WO2013080850A1 - Liquid crystal composition and liquid crystal display element - Google Patents

Abstract

Provided is a highly reactive polymerizable compound having high solubility in a liquid crystal composition. Provided is a liquid crystal composition satisfying at least one property among a high maximum temperature of the nematic phase, low minimum temperature of the nematic phase, low viscosity, appropriate optical anisotropy, high negative dielectric anisotropy, high specific resistance, high ultraviolet stability, high heat stability, and other such properties; and having an appropriate balance as relates to two or more properties. Provided is a PSA element having a short response time, large pretilt angle, low residual monomer concentration, high voltage maintenance rate, high contrast ratio, long life, and the like. A polymerizable compound having one linking group or reactive groups that are not the same introduced to obtain stable display by the construction of a polymeric structure having a high degree of polymerization in a step for manufacturing a PSA element, a liquid crystal composition containing the same, and a liquid crystal display element containing this composition.　

Description

Liquid crystal composition and liquid crystal display element

The present invention relates to a liquid crystal composition containing a polymerizable compound that is polymerized by, for example, light or heat. Further, the present invention relates to a liquid crystal display element in which the liquid crystal composition is sealed between substrates and a polymerizable compound contained in the liquid crystal composition is polymerized while adjusting a voltage applied to the liquid crystal layer to fix the alignment of the liquid crystal.
The technical field of the present invention mainly relates to a liquid crystal composition suitable for an AM (active matrix) device and the like, and an AM device containing the composition. In particular, regarding a liquid crystal composition having a negative dielectric anisotropy, an IPS (in-plane switching) mode, an FFS (fringe field switching) mode, a VA (vertical alignment) mode, or a PSA (polymer sustained alignment) containing the composition. ) Mode elements. The VA mode includes an MVA (multi-domain vertical alignment) mode, a PVA (patterned vertical alignment) mode, and the like.

In the liquid crystal display element, the classification based on the operation mode of the liquid crystal includes PC (phase change), TN (twisted nematic), STN (super twisted nematic), ECB (electrically controlled birefringence), OCB (optically compensated bend), IPS ( in-plane switching, FFS (fringe field switching), VA (vertical alignment), PSA (polymer sustained alignment) mode, and the like. The classification based on the element drive system is PM (passive matrix) and AM (active matrix). PM is classified into static and multiplex, and AM is classified into TFT (thin film insulator), MIM (metal insulator metal), and the like. TFTs are classified into amorphous silicon and polycrystalline silicon. The latter is classified into a high temperature type and a low temperature type according to the manufacturing process. The classification based on the light source includes a reflection type using natural light, a transmission type using backlight, and a semi-transmission type using both natural light and backlight.

These elements contain a liquid crystal composition having appropriate characteristics. This liquid crystal composition has a nematic phase. In order to obtain an AM device having good general characteristics, the general characteristics of the composition are improved. The relationships in the two general characteristics are summarized in Table 1 below. The general characteristics of the composition will be further described based on a commercially available AM device. The temperature range of the nematic phase is related to the temperature range in which the device can be used. A preferred upper limit temperature of the nematic phase is about 70 ° C. or more, and a preferred lower limit temperature of the nematic phase is about −10 ° C. or less. The viscosity of the composition is related to the response time of the device. A short response time is preferred for displaying moving images on the device. Therefore, a small viscosity in the composition is preferred. Small viscosities at low temperatures are more preferred.

The optical anisotropy of the composition is related to the contrast ratio of the device. The product (Δn × d) of the optical anisotropy (Δn) of the composition and the cell gap (d) of the device is designed to maximize the contrast ratio. The appropriate product value depends on the type of operation mode. The range is about 0.30 μm to about 0.40 μm for the VA mode or PSA mode device, and the range is about 0.20 μm to about 0.30 μm for the IPS mode device. In this case, a composition having a large optical anisotropy is preferable for a device having a small cell gap. The dielectric anisotropy having a large absolute value in the composition contributes to a low threshold voltage, a small power consumption and a large contrast ratio in the device. Therefore, a dielectric anisotropy having a large absolute value is preferable. A large specific resistance in the composition contributes to a large voltage holding ratio and a large contrast ratio in the device. Therefore, a composition having a large specific resistance not only at room temperature but also at a high temperature in the initial stage is preferable. A composition having a large specific resistance not only at room temperature but also at a high temperature after being used for a long time is preferable. The stability of the composition against ultraviolet rays and heat is related to the lifetime of the liquid crystal display device. When their stability is high, the lifetime of the device is long. Such characteristics are preferable for an AM device used in a liquid crystal projector, a liquid crystal television, and the like.

A composition having a positive dielectric anisotropy is used for an AM device having a TN mode. On the other hand, a composition having negative dielectric anisotropy is used for an AM device having a VA mode. In an AM device having an IPS mode and an FFS mode, a composition having a positive or negative dielectric anisotropy is used. In an AM device having a PSA mode, a composition having a positive or negative dielectric anisotropy is used. Examples of liquid crystal compositions having negative dielectric anisotropy are disclosed in the following Patent Document 1 to Patent Document 6, and the like.

JP 2003-307720 A JP 2004-131704 A JP 2006-133619 A European Patent Application Publication No. 1898894 Special table 2010-537010 Special table 2010-537256

Desirable AM elements have characteristics such as a wide usable temperature range, a short response time, a large contrast ratio, a low threshold voltage, a large voltage holding ratio, and a long lifetime. A shorter response time is desirable even at 1 millisecond. Therefore, desirable properties of the composition include a high maximum temperature of the nematic phase, a low minimum temperature of the nematic phase, a small viscosity, a suitable optical anisotropy, a large positive or negative dielectric anisotropy, a large specific resistance, and a high resistance to ultraviolet light. High stability, high heat stability, etc.
In the PSA mode display, a small amount (for example, about 0.3 wt% to about 1 wt%) of a polymerizable compound (RM) is added to the liquid crystal composition, and after being introduced into the liquid crystal display cell, a voltage is applied between the electrodes. In this state, only the polymerizable compound is polymerized under normal UV irradiation to form a polymer structure in the device. As RM, it is known that a polymerizable mesogenic or liquid crystal compound is particularly suitable as a liquid crystal composition additive monomer.

The above-described polymerizable mesogenic or liquid crystalline compounds generally have a high ability to align liquid crystal molecules. On the other hand, the solubility in the liquid crystal composition is poor, and a large amount cannot be added. By introducing a flexible linking group such as alkylene or ester between the ring structures, the solubility in the liquid crystal composition is improved, but the rigidity of the molecule is weakened and the ability to align the liquid crystal molecules is lowered. The pretilt angle, which is the tilt of the orientation, becomes small. In addition, a polymerizable compound into which two flexible linking groups are introduced is not very suitable for a PSA mode display because it has a high image sticking rate.

One object of the present invention is to provide a high maximum temperature of the nematic phase, a low minimum temperature of the nematic phase, a small viscosity, a suitable optical anisotropy, a large negative dielectric anisotropy, a large specific resistance, and a high stability to ultraviolet light. The liquid crystal composition satisfies at least one characteristic in characteristics such as high stability to heat. Another object is a liquid crystal composition having an appropriate balance regarding at least two properties. Another object is a liquid crystal display device containing such a composition. Another object is a composition having a small optical anisotropy, or a suitable optical anisotropy that is a large optical anisotropy, a negative large dielectric anisotropy, a high stability to ultraviolet light, and the like, and An AM device having a short response time, a large pretilt angle, a small image sticking rate, a small residual monomer concentration, a large voltage holding ratio, a large contrast ratio, a long lifetime, and the like by building a polymer structure in the layer.

Contains at least one compound selected from the group of compounds represented by formula (1) as the first component and at least one compound selected from the group of compounds represented by formula (2) as the second component And a liquid crystal display device containing the composition.

Wherein P ¹ and P ² are independently a group selected from the groups represented by formulas (P-1) to (P-6);

R ¹ and R ² are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons; ring A and ring B are independently 1,4 -Cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, or pyrimidine-2,5-diyl In these, at least one hydrogen may be replaced by halogen, alkyl having 1 to 12 carbons, or alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by halogen; ring C and ring E Are independently 1,4-cyclohexylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, and 3-fluoro-1,4-phenylene; ring D is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5- Methyl-1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, or 7,8-difluorochroman-2,6-diyl; Sp is alkylene having 1 to 6 carbon atoms; Yes, in alkylene, at least one —CH ₂ — may be replaced by —O—, —OCO—, —COO—, or —CH═CH—; Z ¹ , Z ² , and Z ³ are Independently a single bond, ethylene, methyleneoxy, or carbonyloxy; k is 0, 1, 2, or 3; m is 1, 2, or 3; n is 0 or 1 And m The sum of the n is 3 or less.

The present inventors paid attention to the skeleton structure of a polymerizable compound for a liquid crystal display device to which PSA technology is applied, and substituted alkylene with —CH ₂ — with —O— or —CH═CH—. By introducing a linking group in one skeleton structure, introducing a reactive group that is not the same, or introducing a substituent into the ring structure, the solubility in the liquid crystal composition and the pretilt angle are improved and efficient. It was found that the ability to orient the liquid crystal molecules by increasing the PSA effect.

The present invention is particularly effective for improving the performance of a VA liquid crystal display element to which the PSA technology is applied. A VA type device using PSA technology has two substrates provided with a transparent electrode and an alignment control film for aligning liquid crystal molecules, and a liquid crystal composition containing a polymerizable compound is disposed between these substrates, It is a liquid crystal display device manufactured through a process of polymerizing a polymerizable compound while applying a voltage between opposing transparent electrodes of these substrates.

According to the present invention, a liquid crystal material in which an alignment state at the time of applying a voltage is stored in a polymer component can be disposed between substrates, the direction in which the encapsulated liquid crystal molecules are tilted is stored, the response time is shortened, and the degree of image sticking is improved. be able to.
In particular, by using the polymerizable compound of the present invention, it has become possible to deal with a wide range of cell manufacturing processes and to manufacture a high-quality liquid crystal display element.

The advantage of the present invention is high stability against ultraviolet rays or heat for a polymer of a polymerizable mesogenic or liquid crystalline compound. Other advantages of the present invention are a high maximum temperature of the nematic phase, a low minimum temperature of the nematic phase, a small viscosity, a suitable optical anisotropy, a large negative dielectric anisotropy, a large specific resistance, and a high stability to ultraviolet rays. The liquid crystal composition satisfies at least one characteristic in characteristics such as high stability to heat. One aspect of the present invention is a liquid crystal composition having an appropriate balance regarding at least two properties. Another aspect is a liquid crystal display device containing such a composition. Another aspect is a polymerizable compound having high stability to ultraviolet light or heat, a composition having appropriate optical anisotropy, negatively large dielectric anisotropy, high stability to ultraviolet light, and the like, and short The AM device has a response time, a suitable pretilt, a small image sticking rate, a large voltage holding ratio, a large contrast ratio, a long lifetime, and the like.

用語 Terms used in this specification are as follows. The liquid crystal composition of the present invention or the liquid crystal display device of the present invention may be abbreviated as “composition” or “device”, respectively. A liquid crystal display element is a general term for a liquid crystal display panel and a liquid crystal display module. “Liquid crystal compound” means a compound having a liquid crystal phase such as a nematic phase or a smectic phase, or a compound having no liquid crystal phase but useful as a component of a composition. This useful compound has a six-membered ring such as 1,4-cyclohexylene and 1,4-phenylene, and its molecular structure is rod-like. Optically active compounds and polymerizable compounds may be added to the composition. Even if these compounds are liquid crystal compounds, they are classified as additives here. At least one compound selected from the group of compounds represented by formula (1) may be abbreviated as “compound (1)”. “Compound (1)” means one compound or two or more compounds represented by formula (1). The same applies to compounds represented by other formulas. At least one group selected from the group of groups represented by formula (P-1) may be abbreviated as “group (P-1)”. The same applies to groups represented by other formulas. “At least one” of “replaced” indicates that not only the position but also the number can be arbitrarily selected.

