TW201947025A - Liquid crystal composition and liquid crystal display element - Google Patents

Abstract

This composition that includes 0.06 mass% or more of a compound represented by formula (1) and a compound represented by formula (2) and that has a negative dielectric constant anisotropy, has excellent characteristics as a liquid crystal composition. R and X each represent alkyl or the like, A, B, D each represent cyclohexylene or the like, C represents 2,3-difluoro-1,4-phenylene or the like, Z represents a single bond, ethylene, or the like, a is 0-2, and b+c is 3 or less.

Description

Liquid crystal composition and liquid crystal display element

The present invention relates to a liquid crystal composition, a liquid crystal display element containing the composition, and the like. In particular, it relates to a liquid crystal composition having a negative dielectric anisotropy and a liquid crystal display element containing the composition and having a mode such as IPS, VA, FFS, FPA, and the like. It also relates to a polymer-stabilized alignment type liquid crystal display element.

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

The liquid crystal display element contains a liquid crystal composition having a nematic phase. This composition has appropriate characteristics. By improving the characteristics of the composition, an AM device having good characteristics can be obtained. The correlation of these characteristics is summarized in Table 1 below. The characteristics of the composition will be further described based on a commercially available AM device. The temperature range of the nematic phase is related to the usable temperature range of the device. A preferable upper limit temperature of the nematic phase is about 70 ° C or higher, and a preferable lower limit temperature of the nematic phase is about -10 ° C or lower. The viscosity of a composition is related to the response time of the device. In order to display moving images with components, a short response time is preferred. A shorter response time is better, even as short as 1 millisecond. Therefore, the viscosity of the composition is preferably small. Low viscosity is better at low temperatures.

[Table 1]

The optical anisotropy of the composition is related to the contrast of the device. Depending on the mode of the device, a large optical anisotropy or a small optical anisotropy is required, that is, the optical anisotropy is appropriate. The product (Δn × d) of the optical anisotropy (Δn) of the composition and the cell gap (d) of the element is designed to maximize the contrast. The appropriate product value depends on the type of operation mode. This value is in the range of about 0.30 μm to about 0.40 μm in the VA mode device and in the range of about 0.20 μm to about 0.30 μm in the IPS mode or FFS mode device. In this case, for a device having a small cell gap, a composition having a large optical anisotropy is preferred. The large dielectric anisotropy of the composition contributes to a low critical voltage of the device, low power consumption, and large contrast. Therefore, the dielectric anisotropy is better. A large resistivity of the composition contributes to a large voltage holding ratio and a large contrast of the device. Therefore, a composition having a large resistivity at the initial stage is preferable. After long-term use, a composition having a large resistivity is preferred. The stability of the composition to light or heat is related to the life of the device. The higher the stability, the longer the life of the element. These characteristics are preferable in the case of AM elements used in liquid crystal displays, liquid crystal televisions, and the like.

In general liquid crystal display elements, vertical alignment of liquid crystal molecules is achieved by a specific polyimide alignment film. In a polymer sustained alignment (PSA) type liquid crystal display device, a polymer and an alignment film are combined. First, a composition to which a small amount of a polymerizable compound is added is injected into a device. Next, the composition is irradiated with ultraviolet rays while a voltage is applied between the substrates of the element. The polymerizable compound is polymerized to form a mesh structure of a polymer in the composition. In this composition, the alignment of the liquid crystal molecules can be controlled by the polymer, so the response time of the element is shortened, and the aging of the image is improved. These effects of polymers can be expected in elements having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.

A composition having a positive dielectric anisotropy is used in an AM device having a TN mode. A composition having a negative dielectric anisotropy is used in an AM device having a VA mode. Compositions with positive or negative dielectric anisotropy are used in AM devices with IPS mode or FFS mode. In a polymer sustained alignment (PSA) type AM device, a composition having a positive or negative dielectric anisotropy is used.

The liquid crystal composition has high stability to various external factors such as heat, light, and electric field according to its use requirements. In liquid crystal displays and the like, since the liquid crystal composition is exposed to the backlight for a long time, it is particularly important for the stability of light. Currently, light-emitting diodes are mainly used as a light source for a backlight. In recent years, the brightness and efficiency of the light-emitting diodes have been improved. Therefore, the demand for a liquid crystal composition having high light stability is further increasing.

Various studies have been conducted so far regarding the stability of liquid crystal compositions. Patent Document 1 discloses a liquid crystal composition containing a hindered amine (HALS) and being stable to light. Patent Document 2 discloses a liquid crystal composition containing a phenol-based antioxidant and stable to heat.
[Prior technical literature]
[Patent Literature]

[Patent Document 1] International Publication No. 2015/079797
[Patent Document 2] International Publication No. 2014/136315

The object of the present invention is to provide an improved stability to light, a high upper temperature of a nematic phase, a low lower temperature of a nematic phase, a low viscosity, a suitable optical anisotropy, a large negative dielectric anisotropy, and a resistance A liquid crystal composition having a large rate and at least one of the characteristics such as high stability to heat. Another additional problem that is better solved together is to provide a liquid crystal composition having an appropriate balance between at least two of these characteristics.
Another object of the present invention is to provide a liquid crystal display element having a liquid crystal composition having excellent characteristics. Another additional issue that is better solved together is to provide a liquid crystal display element with improved display defects such as afterimages and aging. Another additional issue that is better solved together is to provide an AM device having characteristics such as short response time, large voltage retention, low threshold voltage, large contrast, and long life.
Another object of the present invention is to provide a method for stabilizing a liquid crystal composition to light.

The present invention relates to a first additive containing at least one compound selected from the compound represented by formula (1) and a first component containing at least one compound selected from the compound represented by formula (2). A liquid crystal composition having a ratio of 0.06 mass% or more and having a negative dielectric anisotropy, a liquid crystal display element containing the composition, and a method for stabilizing the liquid crystal composition to light.

In formulas (1) and (2), R ¹ is an alkyl group having 1 to 24 carbon atoms or an alkenyl group having 2 to 24 carbon atoms. In this alkyl group, at least one hydrogen may be substituted with fluorine or chlorine. Among these groups, at least one -CH ₂ -may be substituted by -O-, -COO-, or -OCO-; R ² and R ³ are alkyl groups having 1 to 12 carbons, and alkyl groups having 1 to 12 carbons Oxygen, alkenyl having 2 to 12 carbons, alkenyl having 2 to 12 carbons or hydrogen; ring A is 1,4-cyclohexyl, 1,4-cyclohexenyl, tetrahydropyran- 2,5-diyl, 1,3-di 㗁 koushan-2,5-diyl, 1,3-dithiane-2,5-diyl or 1,4-phenylene; ring B and ring D is 1,4-cyclohexyl, 1,4-cyclohexenyl, tetrahydropyran-2,5-diyl, 1,4-phenylene, and at least one hydrogen is replaced by fluorine or chlorine 1,4-phenylene, naphthalene-2,6-diyl, at least one hydrogen substituted with fluorine or chlorine, naphthalene-2,6-diyl, orthofluorene-2,6-diyl, or at least one Ortho-2,6-diyl in which hydrogen is replaced by fluorine or chlorine; ring C is 2,3-difluoro-1,4-phenyl, 2-chloro-3-fluoro-1,4-phenyl Phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, 7,8-difluoroacetone-2 , 6-diyl, 3,4,5,6-tetrafluorofluorene-2,7-diyl, 4,6-difluorodibenzofuran-3,7- Yl, 4,6-difluoro-dibenzothiophene-1,1,6,7- tetrafluoro-3,7-diyl or indan-2,5-diyl; Z ¹ is a single bond, an ethyl group, Vinyl, carbonyloxy, methoxy or difluoro methoxy; Z ² and Z ³ are single bonds, ethyl, vinyl, carbonyloxy or methoxy; X ¹ and X ² is an alkyl group having 1 to 12 carbons; a is 0, 1 or 2; b is 0, 1, 2 or 3; c is 0 or 1; and the sum of b and c is 3 or less.
[Inventive effect]

The invention has the advantages of providing improved stability to light, high upper temperature of nematic phase, low lower temperature of nematic phase, low viscosity, proper optical anisotropy, large negative dielectric anisotropy, and electrical resistance A liquid crystal composition having a large rate and at least one of the characteristics such as high stability to heat.
Another advantage of the present invention is to provide a liquid crystal composition having an appropriate balance between at least two of these characteristics. Another advantage is to provide a liquid crystal display device containing these compositions. In another preferred liquid crystal display element of the present invention, display defects such as afterimages and aging are improved. Another preferred liquid crystal display device of the present invention is an AM device having characteristics such as short response time, large voltage holding ratio, low threshold voltage, large contrast, and long life.
Another advantage of the present invention is to provide a method for stabilizing a liquid crystal composition to light.

The terms used in this specification are described below. The terms "liquid crystal composition" and "liquid crystal display element" may be simply referred to as "composition" and "element", respectively. "Liquid crystal display element" is a generic term for a liquid crystal display panel and a liquid crystal display module. A "liquid crystal compound" is a compound having a liquid crystal phase such as a nematic phase and a smectic phase, and a compound having no liquid crystal phase but intended to adjust characteristics such as the temperature range, viscosity, and dielectric anisotropy of the nematic phase Generic term for compounds mixed in a composition. This compound has, for example, a six-membered ring such as 1,4-cyclohexyl or 1,4-phenylene, and its molecule (liquid crystal molecule) is rod-like. A "polymerizable compound" is a compound added for the purpose of producing a polymer in a composition. In this sense, a liquid crystal compound having an alkenyl group is not classified as a polymerizable compound.

The liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. An additive such as an optically active compound or a polymerizable compound is added to the liquid crystal composition as necessary. Even when an additive is added, the ratio of the liquid crystal compound can be expressed by a mass percentage (% by mass) based on the mass of the liquid crystal composition containing no additive. The proportion of the additive is represented by the mass percentage (% by 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. Exceptionally, the ratio of the polymerization initiator and the polymerization inhibitor is expressed based on the mass of the polymerizable compound.

The "upper limit temperature of the nematic phase" may be simply referred to as the "upper limit temperature". The "lower limit temperature of the nematic phase" is sometimes simply referred to as the "lower limit temperature". The expression "improving the dielectric anisotropy" means increasing a positive value when the composition having a positive dielectric anisotropy, and increasing a negative value when a composition having a negative dielectric anisotropy. "Large voltage retention" means that the element not only has a large voltage retention at room temperature in the initial stage, but also a large voltage retention at temperatures close to the upper limit temperature, and not only at room temperature after long-term use A large voltage holding ratio also has a large voltage holding ratio at a temperature close to the upper limit temperature. The characteristics of a composition or an element are sometimes studied by a change test with time.

The above compound (1z) will be described as an example. In formula (1z), the α and β symbols surrounded by hexagons correspond to the rings α and β, respectively, and represent rings such as a six-membered ring and a condensed ring. When the subscript 'x' is 2, there are two rings α. The two groups represented by the two rings α may be the same or different. When the subscript 'x' is greater than 2, this rule applies to any two rings α. This rule also applies to other tokens such as the linker Z. A diagonal line across one side of the ring β indicates that any hydrogen on the ring β may be substituted with a substituent (-Sp-P). The subscript 'y' indicates the number of substituted substituents. When the subscript 'y' is 0, there is no such substitution. When the subscript 'y' is 2 or more, there are a plurality of substituents (-Sp-P) on the ring β. The "may be the same or may be different" rule also applies in this case. Furthermore, this rule also applies to the case where the symbol of Ra is used for a plurality of compounds.

In the formula (1z), for example, the expression "Ra and Rb are alkyl, alkoxy, or alkenyl" means that Ra and Rb are independently selected from the group of alkyl, alkoxy, and alkenyl. That is, the base represented by Ra and the base represented by Rb may be the same or may be different.

At least one compound selected from the compounds represented by formula (1z) may be simply referred to as "compound (1z)". "Compound (1z)" represents one compound, a mixture of two compounds, or a mixture of three or more compounds represented by formula (1z). The same applies to compounds represented by other formulas. The expression "at least one compound selected from the compounds represented by formula (1z) and formula (2z)" indicates at least one compound selected from the group of compound (1z) and compound (2z).

The expression "at least one 'A'" indicates that the number of 'A' is arbitrary. Regarding the expression "at least one 'A' may be replaced by 'B'", when the number of 'A' is one, the position of 'A' is arbitrary, and when the number of 'A' is two or more, the Positions such as can also be selected indefinitely. The expression "at least one -CH ₂ -may be substituted with -O-" is sometimes used. At this time, -CH ₂ -CH ₂ -CH ₂ -can be converted to -O-CH ₂ -O- by non-adjacent -CH ₂ -substituted with -O-. However, adjacent -CH ₂ -will not be replaced by -O-. This is because -OO-CH _2- (peroxide) is formed in this substitution.

For example, in Ra and Rb of formula (1z), the alkyl group is linear or branched, and does not contain a cyclic alkyl group. Compared to a branched alkyl group, a linear alkyl group is preferred. The same applies to terminal groups such as alkoxy and alkenyl.

Regarding the three-dimensional configuration related to 1,4-cyclohexyl, the trans form is better than the cis form to increase the upper limit temperature. 2-Fluoro-1,4-phenylene is asymmetric to the left and right, so there are left (L) and right (R) orientations.

The same applies to divalent groups such as tetrahydropyran-2,5-diyl. The same applies to a linking group such as carbonyloxy (-COO- or -OCO-).

The present invention includes the following items.

Item 1. A liquid crystal composition comprising, as a first additive, at least one compound selected from the compound represented by the formula (1), and as a first component, at least one compound selected from the compound represented by the formula (2). The ratio of one additive is 0.06 mass% or more, and the liquid crystal composition has negative dielectric anisotropy.

