz, 2H), 0.88(t, J=6.9Hz, 3H), 0.85-0.65( br, 1H).

Synthesis Example 3

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

Step 1:

Under nitrogen atmosphere, compound (T-1) (10.00g, 34.20mmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine (6.03g, 38.8mmol), DMAP · TFA (4- Dimethylaminopyridine trifluoroacetate) (2.42 g, 10.2 mmol), and dichloromethane (100 ml) were put into a reactor and cooled to 0°C. EDC·HCl(1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride) (8.51 g, 44.4 mmol) was added thereto. It heated up to room temperature and stirred for 24 hours. The reaction mixture was washed with a saturated aqueous sodium hydrogen chloride solution and then water, 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 process:

Compound (T-7) (12.38 g, 28.68 mmol), 20% palladium hydroxide (0.62 g), and IPA (120 ml) were put into a reactor, followed by stirring at room temperature under a hydrogen atmosphere for 24 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-8) (8.58 g, yield 87.4%).

Step 3:

In a nitrogen atmosphere, 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), DMAP·TFA (0.89 g, 3.8 mmol) and dichloromethane (40 ml) were put into a reactor and cooled to 0°C. EDC·HCl (3.14 g, 16.4 mmol) was added thereto. It heated up to room temperature and stirred for 21 hours. The reaction mixture was washed with a saturated aqueous sodium hydrogen chloride solution and then water, and dried over anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (ethyl acetate to acetone). Recrystallized from a mixed solvent of heptane/ethyl acetate = 4/1 (volume ratio) to obtain 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.

Step 1:

Under nitrogen atmosphere, succinic anhydride (20.05g, 200.4mmol), 4-hydroxy-2,2,6,6-tetramethylpiperidine (30.00g, 190.8mmol), DMAP (2.33g, 19.1mmol), and Toluene (500 ml) was put into a reactor, and it stirred under reflux for 5 hours. After cooling to room temperature, the precipitate was collected by filtration, and the precipitate was sufficiently washed with tetrahydrofuran to obtain compound (T-9) (47.26 g, yield 96.3%).

Second process:

In a nitrogen atmosphere, 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), DMAP·TFA (1.10 g, 4.66 mmol), and dichloromethane (40 ml) were put into a reactor and cooled to 0°C. EDC·HCl (3.87 g, 20.21 mmol) was added thereto. It heated up to room temperature and stirred for 17 hours. The reaction mixture was washed with a saturated aqueous sodium hydrogen chloride solution and then water, and dried over anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (ethyl acetate to acetone). Recrystallized from a mixed solvent of heptane/ethyl acetate = 2/1 (volume ratio) to obtain compound (1-1-8) (3.46 g, yield 54.1%).

Melting point: 105.2°C.

Examples of the composition are shown below. Component compounds are represented by symbols based on the definitions in Table 3 below. In Table 3, the configuration for 1,4-cyclohexylene is trans. The numbers in parentheses after the symbolized compound indicate the formula to which the compound belongs. The sign of (-) means other liquid crystal compounds. The ratio (percentage) of the liquid crystal compound is a mass percentage (mass%) based on the mass of the liquid crystal composition containing no additives. Finally, the characteristic values of the composition are summarized and shown.

[Table 3]

[Example 1]

The composition (1) described above was prepared. Compound (1-1-1) was added to the composition (1) in a proportion of 0.15% by mass. The line afterimage (LISP) was measured by the method described in Measurement (16) and found to be 2.3%.

NI=88.8°C; Tc<-20°C; Δn=0.101; Δε=13.4; Vth=1.34V; η = 20.6 mPa·s; γ1=123.7mPa·s.

[Comparative Example 1]

Comparative compound (A-1) was added to the composition (1) described in Example 1 in a proportion of 0.15% by mass. The line afterimage (LISP) by the method described in measurement (16) was 3.0%. Together with the results of Example 1, they are summarized in Table 4 and shown. 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). The characteristic with high effect of suppressing line afterimage is a characteristic required for long-term use of the device. Therefore, it can be seen that the composition of the present invention is excellent.

[Table 4]

[Example 2]

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

[Comparative Example 2]

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

[Table 5] Comparison of lower limit temperature (Tc)

[Example 3]

Compound (1-1-3) was added to this composition in a proportion of 0.15% by mass.