The upper limit temperature of the nematic phase may be abbreviated as “upper limit temperature”. The lower limit temperature of the nematic phase may be abbreviated as “lower limit temperature”. "High specific resistance" means that the composition has a large specific resistance not only at room temperature in the initial stage but also at a temperature close to the upper limit temperature of the nematic phase. It means having a large specific resistance even at a close temperature. "High voltage holding ratio" means that the device has a large voltage holding ratio not only at room temperature in the initial stage but also at a temperature close to the upper limit temperature of the nematic phase. It means having a large voltage holding ratio even at a temperature close to. When describing characteristics such as optical anisotropy, values obtained by the measurement methods described in the examples are used. The first component is one compound or two or more compounds. The “ratio of the first component” is expressed as a weight ratio (parts by weight) of the first component when the weight of the liquid crystal composition excluding the first component and the polymerizable compound other than the first component is 100. The “ratio of the second component” is expressed as a weight percentage (% by weight) of the second component based on the weight of the liquid crystal composition excluding the first component and a polymerizable compound other than the first component. The “ratio of the third component” is the same as the “ratio of the second component”. The ratio of the additive mixed with the composition is expressed by weight percentage (% by weight) or weight parts per million (ppm) based on the total weight of the liquid crystal composition. The “ratio” is represented by the weight ratio (parts by weight) of the polymerizable compound other than the first component when the weight of the liquid crystal composition excluding the first component and the polymerizable compound other than the first component is 100.

In the chemical formulas of the component compounds, the symbol R ¹ is used for a plurality of compounds. In any two of these compounds, those selected by R ¹ may be the same or different. For example, ^{R 1} of the compound (2) is ethyl, there are cases ^{wherein R 1} is ethyl of the compound (2-1). In some cases, R ^{1 of} compound (2) is ethyl and R ¹ of compound (2-1) is propyl. This rule also applies to R ² , X ¹ , Y ^{1 and the} like.

The present invention includes the following items.
1. Contains at least one compound selected from the group of compounds represented by formula (1) as the first component and at least one compound selected from the group of compounds represented by formula (2) as the second component Liquid crystal composition.

Wherein P ¹ and P ² are independently a group selected from the groups represented by formulas (P-1) to (P-6);

R ¹ and R ² are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons; ring A and ring B are independently 1,4 -Cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, or pyrimidine-2,5-diyl In these, at least one hydrogen may be replaced by halogen, alkyl having 1 to 12 carbons, or alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by halogen; ring C and ring E Are independently 1,4-cyclohexylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, and 3-fluoro-1,4-phenylene; ring D is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5- Methyl-1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, or 7,8-difluorochroman-2,6-diyl; Sp is alkylene having 1 to 6 carbon atoms; Yes, in alkylene, at least one —CH ₂ — may be replaced by —O—, —OCO—, —COO—, or —CH═CH—; Z ¹ , Z ² , and Z ³ are Independently a single bond, ethylene, methyleneoxy, or carbonyloxy; k is 0, 1, 2, or 3; m is 1, 2, or 3; n is 0 or 1 And m The sum of the n is 3 or less.

2. Item 2. The liquid crystal composition according to item 1, wherein the first component is at least one compound selected from the group of compounds represented by formula (1-1) to formula (1-8).

Here, Y ¹ to Y ¹² are independently hydrogen, halogen, alkyl having 1 to 12 carbons, or trifluoromethyl; X ¹ and X ² are independently hydrogen or methyl.

3. Item 1. The first component is at least one compound selected from the group of compounds represented by formula (1-1) to formula (1-8) according to item 2, and Y ¹ to Y ¹² are hydrogen The liquid crystal composition described in 1.

4). The first component is at least one compound selected from the group of compounds represented by formula (1-1) to formula (1-8) according to item 2, wherein formula (1-1) to formula (1- In item 1 wherein at least one of Y ¹ to Y ⁸ is fluorine or trifluoromethyl in 7) and at least one of Y ¹ to Y ¹² is fluorine or trifluoromethyl in formula (1-8) The liquid crystal composition described.

5. Item 5. The liquid crystal composition according to any one of items 1 to 4, wherein the first component is at least one compound selected from the group of compounds represented by formula (1-1) according to item 2.

6). Item 5. The liquid crystal composition according to any one of items 1 to 4, wherein the first component is at least one compound selected from the group of compounds represented by formula (1-2) according to item 2.

7). Item 7. The liquid crystal composition according to any one of items 1 to 6, wherein the first component comprises at least two compounds selected from the group of compounds represented by formula (1) according to item 1.

8). The first component is at least one compound selected from the group of compounds represented by formula (1) according to item 1, and further contains a polymerizable compound other than the formula (1) according to item 1 8. The liquid crystal composition according to any one of 7 above.

9. Item 9. The liquid crystal composition according to item 1 to 8, wherein the second component is at least one compound selected from the group of compounds represented by formulas (2-1) to (2-19).

Here, R ¹ and R ² are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons.

10. Item 2. The liquid crystal composition according to item 1, wherein the second component is at least one compound selected from the group of compounds represented by formula (2-3) according to item 9.

11. Item 2. The liquid crystal composition according to item 1, wherein the second component is at least one compound selected from the group of compounds represented by formula (2-5) according to item 9.

12 Item 2. The liquid crystal composition according to item 1, wherein the second component is at least one compound selected from the group of compounds represented by formula (2-7) according to item 9.

13. Item 12. The liquid crystal composition according to item 1, wherein the second component is at least one compound selected from the group of compounds represented by formula (2-13) according to item 9.

14 Item 14. The liquid crystal composition according to any one of items 1 to 13, further containing at least one compound selected from the group of compounds represented by formula (3) as a third component.

Here, R ³ and R ⁴ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or carbons in which at least one hydrogen is replaced by fluorine. Ring F, ring G, and ring I are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 3-fluoro. -1,4-phenylene; Z ⁴ and Z ⁵ are independently a single bond, ethylene, methyleneoxy, or carbonyloxy; p is 0, 1, or 2.

15. Item 15. The liquid crystal composition according to item 14, wherein the third component is at least one compound selected from the group of compounds represented by formulas (3-1) to (3-13).

Here, R ³ and R ⁴ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or carbon number in which at least one hydrogen is replaced by fluorine. 2 to 12 alkenyl.

16. Item 15. The liquid crystal composition according to item 14, wherein the third component is at least one compound selected from the group of compounds represented by formula (3-1) in item 15.

17. Item 15. The liquid crystal composition according to item 14, wherein the third component is at least one compound selected from the group of compounds represented by formula (3-7) of item 15.

18. Based on the weight of the liquid crystal composition excluding the first component and the polymerizable compound other than the first component, the proportion of the second component is in the range of 10 wt% to 80 wt%, and the proportion of the third component is 20 wt%. % To 90% by weight of the polymerizable compound other than the first component and the first component with respect to 100 parts by weight of the liquid crystal composition excluding the polymerizable compound other than the first component and the first component. Item 18. The liquid crystal composition according to any one of items 14 to 17, wherein the ratio is in the range of 0.03 to 10 parts by weight.

19. Item 19. The liquid crystal composition according to any one of items 1 to 18, further comprising a polymerization initiator.

20. Item 20. The liquid crystal composition according to any one of items 1 to 19, further comprising a polymerization inhibitor.

21. The upper limit temperature of the nematic phase is 70 ° C. or higher, the optical anisotropy (25 ° C.) at a wavelength of 589 nm is 0.08 or higher, and the dielectric anisotropy (25 ° C.) at a frequency of 1 kHz is −2 or lower. Item 21. The liquid crystal composition according to any one of items 1 to 20.

22. Item 21. A liquid crystal comprising two substrates each having an electrode layer on at least one substrate, and a compound obtained by polymerizing the polymerizable compound in the liquid crystal composition according to any one of items 1 to 21 between the two substrates. A polymer-supported alignment type (PSA) liquid crystal display element characterized by disposing a material.

23. Item 23. The liquid crystal display device according to item 22, wherein the operation mode of the liquid crystal display device is a TN mode, a VA mode, an OCB mode, an IPS mode, or an FFS mode, and the driving method of the liquid crystal display device is an active matrix method.

24. Item 22. A liquid crystal display device according to item 22, wherein the liquid crystal composition according to any one of items 1 to 21 disposed between two substrates is irradiated with light in a voltage application state to polymerize a polymerizable compound. A method for manufacturing a liquid crystal display element.

25. Item 21. Use of the liquid crystal composition according to any one of items 1 to 21 in a liquid crystal display device.

The present invention includes the following items. 1) The above composition further containing an optically active compound, 2) the above composition further containing an additive such as an antioxidant, an ultraviolet absorber, and an antifoaming agent, and 3) the above composition. AM device, 4) a device containing the above composition and having a mode of TN, ECB, OCB, IPS, FFS, VA, or PSA, 5) a transmissive device containing the above composition, 6) Use of the above composition as a composition having a nematic phase, 7) Use as an optically active composition by adding an optically active compound to the above composition.

The composition of the present invention will be described in the following order. First, the constitution of component compounds in the composition will be described. Second, the main characteristics of the component compounds and the main effects of the compounds on the composition will be explained. Third, the combination of components in the composition, the preferred ratio of the components, and the basis thereof will be described. Fourth, a preferred form of the component compound will be described. Fifth, specific examples of component compounds are shown. Sixth, additives that may be mixed into 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 component compounds in the composition will be described. The composition of the present invention is classified into Composition A and Composition B. The composition A may further contain other liquid crystal compounds, additives, impurities and the like in addition to the liquid crystal compound selected from the compound (1), the compound (2), and the compound (3). The “other liquid crystal compound” is a liquid crystal compound different from the compound (1), the compound (2), and the compound (3). Such compounds are mixed into the composition for the purpose of further adjusting the properties. Among the other liquid crystal compounds, a smaller amount of cyano compound is preferable from the viewpoint of stability to heat or ultraviolet light. A more desirable ratio of the cyano compound is 0% by weight. Additives include optically active compounds, antioxidants, ultraviolet absorbers, dyes, antifoaming agents, polymerization initiators, and the like. Impurities are compounds mixed in a process such as synthesis of component compounds. Even if this compound is a liquid crystal compound, it is classified as an impurity here.

Composition B consists essentially of compound (1), compound (2), and compound (3). “Substantially” means that the composition may contain additives and impurities, but does not contain a liquid crystal compound different from these compounds. Composition B has fewer components than composition A. From the viewpoint of reducing the cost, the composition B is preferable to the composition A. The composition A is preferable to the composition B from the viewpoint that the physical properties can be further adjusted by mixing other liquid crystal compounds.

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

When the component compound is mixed with the composition, the main effects of the component compound on the properties of the composition are as follows. Compound (2) increases the absolute value of dielectric anisotropy and decreases the minimum temperature. Compound (3) decreases the viscosity or increases the maximum temperature and decreases the minimum temperature.

Third, the combination of components in the composition, the preferred ratio of the components, and the basis thereof will be described. The combination of the components in the composition is first component + second component and first component + second component + third component.

A desirable ratio of the first component is about 0.05 parts by weight or more for aligning liquid crystal molecules with respect to 100 parts by weight of the liquid crystal composition excluding the first component, and about 10 parts by weight or less for preventing display defects. It is. A more desirable ratio is in the range of approximately 0.1 parts by weight to approximately 2 parts by weight.

A desirable ratio of the second component is approximately 10% by weight or more for increasing the absolute value of the dielectric anisotropy and approximately 80% by weight for decreasing the minimum temperature based on the liquid crystal composition excluding the first component. It is as follows. A more desirable ratio is in the range of approximately 15% by weight to approximately 70% by weight. A particularly preferred ratio is in the range of approximately 20% by weight to approximately 60% by weight.

A desirable ratio of the third component is approximately 20% by weight or more for decreasing the viscosity or increasing the maximum temperature based on the liquid crystal composition excluding the first component, and increases the absolute value of the dielectric anisotropy. Therefore, it is about 90% by weight or less. A more desirable ratio is in the range of approximately 30% by weight to approximately 80% by weight. A particularly preferred ratio is in the range of approximately 40% by weight to approximately 70% by weight.

Fourth, a preferred form of the component compound will be described.
R ¹ and R ² are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons. Desirable R ¹ or R ² is alkyl having 1 to 12 carbons for increasing the stability to ultraviolet light or heat, and alkoxy having 1 to 12 carbons for decreasing the viscosity.
R ³ and R ⁴ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or 2 to 12 carbons in which at least one hydrogen is replaced by fluorine. Of alkenyl. Desirable R ³ or R ⁴ is alkenyl having 2 to 12 carbons for decreasing the viscosity, and alkyl having 1 to 12 carbons for increasing the stability to ultraviolet light or the stability to heat. is there.

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

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

Preferred alkenyl is vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl. More desirable alkenyl is vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl for decreasing the viscosity. The preferred configuration of —CH═CH— in these alkenyls depends on the position of the double bond. Trans is preferable in alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl and 3-hexenyl for decreasing the viscosity. Cis is preferred for alkenyl such as 2-butenyl, 2-pentenyl, and 2-hexenyl. In these alkenyl, linear alkenyl is preferable to branched.

