WO2020217710A1

WO2020217710A1 - Compound, liquid crystal composition, and liquid crystal display element

Info

Publication number: WO2020217710A1
Application number: PCT/JP2020/008675
Authority: WO
Inventors: 智広矢野; 和寛荻田
Original assignee: Jnc株式会社; Jnc石油化学株式会社
Priority date: 2019-04-25
Filing date: 2020-03-02
Publication date: 2020-10-29
Also published as: JPWO2020217710A1; CN113710652A; TW202039802A

Abstract

Provided is a compound having at least one characteristic proprety selected from high chemical stability, high ability to horizontally align liquid crystal molecules, high alignability over a broad range of addition concentrations, proper reactivity, high solubility in liquid crystal compositions, and so forth.　Provided is a compound represented by formula (1).　In formula (1), a and b independently represent 0, 1 or 2 and satisfy the requirement represented by the formula: 0 ≦ a+b ≦ 3, ring A¹, ring A², ring A³ and ring A⁴ independently represent, for example, a 1,4-cyclohexylene group, Z¹, Z², Z³, Z⁴ and Z⁵ independently represent a single bond, an alkylene group having 1 to 10 carbon atoms or the like, Sp¹ and Sp² independently represent a single bond, an alkylene group having 1 to 10 carbon atoms or the like, and P¹ and P² independently represent a specific polymerizable group.

Description

Compounds, liquid crystal compositions and liquid crystal display devices

The present invention relates to compounds, liquid crystal compositions and liquid crystal display devices. More specifically, a polymerizable polar compound having a thioester (-COS-, -SCO-) or a thiosilicate ester (-CH = CHCOS-, -SCOCH = CH-) in the molecule, which comprises this compound and has a dielectric constant. The present invention relates to a liquid crystal composition having positive or negative anisotropy, and a liquid crystal display element containing this composition.

In the liquid crystal display element, the classification based on the operation mode of the liquid crystal molecule is PC (phase change), TN (twisted nematic), STN (super twisted nematic), ECB (electrically controlled birefringence), OCB (optically compensated bend), IPS. (In-plane switching), VA (vertical alignment), FFS (fringe field switching), FPA (field-induced photo-reactive alignment) and other modes. The classifications based on the drive method of the element are PM (passive matrix) and AM (active matrix). PM is classified into static, multiplex and the like, and AM is classified into TFT (thin film transistor), MIM (metal insulator metal) and the like. The classification of TFT is amorphous silicon (amorphous silicon) and polycrystalline silicon (polycrystal silicon). The latter is classified into a high temperature type and a low temperature type according to the manufacturing process. The classification based on the light source is a reflective type that uses natural light, a transmissive type that uses a backlight, and a transflective type that uses both natural light and a backlight.

The liquid crystal display element contains a liquid crystal composition having a nematic phase. This composition has suitable properties. By improving the characteristics of this composition, an AM element having good characteristics can be obtained. The relationship between the two characteristics is summarized in Table 1 below. The properties of the composition will be further described based on commercially available AM devices. The temperature range of the nematic phase is related to the temperature range in which the device can be used. The preferred upper limit temperature of the nematic phase is about 70 ° C. or higher, and the preferred lower limit temperature of the nematic phase is about −10 ° C. or lower. The viscosity of the composition is related to the response time of the device. A short response time is preferred for displaying moving images on the device. A shorter response time of even 1 millisecond is desirable. 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. Depending on the mode of the device, a large optical anisotropy or a small optical anisotropy, that is, an appropriate optical anisotropy is required. The product (Δn × d) of the optical anisotropy (Δn) of the composition and the cell gap (d) of the device is designed to maximize the contrast ratio. The appropriate product value depends on the type of operating mode. This value is about 0.45 μm for devices in modes such as TN. This value ranges from about 0.30 μm to about 0.40 μm for VA mode devices and from about 0.20 μm to about 0.30 μm for IPS or FFS mode devices. In these cases, a composition having a large optical anisotropy is preferable for a device having a small cell gap. The large permittivity anisotropy in the composition contributes to the low threshold voltage, low power consumption and large contrast ratio in the device. Therefore, a large positive or negative dielectric anisotropy is preferable. A large resistivity in the composition contributes to a large voltage retention and a large contrast ratio in the device. Therefore, a composition having a large resistivity at an initial stage not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase is preferable. After long-term use, a composition having a large specific resistance not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase is preferable. The stability of the composition against UV and heat is related to the life of the device. When this stability is high, the life of the device is long. Such characteristics are preferable for AM elements used in liquid crystal projectors, liquid crystal televisions, and the like.

In the AM device having the TN mode, a composition having a positive dielectric anisotropy is used. In the AM device having the VA mode, a composition having a negative dielectric anisotropy is used. In an AM device having an IPS mode or an FFS mode, a composition having positive or negative dielectric anisotropy is used.
In a polymer sustained alignment (PSA) type AM device, a composition having positive or negative dielectric anisotropy is used. In a polymer sustained alignment (PSA) type liquid crystal display element, a liquid crystal composition containing a polymer is used. First, the composition to which a small amount of the polymerizable compound is added is injected into the device. Next, the composition is irradiated with ultraviolet rays while applying a voltage between the substrates of this device. The polymerizable compound polymerizes to form a network structure of the polymer in the composition. In this composition, since the orientation of the liquid crystal molecules can be controlled by the polymer, the response time of the device is shortened and the burn-in of the image is improved. Such effects of the polymer can be expected for devices having modes such as TN, ECB, OCB, IPS, VA, FFS, FPA.

Instead of an alignment film such as polyimide, a method of controlling the orientation of a liquid crystal by using a low molecular weight compound having a cinnamate group, polyvinyl synnamate, a low molecular weight compound having a chalcone structure, a low molecular weight compound having an azobenzene structure, or a dendrimer is used. It has been reported (Patent Documents 1, 2 or 3). In the method of Patent Documents 1, 2 or 3, first, the low molecular weight compound or polymer is dissolved in the liquid crystal composition as an additive. Next, the additive is phase-separated to form a thin film composed of the low molecular weight compound or polymer on the substrate. Finally, the substrate is irradiated with linearly polarized light at a temperature higher than the upper limit temperature of the liquid crystal composition. When this linearly polarized light dimerizes or isomerizes a low molecular weight compound or polymer, the molecules are arranged in a certain direction. In this method, by selecting the type of low molecular weight compound or polymer, an element in a horizontal orientation mode such as IPS or FFS and an element in a vertical orientation mode such as VA can be manufactured. In this method, it is important that the low molecular weight compound or polymer is easily dissolved at a temperature higher than the upper limit temperature of the liquid crystal composition, and when the temperature is returned to room temperature, the compound is easily phase-separated from the liquid crystal composition. However, it has been difficult to ensure compatibility between the low molecular weight compound or polymer and the liquid crystal composition.