NI=88.8°C; Tc<-20°C; Δn=0.101; Δε=13.4; Vth=1.34V; η = 20.6 mPa·s; γ1 = 123.7 mPa·s; LISP=2.4%.

[Example 4]

Compound (1-1-1) was added to this composition in a proportion of 0.10% by mass.

NI=78.2°C; Tc<-20°C; Δn=0.108; Δε=10.4; Vth=1.35V; ?=17.8 mPa·s; γ1 = 79.9 mPa·s; LISP=2.4%.

[Example 5]

Compound (1-1-3) was added to this composition in a proportion of 0.10% by mass.

NI=78.1°C; Tc<-20°C; Δn=0.108; Δε=10.4; Vth=1.35V; ?=17.8 mPa·s; γ1 = 79.9 mPa·s; LISP=2.5%.

[Example 6]

Compound (1-1-1) was added to this composition in a proportion of 0.10% by mass.

NI=79.6°C; Tc<-20°C; Δn=0.106; Δε=8.5; Vth=1.45V; η=11.6 mPa·s; γ1 = 60.0 mPa·s; LISP =2.3%.

[Example 7]

Compound (1-1-1) was added to this composition in a proportion of 0.10% by mass.

NI=71.2°C; Tc<-20°C; Δn=0.099; Δε=6.1; Vth=1.74V; ?=13.2 mPa·s; γ1=59.3 mPa·s; LISP =2.5%.

[Example 8]

Compound (1-1-4) was added to this composition in a proportion of 0.10% by mass.

NI=78.5°C; Tc<-20°C; Δn=0.095; Δε=3.4; Vth=1.50V; ?=8.4 mPa·s; γ1 = 54.2 mPa·s; LISP=2.5%.

[Example 9]

Compound (1-1-1) was added to this composition in a proportion of 0.10% by mass.

NI=80.2°C; Tc<-20°C; Δn=0.106; Δε=5.8; Vth=1.40V; η=11.6 mPa·s; γ1 = 61.0 mPa·s; LISP =2.3%.

[Example 10]

Compound (1-1-1) was added to this composition in a proportion of 0.12% by mass.

NI=78.2°C; Tc<-20°C; Δn=0.094; Δε=5.6; Vth=1.45V; η=11.5 mPa·s; γ1 = 61.7 mPa·s; LISP =2.3%.

[Example 11]

Compound (1-1-1) was added to this composition in a proportion of 0.15% by mass.

NI=79.8°C; Tc<-20°C; Δn=0.101; Δε=4.6; Vth=1.71V; ?=11.0 mPa·s; γ1=47.2 mPa·s; LISP =2.3%.

[Example 12]

Compound (1-1-1) was added to this composition in a proportion of 0.10% by mass.

NI=78.4°C; Tc<-20°C; Δn=0.088; Δε=5.6; Vth=1.85V; η=13.9 mPa·s; γ1 = 66.9 mPa·s; LISP =2.3%.

[Example 13]

Compound (1-1-1) was added to this composition in a proportion of 0.10% by mass.

NI=82.7°C; Tc<-20°C; Δn=0.093; Δε=6.9; Vth=1.50V; η = 16.3 mPa·s; γ1=65.2 mPa·s; LISP =2.3%.

[Example 14]

Compound (1-1-5) was added to this composition in a proportion of 0.10% by mass.

NI=79.4°C; Tc<-20°C; Δn=0.111; Δε=4.7; Vth=1.86V; η = 9.7 mPa·s; γ1 = 49.9 mPa·s; LISP=2.6%.

[Example 15]

Compound (1-1-1) was added to this composition in a proportion of 0.15% by mass.

NI=82.8°C; Tc<-20°C; Δn=0.086; Δε=3.8; Vth=1.94V; η = 7.5 mPa·s; γ1 = 51.5 mPa·s; LISP=2.4%.

[Example 16]

Compound (1-1-3) was added to this composition in a proportion of 0.10% by mass.

NI=81.7°C; Tc<-20°C; Δn=0.109; Δε=4.8; Vth=1.75V; η=13.3 mPa·s; γ1=57.4 mPa·s; LISP =2.4%.

[Example 17]

Compound (1-1-1) was added to this composition in a proportion of 0.15% by mass.