Preferred examples of alkenyl in which at least one hydrogen is replaced by fluorine are 2,2-difluorovinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro-3-butenyl, 5,5-difluoro-4 -Pentenyl, and 6,6-difluoro-5-hexenyl. Further preferred examples are 2,2-difluorovinyl and 4,4-difluoro-3-butenyl for decreasing the viscosity.

Alkyl does not include cyclic alkyl. Alkoxy does not include cyclic alkoxy. Alkenyl does not include cyclic alkenyl. As the configuration of 1,4-cyclohexylene, trans is preferable to cis for increasing the maximum temperature.

Sp is alkylene having 1 to 6 carbon atoms, and in the alkylene, at least one —CH ₂ — may be replaced by —O—, —OCO—, —COO—, or —CH═CH—. Preferred Sp is alkylene having 1 to 6 carbon atoms for increasing the stability to ultraviolet light or heat, and alkylene in which —CH ₂ — is replaced with —CH═CH— for increasing the solubility in the liquid crystal composition. is there. The configuration of —CH═CH— may be a cis form or a trans form.

P ¹ and P ² are independently a group selected from the groups represented by Formula (P-1) to Formula (P-6).

Desirable P ¹ or P ² is a group (P-1) or a group (P-2) for increasing the reactivity or shortening the response time, and a group (P-1) for increasing the solubility in the liquid crystal composition. -5), and the groups (P-3) and (P-4) are for increasing the stability to ultraviolet light or heat.

Ring A and Ring B are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5 -Diyl, pyrimidine-2,5-diyl, in which at least one hydrogen is halogen, alkyl having 1 to 12 carbons, or alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by halogen It may be substituted, and when k is 2 or 3, any two rings A may be the same or different. Preferred ring A or ring B is at least one hydrogen in order to shorten the response time, halogen, alkyl having 1 to 12 carbons, or alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by halogen. 1,4-phenylene which may be substituted. More preferred ring A or ring B is 1,4-phenylene.
Ring C and Ring E are independently 1,4-cyclohexylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 3-fluoro-1, When 4-phenylene and m is 2 or 3, any two rings C may be the same or different. Preferred ring C or ring E is 1,4-cyclohexylene for decreasing the viscosity, and tetrahydropyran-2,5-diyl for increasing the absolute value of the dielectric anisotropy. 1,4-phenylene for raising. Tetrahydropyran-2,5-diyl is

Ring D is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4,5 -Trifluoronaphthalene-2,6-diyl or 7,8-difluorochroman-2,6-diyl. Preferred ring D is 2,3-difluoro-1,4-phenylene for decreasing the viscosity, and 2-chloro-3-fluoro-1,4-phenylene for decreasing the optical anisotropy. 7,8-Difluorochroman-2,6-diyl for increasing the absolute value of the isotropic property.
Ring F, Ring G, and Ring I are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 3-fluoro-1,4-phenylene. , P is 2, any two rings F may be the same or different. Desirable ring F, ring G or ring I is 1,4-cyclohexylene for decreasing the viscosity or increasing the maximum temperature, and 1,4-phenylene for decreasing the minimum temperature.

Z ¹ , Z ² , and Z ³ are independently a single bond, ethylene, methyleneoxy, or carbonyloxy, and when k is 2 or 3, any two Z ¹ may be the same, Any two Z ² may be the same or different when m is 2 or 3. Preferred Z ¹ is a single bond for increasing the reactivity, and ethylene for increasing the solubility in the liquid crystal composition. Desirable Z ² or Z ³ is a single bond for decreasing the viscosity, ethylene for decreasing the minimum temperature, and methyleneoxy for increasing the absolute value of the dielectric anisotropy.
Z ⁴ and Z ⁵ are independently a single bond, ethylene, methyleneoxy, or carbonyloxy, and when p is 2, the two Z ⁴ may be the same or different. Desirable Z ⁴ or Z ⁵ is a single bond for decreasing the viscosity, ethylene for decreasing the minimum temperature, and carbonyloxy for increasing the maximum temperature.

Y ¹ to Y ¹² are independently hydrogen, halogen, alkyl having 1 to 12 carbons, or trifluoromethyl. Desirable Y ¹ to Y ¹² are hydrogen for increasing the reactivity, and halogen or trifluoromethyl for increasing the solubility in the liquid crystal composition.

X ¹ and X ² are independently hydrogen or methyl. Preferred X ¹ or X ² is methyl for increasing the reactivity, and hydrogen for increasing the stability to ultraviolet light.

k is 0, 1, 2 or 3. Preferred k is 1 for increasing the reactivity.
m is 1, 2 or 3. Preferred m is 1 for decreasing the viscosity, and 2 or 3 for increasing the maximum temperature.
n is 0 or 1. Desirable n is 0 for decreasing the viscosity, and is 1 for decreasing the minimum temperature.
p is 0, 1, or 2. Preferred p is 0 for decreasing the viscosity, and 1 or 2 for increasing the maximum temperature.

Fifth, specific examples of component compounds are shown. In the following preferred compounds, R ⁵ and R ⁸ are linear alkyl having 1 to 12 carbons, linear alkoxy having 1 to 12 carbons, or linear alkenyl having 2 to 12 carbons. is there. R ⁶ is linear alkyl having 1 to 12 carbons or linear alkoxy having 1 to 12 carbons. R ⁷ is linear alkyl having 1 to 12 carbons or linear alkenyl having 2 to 12 carbons. Y ⁴ is hydrogen, halogen, alkyl having 1 to 12 carbons, or trifluoromethyl. X ¹ and X ² are hydrogen or methyl.

Desirable compounds (1) are from the compound (1-1-1) to the compound (1-8-1). More desirable compounds (1) are the compound (1-1-1) to the compound (1-5-1) and the compound (1-8-1). Particularly preferred compounds (1) are the compound (1-1-1) and the compound (1-2-1). Desirable compounds (2) are from the compound (2-1-1) to the compound (2-19-1). More desirable compounds (2) are the compound (2-1-1) to the compound (2-10-1) and the compound (2-12-1) to the compound (2-15-1). Particularly preferred compounds (2) are the compound (2-1-1) to the compound (2-8-1), the compound (2-13-1), and the compound (2-15-1). Desirable compounds (3) are from the compound (3-1-1) to the compound (3-13-1). More desirable compounds (3) are the compound (3-1-1) to the compound (3-7-1) and the compound (3-9-1) to the compound (3-13-1). Particularly preferred compounds (3) are the compound (3-1-1), the compound (3-3-1), the compound (3-7-1), and the compound (3-13-1).

Sixth, additives that may be mixed with the composition will be described. Such additives are optically active compounds, antioxidants, ultraviolet absorbers, dyes, antifoaming agents, polymerization initiators, polymerization inhibitors, and the like. An optically active compound is mixed with the composition for the purpose of inducing a helical structure of liquid crystal to give a twist angle. Examples of such a compound are the compound (4-1) to the compound (4-5). A desirable ratio of the optically active compound is approximately 5% by weight or less. A more desirable ratio is in the range of approximately 0.01% by weight to approximately 2% by weight.

In order to prevent a decrease in specific resistance due to heating in the atmosphere or to maintain a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase after the device has been used for a long time, oxidation prevention An agent is mixed into the composition.

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

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

A dichroic dye such as an azo dye or an anthraquinone dye is mixed with the composition so as to be adapted to a GH (guest host) mode element. A preferred ratio of the dye is in the range of approximately 0.01% by weight to approximately 10% by weight.

In order to prevent foaming, an antifoaming agent such as dimethyl silicone oil or methylphenyl silicone oil is mixed with the composition. A desirable ratio of the antifoaming agent is 1 ppm or more for obtaining the effect thereof, and is about 1000 ppm or less for preventing a poor display. A more desirable ratio is in the range of approximately 1 ppm to approximately 500 ppm.

Since the liquid crystal composition of the present invention contains a polymerizable compound, it is suitable for a PSA (polymer-sustained-alignment) mode device. The composition may further contain a polymerizable compound other than the compound (1). Preferred examples of the polymerizable compound are compounds having a polymerizable group such as acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxirane, oxetane), vinyl ketone and the like. Particularly preferred examples are acrylate or methacrylate derivatives. A desirable ratio of the polymerizable compound is about 0.03 parts by weight or more for obtaining the effect when the weight of the liquid crystal composition is 100 parts by weight, and is 10 parts by weight or less for preventing display defects. . A more desirable ratio is in the range of approximately 0.1 parts by weight to approximately 2 parts by weight. A desirable ratio of the compound (1) in the polymerizable compound is 10% by weight or more. A more desirable ratio is 30% by weight or more. The polymerizable compound is preferably polymerized by UV irradiation or the like in the presence of a suitable initiator such as a photopolymerization initiator. Appropriate conditions for polymerization, the appropriate type of initiator, and the appropriate amount are known to those skilled in the art and are described in the literature. For example, Irgacure 651 (registered trademark; BASF), Irgacure 184 (registered trademark; BASF), or Darocur 1173 (registered trademark; BASF), which are photoinitiators, are suitable for radical polymerization. A preferred proportion of the photopolymerization initiator is in the range of about 0.1% to about 5% by weight of the polymerizable compound, and more preferably in the range of about 1% to about 3% by weight. A process of polymerizing a polymerizable compound while placing a liquid crystal composition containing a polymerizable compound between two substrates in a liquid crystal display element and applying a voltage between opposing electrode layers of these substrates. Alternatively, a liquid crystal composition containing a previously polymerized compound may be disposed between two substrates in the liquid crystal display element.

Examples of the polymerizable compound that may be further contained other than the compound (1) are the compounds (6-1) to (6-9). By adding the compound (1) among the polymerizable compounds, the solubility in the composition can be increased and the reactivity can be increased.

Where R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² are independently acryloyl or methacryloyl, and R ¹³ and R ¹⁴ are independently hydrogen, halogen, or alkyl having 1 to 10 carbons. Z ⁶ and Z ⁷ are simultaneously a single bond or alkylene having 1 to 12 carbons, and in the alkylene, at least one —CH ₂ — may be replaced by —O—; Z ⁸ and Z ⁹ Is independently a single bond or alkylene having 1 to 12 carbons, in which at least one —CH ₂ — may be replaced by —O—; q, r, s are independently , 0, 1, or 2.

Seventh, a method for synthesizing component compounds will be described. Component compounds are Organic Synthesis (OrganicOrSyntheses, sJohn Wiley & Sons, Inc), Organic Reactions (OrganicOrReactions, actionJohn Wiley & Sons, Inc), Comprehensive Organic Synthesis (Comprehensive Organic Synthesis, Pergamon Press) It can be synthesized by appropriately combining known organic synthetic chemistry techniques described in a new experimental chemistry course (Maruzen).

These compounds can be synthesized by known methods. The synthesis method is illustrated. Compound (2-1-1) and compound (2-5-1) are synthesized by the method described in JP-T-2-503441. Compound (3-1-1) and compound (3-5-1) are synthesized by the method described in JP-A-59-176221. Antioxidants are commercially available. A compound of formula (5) in which w is 1 is available from Sigma-Aldrich Corporation. Compound (5) or the like in which w is 7 is synthesized by the method described in US Pat. No. 3,660,505.

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

Finally, the use of the composition will be explained. Most compositions have a minimum temperature of about −10 ° C. or lower, a maximum temperature of about 70 ° C. or higher, and an optical anisotropy in the range of about 0.07 to about 0.20. A device containing this composition has a large voltage holding ratio. This composition is suitable for an AM device. This composition is particularly suitable for a transmissive AM device. A composition having an optical anisotropy in the range of about 0.08 to about 0.25 may be prepared by controlling the ratio of the component compounds or by mixing other liquid crystal compounds. This composition can be used as a composition having a nematic phase, or can be used as an optically active composition by adding an optically active compound.

This composition can be used for an AM device. Further, it can be used for PM elements. This composition can be used for an AM device and a PM device having modes such as PC, TN, STN, ECB, OCB, IPS, VA, and PSA. Use for an AM device having a PSA mode is particularly preferable. These elements may be reflective, transmissive, or transflective. Use in a transmissive element is preferred. It can also be used for an amorphous silicon-TFT device or a polycrystalline silicon-TFT device. It can also be used for an NCAP (nematic-curvilinear-aligned-phase) type device produced by microencapsulating this composition, or a PD (polymer-dispersed) type device in which a three-dimensional network polymer is formed in the composition.