So far, as a compound capable of horizontally aligning a liquid crystal molecule in a liquid crystal display element having no alignment film, Patent Document 2 contains a compound (S-1) (paragraph 0034 of the specification, [Chemical Formula 2]), and a patent. Document 3 describes compound (S-2) (compound of P176 in the specification [14]) and the like. However, these compounds require high-energy light irradiation in order to horizontally orient the liquid crystal molecules with sufficient orientation, and there is a concern that the production time will increase due to long-term light irradiation and that the liquid crystal will be damaged. Yes, improvement is desired.

International Publication No. 2015/146369 International Publication No. 2017/051762 International Publication No. 2017/102068

The first object of the present invention is at least one of high chemical stability, high ability to horizontally orient liquid crystal molecules, high orientation over a wide range of additive concentrations, appropriate reactivity, and high solubility in liquid crystal compositions. It is to provide a compound which has two characteristics and is expected to have a large voltage retention when used in a liquid crystal display element. The second challenge is to include this compound and have a high upper limit temperature of the nematic phase, a lower lower limit temperature of the nematic phase, a small viscosity, proper optical anisotropy, a large positive or negative dielectric anisotropy, a large specific resistance. It is an object of the present invention to provide a liquid crystal composition satisfying at least one of properties such as high stability against ultraviolet rays, high stability against heat, and a large elastic constant. The third problem is that when this composition is contained and the polar compound forms a film in the device by irradiating the composition with ultraviolet rays, the film has appropriate hardness, low permeability of the components to be contacted, and high weather resistance. At least one characteristic of property, at least one characteristic of appropriate volume resistance, wide temperature range in which the device can be used, short response time, high voltage retention, low threshold voltage, large contrast ratio, long life. It is to provide the liquid crystal display element which has.

The present inventors have found that the compound represented by the following formula (1) can solve the above-mentioned problems, and have completed the invention.

(The explanation of the symbols in the formula will be described later)

The first advantages of the present invention are at least chemically high stability, high ability to orient liquid crystal molecules horizontally, high orientation over a wide range of addition concentrations, suitable reactivity, and high solubility in liquid crystal compositions. It is to provide a compound which has one and is expected to have a large voltage retention when used in a liquid crystal display element. The second advantage is that it contains this compound and has a high upper limit temperature of the nematic phase, a lower lower limit temperature of the nematic phase, a small viscosity, suitable optical anisotropy, a large positive or negative dielectric anisotropy, a large specific resistance. It is an object of the present invention to provide a liquid crystal composition satisfying at least one of properties such as high stability against ultraviolet rays, high stability against heat, and a large elastic constant. The third advantage is that the composition contains this composition, and when the polar compound forms a film in the device by irradiating the composition with ultraviolet rays, the film has appropriate hardness, low permeability of the components to be contacted, and high weather resistance. At least one characteristic of property, at least one characteristic of appropriate volume resistance, wide temperature range in which the device can be used, short response time, high voltage retention, low threshold voltage, large contrast ratio, long life. It is to provide the liquid crystal display element which has. By using the liquid crystal composition containing the compound of the present invention, the step of forming the alignment film becomes unnecessary, so that a liquid crystal display element having a reduced manufacturing cost can be obtained.

The usage of terms in this specification is as follows. The terms "liquid crystal composition" and "liquid crystal display element" may be abbreviated as "composition" and "element", respectively. "Liquid crystal display element" is a general term for a liquid crystal display panel and a liquid crystal display module. The "liquid crystal compound" is a compound having a liquid crystal phase such as a nematic phase or a smectic phase, and a compound having no liquid crystal phase, but is composed for the purpose of adjusting characteristics such as temperature range, viscosity, and dielectric anisotropy of the nematic phase. It is a general term for compounds mixed in a product. This compound has a six-membered ring such as 1,4-cyclohexylene and 1,4-phenylene, and its molecular structure is rod-like. The "polymerizable compound" is a compound added for the purpose of forming a polymer in the composition. A "polar compound" helps liquid crystal molecules to align by interacting with polar groups on the substrate surface.

The liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. The proportion (content) of the liquid crystal compound is expressed as a weight percentage (% by weight) based on the weight of the liquid crystal composition. Additives such as optically active compounds, antioxidants, ultraviolet absorbers, dyes, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, and polar compounds are added to the liquid crystal composition as needed. To. The ratio of the additive (addition amount) is expressed as a weight percentage (% by weight) based on the weight of the liquid crystal composition, similarly to the ratio of the liquid crystal compound. Parts per million (ppm) by weight may also be used. The ratio of the polymerization initiator and the polymerization inhibitor is exceptionally expressed based on the weight of the polymerizable compound.

The compound represented by the formula (1) may be abbreviated as "compound (1)". Compound (1) means one compound represented by the formula (1), a mixture of two compounds, or a mixture of three or more compounds. This rule also applies to at least one compound selected from the group of compounds represented by the formula (2). Symbols such as B ¹ , C ¹ , and F enclosed in a hexagon correspond to ring B ¹ , ring C ¹ , and ring F, respectively. The hexagon represents a six-membered ring such as a cyclohexane ring or a benzene ring or a fused ring such as a naphthalene ring. The diagonal lines across this hexagon indicate that any hydrogen on the ring may be replaced by a group such as -Sp ^1- P ¹ . Subscripts such as e indicate the number of replaced groups. When the subscript is 0, there is no such replacement.

The symbol of the terminal groups R ¹¹ was used in a plurality of component compounds. In these compounds, two groups represented by any two R ¹¹ may be the same or different. For example, there are cases where R ^{11 of} compound (2) is ethyl and R ¹¹ of compound (3) is ethyl. In some cases, R ^{11 of} compound (2) is ethyl and R ¹¹ of compound (3) is propyl. This rule also applies to symbols such as other end groups, rings, and binding groups. In the formula (8), when i is 2, two rings ^{D 1} are present. In this compound, two groups two rings D ¹ represents may be the same or different. This rule, i applies to any two rings D ¹ of the case 2 larger. This rule also applies to symbols such as other rings and binding groups.

The expression "at least one'A'" means that the number of'A's is arbitrary. The expression "at least one'A'may be replaced by'B'" is that when the number of'A's is 1, the position of the'A'is arbitrary and the number of'A's is 2. When there is more than one, their positions can be selected without limitation. This rule also applies to the expression "at least one'A' has been replaced by a'B'". The expression "at least one A may be replaced by B, C, or D" is expressed when at least one A is replaced by B, at least one A is replaced by C, and at least. When one A is replaced by D, it means that a plurality of A's are replaced by at least two of B, C and D. For example, alkyl, alkenyl, alkoxy, alkoxy, which may replace at least one -CH _2- (or-(CH ₂ ) _2- ) with -O- (or -CH = CH-). Includes alkyl, alkoxyalkenyl, alkenyloxyalkyl. It is not preferable that two consecutive -CH _2- are replaced with -O- to become -O-O-. Alkyl such as in, -CH ₂ methyl moiety _(-CH 2 -H) - by is replaced by -O- is not preferred also be the -O-H.