In formulas (1) and (2), R ¹ is an alkyl group having 1 to 24 carbon atoms or an alkenyl group having 2 to 24 carbon atoms. In this alkyl group, at least one hydrogen may be substituted with fluorine or chlorine. Among these groups, at least one -CH ₂ -may be substituted by -O-, -COO-, or -OCO-; R ² and R ³ are alkyl groups having 1 to 12 carbons, and alkyl groups having 1 to 12 carbons Oxygen, alkenyl having 2 to 12 carbons, alkenyl having 2 to 12 carbons or hydrogen; ring A is 1,4-cyclohexyl, 1,4-cyclohexenyl, tetrahydropyran- 2,5-diyl, 1,3-di 㗁 koushan-2,5-diyl, 1,3-dithiane-2,5-diyl or 1,4-phenylene; ring B and ring D is 1,4-cyclohexyl, 1,4-cyclohexenyl, tetrahydropyran-2,5-diyl, 1,4-phenylene, and at least one hydrogen is replaced by fluorine or chlorine 1,4-phenylene, naphthalene-2,6-diyl, at least one hydrogen substituted with fluorine or chlorine, naphthalene-2,6-diyl, orthofluorene-2,6-diyl, or at least one Ortho-2,6-diyl in which hydrogen is replaced by fluorine or chlorine; ring C is 2,3-difluoro-1,4-phenyl, 2-chloro-3-fluoro-1,4-phenyl Phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, 7,8-difluoroacetone-2 , 6-diyl, 3,4,5,6-tetrafluorofluorene-2,7-diyl, 4,6-difluorodibenzofuran-3,7- Yl, 4,6-difluoro-dibenzothiophene-1,1,6,7- tetrafluoro-3,7-diyl or indan-2,5-diyl; Z ¹ is a single bond, an ethyl group, Vinyl, carbonyloxy, methoxy or difluoro methoxy; Z ² and Z ³ are single bonds, ethyl, vinyl, carbonyloxy or methoxy; X ¹ and X ² is an alkyl group having 1 to 12 carbons; a is 0, 1 or 2; b is 0, 1, 2 or 3; c is 0 or 1; and the sum of b and c is 3 or less.

Item 2. The liquid crystal composition according to item 1, which contains, as a first component, at least one compound selected from a compound represented by formula (2 ').

In the formula (2 '), R ² ′ and R ³ ′ are an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, and an alkyl group having 2 to 12 carbon atoms. Alkenyloxy or hydrogen; ring B 'and ring D' are 1,4-cyclohexyl, 1,4-cyclohexenyl, tetrahydropyran-2,5-diyl, 1,4-benzene 1,4-phenylene, naphthalene-2,6-diyl substituted with at least 1 hydrogen with fluorine or chlorine, naphthalene-2,6-diyl substituted with at least 1 hydrogen with fluorine or chlorine, or Fluorene-2,6-diyl or at least one hydrogen substituted by fluorine or chlorine fluorene-2,6-diyl, and when b 'is 1 or more, at least one ring B' is tetrahydropyran- 2,5-diyl, and when c 'is 1 or more, at least one ring D' is tetrahydropyran-2,5-diyl; ring C '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, 7,8-difluorofluorene-2,6-diyl, 3,4,5,6-tetrafluorofluorene-2,7-diyl, 4,6-difluorodi Benzofuran-3,7-diyl, 4,6-difluorodibenzothiophene-3,7-diyl or 1,1,6,7-tetrafluoroindane-2,5-diyl; b 'Is 0, 1, or 2; c' is 0 or 1; and the sum of b 'and c' is 1 or 2.

Item 3. The liquid crystal composition according to item 2, which contains, as a first additive, a compound represented by formula (1), wherein in the compound, a in formula (1) is 1 or 2, or a in formula (1) Is 0, and R ¹ is an alkyl group having 1 to 24 carbon atoms not bonded via difluoromethoxy group or an alkenyl group having 2 to 24 carbon atoms not bonded via difluoromethoxy group, and X ¹ and X ² in the formula (1) are n-propyl groups or alkyl groups having 4 to 12 carbon atoms.

Item 4. The liquid crystal composition according to item 2 or 3, which contains as a second component at least one compound selected from the compound represented by formula (3-1).

In formula (3-1), R ⁴ and R ⁵ are an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or at least one hydrogen atom through fluorine or A chlorine-substituted alkenyl group having 2 to 12 carbon atoms.

Item 5. The liquid crystal composition according to any one of items 1 to 4, which contains, as a first additive, at least one compound selected from compounds represented by formula (1-1) to formula (1-9).

In the formulae (1-1) to (1-9), R ¹ is an alkyl group having 1 to 24 carbon atoms or an alkenyl group having 2 to 24 carbon atoms. In the alkyl group, at least one hydrogen may be subjected to fluorine Or chlorine substitution. Among these groups, at least one -CH ₂ -may be substituted with -O-, -COO-, or -OCO-; X ¹ and X ² are alkyl groups having 1 to 12 carbons.

Item 6. The liquid crystal composition according to any one of items 1 to 5, which contains, as a first component, at least one compound selected from the compounds represented by the formula (2-1) to the formula (2-35).




In the formulae (2-1) to (2-35), R ² and R ³ are an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, Alkenyloxy or hydrogen having 2 to 12 carbons.

Item 7. The liquid crystal composition according to any one of items 1 to 6, wherein the proportion of the first additive is in a range of 0.06 mass% to 5 mass%, and the proportion of the first component is in a range of 10 mass% to 90 mass%. Inside.

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

In formula (3), R ⁴ and R ⁵ are an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms or at least one hydrogen is substituted with fluorine or chlorine Alkenyl having 2 to 12 carbons; ring E and ring F are 1,4-cyclohexyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro -1,4-phenylene; Z ⁴ is a single bond, ethyl, vinyl, methoxy or carbonyloxy; d is 1, 2 or 3.

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

In the formulae (3-1) to (3-13), R ⁴ and R ⁵ are an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or An alkenyl group having 2 to 12 carbons with at least one hydrogen substituted with fluorine or chlorine.

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

Item 11. The liquid crystal composition according to any one of items 1 to 10, which contains, as a second additive, at least one compound selected from the polymerizable compounds represented by the formula (4).

In formula (4), ring G and ring K are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, and 1,3-dioxan Benz-2-yl, pyrimidin-2-yl or pyridin-2-yl, in these rings, at least one hydrogen may be passed through fluorine, chlorine, alkyl having 1 to 12 carbons, alkyl having 1 to 12 carbons Oxygen or at least 1 hydrogen substituted with fluorine or chlorine and 1 to 12 carbons; ring J is 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-benzene Naphthalene, 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-di 㗁 koushan-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in which at least 1 hydrogen can pass through Fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least 1 hydrogen substituted with fluorine or chlorine and alkyl having 1 to 12 carbons; Z ⁵ and Z ⁶ are mono Bond or alkylene having 1 to 10 carbons, in which at least 1 -CH ₂ -may be substituted with -O-, -CO-, -COO- or -OCO- ₂ -CH ₂ -Can pass -CH = CH- , -C (CH ₃ ) = CH-, -CH = C (CH ₃ )-or -C (CH ₃ ) = C (CH ₃ )-substitution, in these groups, at least 1 hydrogen may be replaced by fluorine or Chloro-substituted; P ¹ , P ^2, and P ³ are polymerizable groups; Sp ¹ , Sp ^2, and Sp ³ are single bonds or alkylene groups having 1 to 10 carbon atoms. In this alkylene group, at least one -CH ₂ -Can be substituted with -O-, -COO-, -OCO- or -OCOO-, at least 1 -CH ₂ -CH ₂ -Can be substituted with -CH = CH- or -C≡C- In the formula, at least one hydrogen may be substituted by fluorine or chlorine; e is 0, 1 or 2; f, g, and h are 0, 1, 2, 3, or 4; and the sum of f, g, and h is 1 or more.

Item 12. The liquid crystal composition according to item 11, wherein in the formula (4), P ¹ , P ^2, and P ³ are groups selected from polymerizable groups represented by the formula (P-1) to the formula (P-5) .

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

Item 13. The liquid crystal composition according to any one of items 1 to 12, which contains, as a second additive, at least one compound selected from the polymerizable compounds represented by the formula (4-1) to the formula (4-29).



In the formulae (4-1) to (4-29), P ⁴ , P ^5, and P ⁶ are groups selected from the polymerizable groups represented by the formulae (P-1) to (P-3); Sp ¹ , Sp ² and Sp ³ are single bonds or alkylene groups having 1 to 10 carbon atoms. In this alkylene group, at least one -CH ₂ -can pass through -O-, -COO-, -OCO-, or- OCOO- substituted, at least 1 -CH ₂ -CH ₂ -may be substituted with -CH = CH- or -C≡C-, in which at least 1 hydrogen may be substituted with fluorine or chlorine:

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

Item 14. The liquid crystal composition according to any one of items 11 to 13, wherein the proportion of the second additive is in a range of 0.03% by mass to 10% by mass.

Item 15. A liquid crystal display element comprising the liquid crystal composition according to any one of items 1 to 14.

Item 16. The liquid crystal display element according to item 15, wherein the operation mode of the liquid crystal display element is an IPS mode, a VA mode, an FFS mode, or an FPA mode, and the driving method of the liquid crystal display element is an active matrix method.

Item 17. A polymer-stabilized alignment type liquid crystal display element comprising the liquid crystal composition according to any one of items 11 to 14, and a polymerizable compound in the liquid crystal composition is polymerized.

Item 18. A use of the liquid crystal composition according to any one of items 1 to 14 in a liquid crystal display element.

Item 19. Use of the liquid crystal composition according to any one of items 11 to 14 in a polymer-stabilized alignment type liquid crystal display element.

Item 20. Use of the liquid crystal composition according to any one of items 1 to 14 in a liquid crystal projector.

Item 21. A method for stabilizing a liquid crystal composition to light, which is achieved by including, as a first component, a liquid crystal composition having at least one compound selected from the compound represented by formula (2) and having a negative dielectric anisotropy. Among the compounds, at least one compound selected from the compounds represented by formula (1) is added as a first additive.

In formulas (1) and (2), R ¹ is an alkyl group having 1 to 24 carbon atoms or an alkenyl group having 2 to 24 carbon atoms. In this alkyl group, at least one hydrogen may be substituted with fluorine or chlorine. Among these groups, at least one -CH ₂ -may be substituted by -O-, -COO-, or -OCO-; R ² and R ³ are alkyl groups having 1 to 12 carbons, and alkyl groups having 1 to 12 carbons Oxygen, alkenyl having 2 to 12 carbons, alkenyl having 2 to 12 carbons or hydrogen; ring A is 1,4-cyclohexyl, 1,4-cyclohexenyl, tetrahydropyran- 2,5-diyl, 1,3-di 㗁 koushan-2,5-diyl, 1,3-dithiane-2,5-diyl or 1,4-phenylene; ring B and ring D is 1,4-cyclohexyl, 1,4-cyclohexenyl, tetrahydropyran-2,5-diyl, 1,4-phenylene, and at least one hydrogen is replaced by fluorine or chlorine 1,4-phenylene, naphthalene-2,6-diyl, at least one hydrogen substituted with fluorine or chlorine, naphthalene-2,6-diyl, orthofluorene-2,6-diyl, or at least one Ortho-2,6-diyl in which hydrogen is replaced by fluorine or chlorine; ring C is 2,3-difluoro-1,4-phenyl, 2-chloro-3-fluoro-1,4-phenyl Phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, 7,8-difluoroacetone-2 , 6-diyl, 3,4,5,6-tetrafluorofluorene-2,7-diyl, 4,6-difluorodibenzofuran-3,7- Yl, 4,6-difluoro-dibenzothiophene-1,1,6,7- tetrafluoro-3,7-diyl or indan-2,5-diyl; Z ¹ is a single bond, an ethyl group, Vinyl, carbonyloxy, methoxy or difluoro methoxy; Z ² and Z ³ are single bonds, ethyl, vinyl, carbonyloxy or methoxy; X ¹ and X ² is an alkyl group having 1 to 12 carbons; a is 0, 1 or 2; b is 0, 1, 2 or 3; c is 0 or 1; and the sum of b and c is 3 or less.

The present invention also includes the following items. (A) Contains additives selected from optically active compounds, antioxidants different from compound (1), ultraviolet absorbers, matting agents, dyes, defoamers, polymerizable compounds, polymerization initiators, and polymerization inhibitors. The above-mentioned composition of one compound, two compounds, or three or more compounds. (B) An AM device containing the above composition. (C) The above composition further containing a polymerizable compound and a polymer stable alignment (PSA) type AM device containing the composition. (D) A polymer stabilized alignment (PSA) type AM device containing the above composition and polymerizing a polymerizable compound in the composition. (E) A device containing the above composition and having a PC, TN, STN, ECB, OCB, IPS, VA, FFS or FPA mode. (F) A transmissive element containing the above composition. (G) Use of the above composition as a composition having a nematic phase. (H) Use of an optically active composition obtained by adding an optically active compound to the composition.

The composition of the present invention will be described in the following order. First, the composition of the composition will be described. Second, the main characteristics of the component compounds and the main effects of the compounds on the composition or device will be described. Third, the combination of the component compounds of the composition, preferred ratios, and the basis thereof will be described. Fourth, a preferred embodiment of the component compound will be described. Fifth, the preferred component compounds are shown. Sixth, the additives that can be added to the composition will be described. Seventh, a method for synthesizing the component compounds will be described. Finally, the use of the composition will be described.