The liquid crystal display element of the present invention comprises two substrates having an electrode layer on at least one substrate, and a liquid crystal containing the liquid crystal composition of the present invention or a compound obtained by polymerizing the compound of the present invention between the two substrates. It is characterized by arranging the composition. For example, the glass substrate includes two glass substrates called an array substrate and a color filter substrate, and a thin film transistor (TFT), a pixel, a colored layer, and the like are formed on each glass substrate. For example, aluminosilicate glass or aluminoborosilicate glass is used for the glass substrate. As the electrode layer, indium-tin oxide (Indium-Tin Oxide) or indium-zinc oxide (Indium-Zinc Oxide) is generally used.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

The compound obtained by the synthesis was identified by proton nuclear magnetic resonance spectroscopy ( ¹ H-NMR), high performance liquid chromatography (HPLC), ultraviolet / visible spectroscopy (UV / Vis) and the like. The melting point of the compound was determined by differential scanning calorimetry (DSC). First, each analysis method will be described.

¹ H-NMR analysis: DRX-500 (manufactured by Bruker BioSpin) was used as a measuring apparatus. The measurement was carried out by dissolving the sample produced in Examples and the like in a deuterated solvent in which a sample such as CDCl ₃ is soluble and at room temperature under conditions of 500 MHz and 24 times of integration. In the description of the obtained nuclear magnetic resonance spectrum, s is a singlet, d is a doublet, t is a triplet, q is a quartet, and m is a multiplet. Tetramethylsilane (TMS) was used as a reference material for the zero point of the chemical shift δ value.

HPLC analysis: Prominence (LC-20AD; SPD-20A) manufactured by Shimadzu Corporation was used as a measuring apparatus. The column used was YMC-Pack ODS-A (length 150 mm, inner diameter 4.6 mm, particle diameter 5 μm) manufactured by YMC. The eluent was acetonitrile / water (volume ratio: 80/20), and the flow rate was adjusted to 1 mL / min. As a detector, a UV detector, an RI detector, a CORONA detector, or the like was appropriately used. When a UV detector was used, the detection wavelength was 254 nm.
The sample was dissolved in acetonitrile to prepare a 0.1 wt% solution, and 1 μL of the obtained solution was introduced into the sample chamber.
As a recorder, a C-R7Aplus manufactured by Shimadzu Corporation was used. The obtained chromatogram shows the peak retention time and peak area values corresponding to the component compounds.

The peak area ratio in the chromatogram obtained from HPLC corresponds to the ratio of the component compounds. In general, the weight% of the component compound of the analysis sample is not completely the same as the area% of each peak of the analysis sample. However, when the above-described column is used in the present invention, the correction factor is substantially 1. Therefore, the weight% of the component compound in the analysis sample substantially corresponds to the area% of each peak in the analysis sample. This is because there is no significant difference in the correction coefficients of the component liquid crystal compounds. In order to more accurately determine the composition ratio of the liquid crystal compound in the liquid crystal composition from the chromatogram, an internal standard method based on the chromatogram is used. Each liquid crystal compound component (test component) and a reference liquid crystal compound (reference material) weighed accurately by a certain amount are simultaneously measured by HPLC, and the peak of the obtained test component and the peak of the reference material are measured. The relative intensity of the area ratio is calculated in advance. When correction is performed using the relative intensity of the peak area of each component with respect to the reference substance, the composition ratio of the liquid crystal compound in the liquid crystal composition can be accurately determined from the chromatogram.

UV / Vis analysis: PharmaSpec UV-1700 manufactured by Shimadzu Corporation was used as a measuring apparatus. The detection wavelength was 190 nm to 700 nm.
The sample was dissolved in acetonitrile to prepare a 0.01 mmol / L solution, and the sample was placed in a quartz cell (optical path length 1 cm) and measured.

DSC measurement: Using a scanning calorimeter DSC-7 system manufactured by PerkinElmer or a Diamond DSC system, the temperature is increased and decreased at a rate of 3 ° C / min, and the start point of the endothermic peak or exothermic peak accompanying the phase change of the sample is excluded. The melting point was determined by onset.

[Example 1]
(Comparison 1 of solubility in liquid crystal composition)
As a comparison, 1 part by weight of the polymerizable compound (R-1) was added to 100 parts by weight of the liquid crystal composition A, and dissolution was attempted at 25 ° C., but the remaining crystals did not dissolve in the liquid crystal composition.
When 1 part by weight of the polymerizable compound (1-1-1-1) of the present invention was added to 100 parts by weight of the liquid crystal composition A and dissolution was attempted at 25 ° C., the total amount of the compound (1-1-1-1) was dissolved. did. From this comparison, it was found that the compound of the present invention was easily dissolved in the liquid crystal composition. Table 3 shows the results. In the symbols in Table 3, “◯” indicates the result when no crystal was observed, and “X” indicates the result when crystal was observed. The components of the liquid crystal composition A and the ratios thereof are as follows.

In order to evaluate the properties of the composition and the compound contained in the composition, the composition and this compound are used as the measurement object. When the object to be measured was a composition, it was measured as it was as a sample, and the obtained value was described. When the measurement object was a compound, a sample for measurement was prepared by mixing this compound (15% by weight) with mother liquid crystals (85% by weight). The characteristic value of the compound was calculated from the value obtained by the measurement by extrapolation. (Extrapolated value) = {(Measured value of measurement sample) −0.85 × (Measured value of mother liquid crystal)} / 0.15. When the smectic phase (or crystal) is precipitated at 25 ° C. at this ratio, the ratio of the compound and the mother liquid crystal is 10% by weight: 90% by weight, 5% by weight: 95% by weight, 1% by weight: 99% by weight in this order. changed. By this extrapolation method, the maximum temperature, optical anisotropy, viscosity, and dielectric anisotropy values for the compound were determined.

The components of the mother liquid crystals and their proportions are as follows.

Measured characteristic values according to the following method. Many of them are the methods described in the JEITA standard (JEITA ED-2521B) established by the Japan Electronics and Information Technology Industries Association (JEITA ED-2521B) or a modified method thereof. is there.

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

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

Viscosity (bulk viscosity; η; measured at 20 ° C .; mPa · s): An E-type viscometer was used for measurement.

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

Dielectric Anisotropy (Δε; measured at 25 ° C.): The value of dielectric anisotropy was calculated from the equation: Δε = ε∥−ε⊥. The dielectric constants (ε∥ and ε⊥) were measured as follows.
1) Measurement of dielectric constant (ε∥): An ethanol (20 mL) solution of octadecyltriethoxysilane (0.16 mL) was applied to a well-cleaned glass substrate. The glass substrate was rotated with a spinner and then heated at 150 ° C. for 1 hour. A sample was put in a VA element in which the distance between two glass substrates (cell gap) was 4 μm, and the element was sealed with an adhesive that was cured with ultraviolet rays. Sine waves (0.5 V, 1 kHz) were applied to the device, and after 2 seconds, the dielectric constant (ε∥) in the major axis direction of the liquid crystal molecules was measured.
2) Measurement of dielectric constant (ε⊥): A polyimide solution was applied to a well-cleaned glass substrate. After baking this glass substrate, the obtained alignment film was rubbed. A sample was put in a TN device in which the distance between two glass substrates (cell gap) was 9 μm and the twist angle was 80 degrees. Sine waves (0.5 V, 1 kHz) were applied to the device, and after 2 seconds, the dielectric constant (ε⊥) in the minor axis direction of the liquid crystal molecules was measured.

Threshold voltage (Vth; measured at 25 ° C .; V): An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement. The light source is a halogen lamp. A sample is placed in a normally black mode VA element in which the distance between two glass substrates (cell gap) is 4 μm and the rubbing direction is anti-parallel, and an adhesive that cures the element with ultraviolet rays is used. And sealed. The voltage (60 Hz, rectangular wave) applied to this element was increased stepwise from 0V to 20V by 0.02V. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. A voltage-transmittance curve was created in which the transmittance was 100% when the light amount reached the maximum and the transmittance was 0% when the light amount was the minimum. The threshold voltage is a voltage when the transmittance reaches 10%.

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

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

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

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

Response time (τ; measured at 25 ° C .; ms): An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement. The light source is a halogen lamp. The low-pass filter was set to 5 kHz. Adhesion in which a specimen is placed in a normally black mode PVA element in which the distance between two glass substrates (cell gap) is 3.2 μm and the rubbing direction is anti-parallel, and the element is cured with ultraviolet rays. Sealed with an agent. The device was irradiated with ultraviolet rays of 25 mW / cm ² (EXECURE 4000-D type manufactured by HOYA CANDEO OPTRONICS; mercury xenon lamp) for 400 seconds while applying a voltage of 15V. A rectangular wave (60 Hz, 10 V, 0.5 seconds) was applied to this element. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. The transmittance is 100% when the light amount is maximum, and the transmittance is 0% when the light amount is minimum. The response time is the rise time (millisecond) required to change the transmittance from 0% to 90%.

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

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

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

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

The compounds in Comparative Examples and Examples were represented by symbols based on the definitions in Table 4 below. In Table 4, the configuration regarding 1,4-cyclohexylene is trans. In the examples, the number in parentheses after the symbol corresponds to the compound number. The symbol (−) means other liquid crystal compounds. The ratio (percentage) of the liquid crystal compound is a weight percentage (% by weight) based on the weight of the liquid crystal composition excluding the first component, and the liquid crystal composition contains impurities in addition to this. Finally, the characteristic values of the composition are summarized.

[Comparative Example M1]
This composition is a liquid crystal composition having a negative dielectric anisotropy and not containing the first component of the present invention. The components and properties of this composition are as follows.
V-HB (2F, 3F) -O2 (2-1-1) 15%
V-HB (2F, 3F) -O4 (2-1-1) 10%
2-HBB (2F, 3F) -O2 (2-8-1) 4%
3-HBB (2F, 3F) -O2 (2-8-1) 10%
5-HBB (2F, 3F) -O2 (2-8-1) 10%
2-HHB (2F, 3CL) -O2 (2-9-1) 2%
3-HHB (2F, 3CL) -O2 (2-9-1) 3%
4-HHB (2F, 3CL) -O2 (2-9-1) 3%
5-HHB (2F, 3CL) -O2 (2-9-1) 3%
2-HH-3 (3-1-1) 27%
3-HB-O2 (3-2-1) 2%
3-HHB-1 (3-5-1) 3%
3-HHB-3 (3-5-1) 5%
3-HHB-O1 (3-5-1) 3%
NI = 73.8 ° C .; Tc <−20 ° C .; Δn = 0.092; Δε = −3.1; Vth = 2.11 V; τ = 8.0 ms; VHR-1 = 99.1%; VHR-2 = 98.0%; VHR-3 = 98.0%.

[Example M1]
V-HB (2F, 3F) -O2 (2-1-1) 15%
V-HB (2F, 3F) -O4 (2-1-1) 10%
2-HBB (2F, 3F) -O2 (2-8-1) 4%
3-HBB (2F, 3F) -O2 (2-8-1) 10%
5-HBB (2F, 3F) -O2 (2-8-1) 10%
2-HHB (2F, 3CL) -O2 (2-9-1) 2%
3-HHB (2F, 3CL) -O2 (2-9-1) 3%
4-HHB (2F, 3CL) -O2 (2-9-1) 3%
5-HHB (2F, 3CL) -O2 (2-9-1) 3%
2-HH-3 (3-1-1) 27%
3-HB-O2 (3-2-1) 2%
3-HHB-1 (3-5-1) 3%
3-HHB-3 (3-5-1) 5%
3-HHB-O1 (3-5-1) 3%
0.3 parts by weight of the compound (1-1-1-1) as the first component of the present invention was added to 100 parts by weight of the above composition.
MAC-VO-BB-MAC (1-1-1-1)
The properties of this composition are as follows.
NI = 74.3 ° C .; Tc <−20 ° C .; Δn = 0.095; Δε = −3.1; Vth = 2.13 V; VHR-1 = 99.2%; VHR-2 = 98.2%; VHR-3 = 98.3%.

(Method for creating liquid crystal display element)
The alignment agent was applied to two glass substrates with ITO electrodes by a spinner to form a film. After coating, the film was dried by heating at 80 ° C. for about 10 minutes, and then heat-treated at 180 ° C. for 60 minutes to form an alignment film. A gap material was sprayed on one glass substrate, and the other substrate was sealed with an epoxy-based adhesive leaving a liquid crystal inlet, and bonded with the surface on which the alignment film was formed facing inside. A sample of [Example M1], which is a liquid crystal composition described in the present application, was vacuum-injected into this device, the inlet was sealed with a photocuring agent, and the photocuring agent was solidified by irradiation with ultraviolet rays. Next, a heat treatment was performed at 110 ° C. for 30 minutes to prepare a liquid crystal display element. This device was irradiated with 25 mW / cm ² ultraviolet light (EXECURE 4000-D type manufactured by HOYA CANDEO OPTRONICS Co., Ltd .; mercury xenon lamp) for 400 seconds while applying a voltage of 15 V, and finally a liquid crystal display device was produced.
The response time of this liquid crystal display element was τ = 4.3 ms.