Halogen means fluorine, chlorine, bromine, or iodine. Preferred halogens are fluorine or chlorine. A more preferred halogen is fluorine. Alkyl is linear or branched and does not contain cyclic alkyl. Linear alkyl is generally preferred over branched alkyl. The same applies to terminal groups such as alkoxy and alkenyl. The configuration for 1,4-cyclohexylene is preferably trans over cis in order to raise the upper temperature limit of the nematic phase. 2-Fluoro-1,4-phenylene means the following two divalent groups. In the chemical formula, fluorine may be left-facing (L) or right-facing (R). This rule also applies to asymmetric divalent groups generated by removing two hydrogens from the ring, such as tetrahydropyran-2,5-diyl.

The present invention includes the following items and the like.

[1] A compound represented by the formula (1).

In equation (1)
a and b are independently 0, 1 or 2, 0 ≦ a + b ≦ 3, and so on.
Ring A ¹ , Ring A ² , Ring A ³ and Ring A ⁴ are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, Decahydronaphthrene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine- 2,5-diyl, pyridine-2,5-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, perhydrocyclopenta [a] phenanthrene-3,17 -Diyl, or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta [a] phenanthrene-3,17-diyl, In these rings, at least one hydrogen is fluorine, chlorine, alkyl with 1 to 12 carbons, alkenyl with 2 to 12 carbons, alkoxy with 1 to 11 carbons, alkenyloxy with 2 to 11 carbons, -Sp. ^1- P ¹ , and
May be replaced by ² -P ^2, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine,
When a is 2, two rings A ¹ may be different when b is 2, two rings A ⁴ may be different;
Z ¹ , Z ² , Z ³ , Z ⁴ and Z ⁵ are independently single-bonded or alkylenes with 1 to 10 carbon atoms, in which at least one -CH _2- is -O-,-. It may be replaced by S-, -CO-, -COO-, -OCO-, or -OCOO-, and at least one- (CH ₂ ) ₂ -is -CH = CH- or -C≡C-. It may be replaced, in which at least one hydrogen may be replaced with fluorine or chlorine. However, at least one of Z ² , Z ³ , or Z ⁴ is -COS-, -SCO-, -CH = CHCOS-, or -SCOCH = CH-, and Z ² , Z ³ , or Z. -COS- and -OCO- or -SCO- and -COO- are never simultaneously present in the ^4, when a is 2, two ^{Z 1} may be different when b is 2, the two Z ⁵ may be different;
Sp ¹ and Sp ² are independently single-bonded or alkylene with 1 to 10 carbon atoms, in which at least one -CH _2- is -O-, -CO-, -COO-, -OCO. -Or -OCOO- may be replaced, and at least one- (CH ₂ ) _2- may be replaced by -CH = CH- or -C≡C-, at least 1 in these groups. One hydrogen may be replaced with fluorine or chlorine,
If multiple Sp ¹ or Sp ² are present, it may be different from each;
P ¹ and P ² are independent groups represented by any of the formulas (1b) to (1h), and when a plurality of P ¹ or P ² are present, they may be different from each other;

In equations (1b) to (1h),
M ¹ , M ² , M ³ and M ⁴ are independently hydrogen, fluorine, chlorine, alkyl with 1 to 5 carbon atoms, or alkyl with 1 to 5 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. And X ¹ is O or S;
R ² is hydrogen, fluorine, chlorine, or an alkyl having 1 to 5 carbon atoms, in which at least one hydrogen may be replaced by fluorine or chlorine, and at least one -CH _2- is -O-. May be replaced with;
R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently hydrogen or alkyl with 1 to 15 carbon atoms, in which at least one -CH _2- is -O- or-. It may be replaced by S-, at least one- (CH ₂ ) ₂ -may be replaced by -CH = CH- or -C≡C-, and in these groups, at least one hydrogen is fluorine. Alternatively, it may be replaced with chlorine.

[2] In equation (1)
a and b are independently 0, 1 or 2, and 0 ≦ a + b ≦ 2.
Ring A ¹ , Ring A ² , Ring A ³ and Ring A ⁴ are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, Decahydronaphthrene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine- 2,5-diyl, pyridine-2,5-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, perhydrocyclopenta [a] phenanthrene-3,17 -Diyl, or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta [a] phenanthrene-3,17-diyl, In these rings, at least one hydrogen is fluorine, chlorine, alkyl with 1 to 12 carbon atoms, alkenyl with 2 to 12 carbon atoms, alkoxy with 1 to 11 carbon atoms, alkenyloxy with 2 to 11 carbon atoms, -Sp. It may be replaced by ^1- P ¹ or -Sp ^2- P ² , in these groups at least one hydrogen may be replaced by fluorine or chlorine, and when a is 2, two rings A ¹ may be different when b is 2, two rings a ⁴ may be different;
Z ¹ , Z ² , Z ³ , Z ⁴ and Z ⁵ are independently single-bonded,-(CH ₂ ) _2- , -C ≡ C-, -C ≡ C-C ≡ C-, -COO-, -OCO-, -CF ₂ O-, -OCF _2- , -CH ₂ O-, -OCH _2- , -CF = CF-, -CH = CHCOO-, -OCOCH = CH-, -CH = CH-, -CH = CHCO-, -COCH = CH-, -COS-, -SCO-, -CH = CHCOS-, or -SCOCH = CH-, provided that at least in Z ² , Z ³ , or Z ^4. One is -COS-, -SCO-, -CH = CHCOS-, or -SCOCH = CH-, and in Z ² , Z ³ , or Z ⁴ , -COS- and -OCO- or -SCO- and- COO-does not exist at the same time;
When a is 2, two Z ¹ may be different, the two Z ⁵ may be different;
Sp ¹ and Sp ² are independently a single bond or alkylene having 1 to 10 carbon atoms, in the alkylene, at least one of _-CH 2 -, -O -, - COO-, or substituted with -OCO- At least one of-(CH ₂ ) ₂ -may be replaced by -CH = CH-, and in these groups, at least one hydrogen may be replaced by fluorine or chlorine. If multiple Sp ¹ or Sp ² there may be different from each;
P ¹ and P ² are independent groups represented by any of the formulas (1b) to (1h), and when a plurality of P ¹ or P ² are present, they may be different from each other;

In equations (1b) to (1h),
M ¹ , M ² , M ³ and M ⁴ are independently hydrogen, fluorine, chlorine, alkyl with 1 to 5 carbon atoms, or alkyl with 1 to 5 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. And X ¹ is O or S;
R ² is hydrogen, fluorine, chlorine, or an alkyl having 1 to 5 carbon atoms, in which at least one hydrogen may be replaced by fluorine or chlorine, and at least one -CH _2- is -O-. May be replaced with;
R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently hydrogen or alkyl with 1 to 15 carbon atoms, in which at least one -CH _2- is -O- or-. It may be replaced by S-, at least one-(CH ₂ ) ₂ -may be replaced by -CH = CH- or -C≡C-, and in these groups, at least one hydrogen is fluorine. The compound according to [1], which may be replaced with chlorine.

[3] The compound according to [1] or [2], which is represented by any one of formulas (1-1) to (1-3).