First, the composition of the composition will be described. This composition contains a plurality of liquid crystal compounds. This composition may contain additives. Additives are optically active compounds, antioxidants, ultraviolet absorbers, matting agents, dyes, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds, etc. that are different from compound (1). From the viewpoint of a liquid crystal compound, the composition is classified into a composition A and a composition B. In addition to the liquid crystal compound selected from the compound (2) and the compound (3), the composition A may further contain other liquid crystal compounds, additives, and the like. The “other liquid crystal compound” is a liquid crystal compound different from the compound (2) and the compound (3). These compounds are mixed in the composition for the purpose of further adjusting the characteristics.

The composition B is substantially composed of a liquid crystal compound selected from the compound (2) and the compound (3). "Substantially" means that the composition B may contain additives, but does not contain other liquid crystal compounds. Compared to composition A, the number of components of composition B is small. From the viewpoint of cost reduction, the composition B is better than the composition A. From the viewpoint that the characteristics can be further adjusted by mixing other liquid crystal compounds, the composition A is better than the composition B.

Second, the main characteristics of the component compounds and the main effects of the compounds on the composition or device will be described. The main characteristics of the component compounds are summarized in Table 2 based on the effects of the present invention. In the symbols in Table 2, L indicates large or high, M indicates medium, and S indicates small or low. Symbols L, M, and S are classifications based on qualitative comparisons among component compounds, and 0 (zero) means less than S.

[Table 2]

The main effects of the component compounds are as follows. The compound (1) contributes to high light stability and poor display inhibition. Since the compound (1) is added in a small amount, characteristics such as an upper limit temperature, optical anisotropy, and dielectric anisotropy are not affected in most cases. The compound (2) increases the dielectric anisotropy and lowers the lower limit temperature. Compound (3) reduces the viscosity or raises the upper limit temperature. Since the compound (4) is polymerizable, it is imparted to the polymer by polymerization. The polymer stabilizes the alignment of the liquid crystal molecules, thereby shortening the response time of the device and improving the aging of the image.

Third, the combination of the component compounds of the composition, preferred ratios, and the basis thereof will be described. A preferred combination of the component compounds of the composition is compound (1) + compound (2), compound (1) + compound (2) + compound (3), compound (1) + compound (2) + compound (4) or Compound (1) + compound (2) + compound (3) + compound (4). A further preferred combination is compound (1) + compound (2) + compound (3) or compound (1) + compound (2) + compound (3) + compound (4).

The preferred ratio of the compound (1) is about 0.06 mass% or more to improve the stability to light, and it is about 5 mass% or less to reduce the lower limit temperature. A further preferable ratio is in a range of about 0.1% by mass to about 3% by mass. A particularly preferred ratio is in the range of about 0.1% by mass to about 2% by mass.

The preferred ratio of the compound (2) is about 10% by mass or more to increase the dielectric anisotropy, and is about 90% by mass or less to lower the lower limit temperature. A further preferable ratio is in a range of about 20% by mass to about 80% by mass. A particularly preferred ratio is in the range of about 30% by mass to about 70% by mass.

The preferred ratio of the compound (3) is about 10% by mass or more to increase the upper limit temperature or lower the viscosity, and is about 90% by mass or less to improve the dielectric anisotropy. A further preferable ratio is in a range of about 20% by mass to about 80% by mass. A particularly preferred ratio is in the range of about 30% by mass to about 70% by mass.

The compound (4) is added to the composition for the purpose of being suitable for a polymer-stabilized alignment element. A preferred ratio of the compound (4) is about 0.03% by mass or more to align the liquid crystal molecules, and is about 10% by mass or less to prevent display failure of the device. A further preferred ratio is in the range of about 0.1% by mass to about 2% by mass. A particularly preferred ratio is in the range of about 0.2% by mass to about 1% by mass.

The liquid crystal composition of the present invention can exhibit excellent effects as a liquid crystal composition without containing the following compounds. In the following formula, Z ¹ represents a single bond, -CH ₂ CH _2- , -CH = CH-, -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF _2- , -COO-,- OCO-, -C ₂ F _4- , -C≡C-, -CF = CF-, -CH = CHCHO-, or -CH ₂ CF ₂ O-.

In addition, the liquid crystal composition of the present invention can exhibit excellent effects as a liquid crystal composition without containing the following compounds. In the following formula, n represents 2, 3, 4, 5 or 6.

Fourth, a preferred embodiment of the component compound will be described. In formula (1), R ¹ is an alkyl group having 1 to 24 carbon atoms or an alkenyl group having 2 to 24 carbon atoms. In this alkyl group, at least one hydrogen may be substituted with fluorine or chlorine. At least one -CH ₂ -may be substituted with -O-, -COO-, or -OCO-. Preferred R ¹ is an alkyl group having 1 to 7 carbon atoms. X ¹ and X ² are alkyl groups having 1 to 12 carbon atoms. Preferably, X ¹ or X ² is a branched alkyl group having 3 carbon atoms or a branched alkyl group having 4 carbon atoms.

In formula (1), ring A is 1,4-cyclohexyl, 1,4-cyclohexenyl, tetrahydropyran-2,5-diyl, 1,3-di 㗁 koushan-2 , 5-diyl, 1,3-dithiane-2,5-diyl or 1,4-phenylene. The preferred ring A is 1,4-cyclohexyl, 1,4-phenylene, or 1,3-dioxanguchi-2,5-diyl.

In the formula (1), X ¹ and X ² are an alkyl group having 1 to 12 carbon atoms. X ¹ and X ² can be selected from, for example, n-propyl and an alkyl group having 4 to 12 carbon atoms. X ¹ and X ² are preferably selected from branched alkyl groups having 4 to 12 carbon atoms.

Z ¹ is a single bond, ethylene, vinyl, carbonyloxy, methoxy, or difluoro methoxy. Z ¹ can be selected from a single bond, ethylene, vinyl, carbonyloxy and methoxy. Preferably, Z ¹ is a single bond.

a is 0, 1, or 2. Preferably, a is 0 or 1. When a is 0, for example, R ¹ may never have an alkyl group having 1 to 24 carbon atoms bonded via difluoromethoxy group and 1 to 24 carbon atoms not bonded through difluoromethoxy group Choice of alkenyl.

In formulas (2) and (3), R ² and R ³ are an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, an alkenyl group having 2 to 12 carbons, and 2 to 2 carbons 12 alkenyloxy or hydrogen. Preferably, R ² or R ³ is an alkyl group having 1 to 12 carbons to improve stability and an alkoxy group having 1 to 12 carbons to improve dielectric anisotropy. R ⁴ and R ⁵ are an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, an alkenyl group having 2 to 12 carbons or at least 1 hydrogen having 2 to 12 carbon atoms substituted with fluorine or chlorine Alkenyl. Preferably, R4 or R5 is an alkenyl group having 2 to 12 carbon atoms to reduce viscosity and an alkyl group having 1 to 12 carbon atoms to improve stability.

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

Preferred alkoxy groups are methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy or heptyloxy. A further preferred alkoxy group is methoxy or ethoxy to reduce viscosity.

Preferred alkenyl groups are vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3- Pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl or 5-hexenyl. Further preferred alkenyl is vinyl, 1-propenyl, 3-butenyl or 3-pentenyl to reduce viscosity. The preferred stereo configuration of -CH = CH- in these alkenyl groups depends on the position of the double bond. In order to reduce viscosity, etc., in 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl, 3-hexenyl and the like, The formula is better. Among alkenyl groups such as 2-butenyl, 2-pentenyl, and 2-hexenyl, cis is preferred.

Preferred alkenyloxy is vinyloxy, allyloxy, 3-butenyloxy, 3-pentenyloxy or 4-pentenyloxy. Further preferred allyloxy is allyloxy or 3-butenyloxy to reduce viscosity.

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

Preferred examples of the alkenyl group in which at least one hydrogen is substituted by fluorine or chlorine are 2,2-difluorovinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro-3-butenyl , 5,5-difluoro-4-pentenyl or 6,6-difluoro-5-hexenyl. Further preferred examples are 2,2-difluorovinyl or 4,4-difluoro-3-butenyl to reduce viscosity.

Rings B and D are 1,4-cyclohexyl, 1,4-cyclohexenyl, tetrahydropyran-2,5-diyl, 1,4-phenylene, and at least one hydrogen Or chlorine-substituted 1,4-phenylene, naphthalene-2,6-diyl, at least one hydrogen substituted with fluorine or chlorine Or at least one hydrogen substituted with fluorine or chlorine gadolinium-2,6-diyl. Preferred examples of "a 1,4-phenylene substituted with at least one hydrogen by fluorine or chlorine" are 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene Or 2-chloro-3-fluoro-1,4-phenylene. The preferred ring B or ring D is 1,4-cyclohexyl to reduce viscosity, and is tetrahydropyran-2,5-diyl to improve dielectric anisotropy. To improve optical anisotropy. Tetrahydropyran-2,5-diyl is

or

,for

Is better.

Ring C 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, 7,8-difluorocyclofluorene-2,6-diyl, 3,4,5,6-tetrafluorofluorene- 2,7-diyl (FLF4), 4,6-difluorodibenzofuran-3,7-diyl (DBFF2), 4,6-difluorodibenzothiophene-3,7-diyl (DBTF2 ) Or 1,1,6,7-tetrafluoroindane-2,5-diyl (InF4).

The preferred ring C is 2,3-difluoro-1,4-phenylene to reduce viscosity and 2-chloro-3-fluoro-1,4-phenylene to reduce optical anisotropy, which is 7 , 8-difluoro mouth gadolinium-2,6-diyl to improve the dielectric anisotropy.

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

Z ² and Z ³ are a single bond, ethylene, vinyl, carbonyloxy or methoxy. Preferably, Z ² or Z ³ is a single bond to reduce the viscosity, to extend the ethyl group, to lower the lower temperature, and to extend the methoxy group to increase the dielectric anisotropy.

Z ⁴ is a single bond, ethylene, vinyl, methoxy or carbonyloxy. The preferred Z ⁴ is a single bond to reduce viscosity.

Among the methoxy groups, -CH ₂ O- is preferred to -OCH _2- . Among carbonyloxy groups, -COO- is preferred over -OCO-.

b is 0, 1, 2 or 3, c is 0 or 1, and the sum of b and c is 3 or less. Preferably, b is 1 to reduce the viscosity and 2 or 3 to increase the upper limit temperature. Preferably, c is 0 to reduce the viscosity, and 1 is to reduce the lower limit temperature. d is 1, 2 or 3. The preferred d is 1 to reduce the viscosity and 2 or 3 to increase the upper limit temperature.

It is particularly preferred that the liquid crystal composition of the present invention contains, as a first component, at least one compound selected from the compound represented by formula (2 '). Among the compounds represented by the formula (2), in particular, by selecting and using the compound represented by the formula (2 '), it is possible to realize a liquid crystal composition having a high nematic phase upper temperature and a low rotational viscosity.

In the formula (2 '), R ² ′ and R ³ ′ are an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, Alkenyloxy or hydrogen; ring B 'and ring D' are 1,4-cyclohexyl, 1,4-cyclohexenyl, tetrahydropyran-2,5-diyl, 1,4-benzene 1,4-phenylene, naphthalene-2,6-diyl substituted with at least 1 hydrogen with fluorine or chlorine, naphthalene-2,6-diyl substituted with at least 1 hydrogen with fluorine or chlorine, or Fluorene-2,6-diyl or at least one hydrogen substituted by fluorine or chlorine fluorene-2,6-diyl, and when b 'is 1 or more, at least one ring B' is tetrahydropyran- 2,5-diyl, and when c 'is 1 or more, at least one ring D' is tetrahydropyran-2,5-diyl; ring C '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, 7,8-difluorofluorene-2,6-diyl, 3,4,5,6-tetrafluorofluorene-2,7-diyl, 4,6-difluorodi Benzofuran-3,7-diyl, 4,6-difluorodibenzothiophene-3,7-diyl or 1,1,6,7-tetrafluoroindane-2,5-diyl; b 'Is 0, 1, or 2; c' is 0 or 1; and the sum of b 'and c' is 1 or 2.
For the preferable ranges and specific examples of R ² ′, R ³ ′ and ring C ′ in formula (2 ′), refer to the preferable ranges and specific examples of R ² , R ³ and ring C in formula (2). . Tetrahydropyran-2,5-diyl may exist only in ring B ', only in ring D', or both. It is preferable that one tetrahydropyran-2,5-diyl group exists in the compound represented by the formula (2 ′). As a combination of b 'and c', b 'is 1 and c' is 1; b 'is 2 and c' is 0; b 'is 0 and c' is 2; b 'is 1 and Combinations in which c 'is 0, combinations in which b' is 0 and c 'is 1.
The liquid crystal composition of the present invention may contain two or more compounds represented by the formula (2 '). The liquid crystal composition of the present invention preferably contains a compound not represented by the formula (2 ') but included in the formula (2) in addition to the compound represented by the formula (2'). When the liquid crystal composition of the present invention contains a compound represented by the formula (2 '), the ratio of the compound represented by the formula (2') in the liquid crystal composition is preferably 1 to 90% by mass, and 2 to 50% by mass. More preferably, 3 to 30% by mass is more preferable. The liquid crystal composition of the present invention preferably contains a combination of a compound represented by the formula (2 ′) and a compound represented by the formula (3-1).

In Formula (4), P ¹ , P ² and P ³ are polymerizable groups. Preferably, P ¹ , P ² or P ³ is a group selected from polymerizable groups represented by the formula (P-1) to the formula (P-5). More preferably, P ¹ , P ² or P ³ is a radical (P-1) or a radical (P-2). A particularly good base (P-1) is -OCO-CH = CH ₂ or -OCO-C (CH ₃ ) = CH ₂ . The wave line from the base (P-1) to the base (P-5) indicates the bonding site.