[Example M2]
3-H2B (2F, 3F) -O2 (2-2-1) 17%
5-H2B (2F, 3F) -O2 (2-2-1) 16%
3-HHB (2F, 3F) -O2 (2-5-1) 7%
3-HBB (2F, 3F) -O2 (2-8-1) 5%
4-HBB (2F, 3F) -O2 (2-8-1) 6%
5-HBB (2F, 3F) -O2 (2-8-1) 10%
2-HH-3 (3-1-1) 20%
3-HH-4 (3-1-1) 4%
5-HB-O2 (3-2-1) 4%
3-HHB-1 (3-5-1) 4%
5-HBB (F) B-2 (3-13-1) 7%
0.3 parts by weight of the compound (1-1-1-1) as the first component of the present invention was added to 100 parts by weight of the above composition.
MAC-VO-BB-MAC (1-1-1-1)
The characteristics of the obtained composition are as follows.
NI = 76.8 ° C .; Tc <−20 ° C .; Δn = 0.099; Δε = −3.1; Vth = 2.36 V; VHR-1 = 99.1%; VHR-2 = 98.5%; VHR-3 = 98.6%.
The response time of the liquid crystal display device prepared by the method described in Example M1 was τ = 4.6 ms.

[Example M3]
V-HB (2F, 3F) -O2 (2-1-1) 11%
3-H2B (2F, 3F) -O2 (2-2-1) 15%
5-H2B (2F, 3F) -O2 (2-2-1) 5%
3-BB (2F, 3F) -O2 (2-3-1) 5%
3-H1OB (2F, 3F) -O2 (2-4-1) 5%
3-HH2B (2F, 3F) -O2 (2-6-1) 5%
3-HBB (2F, 3F) -O2 (2-8-1) 5%
4-HBB (2F, 3F) -O2 (2-8-1) 6%
5-HBB (2F, 3F) -O2 (2-8-1) 6%
3-HH-4 (3-1-1) 10%
1-BB-3 (3-3-1) 4%
3-HHB-1 (3-5-1) 4%
3-HHB-3 (3-5-1) 5%
3-HHB-O1 (3-5-1) 3%
5-HBB (F) B-2 (3-13-1) 6%
5-HBB (F) B-3 (3-13-1) 5%
0.3 parts by weight of the compound (1-1-1-1) as the first component of the present invention was added to 100 parts by weight of the above composition.
MAC-VO-BB-MAC (1-1-1-1)
The characteristics of the obtained composition are as follows.
NI = 85.3 ° C .; Tc <−20 ° C .; Δn = 0.122; Δε = −3.8; Vth = 2.15V; VHR-1 = 99.2%; VHR-2 = 98.7%; VHR-3 = 98.6%.
The response time of the liquid crystal display device prepared by the method described in Example M1 was τ = 5.3 ms.

[Example M4]
V-HB (2F, 3F) -O2 (2-1-1) 10%
V-HB (2F, 3F) -O4 (2-1-1) 10%
3-H1OB (2F, 3F) -O2 (2-4-1) 6%
3-HBB (2F, 3F) -O2 (2-8-1) 10%
5-HBB (2F, 3F) -O2 (2-8-1) 8%
3-dhHB (2F, 3F) -O2 (2-14-1) 3%
3-HH1OCro (7F, 8F) -5 (2-19-1) 5%
2-HH-5 (3-1-1) 8%
3-HH-4 (3-1-1) 14%
5-HB-O2 (3-2-1) 8%
3-HHB-1 (3-5-1) 3%
3-HHB-O1 (3-5-1) 2%
5-HBB-2 (3-6-1) 4%
3-HHEBH-3 (3-10-1) 2%
3-HHEBH-5 (3-10-1) 2%
3-HBBH-5 (3-11-1) 3%
5-HBB (F) B-2 (3-13-1) 2%
0.3 parts by weight of the compound (1-1-1-1) as the first component of the present invention was added to 100 parts by weight of the above composition.
MAC-VO-BB-MAC (1-1-1-1)
The characteristics of the obtained composition are as follows.
NI = 89.9 ° C .; Tc <−20 ° C .; Δn = 0.100; Δε = −3.0; Vth = 2.30 V; VHR-1 = 99.2%; VHR-2 = 98.6%; VHR-3 = 98.8%.
The response time of the liquid crystal display device prepared by the method described in Example M1 was τ = 5.3 ms.

[Example M5]
V-HB (2F, 3F) -O2 (2-1-1) 10%
3-H2B (2F, 3F) -O2 (2-2-1) 13%
5-H2B (2F, 3F) -O2 (2-2-1) 12%
5-BB (2F, 3F) -O2 (2-3-1) 5%
5-H1OB (2F, 3F) -O2 (2-4-1) 5%
5-HH1OB (2F, 3F) -O2 (2-7-1) 6%
5-HBB (2F, 3F) -O2 (2-8-1) 9%
3-HHB (2F, 3CL) -O2 (2-9-1) 4%
3-HH-4 (3-1-1) 2%
5-HH-V (3-1-1) 5%
3-HHEH-3 (3-4-1) 2%
3-HHEH-5 (3-4-1) 2%
4-HHEH-3 (3-4-1) 2%
4-HHEH-5 (3-4-1) 2%
3-HHB-1 (3-5-1) 4%
3-HHB-3 (3-5-1) 7%
3-HHB-O1 (3-5-1) 4%
3-HHEBH-3 (3-10-1) 3%
3-HHEBH-5 (3-10-1) 3%
0.3 parts by weight of the compound (1-2-1-1) as the first component of the present invention was added to 100 parts by weight of the above composition.
MAC-V-BB-MAC (1-2-1-1)
The characteristics of the obtained composition are as follows.
NI = 89.5 ° C .; Tc <−20 ° C .; Δn = 0.095; Δε = −4.3; Vth = 2.05 V; VHR-1 = 99.1%; VHR-2 = 98.2%; VHR-3 = 98.6%.
The response time of the liquid crystal display device prepared by the method described in Example M1 was τ = 5.5 ms.

[Example M6]
V-HB (2F, 3F) -O2 (2-1-1) 11%
3-H2B (2F, 3F) -O2 (2-2-1) 5%
3-HH1OB (2F, 3F) -O2 (2-7-1) 5%
4-HBB (2F, 3F) -O2 (2-8-1) 4%
5-HBB (2F, 3F) -O2 (2-8-1) 7%
3-HDhB (2F, 3F) -O2 (2-13-1) 5%
3-dhBB (2F, 3F) -O2 (2-15-1) 6%
3-HH1OCro (7F, 8F) -5 (2-19-1) 8%
2-HH-3 (3-1-1) 17%
3-HH-5 (3-1-1) 4%
5-HB-O2 (3-2-1) 6%
1-BB-3 (3-3-1) 5%
3-HHB-1 (3-5-1) 5%
3-HHB-3 (3-5-1) 6%
3-HHB-O1 (3-5-1) 3%
3-B (F) BB-2 (3-8-1) 3%
0.3 parts by weight of the compound (1-6-1-1) as the first component of the present invention was added to 100 parts by weight of the above composition.
MAC-2O-BB (CF3) -MAC (1-6-1-1)
The characteristics of the obtained composition are as follows.
NI = 84.5 ° C .; Tc <−20 ° C .; Δn = 0.103; Δε = −3.1; Vth = 2.22 V; VHR-1 = 99.3%; VHR-2 = 98.5%; VHR-3 = 98.5%.
The response time of the liquid crystal display device prepared by the method described in Example M1 was τ = 4.5 ms.

[Example M7]
V-HB (2F, 3F) -O2 (2-1-1) 10%
3-H2B (2F, 3F) -O2 (2-2-1) 5%
3-BB (2F, 3F) -O2 (2-3-1) 5%
3-H1OB (2F, 3F) -O2 (2-4-1) 6%
3-HBB (2F, 3F) -O2 (2-8-1) 6%
3-HHB (2F, 3CL) -O2 (2-9-1) 3%
3-DhHB (2F, 3F) -O2 (2-12-1) 3%
3-HDhB (2F, 3F) -O2 (2-13-1) 3%
3-HH1OCro (7F, 8F) -5 (2-19-1) 5%
2-HH-3 (3-1-1) 19%
5-HB-O2 (3-2-1) 5%
V2-BB-1 (3-3-1) 3%
3-HHB-1 (3-5-1) 4%
3-HHB-3 (3-5-1) 7%
3-HHB-O1 (3-5-1) 4%
2-BB (F) B-3 (3-7-1) 4%
3-HB (F) BH-3 (3-12-1) 3%
5-HBB (F) B-2 (3-13-1) 5%
To 100 parts by weight of the above composition, 0.3 part by weight of the compound (1-5-1-1) as the first component of the present invention was added.
ACA-BB-AC (1-5-1-1)
The characteristics of the obtained composition are as follows.
NI = 83.3 ° C .; Tc <−20 ° C .; Δn = 0.111; Δε = −2.6; Vth = 2.32 V; VHR-1 = 99.1%; VHR-2 = 98.5%; VHR-3 = 98.5%.
The response time of the liquid crystal display device prepared by the method described in Example M1 was τ = 4.1 ms.

[Example M8]
V-HB (2F, 3F) -O2 (2-1-1) 14%
5-H2B (2F, 3F) -O2 (2-2-1) 5%
3-HBB (2F, 3F) -O2 (2-8-1) 10%
4-HBB (2F, 3F) -O2 (2-8-1) 4%
5-HBB (2F, 3F) -O2 (2-8-1) 5%
3-HH1OCro (7F, 8F) -5 (2-19-1) 7%
2-HH-3 (3-1-1) 23%
3-HH-O1 (3-1-1) 5%
3-HH-V (3-1-1) 3%
4-HHEH-3 (3-4-1) 3%
4-HHEH-5 (3-4-1) 3%
3-HHB-1 (3-5-1) 6%
3-HHB-3 (3-5-1) 6%
3-HHB-O1 (3-5-1) 3%
2-BB (F) B-5 (3-7-1) 3%
To 100 parts by weight of the above composition, 0.3 part by weight of the compound (1-5-1-2) as the first component of the present invention was added.
ACA-BB-MAC (1-5-1-2)
The characteristics of the obtained composition are as follows.
NI = 83.2 ° C .; Tc <−20 ° C .; Δn = 0.093; Δε = −2.6; Vth = 2.25 V; VHR-1 = 99.3%; VHR-2 = 98.7%; VHR-3 = 98.6%.
The response time of the liquid crystal display device prepared by the method described in Example M1 was τ = 4.1 ms.

[Example M9]
3-H2B (2F, 3F) -O2 (2-2-1) 15%
5-H2B (2F, 3F) -O2 (2-2-1) 15%
2-HBB (2F, 3F) -O2 (2-8-1) 3%
3-HBB (2F, 3F) -O2 (2-8-1) 9%
5-HBB (2F, 3F) -O2 (2-8-1) 9%
3-HHB (2F, 3CL) -O2 (2-9-1) 5%
2-HH-5 (3-1-1) 4%
3-HH-4 (3-1-1) 15%
3-HH-V1 (3-1-1) 4%
3-HB-O2 (3-2-1) 12%
3-HHB-3 (3-5-1) 6%
3-HB (F) HH-2 (3-9-1) 3%
0.3 parts by weight of the compound (1-1-1-1) as the first component of the present invention was added to 100 parts by weight of the above composition.
MAC-VO-BB-MAC (1-1-1-1)
The characteristics of the obtained composition are as follows.
NI = 75.2 ° C .; Tc <−20 ° C .; Δn = 0.096; Δε = −2.7; Vth = 2.41 V; VHR-1 = 99.2%; VHR-2 = 98.5%; VHR-3 = 98.5%.
The response time of the liquid crystal display device prepared by the method described in Example M1 was τ = 4.5 ms.

[Example M10]
3-H2B (2F, 3F) -O2 (2-2-1) 17%
5-H2B (2F, 3F) -O2 (2-2-1) 17%
3-HH1OB (2F, 3F) -O2 (2-7-1) 5%
3-HHB (2F, 3CL) -O2 (2-9-1) 4%
4-HHB (2F, 3CL) -O2 (2-9-1) 3%
5-HHB (2F, 3CL) -O2 (2-9-1) 3%
3-HBB (2F, 3CL) -O2 (2-10-1) 8%
2-BB (2F, 3F) B-3 (2-11-1) 4%
3-HH-V (3-1-1) 27%
V-HHB-1 (3-5-1) 7%
2-BB (F) B-3 (3-7-1) 2%
3-HHEBH-3 (3-10-1) 3%
0.3 parts by weight of the compound (1-2-1-1) as the first component of the present invention was added to 100 parts by weight of the above composition.
MAC-V-BB-MAC (1-2-1-1)
The characteristics of the obtained composition are as follows.
NI = 71.9 ° C .; Tc <−20 ° C .; Δn = 0.093; Δε = −2.8; Vth = 2.33 V; VHR-1 = 99.2%; VHR-2 = 98.6%; VHR-3 = 98.6%.
The response time of the liquid crystal display device prepared by the method described in Example M1 was τ = 3.8 ms.