In equations (1-1) to (1-3),
Ring A ¹ , Ring A ² , Ring A ³ and Ring A ⁴ are independent, 1,4-cyclohexylene, 1,4-phenylene, naphthalene-2,6-diyl, pyrimidine-2,5-diyl, Pyridine-2,5-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, or anthracene-2,6-diyl, in which at least one hydrogen is fluorine, chlorine, Replaced by alkyl with 1 to 12 carbons, alkenyl with 2 to 12 carbons, alkoxy with 1 to 11 carbons, alkenyloxy with 2 to 11 carbons, -Sp ^1- P ¹ or -Sp ^2- P ^2. at best, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine, when a is 2, two rings a ¹ may be different when b is 2, 2 One of the rings a ⁴ may be different;
Z ² , Z ³ and Z ⁴ are independently single-bonded,-(CH ₂ ) _2- , -C ≡ C-, -C ≡ C-C ≡ C-, -COO-, -OCO-, -CF _{_{_{_{2 O -, - OCF 2 -}}}} , - CH 2 O -, - OCH 2 -, - CF = CF -, - CH = CHCOO -, - OCOCH = CH -, - CH = CH -, - CH = CHCO-, -COCH = CH -, - COS - , - SCO -, - CH = CHCOS-, or -SCOCH = a CH-, provided ^that at least one among Z 2, ^{Z 3} or ^{Z 4,} are,-COS -, - SCO -, - CH = CHCOS-, or -SCOCH = a ^CH-, ^Z ^2, Z ^{^3,} or in ^{Z 4} -COS- and -OCO- or -SCO- and -COO- simultaneous presence Never;
Sp ¹ and Sp ² are independently single-bonded or alkylene with 1 to 10 carbon atoms, in which at least one -CH _2- is -O-, -COO-, -OCOO-, or-. It may be replaced by OCO-, at least one- (CH ₂ ) ₂ -may be replaced by -CH = CH-, and in these groups at least one hydrogen is replaced by fluorine or chlorine. at best, when a plurality of Sp ¹ or Sp ² are present, it may be different from each;
P ¹ and P ² are independent groups represented by any of the formulas (1b) to (1h), and when a plurality of P ¹ or P ² are present, they may be different from each other;

In equations (1b) to (1h),
M ¹ , M ² , M ³ and M ⁴ are independently hydrogen, fluorine, chlorine, alkyl with 1 to 5 carbon atoms, or alkyl with 1 to 5 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. And X ¹ is O or S;
R ² is hydrogen, fluorine, chlorine, or an alkyl having 1 to 5 carbon atoms, in which at least one hydrogen may be replaced by fluorine or chlorine, and at least one -CH _2- is -O-. May be replaced with;
R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ are independently hydrogen, or alkyl with 1 to 15 carbon atoms, in which at least one -CH _2- is -O- or It may be replaced by —S—, at least one − (CH ₂ ) ₂ − may be replaced by −CH = CH− or −C≡C−, and in these groups, at least one hydrogen It may be replaced with fluorine or chlorine.

[4] In equations (1-1) to (1-3),
Ring A ¹ , Ring A ² , Ring A ³ and Ring A ⁴ are independently 1,4-cyclohexylene, 1,4-phenylene, naphthalene-2,6-diyl, fluorene-2,7-diyl, Or phenanthrene-2,7-diyl, in these rings at least one hydrogen is fluorine, chlorine, alkyl with 1 to 12 carbons, alkenyl with 2 to 12 carbons, alkoxy with 1 to 11 carbons, It may be replaced by alkenyloxy with 2 to 11 carbon atoms, -Sp ^1- P ¹ , or -Sp ^2- P ² ;
Z ² , Z ³ and Z ⁴ are independently single-bonded,-(CH ₂ ) _2- , -C ≡ C-C ≡ C-, -C ≡ C-, -COO-, -OCO-, -CH = CHCOO-, -OCOCH = CH-, -CH = CH-, -CH = CHCO-, -COCH = CH-, -COS-, -SCO-, -CH = CHCOS-, or -SCOCH = CH-. However, at least one of Z ² , Z ³ , or Z ⁴ is -COS-, -SCO-, -CH = CHCOS-, or -SCOCH = CH-, and is Z ² , Z ³ , or. never -COS- and the -OCO- or -SCO- and -COO- are present simultaneously in the Z ^4;
Sp ¹ and Sp ² are independently single-bonded or alkylene with 1 to 10 carbon atoms, in which at least one -CH _2- is -O-, -COO-, -OCOO-, or-. It may be replaced by OCO-, and at least one- (CH ₂ ) ₂ -may be replaced by -CH = CH-, and if multiple Sp ¹ or Sp ² are present, each is different. Well;
P ¹ and P ² are independently represented by any of the formula (1b), the formula (1c), the formula (1d), or the formula (1e), and there are a plurality of P ¹ or P ^2. If so, each may be different;

In equations (1b) to (1e),
M ¹ , M ² , M ³ and M ⁴ are independently hydrogen, fluorine, chlorine, alkyl with 1 to 5 carbon atoms, or alkyl with 1 to 5 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. And X ¹ is O or S;
R ² is hydrogen, fluorine, chlorine, or an alkyl having 1 to 5 carbon atoms, in which at least one hydrogen may be replaced by fluorine or chlorine, and at least one -CH _2- is -O-. May be replaced with;
R ³ , R ⁴ , R ⁵ and R ⁶ are independently hydrogen or alkyl with 1 to 15 carbon atoms, in which at least one -CH _2- is -O- or -S-. It may be replaced, and at least one of-(CH ₂ ) _2- may be replaced by -CH = CH- or -C≡C-, in which at least one hydrogen is fluorine or chlorine. The compound according to [3], which may be replaced.

[5] In equations (1-1) to (1-3),
Ring A ¹ , Ring A ² , Ring A ³ and Ring A ⁴ are independent, 1,4-cyclohexylene, 1,4-phenylene, naphthalene-2,6-diyl, fluorene-2,7-diyl, Alternatively, it may be phenanthrene-2,7-diyl, in which at least one hydrogen may be replaced with fluorine, chlorine, methyl, or ethyl;
Z ² , Z ³ and Z ⁴ are independently single-bonded,-(CH ₂ ) _2- , -C ≡ C-C ≡ C-, -C ≡ C-, -COO-, -OCO-, -CH = CHCOO-, -OCOCH = CH-, -CH = CH-, -CH = CHCO-, -COCH = CH-, -COS-, -SCO-, -CH = CHCOS-, or -SCOCH = CH-. However, at least one of Z ² , Z ³ , or Z ⁴ is -COS-, -SCO-, -CH = CHCOS-, or -SCOCH = CH-, and is Z ² , Z ³ , or. never -COS- and the -OCO- or -SCO- and -COO- are present simultaneously in the Z ^4;
Sp ¹ and Sp ² are independently single-bonded or alkylene with 1 to 10 carbon atoms, in which at least one -CH _2- is -O-, -COO-, -OCOO-, or-. It may be replaced by OCO-, and at least one- (CH ₂ ) ₂ -may be replaced by -CH = CH-, and if multiple Sp ¹ or Sp ² are present, each is different. Well;
P ¹ and ^{P 2} are each independently formula (1b-1), (1b -2), (1b-3), (1b-4), formula (1b-5), (1c -1), (1d -1), a group represented by (1d-2) or (1e-1), where X ² , X ³ , X ⁴ , X ⁵ and X ⁶ are independently O or S [3]. The compound described.