In the radicals (P-1) to (P-5), M ¹ , M ² and M ³ are hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or a carbon number in which at least one hydrogen is replaced by fluorine or chlorine. 1 to 5 alkyl. Preferably, M ¹ , M ² or M ³ is hydrogen or methyl to improve reactivity. Further preferred M ¹ is methyl, and further preferred M ² or M ³ is hydrogen.

In the formulae (4-1) to (4-29), P ⁴ , P ⁵ and P ^{6 are} groups represented by the formulae (P-1) to (P-3). Preferably, P ⁴ , P ⁵ or P ⁶ is a radical (P-1) or a radical (P-2). A further preferred group (P-1) is -OCO-CH = CH ₂ or -OCO-C (CH ₃ ) = CH ₂ . The wave line from the base (P-1) to the base (P-3) indicates the bonding site.

In formula (4), Sp ¹ , Sp ² and Sp ³ are single bonds or alkylene groups having 1 to 10 carbon atoms. In this alkylene group, at least one -CH ₂ -may be passed through -O-,- COO-, -OCO- or -OCOO- substituted, at least 1 -CH ₂ -CH ₂ -may be substituted with -CH = CH- or -C≡C-, in which at least 1 hydrogen may be substituted with fluorine Or chlorine substitution. Preferably, Sp ¹ , Sp ² or Sp ³ is a single bond, -CH ₂ CH _2- , -CH ₂ O-, -OCH _2- , -COO-, -OCO-, -CO-CH = CH- or -CH = CH-CO-. Further preferred Sp ¹ , Sp ² or Sp ³ is a single bond.

Ring G and ring K are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, and pyrimidine 2-yl or pyridin-2-yl, in these rings, at least 1 hydrogen may be passed through fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least 1 hydrogen C1-C12 alkyl substituted with fluorine or chlorine. Preferred ring G or ring K is phenyl. Ring J is 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1 , 4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl , Naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-di 㗁 koushan-2,5-diyl, pyrimidine-2 , 5-diyl or pyridine-2,5-diyl, in these rings, at least 1 hydrogen may be passed through fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or At least one hydrogen is substituted with a fluorine or chlorine substituted C1-C12 alkyl group. Preferred ring J is 1,4-phenylene or 2-fluoro-1,4-phenylene.

Z ⁵ and Z ⁶ are single bonds or alkylene groups having 1 to 10 carbon atoms. In this alkylene group, at least one -CH ₂ -can pass through -O-, -CO-, -COO-, or -OCO- Substitution, at least one -CH ₂ -CH ₂ -can be via -CH = CH-, -C (CH ₃ ) = CH-, -CH = C (CH ₃ )-or -C (CH ₃ ) = C (CH ₃ )-Substitution. In these groups, at least 1 hydrogen may be substituted with fluorine or chlorine. Preferably, Z ⁵ or Z ⁶ is a single bond, -CH ₂ CH _2- , -CH ₂ O-, -OCH _2- , -COO-, or -OCO-. More preferably, Z ⁵ or Z ⁶ is a single bond.

e is 0, 1, or 2. Preferably, e is 0 or 1. f, g, and h are 0, 1, 2, 3, or 4, and the sum of f, g, and h is 1 or more. Preferably, f, g or h is 1 or 2.

Fifth, the preferred component compounds are shown. Preferred compound (1) is the compound (1-1) to compound (1-9) according to item 2. Among these compounds, compound (1-1), compound (1-2), compound (1-4), compound (1-5) or compound (1-8) are preferred, and compound (1-1) , Compound (1-2), compound (1-4) or compound (1-8) are more preferred.

Preferred compound (2) is the compound (2-1) to compound (2-35) according to item 3. Among these compounds, at least one of the first components is compound (2-1), compound (2-3), compound (2-8), compound (2-14) or compound (2-16) is Better. At least two of the first component are compound (2-1) and compound (2-8), compound (2-1) and compound (2-14), compound (2-3) and compound (2-8) , Compound (2-3) and compound (2-14) or a combination of compound (2-3) and compound (2-16) are preferred. In addition, as the compound (2), it is preferable to use at least one compound selected from the group consisting of the compound (2-4), the compound (2-13), and the compound (2-16). Among them, the compound (2-16) is Better.

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

Preferred compound (4) is the compound (4-1) to compound (4-29) according to item 10. Among these compounds, at least one of the second additives is compound (4-1), compound (4-2), compound (4-24), compound (4-25), compound (4-26) Or compound (4-27) is preferred. At least two of the second additive are compound (4-1) and compound (4-2), compound (4-1) and compound (4-18), compound (4-2) and compound (4-24) ), Compound (4-2) and compound (4-25), compound (4-2) and compound (4-26), compound (4-25) and compound (4-26) or compound (4-18) And the combination of compound (4-24) is preferable.

Sixth, the additives that can be added to the composition will be described. These additives are optically active compounds, antioxidants different from compound (1), ultraviolet absorbers, matting agents, dyes, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds, and the like. An optically active compound is added to the composition for the purpose of inducing a twist structure of the liquid crystal molecules and giving a twist angle. Examples of such compounds are compound (5-1) to compound (5-5). The preferable ratio of an optically active compound is about 5 mass% or less. A further preferable ratio is in a range of about 0.01% by mass to about 2% by mass.

Preferable examples of the ultraviolet absorber include a diphenyl ketone derivative, a benzoate derivative, and a triazole derivative. Light stabilizers such as amines having a three-dimensional hindrance are also preferred. Preferable examples of the light stabilizer include compound (6-1) to compound (6-16) and the like. The preferred ratio of these absorbents or stabilizers is about 50 ppm or more to obtain its effect, and it is about 10,000 ppm or less so as not to lower the upper limit temperature or to raise the lower limit temperature. A further preferred ratio is in the range of about 100 ppm to about 10,000 ppm.

A matting agent is a compound that prevents the decomposition of a liquid crystal compound by receiving the light energy absorbed by the liquid crystal compound and converting it into thermal energy. Preferred examples of the matting agent are the compound (7-1) to the compound (7-7) and the like. The preferred ratio of these matting agents is about 50 ppm or more to obtain its effect, and is about 20,000 ppm or less so as not to lower the lower limit temperature. A further preferred ratio is in the range of about 100 ppm to about 10,000 ppm.

A dichroic dye such as an azo-based dye, an anthraquinone-based dye, or the like is added to the composition for a device suitable for a GH (guest host) mode. A preferred ratio of the dye is in the range of about 0.01% by mass to about 10% by mass. Antifoaming agents such as dimethyl silicone oil and methylphenyl silicone oil are added to the composition to prevent foaming. The preferred ratio of the defoaming agent is about 1 ppm or more to obtain its effect, and it is about 1000 ppm or less to prevent display failure. A further preferred ratio is in the range of about 1 ppm to about 500 ppm.

A polymerizable compound is used for a polymer stable alignment (PSA) type device. Compound (4) is suitable for this purpose. A polymerizable compound different from the compound (4) may be added to the composition together with the compound (4). Preferred examples of these polymerizable compounds are acrylates, methacrylates, vinyl compounds, vinyloxy compounds, allyl ethers, epoxy compounds (ethylene oxide, oxetane), and vinyl ketones. And other compounds. A further preferred example is a derivative of acrylate or methacrylate. A preferable ratio of the compound (4) is 10% by mass or more based on the total mass of the polymerizable compound. A more preferable ratio is 50% by mass or more. A particularly good ratio is 80% by mass or more. The optimal ratio is 100% by mass.

A polymerizable compound such as the compound (4) is polymerized by irradiation with ultraviolet rays. It may also be polymerized in the presence of a suitable initiator such as a photopolymerization initiator. Appropriate conditions for polymerization, appropriate types of initiators, and appropriate amounts are known to those skilled in the art and are described in the literature. For example, Irgacure651 (registered trademark; BASF), Irgacure184 (registered trademark; BASF), or Darocur1173 (registered trademark; BASF) as photoinitiators 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 total mass of the polymerizable compound. A further preferable ratio is in a range of about 1% by mass to about 3% by mass.

When storing a polymerizable compound such as the compound (4), a polymerization inhibitor may be added to suppress polymerization. The polymerizable compound is usually added to the composition without removing the polymerization inhibitor. Examples of the polymerization inhibitor are hydroquinone, a hydroquinone derivative such as methylhydroquinone, 4-tert-butylcatechol, 4-methoxyphenol, phenanthrene, and the like.

Seventh, a method for synthesizing the component compounds will be described. These compounds can be synthesized by conventional methods. A synthesis method is exemplified. Compound (1-1) was obtained from Sigma-Aldrich Corporation or was synthesized by a method described in US Pat. No. 3,660,505. Compound (2-1) is synthesized by a method described in Japanese Patent Application Laid-Open No. 2000-053602. Compound (3-1) is synthesized by a method described in Japanese Patent Application Laid-Open No. 59-176221. Compound (4-18) was synthesized by the method described in Japanese Patent Application Laid-Open No. 7-101900.

Compounds without a synthetic method can be synthesized by organic synthesis (Organic Syntheses, John Wiley & Sons, Inc), organic reactions (Organic Reactions, John Wiley & Sons, Inc), comprehensive organic synthesis (Pergamon Press), new Synthesized by methods described in the literature such as Experimental Chemistry Lecture (MaruzenJunkudo Bookstores Co., Ltd.). The composition is prepared from the compound thus obtained by a known method. For example, after mixing the component compounds, they are dissolved by heating.

Finally, the use of the composition will be described. The composition mainly has a lower limit temperature of about -10 ° C or lower, an upper limit temperature of about 70 ° C or higher, and an optical anisotropy in a 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 be prepared by controlling the ratio of the component compounds or by mixing other liquid crystal compounds. It is also possible to prepare a composition having an optical anisotropy in a range of about 0.10 to about 0.30 by trial and error. A device containing the composition has a large voltage holding ratio. This composition is suitable for an AM device. This composition is particularly suitable for a transmissive AM device. This composition can be used as a composition having a nematic phase, and can be used as an optically active composition by adding an optically active compound.

This composition can be used in an AM device. Furthermore, it can be used for a PM device. This composition can be used in AM devices and PM devices having PC, TN, STN, ECB, OCB, IPS, FFS, VA, FPA and other modes. It is particularly good to use in AM devices with TN, OCB, IPS mode or FFS mode. In an AM device having an IPS mode or an FFS mode, when no voltage is applied, the alignment of the liquid crystal molecules may be parallel to the glass substrate or may be perpendicular to the glass substrate. These elements can be reflective, transmissive, or transflective. It is preferably used in a transmissive element. It can also be used in amorphous silicon-TFT elements or polycrystalline silicon-TFT elements. It can also be used for NCAP (nematic curvilinear aligned phase) type elements prepared by microencapsulating the composition or PD (polymer dispersed, polymer dispersed) that forms a three-dimensional mesh-like polymer in the composition. ) Type components.

[Example]

The present invention will be further described in detail through examples. The invention is not limited by these examples. The present invention contains a mixture of the composition of Example 1 and the composition of Example 2. The present invention further contains a mixture obtained by mixing at least two of the compositions of the examples. The synthesized compound was identified by a method such as NMR analysis. The characteristics of the compounds, compositions, and devices were measured by the methods described below.

NMR analysis: DRX-500 manufactured by Bruker BioSpin KK was used for the measurement. In the measurement of ¹ H-NMR, a sample was dissolved in a deuterated solvent such as CDCl _3, and the measurement was performed at room temperature, 500 MHz, and 16 times of accumulation. Tetramethylsilane was used as the internal standard. In the measurement of ¹⁹ F-NMR, CFCl _{3 was} used as an internal standard, and was performed 24 times in total. In the description of the NMR spectrum, s indicates a singlet, d indicates a doublet, t indicates a triplet, q indicates a quartet, quin indicates a quintet, sex indicates a hexaplex, m indicates a multiplet, and br indicates a broad peak .

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

As a solvent for diluting the sample, chloroform, hexane and the like can be used. The following capillary columns can be used to separate constituent compounds. HP-1 manufactured by Agilent Technologies Inc. (length 30m, inner diameter 0.32mm, film thickness 0.25 μm), Restek Corporation Rtx-1 (length 30m, inner diameter 0.32mm, film thickness 0.25 μm), SGE International Pty. Ltd. BP-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm). To prevent overlapping of 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 can be used.

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

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

The following mother liquid crystals were used. The proportion of the component compounds is shown in mass%.

Measurement method: The characteristics were measured in the following manner. These are mostly methods described or improved in the JEITA specification (JEITA · ED-2521B) reviewed and formulated by the Japan Electronics and Information Technology Industries Association (referred to as JEITA). The TN element used for measurement is not equipped with a thin film transistor (TFT).

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

(2) Lower limit temperature (T _C ; ℃) of nematic phase: Put the sample with nematic phase into the glass bottle, and After being stored in the freezer for 10 days, the liquid crystal phase was observed. For example, when the sample is still a nematic phase at -20 ° C and becomes a crystal or a smectic phase at -30 ° C, it is described as T _C <-20 ° C. The lower limit temperature of the nematic phase is sometimes simply referred to as the "lower limit temperature".

(3) Viscosity (whole viscosity; η; measured at 20 ° C; mPa · s): The measurement was performed using an E-type rotary viscometer manufactured by TOKYO KEIKI INC.