[Example M11]
V-HB (2F, 3F) -O2 (2-1-1) 15%
V-HB (2F, 3F) -O4 (2-1-1) 7%
3-HBB (2F, 3F) -O2 (2-8-1) 3%
V-HBB (2F, 3F) -O2 (2-8-1) 10%
V2-HBB (2F, 3F) -O2 (2-8-1) 10%
3-HH1OCro (7F, 8F) -5 (2-19-1) 8%
2-HH-3 (3-1-1) 29%
3-HHB-1 (3-5-1) 6%
3-HHB-3 (3-5-1) 6%
3-HHB-O1 (3-5-1) 6%
0.3 parts by weight of the compound (1-1-1-1) as the first component of the present invention was added to 100 parts by weight of the above composition.
MAC-VO-BB-MAC (1-1-1-1)
The characteristics of the obtained composition are as follows.
NI = 80.9 ° C .; Tc <−20 ° C .; Δn = 0.094; Δε = −3.1; Vth = 2.26 V; VHR-1 = 99.3%; VHR-2 = 98.5%; VHR-3 = 98.6%.
The response time of the liquid crystal display device prepared by the method described in Example M1 was τ = 4.7 ms.

[Example M12]
5-BB (2F, 3F) -O2 (2-3-1) 7%
5-H1OB (2F, 3F) -O2 (2-4-1) 10%
4-HH1OB (2F, 3F) -O2 (2-7-1) 5%
5-HH1OB (2F, 3F) -O2 (2-7-1) 5%
5-HBB (2F, 3CL) -O2 (2-10-1) 6%
2-BB (2F, 3F) B-3 (2-11-1) 3%
3-DhHB (2F, 3F) -O2 (2-12-1) 6%
3-HDhB (2F, 3F) -O2 (2-13-1) 7%
3-HH-V (3-1-1) 30%
3-HH-V1 (3-1-1) 6%
3-HHB-1 (3-5-1) 4%
3-HHB-O1 (3-5-1) 4%
3-B (F) BB-2 (3-8-1) 3%
1O1-HBBH-5 (-) 4%
0.3 parts by weight of the compound (1-1-1-1) as the first component of the present invention was added to 100 parts by weight of the above composition.
MAC-VO-BB-MAC (1-1-1-1)
The characteristics of the obtained composition are as follows.
NI = 90.8 ° C .; Tc <−20 ° C .; Δn = 0.099; Δε = −2.6; VHR-1 = 99.1%; VHR-2 = 98.1%; VHR-3 = 98. 3%.
The response time of the liquid crystal display device prepared by the method described in Example M1 was τ = 4.1 ms.

[Example M13]
3-H2B (2F, 3F) -O2 (2-2-1) 12%
3-HH2B (2F, 3F) -O2 (2-6-1) 5%
2-HBB (2F, 3F) -O2 (2-8-1) 5%
3-HBB (2F, 3F) -O2 (2-8-1) 7%
5-HBB (2F, 3F) -O2 (2-8-1) 4%
3-HH2B (2F, 3F, 6Me) -O2
(2-16-1) 5%
3-HH1OB (2F, 3F, 6Me) -O2
(2-17-1) 6%
3-HH1OCro (7F, 8F) -5
(2-19-1) 4%
4-HH-V (3-1-1) 15%
5-HH-V (3-1-1) 23%
3-HH-V1 (3-1-1) 6%
V-HHB-1 (3-5-1) 5%
V2-HHB-1 (3-5-1) 3%
0.3 parts by weight of the compound (1-1-1-1) as the first component of the present invention was added to 100 parts by weight of the above composition.
MAC-VO-BB-MAC (1-1-1-1)
The characteristics of the obtained composition are as follows.
NI = 88.5 ° C .; Tc <−20 ° C .; Δn = 0.092; Δε = −2.9; VHR-1 = 99.4%; VHR-2 = 98.5%; VHR-3 = 98. 7%.
The response time of the liquid crystal display device prepared by the method described in Example M1 was τ = 4.7 ms.

[Example M14]
3-HB (2F, 3F) -O2 (2-1-1) 8%
3-HHB (2F, 3F) -O2 (2-5-1) 10%
3-HBB (2F, 3F) -O2 (2-8-1) 7%
5-HBB (2F, 3F) -O2 (2-8-1) 5%
3-dhBB (2F, 3F) -O2 (2-15-1) 6%
3-HH1OB (2F, 3F, 6Me) -O2
(2-17-1) 6%
3-H1OCro (7F, 8F) -5 (2-18-1) 5%
3-HH-V (3-1-1) 40%
1-HH-2V1 (3-1-1) 6%
3-HHEBH-3 (3-10-1) 4%
3-HHEBH-4 (3-10-1) 3%
0.3 parts by weight of the compound (1-2-1-1) as the first component of the present invention was added to 100 parts by weight of the above composition.
MAC-V-BB-MAC (1-2-1-1)
The characteristics of the obtained composition are as follows.
NI = 84.7 ° C .; Tc <−20 ° C .; Δn = 0.090; Δε = −3.1; VHR-1 = 99.1%; VHR-2 = 98.6%; VHR-3 = 98. 6%.
The response time of the liquid crystal display device prepared by the method described in Example M1 was τ = 4.0 ms.

[Example M15]
V-HB (2F, 3F) -O2 (2-1-1) 12%
V-HB (2F, 3F) -O4 (2-1-1) 5%
3-H2B (2F, 3F) -O2 (2-2-1) 15%
3-BB (2F, 3F) -O2 (2-3-1) 4%
3-HBB (2F, 3F) -O2 (2-8-1) 7%
4-HBB (2F, 3F) -O2 (2-8-1) 6%
5-HBB (2F, 3F) -O2 (2-8-1) 6%
2-BB (2F, 3F) B-4 (2-11-1) 3%
2-HH-5 (3-1-1) 5%
3-HH-4 (3-1-1) 14%
3-HHB-1 (3-5-1) 4%
3-HHB-3 (3-5-1) 5%
3-HHB-O1 (3-5-1) 3%
5-HBB (F) B-2 (3-13-1) 6%
1O1-HBBH-5 (-) 5%
0.3 parts by weight of the compound (1-2-1-1) as the first component of the present invention was added to 100 parts by weight of the above composition.
MAC-V-BB-MAC (1-2-1-1)
The characteristics of the obtained composition are as follows.
NI = 88.7 ° C .; Tc <−20 ° C .; Δn = 0.115; Δε = −3.3; VHR-1 = 99.2%; VHR-2 = 98.5%; VHR-3 = 98. 6%.
The response time of the liquid crystal display device prepared by the method described in Example M1 was τ = 4.9 ms.

[Example M16]
3-HB (2F, 3F) -O2 (2-1-1) 5%
3-H2B (2F, 3F) -O2 (2-2-1) 19%
5-H2B (2F, 3F) -O2 (2-2-1) 5%
3-HHB (2F, 3F) -O2 (2-5-1) 8%
5-HHB (2F, 3F) -O2 (2-5-1) 7%
3-HBB (2F, 3F) -O2 (2-8-1) 10%
4-HBB (2F, 3F) -O2 (2-8-1) 5%
3-HDhB (2F, 3F) -O2 (2-13-1) 5%
2-HH-3 (3-1-1) 20%
3-HH-4 (3-1-1) 7%
3-HHB-1 (3-5-1) 4%
V-HHB-1 (3-5-1) 3%
5-B (F) BB-2 (3-8-1) 2%
0.15 parts by weight of the compound (1-1-1-1) which is the first component of the present invention is added to 100 parts by weight of the above composition, and the polymerizable compound (6-1-1) which is not the first component of the present invention. ) Was added at 0.15 parts by weight.
MAC-VO-BB-MAC (1-1-1-1)
MAC-BB-MAC (6-1-1)
The characteristics of the obtained composition are as follows.
NI = 78.8 ° C .; Tc <−20 ° C .; Δn = 0.090; Δε = −3.5; VHR-1 = 99.1%; VHR-2 = 98.3%; VHR-3 = 98. 4%.
The response time of the liquid crystal display device prepared by the method described in Example M1 was τ = 4.2 ms.

[Example M17]
V-HB (2F, 3F) -O2 (2-1-1) 5%
3-H2B (2F, 3F) -O2 (2-2-1) 10%
5-H2B (2F, 3F) -O2 (2-2-1) 10%
3-HHB (2F, 3F) -O2 (2-5-1) 8%
5-HHB (2F, 3F) -O2 (2-5-1) 6%
3-HH1OB (2F, 3F) -O2 (2-7-1) 5%
3-HBB (2F, 3F) -O2 (2-8-1) 10%
4-HBB (2F, 3F) -O2 (2-8-1) 5%
3-HDhB (2F, 3F) -O2 (2-13-1) 5%
2-HH-3 (3-1-1) 20%
3-HH-4 (3-1-1) 7%
3-HHB-1 (3-5-1) 4%
3-HHB-3 (3-5-1) 3%
5-B (F) BB-2 (3-8-1) 2%
0.15 parts by weight of the compound (1-1-1-1) which is the first component of the present invention is added to 100 parts by weight of the above composition, and the polymerizable compound (6-1-2) which is not the first component of the present invention. ) Was added in an amount of 0.15 parts by weight.
MAC-VO-BB-MAC (1-1-1-1)
MAC-B (2F) B-MAC (6-1-2)
The characteristics of the obtained composition are as follows.
NI = 83.7 ° C .; Tc <−20 ° C .; Δn = 0.090; Δε = −3.6; VHR-1 = 99.2%; VHR-2 = 98.3%; VHR-3 = 98. 6%.
The response time of the liquid crystal display device prepared by the method described in Example M1 was τ = 4.4 ms.

[Example M18]
3-H2B (2F, 3F) -O2 (2-2-1) 19%
5-H2B (2F, 3F) -O2 (2-2-1) 10%
3-HHB (2F, 3F) -O2 (2-5-1) 8%
5-HHB (2F, 3F) -O2 (2-5-1) 5%
3-HBB (2F, 3F) -O2 (2-8-1) 10%
4-HBB (2F, 3F) -O2 (2-8-1) 5%
3-dhBB (2F, 3F) -O2 (2-15-1) 5%
2-HH-3 (3-1-1) 20%
2-HH-5 (3-1-1) 5%
3-HHB-1 (3-5-1) 5%
3-HHB-3 (3-5-1) 3%
5-B (F) BB-2 (3-8-1) 5%
0.15 parts by weight of the compound (1-1-1-1) as the first component of the present invention and 0.15 parts by weight of the compound (1-1-1-2) were added to 100 parts by weight of the composition. .
MAC-VO-BB-MAC (1-1-1-1)
MAC-VO-BB-AC (1-1-1-2)
The characteristics of the obtained composition are as follows.
NI = 81.1 ° C .; Tc <−20 ° C .; Δn = 0.100; Δε = −3.4; VHR-1 = 99.2%; VHR-2 = 98.5%; VHR-3 = 98. 6%.
The response time of the liquid crystal display device prepared by the method described in Example M1 was τ = 4.4 ms.

[Example M19]
3-H2B (2F, 3F) -O2 (2-2-1) 10%
5-H2B (2F, 3F) -O2 (2-2-1) 10%
3-BB (2F, 3F) -O2 (2-3-1) 5%
3-HHB (2F, 3F) -O2 (2-5-1) 8%
5-HHB (2F, 3F) -O2 (2-5-1) 5%
3-HBB (2F, 3F) -O2 (2-8-1) 10%
2-BB (2F, 3F) B-3 (2-11-1) 5%
3-HDhB (2F, 3F) -O2 (2-13-1) 5%
2-HH-3 (3-1-1) 20%
3-HH-4 (3-1-1) 7%
3-HH-V1 (3-1-1) 3%
3-HHB-1 (3-5-1) 4%
3-HHB-3 (3-5-1) 3%
5-B (F) BB-2 (3-8-1) 5%
To 100 parts by weight of the above composition, 0.1 part by weight of the compound (1-1-1-1) as the first component of the present invention and 0.1 part by weight of the compound (1-1-1-2) are added. Then, 0.1 part by weight of the polymerizable compound (6-1-2) which is not the first component of the present invention was added.
MAC-VO-BB-MAC (1-1-1-1)
MAC-VO-BB-AC (1-1-1-2)
MAC-B (2F) B-MAC (6-1-2)
The characteristics of the obtained composition are as follows.
NI = 79.0 ° C .; Tc <−20 ° C .; Δn = 0.101; Δε = −3.0; VHR-1 = 99.4%; VHR-2 = 98.7%; VHR-3 = 98. 8%.
The response time of the liquid crystal display device prepared by the method described in Example M1 was τ = 3.9 ms.