[6] In the compounds represented by the formulas (1-1) to (1-3), any one of Z ² , Z ³ , or Z ⁴ is -COS- or -SCO-, [ 3] The compound according to.

[7] The compound according to any one of [1] to [6], which is represented by any one of the following formulas.

P ¹ and ^{P 2} are each independently formula (1b-1), (1b -2), (1b-3), (1b-4), formula (1b-5), (1c -1), (1d -1), a group represented by (1d-2) or (1e-1), where X ² , X ³ , X ⁴ , X ⁵ and X ⁶ are independently O or S;
Sp ¹ and Sp ² are independently single bonds or alkylenes having 1 to 10 carbon atoms, in which at least one -CH _2- is -O-, -COO-, -OCOO-, or-. It may be replaced by OCO-, and at least one- (CH ₂ ) _2- may be replaced by -CH = CH-;
In partial structures other than P ¹ , P ² , Sp ¹ and Sp ² , at least one hydrogen may be replaced with fluorine, chlorine, methyl, or ethyl.

[8] Equations (1-1-1) to (1-1-7), (1-2-1) to (1-2-14), (1-3-1), or (1-3-1) In the compound represented by 2), Sp ¹ and Sp ² are independently alkylenes having 1 to 10 carbon atoms, and in this alkylene, at least one -CH _2- is -O-, -COO-,. The compound according to [7], which may be replaced by -OCOO-, or -OCO-, and at least one- (CH ₂ ) ₂ -may be replaced by -CH = CH-.

[9] A liquid crystal composition containing at least one of the compounds according to any one of [1] to [8].

[10] The liquid crystal composition according to [9], further containing at least one compound selected from the group of compounds represented by formulas (2) to (4).

In equations (2) to (4),
R ¹¹ and R ¹² are independently alkyl with 1 to 10 carbon atoms or alkenyl with 2 to 10 carbon atoms, even if at least one -CH _2- is replaced with -O- in the alkyl and alkenyl. Well, at least one hydrogen may be replaced by fluorine;
Ring B ¹ , Ring B ² , Ring B ³ , and Ring B ⁴ are independent, 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro-. 1,4-phenylene, or pyrimidine-2,5-diyl;
Z ¹¹ , Z ¹² , and Z ¹³ are independently single-bonded,-(CH ₂ ) _2- , -CH = CH-, -C≡C-, or -COO-.

[11] The liquid crystal composition according to [9] or [10], which further contains at least one compound selected from the group of compounds represented by formulas (5) to (7).

In equations (5) to (7),
R ¹³ is an alkyl having 1 to 10 carbon atoms or an alkenyl having 2 to 10 carbon atoms, in which at least one -CH _2- may be replaced with -O-, and at least one hydrogen is. May be replaced with fluorine;
X ¹¹ is fluorine, chlorine, -OCF ₃ , -OCHF ₂ , -CF ₃ , -CHF ₂ , -CH ₂ F, -OCF ₂ CHF ₂ , or -OCF ₂ CHFCF ₃ ;
Ring C ¹ , Ring C ² , and Ring C ³ are independently 1,4-cyclohexylene, 1,4-phenylene, where at least one hydrogen may be replaced by fluorine, tetrahydropyran-2,5-diyl. , 1,3-dioxane-2,5-diyl, or pyrimidine-2,5-diyl;
Z ¹⁴ , Z ¹⁵ and Z ¹⁶ are independently single-bonded,-(CH ₂ ) _2- , -CH = CH-, -C≡C-, -COO-, -CF ₂ O-, -OCF ₂ _{-, - CH 2 O -,} - CF = CF -, - CH = CF- or - _(CH _{2) 4} - a and;
L ¹¹ and L ¹² are independently hydrogen or fluorine.

[12] The liquid crystal composition according to any one of [9] to [11], which further contains at least one compound selected from the group of compounds represented by the formula (8).

In equation (8)
R ¹⁴ is an alkyl having 1 to 10 carbon atoms or an alkenyl having 2 to 10 carbon atoms, in which at least one -CH _2- may be replaced with -O-, and at least one hydrogen is. May be replaced with fluorine;
X ¹² is -C≡N or -C≡C-C≡N;
Ring D ¹ is independently 1,4-cyclohexylene, 1,4-phenylene in which at least one hydrogen may be replaced by fluorine, tetrahydropyran-2,5-diyl, 1,3-dioxane-2, 5-dioxane, or pyrimidine-2,5-dioxane;
Z ¹⁷ is independently a single _{_{bond, - (CH 2) 2 -}} , - C≡C -, - COO -, - CF 2 O -, - OCF 2 -, or _-CH 2 O-;
L ¹³ and L ¹⁴ are independently hydrogen or fluorine;
i is 1, 2, 3, or 4.

[13] The liquid crystal composition according to any one of [9] to [12], further containing at least one compound selected from the group of compounds represented by the formulas (9) to (15). ..

In equations (9) to (15),
R ¹⁵ and R ¹⁶ are independently alkyls with 1 to 10 carbon atoms or alkenyl with 2 to 10 carbon atoms, even if at least one -CH _2- is replaced with -O- in the alkyl and alkenyl. Well, at least one hydrogen may be replaced by fluorine;
R ¹⁷ is hydrogen, fluorine, an alkyl having 1 to 10 carbon atoms, or an alkenyl having 2 to 10 carbon atoms, in which at least one -CH _2- may be replaced with -O-. , At least one hydrogen may be replaced by fluorine;
Ring E ¹ , Ring E ² , Ring E ³ , and Ring E ⁴ may independently replace 1,4-cyclohexylene, 1,4-cyclohexenylene, and at least one hydrogen with fluorine 1, 4-Phenylene, tetrahydropyran-2,5-diyl, or decahydronaphthalene-2,6-diyl;
Rings E ⁵ and E ⁶ are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, or decahydronaphthalene-2,6. -Jeil;
^{^{^{Z 18, Z 19, Z 20}}} , and ^{Z 21} are independently a single _{_{bond, - (CH 2) 2 -}} , - COO -, - CH 2 O -, - OCF 2 -, or -OCF ₂ CH ₂ CH _2- is;
L ¹⁵ and L ¹⁶ are independently fluorine or chlorine;
S ¹¹ is hydrogen or methyl;
X is -CHF- or -CF _2- ;
j, k, m, n, p, q, r, and s are independently 0 or 1, and the sum of k, m, n, and p is 1 or 2, q, r, and The sum of s is 0, 1, 2, or 3, and t is 1, 2, or 3.

[14] The liquid crystal composition according to any one of [9] to [13], which contains at least one polymerizable compound selected from the group of compounds represented by the formula (16).