(4) Viscosity (rotational viscosity; γ1; measured at 25 ° C; mPa · s): The measurement was performed using TOYO Corporation's rotational viscosity coefficient measurement system LCM-2. A sample was injected into a VA device having a distance (cell gap) between two glass substrates of 10 μm. A rectangular wave (55V, 1ms) was applied to the device. The peak current and peak time of the transient current generated by the application were measured. Using these measurements and dielectric anisotropy, values for rotational viscosity were obtained. The dielectric anisotropy was measured by the method described in Measurement (6).

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

(6) Dielectric anisotropy (Δε; measured at 25 ° C): The value of the dielectric anisotropy was calculated from the formula Δε = ε∥-ε⊥. The dielectric constants (ε∥ and ε⊥) were measured as follows.
1) Measurement of dielectric constant (ε∥): A cleaned glass substrate was coated with a solution of octadecyltriethoxysilane (0.16 mL) in ethanol (20 mL). After the glass substrate was rotated in a spinner, it was heated at 150 ° C. for 1 hour. The sample was injected into a VA device having a gap (cell gap) between two glass substrates of 4 μm, and the device was sealed with an ultraviolet curing adhesive. A sine wave (0.5 V, 1 kHz) was applied to the device, and the dielectric constant (ε∥) on the long axis of the liquid crystal molecules was measured after 2 seconds.
2) Measurement of dielectric constant (ε⊥): The cleaned glass substrate was coated with a polyfluorene imine solution. After firing the glass substrate, the obtained alignment film was subjected to a rubbing treatment. The sample was injected into a TN device having a gap (cell gap) between two glass substrates of 9 μm and a twist angle of 80 degrees. A sine wave (0.5 V, 1 kHz) was applied to the device, and the dielectric constant (ε⊥) on the minor axis of the liquid crystal molecules was measured after 2 seconds.

(7) Threshold voltage (Vth; measured at 25 ° C; V): The LCD5100 brightness meter made by OTSUKA ELECTRONICS Co., LTD was used for the measurement. The light source is a halogen lamp. The sample was injected into a normal black mode VA device with a gap (cell gap) between two glass substrates of 4 μm and a rubbing direction in antiparallel, and sealed with an ultraviolet curing adhesive. The element. From 0V to 20V, the voltage (60Hz, rectangular wave) applied to the element is gradually increased in increments of 0.02V. At this time, the element was irradiated with light from a vertical direction, and the amount of light transmitted through the element was measured. A voltage-transmittance curve was prepared with a transmittance of 100% when the light amount became maximum and a transmittance of 0% when the light amount became minimum. The threshold voltage is represented by a voltage at a transmittance of 10%.

(8) Voltage holding ratio (VHR-1; measured at 60 ° C;%): The TN element used for measurement has a polyimide alignment film, and the interval (cell gap) between the two glass substrates is 5 μm. After the sample was injected, the device was sealed with an adhesive hardened by ultraviolet rays. A pulse voltage (at 1 V, 60 microseconds) was applied to the TN device, and the TN device was charged. A high-speed voltmeter was used to measure the attenuated voltage for 1,000 milliseconds, and the area A between the voltage curve and the horizontal axis in a unit cycle was obtained. The area B is the area without attenuation. The voltage holding ratio is expressed as a percentage of the area A to the area B.

(9) Voltage retention rate (VHR-2; measured at 60 ° C;%): After standing for 2 weeks on the LED backlight, the voltage retention rate was measured to evaluate the stability to the LED backlight. The TN element used for the measurement has a polyimide alignment film, and the cell gap is 5 μm. In the measurement of VHR-2, the attenuated voltage was measured for 1000 milliseconds. The composition with a large VHR-2 has great stability to the LED backlight.

(10) Voltage retention (VHR-3; measured at 60 ° C;%): After standing for 2 weeks on the LED backlight, the voltage retention was measured to evaluate the stability to the LED backlight. The TN element used for measurement has a photo-alignment film, and the cell gap is 4 μm. In the VHR-3 measurement, the attenuated voltage was measured for 3 milliseconds. The composition with a large VHR-3 has great stability to the LED backlight.

(11) Response time (τ; measured at 25 ° C; ms): The LCD5100 brightness meter manufactured by OTSUKA ELECTRONICS Co., LTD was used for the measurement. The light source is a halogen lamp. The low-pass filter is set to 5kHz. The sample was injected into a normally black mode VA device in which the interval (cell gap) between two glass substrates was 4 μm and the rubbing direction was antiparallel. The element was sealed with an adhesive hardened by ultraviolet rays. A rectangular wave (60 Hz, 10 V, 0.5 seconds) was applied to the device. At this time, the element was irradiated with light from a vertical direction, and the amount of light transmitted through the element was measured. When the light amount becomes maximum, the transmittance is regarded as 100%, and when the light amount becomes minimum, the transmittance is regarded as 0%. Response time is represented by the time (fall time; milliseconds) required for the transmittance to change from 90% to 10%.

(12) Electrical resistivity (ρ; measured at 25 ° C; Ωcm): Inject 1.0 mL of a sample into a container provided with an electrode. A DC voltage (10 V) was applied to the container, and a DC current after 10 seconds was measured. The resistivity was calculated from the following formula. (Resistivity) = ｛(voltage) × (capacity of the container)｝ / ｛(DC current) × (vacuum dielectric constant)｝.

(13) Line image sticking parameter (LISP;%): A line afterimage is generated by applying electrical stress to the liquid crystal display element. The brightness of the area with the line afterimage and the brightness of the remaining area were measured. Calculate the ratio of the brightness reduction due to the line afterimage, and express the size of the line afterimage based on the ratio.
13a) Measurement of brightness: An image of the element was taken using an imaging color brightness meter (manufactured by Radiant Zemax, PM-1433F-0). This image was analyzed using software (Prometric 9.1, manufactured by Radiant Imaging), and the brightness of each area of the element was calculated. The light source uses an LED backlight with an average brightness of 3500cd / m ² .

13b) Setting of stress voltage: Inject the sample into an FFS device with a cell structure of 3.5 μm and a matrix structure (16 cells in 4 cells x 4 cells in 4 cells), and seal the cell with an ultraviolet curing adhesive. element. Polarizing plates are arranged on the upper and lower surfaces of the element so that the polarization axes are orthogonal to each other. This element was irradiated with light and a voltage (rectangular wave, 60 Hz) was applied. The voltage was gradually increased in the range of 0V to 7.5V in 0.1V increments, and the brightness of transmitted light at each voltage was measured. The voltage when the brightness becomes extremely large is referred to as V255. The voltage when the brightness becomes 21.6% of V255 (that is, 127 gray scales) is simply referred to as V127.

13c) Stress conditions: V255 (rectangular wave, 30Hz) and 0.5V (rectangular wave, 30Hz) are applied to the element at 60 ° C for 23 hours and a checkerboard pattern is displayed. Next, V127 (rectangular wave, 0.25 Hz) was applied, and the brightness was measured under an exposure time of 4000 milliseconds.

13d) Calculation of line afterimage: 4 units (2 units by 2 units by 2 units) in the center of the 16 units are used for calculation. The 4 units are divided into 25 regions (5 units in a vertical direction and 5 units in a horizontal direction). The average brightness of 4 areas (2 units by 2 units) located at four corners is referred to as brightness A for short. The area obtained by removing the four corner areas from the 25 areas is cross-shaped. In the four areas obtained by excluding the central intersection area from the cross-shaped area, the minimum value of the brightness is simply referred to as the brightness B. The line afterimage was calculated from the following formula. (Line afterimage) = (Brightness A-Brightness B) / Brightness A × 100.

(14) Scalability: A qualitative evaluation of the scalability of the additive was made by applying a voltage to the element and measuring the brightness. The measurement of brightness was performed in the same manner as in the above item 13a. The voltage (V127) was set in the same manner as in the above item 14b. Among them, a VA element is used instead of the FFS element. The brightness was measured as follows. First, a DC voltage (2V) was applied to the element for 2 minutes. Secondly, V127 (rectangular wave, 0.05 Hz) was applied, and the brightness was measured under an exposure time of 4000 milliseconds. Based on the results, scalability was evaluated.

Examples of the composition are shown below. The component compounds are indicated by symbols based on the definitions in Table 3 below. In Table 3, the stereo configuration related to 1,4-cyclohexyl is trans. The number in parentheses after the mark corresponds to the number of the compound. The (-) symbol indicates another liquid crystal compound. The ratio (percentage) of the liquid crystal compound is a mass percentage (mass%) based on the mass of the liquid crystal composition. Finally, the characteristic values of the composition are summarized.

[table 3]

[Comparative Example 1]
3-HB （2F, 3F） -O2 （2-1） 18%
5-HB （2F, 3F） -O2 （2-1） 16.5%
3-HHB （2F, 3F） -O2 （2-8） 10%
5-HHB (2F, 3F) -O2 (2-8) 4.5%
3-HBB （2F, 3F） -O2 （2-14） 12%
4-HBB （2F, 3F） -O2 （2-14） 12%
3-HHB-1 (3-5) 2%
3-HBB-2 (3-6) 6%
5-B (F) BB-2 (3-7) 10%
5-B (F) BB-3 (3-7) 9%
NI = 101.7 ℃; Tc <-20 ℃; Δn = 0.150; Δε = -4.3; γ1 = 253mPa · s; VHR-2 = 82.1%.

The composition in which the compound (1-1-2) was added to the composition of Comparative Example 1 was defined as Example 1.
[Example 1]
3-HB （2F, 3F） -O2 （2-1） 18%
5-HB （2F, 3F） -O2 （2-1） 16.5%
3-HHB （2F, 3F） -O2 （2-8） 10%
5-HHB (2F, 3F) -O2 (2-8) 4.5%
3-HBB （2F, 3F） -O2 （2-14） 12%
4-HBB （2F, 3F） -O2 （2-14） 12%
3-HHB-1 (3-5) 2%
3-HBB-2 (3-6) 6%
5-B (F) BB-2 (3-7) 10%
5-B (F) BB-3 (3-7) 9%
Compound (1-1-2) was added to this composition at a ratio of 0.060% by mass.
NI = 101.6 ℃; Tc <-20 ℃; Δn = 0.150; Δε = -4.3; γ1 = 253mPa · s; VHR-2 = 90.3%.

[Example 2]
3-HB （2F, 3F） -O2 （2-1） 18%
5-HB （2F, 3F） -O2 （2-1） 16.5%
3-HHB （2F, 3F） -O2 （2-8） 10%
5-HHB (2F, 3F) -O2 (2-8) 4.5%
3-HBB （2F, 3F） -O2 （2-14） 12%
4-HBB （2F, 3F） -O2 （2-14） 12%
3-HHB-1 (3-5) 2%
3-HBB-2 (3-6) 6%
5-B (F) BB-2 (3-7) 10%
5-B (F) BB-3 (3-7) 9%
Compound (1-1-2) was added to this composition at a ratio of 0.10% by mass.
NI = 101.4 ℃; Tc <-20 ℃; Δn = 0.150; Δε = -4.3; γ1 = 253mPa · s; VHR-2 = 93.7%.

[Example 3]
3-HB （2F, 3F） -O2 （2-1） 13%
5-HB （2F, 3F） -O2 （2-1） 13%
3-H2B (2F, 3F) -O2 (2-2) 9%
V-HHB (2F, 3F) -O1 (2-8) 4%
V-HHB (2F, 3F) -O2 (2-8) 10%
3-HHB （2F, 3F） -O2 （2-8） 6%
3-HH-V (3-1) 20%
V-HBB-2 (3-6) 11%
3-HBB-2 (3-6) 14%
Compound (1-1-2) was added to this composition at a ratio of 0.10% by mass.
NI = 74.5 ℃; Tc <-20 ℃; Δn = 0.103; Δε = -2.9; γ1 = 94mPa · s; VHR-2 = 90.5%.

[Example 4]
V2-BB （2F, 3F） -O2 （2-6） 8%
3-BB （2F, 3F） -O2 （2-6） 3%
V-HHB (2F, 3F) -O1 (2-8) 4%
V-HHB (2F, 3F) -O2 (2-8) 6%
2-HHB （2F, 3F） -O2 （2-8） 3%
3-HHB （2F, 3F） -O2 （2-8） 6%
3-dhBB (2F, 3F) -O2 (2-16) 6.5%
3-HB (2F) B (2F, 3F) -O2 (2-18) 18%
V-HH-V (3-1) 35.5%
V-HHB-1 (3-5) 5%
V-HBB-2 (3-6) 5%
Compound (1-1-2) was added to this composition at a ratio of 0.10% by mass.
NI = 80.2 ℃; Tc <-20 ℃; Δn = 0.110; Δε = -3.0; γ1 = 73mPa · s; VHR-2 = 85.5%.

[Example 5]
3-HB （2F, 3F） -O4 （2-1） 6%
3-H2B (2F, 3F) -O2 (2-2) 8%
3-H1OB (2F, 3F) -O2 (2-3) 5%
3-BB （2F, 3F） -O2 （2-6） 10%
2-HHB （2F, 3F） -O2 （2-8） 7%
3-HHB （2F, 3F） -O2 （2-8） 7%
5-HHB (2F, 3F) -O2 (2-8) 7%
2-HBB （2F, 3F） -O2 （2-14） 4%
3-HBB （2F, 3F） -O2 （2-14） 7%
5-HBB (2F, 3F) -O2 (2-14) 6%
3-HH-V (3-1) 11%
1-BB-3 (3-3) 6%
3-HHB-1 (3-5) 4%
3-HHB-O1 (3-5) 4%
3-HBB-2 (3-6) 4%
3-B (F) BB-2 (3-7) 4%
Compound (1-1-1) was added to this composition at a ratio of 0.070% by mass.
NI = 87.6 ℃; Tc <-20 ℃; Δn = 0.126; Δε = -4.5; η = 25.3mPa · s; VHR-2 = 89.6%.