[Example M20]
V-HB (2F, 3F) -O2 (2-1-1) 5%
3-H2B (2F, 3F) -O2 (2-2-1) 10%
3-BB (2F, 3F) -O2 (2-3-1) 5%
3-HHB (2F, 3F) -O2 (2-5-1) 8%
5-HHB (2F, 3F) -O2 (2-5-1) 6%
3-HH1OB (2F, 3F) -O2 (2-7-1) 5%
3-HBB (2F, 3F) -O2 (2-8-1) 10%
5-HBB (2F, 3F) -O2 (2-8-1) 5%
3-HHB (2F, 3CL) -O2 (2-9-1) 3%
3-HDhB (2F, 3F) -O2 (2-13-1) 5%
2-HH-3 (3-1-1) 22%
3-HH-4 (3-1-1) 7%
3-HHB-1 (3-5-1) 4%
2-BB (F) B-5 (3-7-1) 3%
5-B (F) BB-3 (3-8-1) 2%
To 100 parts by weight of the above composition, 0.1 part by weight of the compound (1-1) as the first component of the present invention and 0.1 part by weight of the compound (1-1-1-2) are added. 0.1 parts by weight of the polymerizable compound (6-1-2) which is not the first component was added.
MAC-VO-BB (F) -MAC (1-1)
MAC-VO-BB-AC (1-1-1-2)
MAC-B (2F) B-MAC (6-1-2)
The characteristics of the obtained composition are as follows.
NI = 86.1 ° C .; Tc <−20 ° C .; Δn = 0.098; Δε = −3.6; VHR-1 = 99.2%; VHR-2 = 98.4%; VHR-3 = 98. 7%.
The response time of the liquid crystal display device prepared by the method described in Example M1 was τ = 3.9 ms.

[Example M21]
3-H2B (2F, 3F) -O2 (2-2-1) 19%
5-BB (2F, 3F) -O2 (2-3-1) 5%
3-HHB (2F, 3F) -O2 (2-5-1) 8%
5-HHB (2F, 3F) -O2 (2-5-1) 7%
3-HBB (2F, 3F) -O2 (2-8-1) 5%
5-HBB (2F, 3F) -O2 (2-8-1) 5%
2-BB (2F, 3F) B-3 (2-11-1) 5%
5-dhBB (2F, 3F) -O2 (2-15-1) 5%
2-HH-3 (3-1-1) 22%
3-HH-5 (3-1-1) 3%
3-HH-O1 (3-1-1) 3%
3-HHB-1 (3-5-1) 5%
3-HHB-O1 (3-5-1) 3%
2-B (F) BB-5 (3-8-1) 5%
To 100 parts by weight of the above composition, 0.1 part by weight of the compound (1-1) as the first component of the present invention and 0.1 part by weight of the compound (1-8-1-1) are added. 0.1 parts by weight of the polymerizable compound (6-1-2) which is not the first component was added.
MAC-VO-BB (F) -MAC (1-1)
MAC-VO-BB (F) B-MAC (1-8-1-1)
MAC-B (2F) B-MAC (6-1-2)
The characteristics of the obtained composition are as follows.
NI = 81.7 ° C .; Tc <−20 ° C .; Δn = 0.104; Δε = −3.1; VHR-1 = 99.3%; VHR-2 = 98.5%; VHR-3 = 98. 7%.
The response time of the liquid crystal display device prepared by the method described in Example M1 was τ = 4.3 ms.

[Example M22]
V-HB (2F, 3F) -O2 (2-1-1) 5%
3-H2B (2F, 3F) -O2 (2-2-1) 13%
5-BB (2F, 3F) -O2 (2-3-1) 5%
3-HHB (2F, 3F) -O2 (2-5-1) 8%
5-HHB (2F, 3F) -O2 (2-5-1) 6%
2-HH1OB (2F, 3F) -O2 (2-7-1) 5%
3-HBB (2F, 3F) -O2 (2-8-1) 10%
5-HBB (2F, 3F) -O2 (2-8-1) 5%
2-HDhB (2F, 3F) -O2 (2-13-1) 5%
2-HH-3 (3-1-1) 22%
3-HH-4 (3-1-1) 7%
3-HHB-1 (3-5-1) 4%
2-BB (F) B-5 (3-7-1) 3%
5-B (F) BB-3 (3-8-1) 2%
To 100 parts by weight of the above composition, 0.3 part by weight of the compound (1-1-1-3) as the first component of the present invention was added.
AC-VO-BB-MAC (1-1-1-3)
The characteristics of the obtained composition are as follows.
NI = 80.0 ° C .; Tc <−20 ° C .; Δn = 0.096; Δε = −3.6; VHR-1 = 99.0%; VHR-2 = 98.1%; VHR-3 = 98. 5%.
The response time of the liquid crystal display device prepared by the method described in Example M1 was τ = 4.6 ms.

[Example M23]
V-HB (2F, 3F) -O2 (2-1-1) 5%
3-H2B (2F, 3F) -O2 (2-2-1) 10%
3-BB (2F, 3F) -O2 (2-3-1) 5%
3-HHB (2F, 3F) -O2 (2-5-1) 8%
5-HHB (2F, 3F) -O2 (2-5-1) 6%
2-HH1OB (2F, 3F) -O2 (2-7-1) 5%
3-HBB (2F, 3F) -O2 (2-8-1) 10%
2-BB (2F, 3F) B-4 (2-11-1) 8%
3-HDhB (2F, 3F) -O2 (2-13-1) 5%
2-HH-3 (3-1-1) 20%
3-HH-4 (3-1-1) 9%
3-HHB-1 (3-5-1) 4%
2-BB (F) B-5 (3-7-1) 3%
5-B (F) BB-3 (3-8-1) 2%
0.285 parts by weight of the compound (1-1-1-1) as the first component of the present invention and 0.015 parts by weight of the compound (1-1-1-4) were added to 100 parts by weight of the composition. .
MAC-VO-BB-MAC (1-1-1-1)
AC-VO-BB-AC (1-1-1-4)
The characteristics of the obtained composition are as follows.
NI = 81.7 ° C .; Tc <−20 ° C .; Δn = 0.106; Δε = −3.3; VHR-1 = 99.3%; VHR-2 = 98.7%; VHR-3 = 98. 9%.
The response time of the liquid crystal display device prepared by the method described in Example M1 was τ = 4.4 ms.

[Example M24]
V-HB (2F, 3F) -O2 (2-1-1) 5%
3-H2B (2F, 3F) -O2 (2-2-1) 10%
3-BB (2F, 3F) -O2 (2-3-1) 5%
3-HHB (2F, 3F) -O2 (2-5-1) 8%
5-HHB (2F, 3F) -O2 (2-5-1) 6%
3-HH1OB (2F, 3F) -O2 (2-7-1) 5%
3-HBB (2F, 3F) -O2 (2-8-1) 10%
3-HHB (2F, 3CL) -O2 (2-9-1) 2%
3-HDhB (2F, 3F) -O2 (2-13-1) 4%
3-dhBB (2F, 3F) -O2 (2-15-1) 5%
2-HH-3 (3-1-1) 22%
5-HB-3 (3-2-1) 7%
3-HHB-1 (3-5-1) 8%
2-BB (F) B-3 (3-7-1) 3%
In 100 parts by weight of the above composition, 0.1 part by weight of the compound (1-1) as the first component of the present invention, 0.1 part by weight of the compound (1-1-1-4), and the compound (1- 8-1-2) was added in an amount of 0.1 part by weight.
MAC-VO-BB (CF3) -MAC (1-1)
AC-VO-BB-AC (1-1-1-4)
MAC-VO-BB (2F) B-MAC (1-8-1-2)
The characteristics of the obtained composition are as follows.
NI = 81.7 ° C .; Tc <−20 ° C .; Δn = 0.098; Δε = −3.5; VHR-1 = 99.1%; VHR-2 = 98.5%; VHR-3 = 98. 1%.
The response time of the liquid crystal display device prepared by the method described in Example M1 was τ = 4.5 ms.

[Example M25]
3-HB (2F, 3F) -O4 (2-1-1) 5%
5-H2B (2F, 3F) -O2 (2-2-1) 10%
3-BB (2F, 3F) -O2 (2-3-1) 5%
3-HHB (2F, 3F) -O2 (2-5-1) 8%
5-HHB (2F, 3F) -O2 (2-5-1) 6%
3-HH1OB (2F, 3F) -O2 (2-7-1) 5%
3-HBB (2F, 3F) -O2 (2-8-1) 7%
3-HHB (2F, 3CL) -O2 (2-9-1) 3%
3-HDhB (2F, 3F) -O2 (2-13-1) 5%
2-HH-3 (3-1-1) 22%
3-HH-4 (3-1-1) 7%
1-BB-3 (3-3-1) 5%
3-HHB-1 (3-5-1) 4%
5-B (F) BB-3 (3-8-1) 5%
5-HBB (F) B-2 (3-13-1) 3%
0.05 parts by weight of the compound (1-1-1-4) as the first component of the present invention and 0.2 parts by weight of the compound (1-8-1-3) are added to 100 parts by weight of the above composition. Then, 0.15 parts by weight of the polymerizable compound (6-1-2) which is not the first component of the present invention was added.
AC-VO-BB-AC (1-1-1-4)
MAC-VO-B (2F) BB-MAC (1-8-1-3)
MAC-B (2F) B-MAC (6-1-2)
The characteristics of the obtained composition are as follows.
NI = 82.8 ° C .; Tc <−20 ° C .; Δn = 0.099; Δε = −3.1; VHR-1 = 99.1%; VHR-2 = 98.0%; VHR-3 = 98. 5%.
The response time of the liquid crystal display device prepared by the method described in Example M1 was τ = 4.2 ms.

[Example M26]
V-HB (2F, 3F) -O2 (2-1-1) 5%
3-H2B (2F, 3F) -O2 (2-2-1) 10%
5-BB (2F, 3F) -O4 (2-3-1) 5%
3-HHB (2F, 3F) -O2 (2-5-1) 8%
5-HHB (2F, 3F) -O2 (2-5-1) 6%
5-HH1OB (2F, 3F) -O2 (2-7-1) 5%
3-HBB (2F, 3F) -O2 (2-8-1) 10%
5-HDhB (2F, 3F) -O2 (2-13-1) 5%
2-HH-3 (3-1-1) 18%
2-HH-5 (3-1-1) 7%
3-HB-O2 (3-2-1) 7%
3-HHB-3 (3-5-1) 5%
3-B (F) BB-2 (3-8-1) 4%
5-HBB (F) B-3 (3-13-1) 5%
In 100 parts by weight of the composition, 0.1 part by weight of the compound (1-1-1-1) as the first component of the present invention, 0.1 part by weight of the compound (1-3-1-1), and 0.1 part by weight of compound (1-8-1-2) was added.
MAC-VO-BB-MAC (1-1-1-1)
MAC-1V-BB-MAC (1-3-1-1)
MAC-VO-BB (2F) B-MAC (1-8-1-2)
The characteristics of the obtained composition are as follows.
NI = 88.0 ° C .; Tc <−20 ° C .; Δn = 0.103; Δε = −3.3; VHR-1 = 99.3%; VHR-2 = 98.5%; VHR-3 = 98. 9%.
The response time of the liquid crystal display device prepared by the method described in Example M1 was τ = 4.5 ms.

[Example M27]
5-HB (2F, 3F) -O2 (2-1-1) 5%
3-H2B (2F, 3F) -O4 (2-2-1) 10%
3-BB (2F, 3F) -O2 (2-3-1) 5%
3-HHB (2F, 3F) -O2 (2-5-1) 9%
5-HHB (2F, 3F) -O2 (2-5-1) 8%
2-HH1OB (2F, 3F) -O2 (2-7-1) 5%
5-HBB (2F, 3F) -O2 (2-8-1) 5%
2-BB (2F, 3F) B-4 (2-11-1) 10%
2-HDhB (2F, 3F) -O2 (2-13-1) 5%
2-HH-3 (3-1-1) 22%
3-HH-4 (3-1-1) 7%
3-HHB-1 (3-5-1) 4%
5-B (F) BB-3 (3-8-1) 5%
0.1 parts by weight of the compound (1-1-1-1) as the first component of the present invention, 0.15 parts by weight of the compound (1-1-1-3), and 100 parts by weight of the composition 0.1 part by weight of the compound (1-8-1-3) was added.
MAC-VO-BB-MAC (1-1-1-1)
AC-VO-BB-MAC (1-1-1-3)
MAC-VO-B (2F) BB-MAC (1-8-1-3)
The characteristics of the obtained composition are as follows.
NI = 80.7 ° C .; Tc <−20 ° C .; Δn = 0.104; Δε = −3.3; VHR-1 = 99.3%; VHR-2 = 98.4%; VHR-3 = 98. 5%.
The response time of the liquid crystal display device prepared by the method described in Example M1 was τ = 4.5 ms.