In equation (16)
Rings F and I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidine-2-yl, or pyridine. -2-yl, in these rings at least one hydrogen is fluorine, chlorine, alkyl with 1 to 12 carbon atoms, or at least one hydrogen is alkyl with 1 to 12 carbon atoms with fluorine or chlorine replaced. May be replaced with;
Ring G is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, Naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene- 2,7-Diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in these rings. , At least one hydrogen is replaced with fluorine, chlorine, alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms, or alkyl with 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. May;
Z ²² and Z ²³ are independently single bonds or alkylenes with 1 to 10 carbon atoms, in which at least one -CH _2- is -O-, -CO-, -COO-, or-. It may be replaced by OCO-, and at least one- (CH ₂ ) _2- is -CH = CH-, -C (CH ₃ ) = CH-, -CH = C (CH ₃ )-, or -C. It may be replaced by (CH ₃ ) = C (CH ₃ )-and at least one hydrogen in these groups may be replaced by fluorine or chlorine;
P ^11, ^{P 12,} and ^{P 13} are independently a polymerizable group selected from the group of radicals represented by the formula (P-1) by the formula (P-5);

M ¹¹ , M ¹² , and M ¹³ are independently hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or alkyl having 1 to 5 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine;
Sp ¹¹ , Sp ¹² , and Sp ¹³ are independently single bonds or alkylenes with 1 to 10 carbon atoms, in which at least one -CH _2- is -O-, -COO-, -OCO. -Or -OCOO- may be replaced, and at least one- (CH ₂ ) _2- may be replaced with -CH = CH- or -C≡C-, at least 1 in these groups. One hydrogen may be replaced with fluorine or chlorine;
u is 0, 1, or 2;
f, g, and h are independently 0, 1, 2, 3, or 4, and the sum of f, g, and h is greater than or equal to 2.

[15] In any one of [9] to [14], which contains at least one polymerizable compound selected from the group of compounds represented by the formulas (16-1) to (16-27). The liquid crystal composition described.

In equations (16-1) to (16-27),
P ¹¹ , P ¹² , and P ¹³ are independently polymerizable groups selected from the group of groups represented by the formulas (P-1) to (P-3), wherein M ¹¹ , M. ^12, and M ¹³ are independently hydrogen, fluorine, alkyl of C 1 -C 5 alkyl or at least one hydrogen is from 1 carbon atoms is replaced by fluorine or chlorine, 5;

Sp ¹¹ , Sp ¹² , and Sp ¹³ are independently single bonds or alkylenes with 1 to 10 carbon atoms, in which at least one -CH _2- is -O-, -COO-, -OCO. -Or -OCOO- may be replaced, and at least one- (CH ₂ ) _2- may be replaced with -CH = CH- or -C≡C-, at least 1 in these groups. One hydrogen may be replaced with fluorine or chlorine.

[16] Polymerizable compounds other than the formulas (1) and (16), polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, and defoamers. The liquid crystal composition according to any one of [9] to [15], further containing at least one of.

[17] A liquid crystal display device containing the liquid crystal composition according to any one of [9] to [16].

The present invention also includes the following sections. (A) Further contains at least two additives such as a polymerizable compound, a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, and an antifoaming agent. The above liquid crystal composition. (B) A polymerizable composition prepared by adding a polymerizable compound different from the compound (1) or the compound (16) to the above liquid crystal composition. (C) A polymerizable composition prepared by adding compound (1) and compound (16) to the above liquid crystal composition. (D) A liquid crystal composite prepared by polymerizing a polymerizable composition. (E) A polymer-supported orientation type device containing this liquid crystal composite. (F) A polymerizable composition prepared by adding a compound (1), a compound (16), and a polymerizable compound different from the compound (1) or the compound (16) to the above liquid crystal composition is used. A polymer-supported orientation type element created by this.
Aspects of compound (1), synthesis of compound (1), a liquid crystal composition, and a liquid crystal display element will be described in order.

1. 1. Aspects of Compound (1) The compound (1) according to the embodiment of the present invention contains at least one thioester (-COS-, -SCO-) or thiocinnamic acid ester (-CH = CHCOS-, -SCOCH = CH-). It is a polar compound having a polymerizable group having the above as a bonding group. Compound (1) has high light absorption characteristics and high light absorption characteristics by having a structure such as thioester (-COS-, -SCO-) or thiosilicate ester (-CH = CHCOS-, -SCOCH = CH-) in the molecule. It has the property of absorbing light in a relatively long wavelength region, and exhibits sufficient properties with short-time or low-energy light irradiation as compared with compounds in which they do not exist.

One of the uses of compound (1) is an additive for a liquid crystal composition used in a liquid crystal display element. Compound (1) is added for the purpose of horizontally controlling the orientation of liquid crystal molecules. Such additives are preferably chemically stable under the condition of being sealed in the device, have high solubility in the liquid crystal composition, and have a high voltage retention when used in the liquid crystal display device. .. Compound (1) satisfies such properties to a large extent.

A preferred example of compound (1) will be described. Preferred examples of compounds of ^{^{^{(1) R 1, Z 1}}} ~ Z 5, A 1 ~ A 4, Sp 1, Sp 2, P 1, P 2, a and b are applied to the sub-formulas of compound (1) Will be done. In compound (1), the properties can be arbitrarily adjusted by appropriately combining the types of these groups. Compound (1) may contain more isotopes such as ² H (deuterium) and ¹³ C than the natural abundance ratio, as there are no significant differences in the properties of the compounds.

Ring A ¹ , Ring A ² , Ring A ³ and Ring A ⁴ are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, Decahydronaphthrene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine- 2,5-diyl, pyridine-2,5-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, perhydrocyclopenta [a] phenanthrene-3,17 -Diyl, 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta [a] phenanthrene-3,17-diyl, these In the ring of, at least one hydrogen is fluorine, chlorine, alkyl with 1 to 12 carbon atoms, alkenyl with 2 to 12 carbon atoms, alkoxy with 1 to 11 carbon atoms, alkenyloxy with 2 to 11 carbon atoms, -Sp ¹ It may be replaced by -P ¹ or -Sp ^2- P ² , and in these groups at least one hydrogen may be replaced by fluorine or chlorine, and when a is 2, two rings A ¹ It may be different when b is 2, the two rings a ⁴ may be different.

Preferred rings A ¹ , A ² , A ³ and A ⁴ are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, decahydro. Naphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2, 5-diyl, pyridine-2,5-diyl, perhydrocyclopenta [a] phenanthrene-3,17-diyl, 2,3,4,7,8,9,10,11,12,13,14,15 , 16,17-Tetradecahydrocyclopenta [a] Phenanthrene-3,17-diyl, preferably c is 1 or 2, and in these rings, at least one hydrogen is fluorine, chlorine, 1 carbon. It may be replaced by an alkyl from 12 to an alkenyl having 2 to 12 carbons, an alkoxy having 1 to 11 carbons, or an alkenyloxy having 2 to 11 carbons, and in these groups, at least one hydrogen is fluorine or It may be replaced with chlorine. More preferably, 1,4-cyclohexylene, 1,4-phenylene, perhydrocyclopenta [a] phenanthrene-3,17-diyl, or 2,3,4,7,8,9,10,11, 12,13,14,15,16,17-tetradecahydrocyclopenta [a] phenanthrene-3,17-diyl, in these rings at least one hydrogen is fluorine or alkyl with 1 to 5 carbon atoms. May be replaced with. Particularly preferred are 1,4-cyclohexylene, 1,4-phenylene, or perhydrocyclopenta [a] phenanthrene-3,17-diyl, in which at least one hydrogen is fluorine, methyl, Alternatively, it may be replaced with ethyl.