[Example 6]
3-HB （2F, 3F） -O2 （2-1） 5%
5-HB （2F, 3F） -O2 （2-1） 7%
3-BB （2F, 3F） -O2 （2-6） 8%
3-HHB （2F, 3F） -O2 （2-8） 5%
5-HHB （2F, 3F） -O2 （2-8） 4%
3-HH1OB (2F, 3F) -O2 (2-10) 5%
2-HBB （2F, 3F） -O2 （2-14） 3%
3-HBB （2F, 3F） -O2 （2-14） 9%
4-HBB (2F, 3F) -O2 (2-14) 4%
5-HBB （2F, 3F） -O2 （2-14） 8%
2-BB (2F, 3F) B-3 (2-19) 4%
3-HH-V (3-1) 27%
3-HH-V1 (3-1) 6%
V-HHB-1 (3-5) 5%
Compound (1-1-2) was added to this composition at a ratio of 0.10% by mass.
NI = 81.2 ℃; Tc <-20 ℃; Δn = 0.107; Δε = -3.2; η = 15.5mPa · s; VHR-2 = 91.3%.

[Example 7]
3-H2B (2F, 3F) -O2 (2-2) 7%
3-HHB （2F, 3F） -O2 （2-8） 8%
3-HH1OB (2F, 3F) -O2 (2-10) 8%
2-HchB （2F, 3F） -O2 （2-12） 8%
3-HDhB （2F, 3F） -O2 （2-13） 3%
5-HDhB (2F, 3F) -O2 (2-13) 4%
2-BB (2F, 3F) B-3 (2-19) 7%
2-BB (2F, 3F) B-4 (2-19) 7%
4-HH-V (3-1) 15%
3-HH-V1 (3-1) 6%
1-HH-2V1 (3-1) 6%
3-HH-2V1 (3-1) 4%
V2-BB-1 (3-3) 5%
1V2-BB-1 (3-3) 5%
3-HHB-1 (3-5) 3%
3-HB （F） BH-3 （3-12） 4%
Compound (1-1-2) was added to this composition at a ratio of 0.10% by mass.
NI = 88.2 ℃; Tc <-20 ℃; Δn = 0.115; Δε = -2.1; η = 18.3mPa · s; VHR-2 = 92.2%.

[Example 8]
V2-H2B (2F, 3F) -O2 (2-2) 8%
V2-H1OB (2F, 3F) -O4 (2-3) 4%
3-BB （2F, 3F） -O2 （2-6） 7%
2-HHB （2F, 3F） -O2 （2-8） 7%
3-HHB （2F, 3F） -O2 （2-8） 7%
3-HH2B (2F, 3F) -O2 (2-9) 7%
5-HH2B (2F, 3F) -O2 (2-9) 4%
V-HH2B (2F, 3F) -O2 (2-9) 6%
V2-HBB (2F, 3F) -O2 (2-14) 5%
V-HBB (2F, 3F) -O2 (2-14) 5%
V-HBB (2F, 3F) -O4 (2-14) 6%
2-HH-3 (3-1) 12%
1-BB-5 (3-3) 12%
3-HHB-1 (3-5) 4%
3-HHB-O1 (3-5) 3%
3-HBB-2 (3-6) 3%
Compound (1-2-1) was added to the composition at a ratio of 0.080% by mass.
NI = 89.9 ℃; Tc <-20 ℃; Δn = 0.122; Δε = -4.2; η = 23.4mPa · s; VHR-2 = 87.0%.

[Example 9]
3-HB （2F, 3F） -O2 （2-1） 3%
V-HB （2F, 3F） -O2 （2-1） 3%
V2-HB （2F, 3F） -O2 （2-1） 5%
5-H2B (2F, 3F) -O2 (2-2) 5%
V2-BB （2F, 3F） -O2 （2-6） 3%
1V2-BB （2F, 3F） -O2 （2-6） 3%
3-HHB （2F, 3F） -O2 （2-8） 6%
V-HHB (2F, 3F) -O2 (2-8) 6%
V-HHB (2F, 3F) -O4 (2-8) 5%
V2-HHB (2F, 3F) -O2 (2-8) 4%
V-HHB （2F, 3Cl） -O2 （2-11） 3%
V2-HBB (2F, 3F) -O2 (2-14) 5%
V-HBB (2F, 3F) -O2 (2-14) 4%
V-HBB (2F, 3F) -O4 (2-14) 5%
V2-BB (2F, 3F) B-1 (2-19) 4%
3-HH-V (3-1) 27%
3-HH-V1 (3-1) 6%
V-HHB-1 (3-5) 3%
Compound (1-1-2) was added to this composition at a ratio of 0.060% by mass.
NI = 77.1 ℃; Tc <-20 ℃; Δn = 0.101; Δε = -3.0; η = 13.9mPa · s; VHR-2 = 85.3%.

[Example 10]
3-HB （2F, 3F） -O4 （2-1） 6%
3-H2B (2F, 3F) -O2 (2-2) 8%
3-H1OB (2F, 3F) -O2 (2-3) 4%
3-BB （2F, 3F） -O2 （2-6） 7%
2-HHB （2F, 3F） -O2 （2-8） 6%
3-HHB （2F, 3F） -O2 （2-8） 10%
5-HHB （2F, 3F） -O2 （2-8） 8%
2-HBB （2F, 3F） -O2 （2-14） 5%
3-HBB （2F, 3F） -O2 （2-14） 7%
5-HBB (2F, 3F) -O2 (2-14) 5%
2-HH-3 (3-1) 12%
1-BB-3 (3-3) 6%
3-HHB-1 (3-5) 3%
3-HHB-O1 (3-5) 4%
3-HBB-2 (3-6) 6%
3-B (F) BB-2 (3-7) 3%
Compound (1-1-2) was added to this composition at a ratio of 0.080% by mass.
NI = 93.0 ℃; Tc <-20 ℃; Δn = 0.124; Δε = -4.5; η = 25.0mPa · s; VHR-2 = 88.4%.

[Example 11]
V-HB （2F, 3F） -O2 （2-1） 7%
V2-BB （2F, 3F） -O2 （2-6） 10%
V-HHB (2F, 3F) -O1 (2-8) 7%
V-HHB (2F, 3F) -O2 (2-8) 9%
V2-HHB (2F, 3F) -O2 (2-8) 8%
3-HH2B (2F, 3F) -O2 (2-9) 9%
V-HBB (2F, 3F) -O2 (2-14) 8%
V-HBB (2F, 3F) -O4 (2-14) 6%
3-HH-V (3-1) 15%
3-HH-V1 (3-1) 6%
2-HH-3 (3-1) 9%
3-HH-5 (3-1) 3%
1V2-HH-3 (3-1) 3%
Compound (1-4-1) was added to this composition at a ratio of 0.060% by mass.
NI = 87.5 ℃; Tc <-20 ℃; Δn = 0.100; Δε = -3.4; η = 18.9mPa · s; VHR-2 = 86.5%.

[Example 12]
3-HB （2F, 3F） -O2 （2-1） 7%
5-HB （2F, 3F） -O2 （2-1） 7%
3-BB （2F, 3F） -O2 （2-6） 8%
3-HHB （2F, 3F） -O2 （2-8） 4%
5-HHB (2F, 3F) -O2 (2-8) 5%
3-HH1OB (2F, 3F) -O2 (2-10) 5%
2-HBB （2F, 3F） -O2 （2-14） 3%
3-HBB （2F, 3F） -O2 （2-14） 8%
4-HBB (2F, 3F) -O2 (2-14) 5%
5-HBB （2F, 3F） -O2 （2-14） 8%
2-BB (2F, 3F) B-3 (2-19) 4%
3-HH-V (3-1) 33%
V-HHB-1 (3-5) 3%
Compound (1-1-2) was added to this composition at a ratio of 0.10% by mass.
NI = 76.4 ℃; Tc <-20 ℃; Δn = 0.104; Δε = -3.2; η = 15.6mPa · s; VHR-2 = 91.2%.

[Example 13]
2-H1OB (2F, 3F) -O2 (2-3) 6%
3-H1OB (2F, 3F) -O2 (2-3) 4%
3-BB （2F, 3F） -O2 （2-6） 3%
2-HH1OB (2F, 3F) -O2 (2-10) 14%
2-HBB （2F, 3F） -O2 （2-14） 7%
3-HBB （2F, 3F） -O2 （2-14） 11%
5-HBB （2F, 3F） -O2 （2-14） 9%
2-HH-3 (3-1) 5%
3-HH-VFF (3-1) 30%
1-BB-3 (3-3) 5%
3-HHB-1 (3-5) 3%
3-HBB-2 (3-6) 3%
Compound (1-5-1) was added to this composition at a ratio of 0.070% by mass.
NI = 78.3 ℃; Tc <-20 ℃; Δn = 0.103; Δε = -3.2; η = 17.7mPa · s; VHR-2 = 89.0%.

[Example 14]
V-HB （2F, 3F） -O2 （2-1） 10%
V2-HB （2F, 3F） -O2 （2-1） 10%
2-H1OB (2F, 3F) -O2 (2-3) 3%
3-H1OB (2F, 3F) -O2 (2-3) 3%
2O-BB （2F, 3F） -O2 （2-6） 3%
V2-BB （2F, 3F） -O2 （2-6） 8%
V2-HHB (2F, 3F) -O2 (2-8) 5%
V-HHB (2F, 3Cl) -O2 (2-11) 7%
2-HBB （2F, 3F） -O2 （2-14） 3%
3-HBB （2F, 3F） -O2 （2-14） 3%
V-HBB (2F, 3F) -O2 (2-14) 6%
V-HBB (2F, 3F) -O4 (2-14) 8%
3-HH-4 (3-1) 14%
V-HHB-1 (3-5) 10%
3-HBB-2 (3-6) 7%
Compound (1-1-2) was added to this composition at a ratio of 0.070% by mass.
NI = 75.9 ℃; Tc <-20 ℃; Δn = 0.114; Δε = -3.9; η = 24.7mPa · s; VHR-2 = 86.6%.

[Example 15]
3-HB （2F, 3F） -O2 （2-1） 3%
2O-B (2F) B (2F, 3F) -O2 (2-7) 5%
2O-B (2F) B (2F, 3F) -O4 (2-7) 12%
2-HHB （2F, 3F） -O2 （2-8） 4%
3-HHB （2F, 3F） -O2 （2-8） 8%
5-HBB (2F, 3F) -O2 (2-14) 4%
3-dhBB （2F, 3F） -O2 （2-16） 8%
3-HB (2F, 3F) B-2 (2-17) 4%
3-HH-V (3-1) 33%
3-HH-V1 (3-1) 5%
3-HB-O2 (3-2) 3%
1-BB-3 (3-3) 3%
3-HHB-1 (3-5) 6%
2-BB (F) B-3 (3-8) 2%
Compound (1-1-2) was added to this composition at a ratio of 0.090% by mass.
NI = 72.6 ℃; Tc <-20 ℃; Δn = 0.105; Δε = -2.5; η = 15.7mPa · s; VHR-2 = 88.9%.

[Example 16]
3-HB （2F, 3F） -O4 （2-1） 6%
3-H2B (2F, 3F) -O2 (2-2) 8%
3-H1OB (2F, 3F) -O2 (2-3) 4%
3-BB （2F, 3F） -O2 （2-6） 7%
2-HHB （2F, 3F） -O2 （2-8） 7%
3-HHB （2F, 3F） -O2 （2-8） 7%
3-HH2B (2F, 3F) -O2 (2-9) 7%
5-HH2B (2F, 3F) -O2 (2-9) 4%
2-HBB （2F, 3F） -O2 （2-14） 5%
3-HBB （2F, 3F） -O2 （2-14） 5%
4-HBB (2F, 3F) -O2 (2-14) 6%
2-HH-3 (3-1) 12%
1-BB-5 (3-3) 12%
3-HHB-1 (3-5) 4%
3-HHB-O1 (3-5) 3%
3-HBB-2 (3-6) 3%
Compound (1-3-1) was added to this composition at a ratio of 0.10% by mass.
NI = 82.8 ℃; Tc <-20 ℃; Δn = 0.118; Δε = -4.4; η = 22.5mPa · s; VHR-2 = 90.9%.

[Example 17]
3-HB （2F, 3F） -O2 （2-1） 7%
5-HB （2F, 3F） -O2 （2-1） 7%
3-BB （2F, 3F） -O2 （2-6） 8%
3-HHB （2F, 3F） -O2 （2-8） 5%
5-HHB （2F, 3F） -O2 （2-8） 4%
3-HH1OB (2F, 3F) -O2 (2-10) 4%
2-HBB （2F, 3F） -O2 （2-14） 3%
3-HBB （2F, 3F） -O2 （2-14） 8%
4-HBB (2F, 3F) -O2 (2-14) 5%
5-HBB （2F, 3F） -O2 （2-14） 8%
2-BB (2F, 3F) B-3 (2-19) 5%
3-HH-V (3-1) 27%
3-HH-V1 (3-1) 6%
V-HHB-1 (3-5) 3%
Compound (1-8-1) was added to the composition at a ratio of 0.080% by mass.
NI = 78.1 ℃; Tc <-20 ℃; Δn = 0.107; Δε = -3.2; η = 15.9mPa · s; VHR-2 = 92.0%.