NI=78.0°C; Tc<-20°C; Δn=0.101; Δε=6.7; Vth=1.45V; ?=17.8 mPa·s; γ1 = 67.8 mPa·s; LISP =2.3%.

[Example 18]

Compound (1-1-7) was added to this composition in a proportion of 0.10% by mass.

NI=77.8°C; Tc<-20°C; Δn=0.108; Δε=10.4; Vth=1.35V; ?=17.8 mPa·s; γ1 = 79.9 mPa·s; LISP=1.9%.

[Example 19]

Compound (1-1-8) was added to this composition in a proportion of 0.10% by mass.

NI=77.8°C; Tc<-20°C; Δn=0.108; Δε=10.4; Vth=1.35V; ?=17.8 mPa·s; γ1 = 79.9 mPa·s; LISP=2.2%.

[Example 20]

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

[Example 21]

Compound (1-1-2) 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 spreadability of this compound was qualitatively evaluated from FIG. 2 as the measurement result (Table 6).

[Comparative Example 3]

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 spreadability of this compound was qualitatively evaluated from FIG. 3 as the measurement result. These results are summarized in Table 6 together with the results of Examples 20 and 21, and are shown.

[Table 6] Comparison of spreadability

1 to 3 are photographs of devices. The injection port was located at the bottom of the photograph (not shown), from which a composition containing an additive was injected. In Figs. 1 and 2, the size of the luminance was different, but the luminance was uniform as a whole. This indicates 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 element was filled with the liquid crystal composition, but the additive contained in the composition did not reach the entire element. From these results, it was found that in Examples 20 and 21, the spreadability was good, and in Comparative Example 3, the spreadability was poor.

Line afterimage, lower limit temperature (solubility at low temperature), and a comparative experiment of spreadability were performed, and the result was put together in Tables 4, 5, and 6 and shown. In either case, compound (1) provided superior results compared to the comparative compound. Therefore, it can be concluded that the composition of the present invention has excellent properties.

[Industrial availability]

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

Claims (20)

As an additive, to have at least two or a monovalent group represented by the formula (S), in groups of these monovalent, and tiling a group represented by R ¹ are represented by the other R ¹ contains a different compound, a positive (+ A liquid crystal composition having a dielectric anisotropy of ):

In the above formula (S), R ¹ is hydrogen, alkyl having 1 to 12 carbon atoms, alkoxy, hydroxy or oxy radical having 1 to 12 carbon atoms; R is a C1-C12 alkyl. The method of claim 1,
In the monovalent group represented by the formula (S), R is methyl. The method of claim 1,
As an additive, a liquid crystal composition containing at least one compound selected from the group of compounds represented by the following formula (1):

In the above formulas (1) and (S-1), R ¹ is hydrogen, alkyl having 1 to 12 carbon atoms, alkoxy, hydroxy or oxy radical having 1 to 12 carbon atoms, wherein the group represented by R ¹ Different from the group represented by another 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-2,5-diyl or pyridin-2,5-diyl, and these In the ring, at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkyl having 1 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine, or formula (S May be substituted with a group represented by -1); Z ¹ and Z ² are independently a single bond or an alkylene having 1 to 20 carbon atoms, and in this alkylene, at least one of -CH ₂ -is -O-, -COO-, -OCO-, or -OCOO- May be substituted with, in these groups, at least one hydrogen may be substituted with fluorine, chlorine or a group represented by formula (S-1); Z ³ is a single bond or an alkylene having 1 to 20 carbon atoms, and in this alkylene, at least one -CH ₂ -may be substituted with -O-, -COO-, -OCO-, or -OCOO-, In these groups, at least one hydrogen may be substituted with fluorine or chlorine; a is 0, 1, 2 or 3. The method of claim 1,
As an additive, a liquid crystal composition containing at least one compound selected from the group of compounds represented by the following formulas (1-1) to (1-9):

In the above formulas (1-1) to (1-9), R ² is an alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, a hydroxy or oxy radical; Z ⁴ is alkylene having 1 to 15 carbon atoms; Z ⁵ and Z ⁶ are independently alkylene having 1 to 5 carbon atoms; Z ⁷ and Z ⁸ are independently a single bond or an alkylene having 1 to 20 carbon atoms, and in this alkylene, at least one of -CH ₂ -is -O-, -COO-, -OCO-, or -OCOO- May be substituted, and in these groups, at least one hydrogen may be substituted with fluorine or chlorine; X ¹ is hydrogen or fluorine. The method of claim 1,
The liquid crystal composition in which the proportion of the additive is in the range of 0.005% by mass to 1% by mass. The method of claim 1,
A liquid crystal composition containing at least one compound selected from the group of compounds represented by the following formula (2) as the first component:

In the formula (2), R ³ is alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, or alkenyl having 2 to 12 carbon atoms; 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 fluorine; Y ¹ is fluorine, chlorine, alkyl having 1 to 12 carbons in which at least one hydrogen is substituted with fluorine or chlorine, alkoxy having 1 to 12 carbons in which at least one hydrogen is substituted with fluorine or chlorine, or at least one hydrogen Alkenyloxy having 2 to 12 carbon atoms substituted with fluorine or chlorine; b is 1, 2, 3 or 4. The method of claim 6,
A liquid crystal composition containing at least one compound selected from the group of compounds represented by the following formulas (2-1) to (2-35) as the first component:

In the above 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. The method of claim 6,
The liquid crystal composition in which the proportion of the first component is in the range of 5% by mass to 90% by mass. The method of claim 1,
A liquid crystal composition containing at least one compound selected from the group of compounds represented by the following formula (3) as a second component:

In the 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 substituted with fluorine or chlorine. 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. The method of claim 9,
A liquid crystal composition containing at least one compound selected from the group of compounds represented by the following formulas (3-1) to (3-13) as a second component:

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 at least One hydrogen is an alkenyl having 2 to 12 carbon atoms substituted with fluorine or chlorine. The method of claim 9,
The liquid crystal composition in which the proportion of the second component is in the range of 5% by mass to 90% by mass. The method of claim 6,
A liquid crystal composition containing at least one compound selected from the group of compounds represented by the following formula (3) as a second component:

In the 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 substituted with fluorine or chlorine. 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. The method of claim 1,
A liquid crystal composition containing at least one compound selected from the group of compounds represented by the following formula (4) as a third component:

In the 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; 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 substituted with 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, 3,4,5-trifluoronaphthalene-2,6-diyl or 7,8-difluorochroman-2,6-diyl; Z ¹¹ and Z ¹² are independently a single bond, ethylene, carbonyloxy or methyleneoxy; d is 1, 2 or 3 and e is 0 or 1; The sum of d and e is 3 or less. The method of claim 13,
A liquid crystal composition containing at least one compound selected from the group of compounds represented by the following formulas (4-1) to (4-22) as a third component:

In the formulas (4-1) to (4-22), R ⁶ and R ⁷ are independently alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, or 2 to carbon atoms. 12 alkenyloxy. The method of claim 13,
The liquid crystal composition in which the proportion of the third component is in the range of 3% by mass to 25% by mass. The method of claim 6,
A liquid crystal composition containing at least one compound selected from the group of compounds represented by the following formula (4) as a third component:

In the 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; 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 substituted with 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, 3,4,5-trifluoronaphthalene-2,6-diyl or 7,8-difluorochroman-2,6-diyl; Z ¹¹ and Z ¹² are independently a single bond, ethylene, carbonyloxy or methyleneoxy; d is 1, 2 or 3 and e is 0 or 1; The sum of d and e is 3 or less. The method of claim 12,
A liquid crystal composition containing at least one compound selected from the group of compounds represented by the following formula (4) as a third component:

In the 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; 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 substituted with 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, 3,4,5-trifluoronaphthalene-2,6-diyl or 7,8-difluorochroman-2,6-diyl; Z ¹¹ and Z ¹² are independently a single bond, ethylene, carbonyloxy or methyleneoxy; d is 1, 2 or 3 and e is 0 or 1; The sum of d and e is 3 or less. The method of claim 1,
Liquid crystals with an upper limit temperature of 70°C or more of the nematic phase, optical anisotropy at a wavelength of 589 nm (measured at 25°C) of 0.07 or more, and a dielectric anisotropy at a frequency of 1 kHz (measured at 25°C) of 2 or more Composition. A liquid crystal display device containing the liquid crystal composition according to claim 1. The method of claim 19,
A liquid crystal display device in which an operation mode of the liquid crystal display device is a TN mode, an ECB mode, an OCB mode, an IPS mode, an FFS mode, or an FPA mode, and a driving method of the liquid crystal display device is an active matrix system.

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