Z ¹ , Z ² , Z ³ , Z ⁴ and Z ⁵ are independently single-bonded,-(CH ₂ ) _2- , -C ≡ C-, -C ≡ C-C ≡ C-, -COO-, -OCO-, -CF ₂ O-, -OCF _2- , -CH ₂ O-, -OCH _2- , -CF = CF-, -CH = CHCOO-, -OCOCH = CH-, -CH = CH-, -CH = CHCO-, -COCH = CH-, -COS-, -SCO-, -CH = CHCOS-, or -SCOCH = CH-, provided that at least in Z ² , Z ³ , or Z ^4. one, -COS -, - SCO -, - CH = CHCOS-, or -SCOCH = a CH-, when a is 2, two ^{Z 1} may be different, two ^{Z 5} are different You may be.
Preferred Z ¹ , Z ² , Z ³ , Z ⁴ and Z ⁵ are independently single-bonded,-(CH ₂ ) _2- , -CH = CH-, -C≡C-, -COO-, -OCO- _{_{_{_{, -CF 2 O -, - OCF}}}} 2 -, - CH 2 O -, - OCH 2 -, - CF = CF -, - COS -, - SCO -, - CH = CHCOS-, or -SCOCH = CH- in is there. More preferably, a single _{_{bond, - (CH 2) 2 -}} , - CH = CH -, - COS -, - SCO -, - CH = CHCOS-, or -SCOCH = a CH-. Particularly preferred are single bonds, -COS-, -SCO-, -CH = CHCOS-, or -SCOCH = CH-.

Sp ¹ and Sp ² are independently single-bonded or alkylene with 1 to 10 carbon atoms, in which at least one -CH _2- is -O-, -CO-, -COO-, -OCO. -Or -OCOO- may be replaced, and at least one- (CH ₂ ) _2- may be replaced with -CH = CH- or -C≡C-, at least 1 in these groups. One hydrogen may be replaced with fluorine or chlorine.
Preferred Sp ¹ and Sp ² are independently single bonds, alkylenes with 1 to 6 carbon atoms, alkylene with 1 to 6 carbon atoms in which one -CH _2- has been replaced with -O-, or -OCOO-. .. More preferably, it is an alkylene having 1 to 6 carbon atoms or -OCOO-.

P ¹ and P ² are independent groups represented by any of the formulas (1b) to (1h).

Preferred P ¹ and P ² are independently represented by any of (1b), (1c), (1d), and (1e).

Preferred M ¹ , M ² , M ³ and M ⁴ are independently hydrogen, fluorine, methyl, ethyl, or trifluoromethyl. More preferably, it is hydrogen.

R ² is hydrogen, fluorine, chlorine, or an alkyl having 1 to 5 carbon atoms, in which at least one hydrogen may be replaced by fluorine or chlorine, and at least one -CH _2- is -O-. May be replaced with.

Preferred R ² is hydrogen, fluorine, methyl, ethyl, methoxymethyl, or trifluoromethyl. More preferably, it is hydrogen.

R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently hydrogen, or linear, branched or cyclic alkyl with 1 to 15 carbon atoms, in which at least one − CH _2- may be replaced by -O- or -S-, and at least one- (CH ₂ ) _2- may be replaced by -CH = CH- or -C≡C-, these. At least one hydrogen may be replaced by fluorine or chlorine.

Preferred R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently hydrogen, linear alkyl with 1-10 carbon atoms, linear alkoxy with 2-10 carbon atoms, 1-10 carbon atoms. Linear alkoxy, or cyclic alkyl having 3 to 6 carbon atoms. More preferably, it is hydrogen, a linear alkyl having 2 to 6 carbon atoms, a linear alkenyl having 2 to 6 carbon atoms, a linear alkoxy having 1 to 5 carbon atoms, or a cyclic alkyl having 4 to 6 carbon atoms. ..

X ¹ is O or S.

More preferred groups are formulas (1b-1), (1b-2), (1b-3), (1b-4), formulas (1b-5), (1c-1), (1d-1) (1d). -2) or a group represented by (1e-1).

In formulas (1b) to (1h), M ¹ and M ² independently have hydrogen, fluorine, chlorine, an alkyl having 1 to 5 carbon atoms, or at least one hydrogen having a carbon number replaced by fluorine or chlorine. It is an alkyl of 1 to 5, and X ² , X ³ , X ⁴ , X ⁵ and X ⁶ are independently O or S.

A and b are independently 0, 1 or 2, preferably 0 ≦ a + b ≦ 2.

Preferred examples of the compound (1) are formulas (1-1) to (1-3).

In equations (1-1) to (1-3),
Ring A ¹ , Ring A ² , Ring A ³ and Ring A ⁴ are independent, 1,4-cyclohexylene, 1,4-phenylene, naphthalene-2,6-diyl, pyrimidine-2,5-diyl, Pyridine-2,5-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, and at least one hydrogen in these rings is fluorine, chlorine, carbon. Replaced by alkyl numbers 1 to 12, alkenyl with 2 to 12 carbons, alkoxy with 1 to 11 carbons, alkenyloxy with 2 to 11 carbons, -Sp ^1- P ¹ or -Sp ^2- P ^2. in even better, these groups, at least one hydrogen may be replaced by fluorine or chlorine, when a is 2, two rings a ¹ may be different when b is 2, the two ring A ⁴ may be different;
In these rings, at least one hydrogen is fluorine, chlorine, alkyl with 1 to 12 carbons, alkenyl with 2 to 12 carbons, alkoxy with 1 to 11 carbons, alkenyloxy with 2 to 11 carbons, -Sp. It may be replaced with ^1- P ¹ or -Sp ^2- P ² , and in these groups at least one hydrogen may be replaced with fluorine or chlorine;
Z ² , Z ³ and Z ⁴ are independently single-bonded,-(CH ₂ ) _2- , -C ≡ C-, -C ≡ C-C ≡ C-, -COO-, -OCO-, -CF _{_{_{_{2 O -, - OCF 2 -}}}} , - CH 2 O -, - OCH 2 -, - CF = CF -, - CH = CHCOO -, - OCOCH = CH -, - CH = CH -, - CH = CHCO-, -COCH = CH -, - COS - , - SCO -, - CH = CHCOS-, or -SCOCH = a CH-, provided ^that at least one among Z 2, ^{Z 3} or ^{Z 4,} are,-COS -, -SCO-, -CH = CHCOS-, or -SCOCH = CH-;
Sp ¹ and Sp ² are independently single-bonded or alkylene with 1 to 10 carbon atoms, in which at least one -CH _2- is -O-, -COO-, -OCOO-, or-. It may be replaced by OCO-, at least one- (CH ₂ ) ₂ -may be replaced by -CH = CH-, and in these groups at least one hydrogen is replaced by fluorine or chlorine. at best, if there are a plurality of Sp ¹ or Sp ² in the structure, it may be different from each;
P ¹ and P ² are independent groups represented by any of the formulas (1b) to (1h), and when a plurality of P ¹ or P ² are present in the structure, they are different from each other. Well;