[Example 18]
3-HB （2F, 3F） -O2 （2-1） 10%
5-HB （2F, 3F） -O2 （2-1） 10%
3-H2B (2F, 3F) -O2 (2-2) 8%
5-H2B (2F, 3F) -O2 (2-2) 8%
3-HDhB （2F, 3F） -O2 （2-13） 5%
2-HBB （2F, 3F） -O2 （2-14） 6%
3-HBB （2F, 3F） -O2 （2-14） 8%
4-HBB (2F, 3F) -O2 (2-14) 7%
5-HBB (2F, 3F) -O2 (2-14) 7%
3-HH-4 (3-1) 14%
V-HHB-1 (3-5) 10%
3-HBB-2 (3-6) 7%
Compound (1-1-3) was added to this composition at a ratio of 0.080% by mass.
NI = 88.5 ℃; Tc <-20 ℃; Δn = 0.108; Δε = -3.8; η = 24.6mPa · s; VHR-2 = 89.1%.

[Example 19]
2O-B (2F) B (2F, 3F) -O2 (2-7) 6%
2O-B (2F) B (2F, 3F) -O4 (2-7) 13%
2-HHB （2F, 3F） -O2 （2-8） 4%
3-HHB （2F, 3F） -O2 （2-8） 4%
3-HHB （2F, 3F） -1 （2-8） 4%
3-dhBB （2F, 3F） -O2 （2-16） 5%
3-HB (2F) B (2F, 3F) -O2 (2-18) 7%
V-H2BBB (2F, 3F) -O2 (2-25) 5%
3-HH-V (3-1) 42%
3-HH-V1 (3-1) 5%
1-BB-3 (3-3) 3%
V-HHB-1 (3-5) 2%
Compound (1-1-2) was added to this composition at a ratio of 0.070% by mass.
NI = 71.8 ℃; Tc <-20 ℃; Δn = 0.103; Δε = -2.5; η = 14.2mPa · s; VHR-2 = 86.4%.

[Example 20]
3-HB （2F, 3F） -O4 （2-1） 15%
3-chB （2F, 3F） -O2 （2-5） 7%
2-HchB （2F, 3F） -O2 （2-12） 8%
3-HBB （2F, 3F） -O2 （2-14） 8%
4-HBB (2F, 3F) -O2 (2-14) 5%
5-HBB (2F, 3F) -O2 (2-14) 7%
3-dhBB （2F, 3F） -O2 （2-16） 5%
5-HH-V (3-1) 18%
7-HB-1 (3-2) 5%
V-HHB-1 (3-5) 7%
V2-HHB-1 (3-5) 7%
3-HBB (F) B-3 (3-13) 8%
Compound (1-1-2) was added to this composition at a ratio of 0.060% by mass.
NI = 98.8 ℃; Tc <-20 ℃; Δn = 0.111; Δε = -3.2; η = 23.9mPa · s; VHR-2 = 87.7%.

[Example 21]
3-H2B (2F, 3F) -O2 (2-2) 18%
5-H2B (2F, 3F) -O2 (2-2) 17%
3-HHB （2F, 3Cl） -O2 （2-11） 5%
3-HDhB （2F, 3F） -O2 （2-13） 5%
3-HBB （2F, 3Cl） -O2 （2-15） 8%
5-HBB (2F, 3Cl) -O2 (2-15) 7%
3-HH-V (3-1) 11%
3-HH-VFF (3-1) 7%
3-HHEH-3 (3-4) 4%
3-HB （F） HH-2 （3-10） 4%
3-HHEBH-3 (3-11) 4%
F3-HH-V (-) 10%
Compound (1-1-2) was added to this composition at a ratio of 0.15% by mass.
NI = 77.5 ℃; Tc <-20 ℃; Δn = 0.084; Δε = -2.6; η = 22.8mPa · s; VHR-2 = 91.2%.

[Example 22]
3-HB （2F, 3F） -O2 （2-1） 8%
3-H2B (2F, 3F) -O2 (2-2) 10%
3-BB （2F, 3F） -O2 （2-6） 10%
2O-BB （2F, 3F） -O2 （2-6） 3%
2-HHB （2F, 3F） -O2 （2-8） 4%
3-HHB （2F, 3F） -O2 （2-8） 7%
2-HHB （2F, 3F） -1 （2-8） 5%
3-HDhB (2F, 3F) -O2 (2-13) 6%
2-HBB （2F, 3F） -O2 （2-14） 4%
3-HBB （2F, 3F） -O2 （2-14） 7%
3-dhBB （2F, 3F） -O2 （2-16） 4%
2-BB (2F, 3F) B-3 (2-19) 6%
2-BB (2F, 3F) B-4 (2-19) 6%
3-HH1OCro (7F, 8F) -5 (2-27) 4%
3-HH-V (3-1) 11%
1-BB-5 (3-3) 5%
Compound (1-1-2) was added to this composition at a ratio of 0.10% by mass.
NI = 70.6 ℃; Tc <-20 ℃; Δn = 0.129; Δε = -4.3; η = 27.0mPa · s; VHR-2 = 89.3%.

[Example 23]
3-HB （2F, 3F） -O2 （2-1） 5%
V2-BB （2F, 3F） -O2 （2-6） 8%
3-HHB （2F, 3F） -O2 （2-8） 6%
V-HHB (2F, 3F) -O2 (2-8) 7%
V-HHB (2F, 3F) -O4 (2-8) 4%
2-HBB （2F, 3F） -O2 （2-14） 2%
3-HBB （2F, 3F） -O2 （2-14） 6%
V-HBB (2F, 3F) -O2 (2-14) 7%
V-HBB (2F, 3F) -O4 (2-14) 6%
2-BB (2F, 3F) B-3 (2-19) 5%
V-HH-V (3-1) 24%
V-HH-V1 (3-1) 20%
Compound (1-1-2) was added to this composition at a ratio of 0.10% by mass.
NI = 73.5 ℃; Tc <-20 ℃; Δn = 0.106; Δε = -2.7; η = 17.0mPa · s; VHR-2 = 90.5%.

[Example 24]
3-DhB (2F, 3F) -O2 (2-4) 5%
2-BB （2F, 3F） -O2 （2-6） 9%
3-BB （2F, 3F） -O2 （2-6） 9%
3-HH2B (2F, 3F) -O2 (2-9) 6%
3-HDhB （2F, 3F） -O2 （2-13） 14%
2-HBB （2F, 3F） -O2 （2-14） 2%
3-HBB （2F, 3F） -O2 （2-14） 6%
V-HBB (2F, 3F) -O2 (2-14) 7%
2-HH-3 (3-1) 19%
3-HHB-1 (3-5) 3%
V-HHB-1 (3-5) 10%
V2-HHB-1 (3-5) 10%
Compound (1-1-2) was added to this composition at a ratio of 0.060% by mass.
NI = 86.0 ℃; Tc <-20 ℃; Δn = 0.110; Δε = -3.8; η = 22.9mPa · s; VHR-2 = 88.1%.

[Example 25]
3-HB （2F, 3F） -O2 （2-1） 11.5%
2-BB （2F, 3F） -O2 （2-6） 3%
V2-BB （2F, 3F） -O2 （2-6） 3%
3-BB （2F, 3F） -O2 （2-6） 9%
2-HHB （2F, 3F） -O2 （2-8） 4%
3-HHB （2F, 3F） -O2 （2-8） 8%
5-HHB (2F, 3F) -O2 (2-8) 6%
V-HHB (2F, 3F) -O1 (2-8) 4%
V-HHB (2F, 3F) -O2 (2-8) 9.5%
3-HH2B (2F, 3F) -O2 (2-9) 6%
3-HH-V (3-1) 27%
3-HH-VFF (3-1) 4%
V-HBB-2 (3-6) 5%
Compound (1-1-2) was added to this composition at a ratio of 0.10% by mass.
NI = 74.8 ℃; Tc <-20 ℃; Δn = 0.096; Δε = -3.5; γ1 = 92mPa · s; VHR-3 = 83.3%

[Example 26]
3-HB （2F, 3F） -O2 （2-1） 18%
5-HB （2F, 3F） -O2 （2-1） 16.5%
3-HHB （2F, 3F） -O2 （2-8） 10%
5-HHB (2F, 3F) -O2 (2-8) 4.5%
3-HBB （2F, 3F） -O2 （2-14） 12%
4-HBB （2F, 3F） -O2 （2-14） 12%
3-HHB-1 (3-5) 2%
3-HBB-2 (3-6) 6%
5-B (F) BB-2 (3-7) 10%
5-B (F) BB-3 (3-7) 9%
Compound (1-1-2) was added to this composition at a ratio of 0.50% by mass.
NI = 99.3 ℃; Tc <-20 ℃; Δn = 0.149; Δε = -4.3; γ1 = 247mPa · s; VHR-2 = 95.0%.

[Example 27]
3-HB （2F, 3F） -O2 （2-1） 18%
5-HB （2F, 3F） -O2 （2-1） 16.5%
3-HHB （2F, 3F） -O2 （2-8） 10%
5-HHB (2F, 3F) -O2 (2-8) 4.5%
3-HBB （2F, 3F） -O2 （2-14） 12%
4-HBB （2F, 3F） -O2 （2-14） 12%
3-HHB-1 (3-5) 2%
3-HBB-2 (3-6) 6%
5-B (F) BB-2 (3-7) 10%
5-B (F) BB-3 (3-7) 9%
Compound (1-1-2) was added to this composition at a ratio of 1.00% by mass.
NI = 97.0 ℃; Tc <-20 ℃; Δn = 0.147; Δε = -4.2; γ1 = 241mPa · s; VHR-2 = 96.0%.

[Example 28]
3-HB （2F, 3F） -O2 （2-1） 18%
5-HB （2F, 3F） -O2 （2-1） 16.5%
3-HHB （2F, 3F） -O2 （2-8） 10%
5-HHB (2F, 3F) -O2 (2-8) 4.5%
3-HBB （2F, 3F） -O2 （2-14） 12%
4-HBB （2F, 3F） -O2 （2-14） 12%
3-HHB-1 (3-5) 2%
3-HBB-2 (3-6) 6%
5-B (F) BB-2 (3-7) 10%
5-B (F) BB-3 (3-7) 9%
Compound (1-1-2) was added to this composition at a ratio of 2.00% by mass.
NI = 92.3 ℃; Tc <-20 ℃; Δn = 0.144; Δε = -4.1; γ1 = 229mPa · s; VHR-2 = 96.2%.

[Example 29]
3-HB （2F, 3F） -O2 （2-1） 10%
5-HB （2F, 3F） -O2 （2-1） 11%
2-HHB （2F, 3F） -O2 （2-8） 3%
3-HHB （2F, 3F） -O2 （2-8） 10%
5-HHB （2F, 3F） -O2 （2-8） 10%
2-HBB （2F, 3F） -O2 （2-14） 6%
3-HBB （2F, 3F） -O2 （2-14） 7%
3-HB (2F, 3F) B-2 (2-17) 4%
2-HH-3 (3-1) 15%
3-HH-4 (3-1) 4%
1-BB-3 (3-3) 3%
3-HHB-1 (3-5) 5%
3-HBB-2 (3-6) 12%
Compound (1-8-1) was added to this composition at a ratio of 0.20% by mass.
NI = 94.2 ℃; Tc <-20 ℃; Δn = 0.109; Δε = -3.3; γ1 = 147.85mPa · s; VHR-2 = 86.6%.

[Example 30]
2-H1OB (2F, 3F) -O2 (2-3) 7%
3-H1OB (2F, 3F) -O2 (2-3) 7%
3-HHB （2F, 3F） -O2 （2-8） 4%
2-HBB （2F, 3F） -O2 （2-14） 4%
3-HBB （2F, 3F） -O2 （2-14） 8%
4-HBB (2F, 3F) -O2 (2-14) 4%
5-HBB （2F, 3F） -O2 （2-14） 9%
3-dhBB （2F, 3F） -O2 （2-16） 4%
2-HH-3 (3-1) 18%
2-HH-5 (3-1) 2%
3-HH-4 (3-1) 3%
3-HH-5 (3-1) 3%
3-HB-O2 (3-2) 17%
3-HBB-2 (3-6) 10%
Compound (1-9-1) was added to this composition at a ratio of 0.10% by mass.
NI = 78.4 ℃; Tc <-20 ℃; Δn = 0.105; Δε = -2.7; γ1 = 94mPa · s; VHR-2 = 94.9%.

[Example 31]
2-H1OB (2F, 3F) -O2 (2-3) 7%
3-H1OB (2F, 3F) -O2 (2-3) 7%
3-DhB (2F, 3F) -O2 (2-4) 5%
3-HHB （2F, 3F） -O2 （2-8） 5%
2-HBB （2F, 3F） -O2 （2-14） 4%
3-HBB （2F, 3F） -O2 （2-14） 9%
4-HBB (2F, 3F) -O2 (2-14) 4%
5-HBB （2F, 3F） -O2 （2-14） 9%
3-dhBB （2F, 3F） -O2 （2-16） 4%
2-HH-3 (3-1) 18%
3-HH-4 (3-1) 3%
3-HH-5 (3-1) 3%
3-HB-O2 (3-2) 5%
1-BB-2 (3-3) 5%
3-HHB-1 (3-5) 3%
3-HBB-2 (3-5) 9%
Compound (1-2-1) was added to this composition at a ratio of 0.10% by mass.
NI = 76.3 ℃; Tc <-20 ℃; Δn = 0.109; Δε = -3.3; η = 20.6mPa · s; γ1 = 108mPa · s; VHR-2 = 87.8%.

[Example 32]
In Example 30, a liquid crystal composition was prepared under the same conditions as in Example 30, except that the same amount of compound (1-4-1) was added instead of compound (1-9-1).

[Example 33]
In Example 30, a liquid crystal composition was prepared under the same conditions as in Example 30 except that the same amount of compound (1-8-1) was added instead of compound (1-9-1).