[Example M28]
V-HB (2F, 3F) -O3 (2-1-1) 5%
3-H2B (2F, 3F) -O2 (2-2-1) 10%
3-BB (2F, 3F) -O2 (2-3-1) 5%
5-HHB (2F, 3F) -O2 (2-5-1) 8%
3-HH1OB (2F, 3F) -O2 (2-7-1) 5%
3-HBB (2F, 3F) -O2 (2-8-1) 10%
3-HHB (2F, 3CL) -O2 (2-9-1) 3%
5-BB (2F, 3F) B-2 (2-11-1) 10%
3-HDhB (2F, 3F) -O2 (2-13-1) 5%
2-HH-3 (3-1-1) 20%
3-HH-4 (3-1-1) 7%
5-HB-3 (3-2-1) 3%
3-HHB-1 (3-5-1) 3%
2-BB (F) B-5 (3-7-1) 3%
5-HBB (F) B-2 (3-13-1) 3%
In 100 parts by weight of the above composition, 0.1 part by weight of the compound (1-1-1-4) as the first component of the present invention, 0.1 part by weight of the compound (1-8-1-2), and 0.1 part by weight of the compound (1-8-1-3) was added.
AC-VO-BB-AC (1-1-1-4)
MAC-VO-BB (2F) B-MAC (1-8-1-2)
MAC-VO-B (2F) BB-MAC (1-8-1-3)
The characteristics of the obtained composition are as follows.
NI = 81.6 ° C .; Tc <−20 ° C .; Δn = 0.109; Δε = −3.2; VHR-1 = 99.2%; VHR-2 = 98.7%; VHR-3 = 98. 9%.
The response time of the liquid crystal display device prepared by the method described in Example M1 was τ = 4.5 ms.

[Example M29]
3-HB (2F, 3F) -O2 (2-1-1) 5%
3-H2B (2F, 3F) -O4 (2-2-1) 8%
2-BB (2F, 3F) -O2 (2-3-1) 5%
3-HHB (2F, 3F) -O2 (2-5-1) 8%
5-HHB (2F, 3F) -O2 (2-5-1) 6%
3-HH1OB (2F, 3F) -O2 (2-7-1) 5%
5-HBB (2F, 3F) -O2 (2-8-1) 5%
3-HDhB (2F, 3F) -O2 (2-13-1) 8%
5-dhBB (2F, 3F) -O2 (2-15-1) 5%
2-HH-3 (3-1-1) 20%
3-HH-4 (3-1-1) 8%
1-BB-3 (3-3-1) 5%
3-HHB-1 (3-5-1) 4%
5-B (F) BB-2 (3-8-1) 5%
5-HBB (F) B-3 (3-13-1) 3%
To 100 parts by weight of the above composition, 0.1 part by weight of the compound (1-1-1-3) as the first component of the present invention and 0.1 part by weight of the compound (1-8-1-2) are added. Then, 0.1 part by weight of the polymerizable compound (6-1-2) which is not the first component of the present invention was added.
AC-VO-BB-MAC (1-1-1-3)
MAC-VO-BB (2F) B-MAC (1-8-1-2)
MAC-B (2F) B-MAC (6-1-2)
The characteristics of the obtained composition are as follows.
NI = 84.1 ° C .; Tc <−20 ° C .; Δn = 0.100; Δε = −3.2; VHR-1 = 99.2%; VHR-2 = 98.4%; VHR-3 = 98. 7%.
The response time of the liquid crystal display device prepared by the method described in Example M1 was τ = 4.3 ms.

[Example M30]
V-HB (2F, 3F) -O3 (2-1-1) 5%
3-H2B (2F, 3F) -O2 (2-2-1) 10%
3-BB (2F, 3F) -O2 (2-3-1) 5%
5-HHB (2F, 3F) -O2 (2-5-1) 8%
3-HH1OB (2F, 3F) -O2 (2-7-1) 5%
3-HBB (2F, 3F) -O2 (2-8-1) 10%
3-HHB (2F, 3CL) -O2 (2-9-1) 3%
5-BB (2F, 3F) B-2 (2-11-1) 10%
3-HDhB (2F, 3F) -O2 (2-13-1) 5%
2-HH-3 (3-1-1) 20%
3-HH-4 (3-1-1) 7%
5-HB-3 (3-2-1) 3%
3-HHB-1 (3-5-1) 3%
2-BB (F) B-5 (3-7-1) 3%
5-HBB (F) B-2 (3-13-1) 3%
In 100 parts by weight of the composition, 0.1 part by weight of the compound (1-8-1-4) as the first component of the present invention, 0.1 part by weight of the compound (1-8-1-5), and 0.1 part by weight of compound (6-1-2) was added.
AC-VO-BB (2F) B-AC (1-8-1-4)
AC-VO-BB (2F) B-MAC (1-8-1-5)
MAC-B (2F) B-MAC (6-1-2)
The characteristics of the obtained composition are as follows.
NI = 81.7 ° C .; Tc <−20 ° C .; Δn = 0.109; Δε = −3.1; VHR-1 = 99.1%; VHR-2 = 98.5%; VHR-3 = 98. 8%.
The response time of the liquid crystal display device prepared by the method described in Example M1 was τ = 4.1 ms.

The compositions of Example M1 to Example M30 have a shorter response time than that of Comparative Example M1. Therefore, the liquid crystal composition according to the present invention has more excellent characteristics than the liquid crystal composition shown in Comparative Example M1.

Claims (25)

1. Contains at least one compound selected from the group of compounds represented by formula (1) as the first component and at least one compound selected from the group of compounds represented by formula (2) as the second component Liquid crystal composition.
   

   

   
   Wherein P ¹ and P ² are independently a group selected from the groups represented by formulas (P-1) to (P-6);
   

   

   
   R ¹ and R ² are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons; ring A and ring B are independently 1,4 -Cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, or pyrimidine-2,5-diyl In these, at least one hydrogen may be replaced by halogen, alkyl having 1 to 12 carbons, or alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by halogen; ring C and ring E Are independently 1,4-cyclohexylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, and 3-fluoro-1,4-phenylene; ring D is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5- Methyl-1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, or 7,8-difluorochroman-2,6-diyl; Sp is alkylene having 1 to 6 carbon atoms; Yes, in alkylene, at least one —CH ₂ — may be replaced by —O—, —OCO—, —COO—, or —CH═CH—; Z ¹ , Z ² , and Z ³ are Independently a single bond, ethylene, methyleneoxy, or carbonyloxy; k is 0, 1, 2, or 3; m is 1, 2, or 3; n is 0 or 1 And m The sum of the n is 3 or less.
2. 2. The liquid crystal composition according to claim 1, wherein the first component is at least one compound selected from the group of compounds represented by formula (1-1) to formula (1-8).
   

   

   
   Here, Y ¹ to Y ¹² are independently hydrogen, halogen, alkyl having 1 to 12 carbons, or trifluoromethyl; X ¹ and X ² are independently hydrogen or methyl.
3. The first component is at least one compound selected from the group of compounds represented by formula (1-1) to formula (1-8) according to claim 2, and Y ¹ to Y ¹² are hydrogen. Item 2. A liquid crystal composition according to item 1.
4. The first component is at least one compound selected from the group of compounds represented by formula (1-1) to formula (1-8) according to claim 2, wherein formula (1-1) to formula (1) -7) wherein at least one of Y ¹ to Y ⁸ is fluorine or trifluoromethyl, and in formula (1-8), at least one of Y ¹ to Y ¹² is fluorine or trifluoromethyl. 2. The liquid crystal composition according to 1.
5. The liquid crystal composition according to any one of claims 1 to 4, wherein the first component is at least one compound selected from the group of compounds represented by formula (1-1) according to claim 2.
6. The liquid crystal composition according to any one of claims 1 to 4, wherein the first component is at least one compound selected from the group of compounds represented by formula (1-2) according to claim 2.
7. The liquid crystal composition according to any one of claims 1 to 6, wherein the first component comprises at least two compounds selected from the group of compounds represented by formula (1) according to claim 1.
8. The first component is at least one compound selected from the group of compounds represented by formula (1) according to claim 1, and further contains a polymerizable compound other than formula (1) according to claim 1. Item 8. The liquid crystal composition according to any one of items 1 to 7.
9. 9. The liquid crystal composition according to claim 1, wherein the second component is at least one compound selected from the group of compounds represented by formulas (2-1) to (2-19).
   

   

   
   

   

   
   Here, R ¹ and R ² are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons.
10. The liquid crystal composition according to claim 1, wherein the second component is at least one compound selected from the group of compounds represented by formula (2-3) according to claim 9.
11. The liquid crystal composition according to claim 1, wherein the second component is at least one compound selected from the group of compounds represented by formula (2-5) according to claim 9.
12. The liquid crystal composition according to claim 1, wherein the second component is at least one compound selected from the group of compounds represented by formula (2-7) according to claim 9.
13. The liquid crystal composition according to claim 1, wherein the second component is at least one compound selected from the group of compounds represented by formula (2-13) according to claim 9.
14. The liquid crystal composition according to claim 1, further comprising at least one compound selected from the group of compounds represented by formula (3) as a third component.
    

    

    
    Here, R ³ and R ⁴ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or carbons in which at least one hydrogen is replaced by fluorine. Ring F, ring G, and ring I are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 3-fluoro. -1,4-phenylene; Z ⁴ and Z ⁵ are independently a single bond, ethylene, methyleneoxy, or carbonyloxy; p is 0, 1, or 2.
15. The liquid crystal composition according to claim 14, wherein the third component is at least one compound selected from the group of compounds represented by formulas (3-1) to (3-13).
    

    

    
    Here, R ³ and R ⁴ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or carbon number in which at least one hydrogen is replaced by fluorine. 2 to 12 alkenyl.
16. The liquid crystal composition according to claim 14, wherein the third component is at least one compound selected from the group of compounds represented by formula (3-1) of claim 15.
17. The liquid crystal composition according to claim 14, wherein the third component is at least one compound selected from the group of compounds represented by formula (3-7) of claim 15.
18. Based on the weight of the liquid crystal composition excluding the first component and the polymerizable compound other than the first component, the ratio of the second component is in the range of 10 wt% to 80 wt%, and the ratio of the third component is 20 wt%. % To 90% by weight of the polymerizable compound other than the first component and the first component with respect to 100 parts by weight of the liquid crystal composition excluding the polymerizable compound other than the first component and the first component. The liquid crystal composition according to any one of claims 14 to 17, wherein the ratio is in the range of 0.03 parts by weight to 10 parts by weight.
19. The liquid crystal composition according to claim 1, further comprising a polymerization initiator.
20. The liquid crystal composition according to any one of claims 1 to 19, further comprising a polymerization inhibitor.
21. The upper limit temperature of the nematic phase is 70 ° C. or higher, the optical anisotropy (25 ° C.) at a wavelength of 589 nm is 0.08 or higher, and the dielectric anisotropy (25 ° C.) at a frequency of 1 kHz is −2 or lower. The liquid crystal composition according to any one of claims 1 to 20.
22. It is comprised from two board | substrates which have an electrode layer in at least one board | substrate, The compound which the polymeric compound in the liquid-crystal composition of any one of Claim 1 to 21 superposed | polymerized between these two board | substrates contains A polymer-supported alignment type (PSA) liquid crystal display element characterized by disposing a liquid crystal material.
23. The liquid crystal display element according to claim 22, wherein the operation mode of the liquid crystal display element is a TN mode, a VA mode, an OCB mode, an IPS mode, or an FFS mode, and the driving method of the liquid crystal display element is an active matrix method.
24. The liquid crystal display element according to claim 22 is disposed between two substrates, and the liquid crystal composition according to any one of claims 1 to 21 is irradiated with light in a voltage applied state to polymerize a polymerizable compound. The manufacturing method of the liquid crystal display element manufactured by this.
25. Use of the liquid crystal composition according to any one of claims 1 to 21 in a liquid crystal display device.