The voltage holding ratio (VHR-2) of the composition of Comparative Example 1 was 82.1%. On the other hand, the voltage holding ratio (VHR-2) of the composition of Example 1 was 90.3%. As such, the composition of the example has a larger voltage holding ratio (VHR-2) than the composition of the comparative example. Therefore, it was concluded that the liquid crystal composition of the present invention has excellent characteristics.
[Industrial availability]

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

no

no

Claims (21)

A liquid crystal composition comprising, as a first additive, at least one compound selected from the compound represented by the formula (1), and as a first component, at least one compound selected from the compound represented by the formula (2). A ratio of an additive is 0.06 mass% or more, and the liquid crystal composition has negative dielectric anisotropy, In formulas (1) and (2), R ¹ is an alkyl group having 1 to 24 carbon atoms or an alkenyl group having 2 to 24 carbon atoms. In this alkyl group, at least one hydrogen may be substituted with fluorine or chlorine. Among these groups, at least one -CH ₂ -may be substituted by -O-, -COO-, or -OCO-; R ² and R ³ are alkyl groups having 1 to 12 carbons, and alkyl groups having 1 to 12 carbons Oxygen, alkenyl having 2 to 12 carbons, alkenyl having 2 to 12 carbons or hydrogen; ring A is 1,4-cyclohexyl, 1,4-cyclohexenyl, tetrahydropyran- 2,5-diyl, 1,3-di 㗁 koushan-2,5-diyl, 1,3-dithiane-2,5-diyl or 1,4-phenylene; ring B and ring D is 1,4-cyclohexyl, 1,4-cyclohexenyl, tetrahydropyran-2,5-diyl, 1,4-phenylene, and at least one hydrogen is replaced by fluorine or chlorine 1,4-phenylene, naphthalene-2,6-diyl, at least one hydrogen substituted with fluorine or chlorine, naphthalene-2,6-diyl, orthofluorene-2,6-diyl, or at least one Ortho-2,6-diyl in which hydrogen is replaced by fluorine or chlorine; ring C is 2,3-difluoro-1,4-phenyl, 2-chloro-3-fluoro-1,4-phenyl Phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, 7,8-difluoroacetone-2 , 6-diyl, 3,4,5,6-tetrafluorofluorene-2,7-diyl, 4,6-difluorodibenzofuran-3,7- Yl, 4,6-difluoro-dibenzothiophene-1,1,6,7- tetrafluoro-3,7-diyl or indan-2,5-diyl; Z ¹ is a single bond, an ethyl group, Vinyl, carbonyloxy, methoxy or difluoro methoxy; Z ² and Z ³ are single bonds, ethyl, vinyl, carbonyloxy or methoxy; X ¹ and X ² is an alkyl group having 1 to 12 carbons; a is 0, 1 or 2; b is 0, 1, 2 or 3; c is 0 or 1; and the sum of b and c is 3 or less. The liquid crystal composition according to item 1 of the scope of patent application, which contains, as a first component, at least one compound selected from compounds represented by formula (2 '), In the formula (2 '), R ² ′ and R ³ ′ are an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, and an alkyl group having 2 to 12 carbon atoms. Alkenyloxy or hydrogen; ring B 'and ring D' are 1,4-cyclohexyl, 1,4-cyclohexenyl, tetrahydropyran-2,5-diyl, 1,4-benzene 1,4-phenylene, naphthalene-2,6-diyl substituted with at least 1 hydrogen with fluorine or chlorine, naphthalene-2,6-diyl substituted with at least 1 hydrogen with fluorine or chlorine, or Fluorene-2,6-diyl or at least one hydrogen substituted by fluorine or chlorine fluorene-2,6-diyl, and when b 'is 1 or more, at least one ring B' is tetrahydropyran- 2,5-diyl, and when c 'is 1 or more, at least one ring D' is tetrahydropyran-2,5-diyl; ring C '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, 7,8-difluorofluorene-2,6-diyl, 3,4,5,6-tetrafluorofluorene-2,7-diyl, 4,6-difluorodi Benzofuran-3,7-diyl, 4,6-difluorodibenzothiophene-3,7-diyl or 1,1,6,7-tetrafluoroindane-2,5-diyl; b 'Is 0, 1, or 2; c' is 0 or 1; and the sum of b 'and c' is 1 or 2. The liquid crystal composition according to item 2 of the scope of patent application, which contains, as a first additive, a compound represented by formula (1), in which a is 1 or 2, or formula (1) A) in 0), and R ¹ is an alkyl group having 1 to 24 carbon atoms not bonded via difluoromethoxy group or 2 to 24 carbon atoms not bonded via difluoromethoxy group Alkenyl, and X ¹ and X ² in formula (1) are n-propyl or alkyl having 4 to 12 carbons. The liquid crystal composition according to item 2 of the patent application scope, which contains as a second component at least one compound selected from the compound represented by formula (3-1), In formula (3-1), R ⁴ and R ⁵ are an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or at least one hydrogen atom through fluorine or A chlorine-substituted alkenyl group having 2 to 12 carbon atoms. The liquid crystal composition according to any one of claims 1 to 4 of the scope of patent application, which as a first additive contains at least one selected from the compounds represented by formula (1-1) to formula (1-9) 1 compound, In the formulae (1-1) to (1-9), R ¹ is an alkyl group having 1 to 24 carbon atoms or an alkenyl group having 2 to 24 carbon atoms. In the alkyl group, at least one hydrogen may be subjected to fluorine Or chlorine substitution. Among these groups, at least one -CH ₂ -may be substituted with -O-, -COO-, or -OCO-; X ¹ and X ² are alkyl groups having 1 to 12 carbons. The liquid crystal composition according to any one of claims 1 to 4 of the scope of patent application, which contains as a first component at least 1 selected from the compounds represented by formula (2-1) to formula (2-35) Compounds, In the formulae (2-1) to (2-35), R ² and R ³ are an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, Alkenyloxy or hydrogen having 2 to 12 carbons. The liquid crystal composition according to any one of claims 1 to 4 in the scope of patent application, wherein The proportion of the first additive is in a range of 0.06 mass% to 5 mass%, and the proportion of the first component is in a range of 10 mass% to 90 mass%. The liquid crystal composition according to any one of claims 1 to 4 of the patent application scope, which contains as a second component at least one compound selected from the compound represented by formula (3), In formula (3), R ⁴ and R ⁵ are an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms or at least one hydrogen is substituted with fluorine or chlorine Alkenyl having 2 to 12 carbons; ring E and ring F are 1,4-cyclohexyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro -1,4-phenylene; Z ⁴ is a single bond, ethyl, vinyl, methoxy or carbonyloxy; d is 1, 2 or 3. The liquid crystal composition according to any one of claims 1 to 4 of the scope of patent application, which contains, as a second component, at least 1 selected from the compounds represented by formula (3-1) to formula (3-13) Compounds, In the formulae (3-1) to (3-13), R ⁴ and R ⁵ are an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or An alkenyl group having 2 to 12 carbons with at least one hydrogen substituted with fluorine or chlorine. The liquid crystal composition according to item 8 of the scope of patent application, wherein The proportion of the second component is in a range of 10% by mass to 90% by mass. The liquid crystal composition according to any one of claims 1 to 4 of the scope of patent application, which contains, as a second additive, at least one compound selected from the polymerizable compounds represented by formula (4), In formula (4), ring G and ring K are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, and 1,3-dioxolan Benz-2-yl, pyrimidin-2-yl or pyridin-2-yl, in these rings, at least one hydrogen may be passed through fluorine, chlorine, alkyl having 1 to 12 carbons, alkyl having 1 to 12 carbons Oxygen or at least 1 hydrogen substituted with fluorine or chlorine and 1 to 12 carbons; ring J is 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-benzene Naphthalene, 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-di 㗁 koushan-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in which at least 1 hydrogen can pass through Fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least 1 hydrogen substituted with fluorine or chlorine and alkyl having 1 to 12 carbons; Z ⁵ and Z ⁶ are mono Bond or alkylene having 1 to 10 carbons, in which at least 1 -CH ₂ -may be substituted with -O-, -CO-, -COO- or -OCO-, at least 1 -CH ₂ -CH ₂ -Can pass -CH = CH- , -C (CH ₃ ) = CH-, -CH = C (CH ₃ )-or -C (CH ₃ ) = C (CH ₃ )-substitution, in these groups, at least 1 hydrogen may be replaced by fluorine or Chloro-substituted; P ¹ , P ^2, and P ³ are polymerizable groups; Sp ¹ , Sp ^2, and Sp ³ are single bonds or alkylene groups having 1 to 10 carbon atoms. In this alkylene group, at least one -CH ₂ -may be substituted with -O-, -COO-, -OCO-, or -OCOO-, at least one -CH ₂ -CH ₂ -may be substituted with -CH = CH- or -C≡C- In the formula, at least one hydrogen may be substituted by fluorine or chlorine; e is 0, 1 or 2; f, g, and h are 0, 1, 2, 3, or 4; and the sum of f, g, and h is 1 or more. The liquid crystal composition according to item 11 of the scope of patent application, wherein in formula (4), P ¹ , P ^2, and P ³ are selected from the polymerizable properties represented by formula (P-1) to formula (P-5) Base in base, In the formulae (P-1) to (P-5), M ¹ , M ² and M ³ are hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms or a carbon number in which at least one hydrogen is replaced by fluorine or chlorine. 1 to 5 alkyl. The liquid crystal composition according to any one of claims 1 to 4 of the patent application scope, which contains as a second additive a polymerizable compound represented by the formula (4-1) to the formula (4-29). At least 1 compound, In the formulae (4-1) to (4-29), P ⁴ , P ^5, and P ⁶ are groups selected from the polymerizable groups represented by the formulae (P-1) to (P-3); Sp ¹ , Sp ² and Sp ³ are single bonds or alkylene groups having 1 to 10 carbon atoms. In this alkylene group, at least one -CH ₂ -can pass through -O-, -COO-, -OCO-, or- OCOO- substituted, at least 1 -CH ₂ -CH ₂ -may be substituted with -CH = CH- or -C≡C-, in which at least 1 hydrogen may be substituted with fluorine or chlorine; In the formulae (P-1) to (P-3), M ¹ , M ^2, and M ³ are hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or a carbon number in which at least one hydrogen is replaced by fluorine or chlorine. 1 to 5 alkyl. The liquid crystal composition according to item 11 of the patent application scope, wherein The ratio of the second additive is in a range of 0.03% by mass to 10% by mass. A liquid crystal display element comprising the liquid crystal composition according to any one of the first to the fourteenth in the scope of patent application. The liquid crystal display element according to item 15 of the scope of patent application, wherein The operation mode of the liquid crystal display element is IPS mode, VA mode, FFS mode, or FPA mode, and the driving method of the liquid crystal display element is an active matrix method. A polymer-stabilized alignment type liquid crystal display device includes the liquid crystal composition described in any one of claims 11 to 14 in the scope of patent application, and the polymerizable compound in the liquid crystal composition is polymerized. A use of a liquid crystal composition as described in any one of claims 1 to 14 in a patent application in a liquid crystal display element. A use of the liquid crystal composition as described in any one of claims 11 to 14 in a patent application scope for a polymer-stabilized alignment type liquid crystal display element. A use of a liquid crystal composition as described in any one of claims 1 to 14 in a patent application in a liquid crystal projector. A method for stabilizing a liquid crystal composition to light, which is achieved by including, as a first component, a liquid crystal composition having at least one compound selected from the compound represented by formula (2) and having a negative dielectric anisotropy. And at least one compound selected from the compounds represented by formula (1) is added as a first additive, In formulas (1) and (2), R ¹ is an alkyl group having 1 to 24 carbon atoms or an alkenyl group having 2 to 24 carbon atoms. In this alkyl group, at least one hydrogen may be substituted with fluorine or chlorine. Among these groups, at least one -CH ₂ -may be substituted by -O-, -COO-, or -OCO-; R ² and R ³ are alkyl groups having 1 to 12 carbons, and alkyl groups having 1 to 12 carbons Oxygen, alkenyl having 2 to 12 carbons, alkenyl having 2 to 12 carbons or hydrogen; ring A is 1,4-cyclohexyl, 1,4-cyclohexenyl, tetrahydropyran- 2,5-diyl, 1,3-di 㗁 koushan-2,5-diyl, 1,3-dithiane-2,5-diyl or 1,4-phenylene; ring B and ring D is 1,4-cyclohexyl, 1,4-cyclohexenyl, tetrahydropyran-2,5-diyl, 1,4-phenylene, and at least one hydrogen is replaced by fluorine or chlorine 1,4-phenylene, naphthalene-2,6-diyl, at least one hydrogen substituted with fluorine or chlorine, naphthalene-2,6-diyl, orthofluorene-2,6-diyl, or at least one Ortho-2,6-diyl in which hydrogen is replaced by fluorine or chlorine; ring C is 2,3-difluoro-1,4-phenyl, 2-chloro-3-fluoro-1,4-phenyl Phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, 7,8-difluoroacetone-2 , 6-diyl, 3,4,5,6-tetrafluorofluorene-2,7-diyl, 4,6-difluorodibenzofuran-3,7- Yl, 4,6-difluoro-dibenzothiophene-1,1,6,7- tetrafluoro-3,7-diyl or indan-2,5-diyl; Z ¹ is a single bond, an ethyl group, Vinyl, carbonyloxy, methoxy or difluoro methoxy; Z ² and Z ³ are single bonds, ethyl, vinyl, carbonyloxy or methoxy; X ¹ and X ² is an alkyl group having 1 to 12 carbons; a is 0, 1 or 2; b is 0, 1, 2 or 3; c is 0 or 1; and the sum of b and c is 3 or less.