In formulas (1b) to (1h), M ¹ , M ² , M ³ and M ⁴ are independently hydrogen, fluorine, chlorine, alkyl having 1 to 5 carbon atoms, or at least one hydrogen is fluorine or chlorine. The substituted alkyl with 1 to 5 carbon atoms, where X ¹ is O or S;
R ² is hydrogen, fluorine, chlorine, or an alkyl having 1 to 5 carbon atoms, in which at least one hydrogen may be replaced by fluorine or chlorine, and at least one -CH _2- is -O-. May be replaced with;
R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ are independently hydrogen, or alkyl with 1 to 15 carbon atoms, in which at least one -CH _2- is -O- or It may be replaced by —S—, at least one − (CH ₂ ) ₂ − may be replaced by −CH = CH− or −C≡C−, and in these groups, at least one hydrogen It may be replaced with fluorine or chlorine.

In the compound represented by the formula (1-1), the formula (1-2), or the formula (1-3), any one of Z ² , Z ³ , or Z ⁴ is -COS- or -SCO. -Preferably.
Further, in the compound represented by the formula (1-1), the formula (1-2), or the formula (1-3), any one of Z ² , Z ³ , or Z ⁴ has -CH = CHCOS. -Or-SCOCH = CH-is preferable.

The compound (1) is preferably a compound represented by the following formula.

Specific examples of compound (1) will be described in Examples described later.

Formulas (2) to (15) represent the component compounds of the liquid crystal composition. Compounds (2) to (4) have small dielectric anisotropy. Compounds (5) to (7) have a very large dielectric anisotropy. Since compound (8) has a cyano group, it has a larger positive dielectric anisotropy. Compounds (9) to (16) have a large negative dielectric anisotropy. Specific examples of these compounds will be described later.

In compound (16), P ¹¹ , P ¹² , and P ¹³ are independently polymerizable groups.

Preferred P ¹¹ , P ¹² and P ¹³ are polymerizable groups selected from the group of groups represented by formulas (P-1) to (P-5). More preferred P ¹¹ , P ¹² , and P ¹³ are groups (P-1), groups (P-2), or groups (P-3). A particularly preferred group (P-1) is -OCO-CH = CH ₂ or -OCO-C (CH ₃ ) = CH ₂ . The wavy line from the group (P-1) to the group (P-5) indicates the site to be bonded.

From group (P-1) to group (P-5), M ¹¹ , M ¹² , and M ¹³ are independently hydrogen, fluorine, alkyl with 1 to 5 carbon atoms, or at least one hydrogen is fluorine or chlorine. It is an alkyl having 1 to 5 carbon atoms replaced with.
Preferred M ¹¹ , M ¹² , and M ¹³ are hydrogen or methyl to increase reactivity. The more preferred M ¹¹ is methyl and the more preferred M ¹² and M ¹³ are hydrogen.

Preferred Sp ¹¹ , Sp ¹² , and Sp ¹³ are single bonds.

Rings F and I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidin-2-yl, or pyridine. -2-yl, in these rings at least one hydrogen is fluorine, chlorine, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, or at least one hydrogen is replaced with fluorine or chlorine. It may be replaced with an alkyl having 1 to 12 carbon atoms.

Preferred rings F and I are phenyl. Ring G is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, Naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene- 2,7-Diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in these rings. , At least one hydrogen is replaced with fluorine, chlorine, alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms, or alkyl with 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. You may. A particularly preferred ring G is 1,4-phenylene or 2-fluoro-1,4-phenylene.

Z ²² and Z ²³ are independently single bonds or alkylenes with 1 to 10 carbon atoms, in which at least one -CH _2- is -O-, -CO-, -COO-, or-. It may be replaced by OCO-, and at least one- (CH ₂ ) _2- is -CH = CH-, -C (CH ₃ ) = CH-, -CH = C (CH ₃ )-, or -C. It may be replaced by (CH ₃ ) = C (CH ₃ )-and at least one hydrogen in these groups may be replaced by fluorine or chlorine.

Preferred Z ²² and Z ²³ are single bonds,-(CH ₂ ) _2- , -CH ₂ O-, -OCH _2- , -COO-, or -OCO-. More preferred Z ²² and Z ²³ are single bonds.

U is 0, 1, or 2.

The preferred u is 0 or 1. f, g, and h are independently 0, 1, 2, 3, or 4, and the sum of f, g, and h is greater than or equal to 1. The preferred f, g, or h is 1 or 2.

2. Synthesis of Compound (1) A method for synthesizing compound (1) will be described. Compound (1) can be synthesized by appropriately combining synthetic organic chemistry methods. Compounds for which the synthetic method was not described are "Organic Syntheses" (John Wiley & Sons, Inc), "Organic Reactions" (Organic Reactions, John Wiley & Sons, Inc), and "Comprehensive Organic". -Syntheses by the methods described in books such as "Comprehensive Organic Synthesis, Pergamon Press" and "New Experimental Chemistry Course" (Maruzen).

2-1. Generation of Binding Groups Z ¹ , Z ² , Z ³ , Z ⁴ and Z ⁵ Examples of methods for generating binding groups in compound (1) are as follows. In this scheme, MSG ¹ (or MSG ² ) is a monovalent organic group having at least one ring. The monovalent organic groups represented by a plurality of MSG ¹ (or MSG ²⁾ may be the same or different. Compounds (1A) to (1L) correspond to compound (1) or an intermediate of compound (1).

(I) Formation of Single Bond Arylboric acid (21) and compound (22) are reacted in the presence of a carbonate and a tetrakis (triphenylphosphine) palladium catalyst to synthesize compound (1A). This compound (1A) is also synthesized by reacting compound (23) with n-butyllithium and then zinc chloride, and reacting compound (22) in the presence of a dichlorobis (triphenylphosphine) palladium catalyst.

(II) Production of -COO- and -OCO- The compound (23) is reacted with n-butyllithium and then carbon dioxide to obtain a carboxylic acid (24). The carboxylic acid (24) and the phenol (25) derived from the compound (21) were dehydrated in the presence of DCC (1,3-dicyclohexylcarbodiimide) and DMAP (4-dimethylaminopyridine) to give -COO-. Synthesize the compound (1B) having. Compounds with -OCO- are also synthesized by this method.

(III) -Production of -CF ₂ O- and -OCF _2- Compound (1B) is sulfurized with Lawesson's reagent to obtain compound (26). Compound (26) is fluorinated with a hydrogen fluoride pyridine complex and NBS (N-bromosuccinimide) to synthesize compound (1C) having -CF ₂ O-. See M. Kuroboshi et al., Chem. Lett., 1992, 827. Compound (1C) is also synthesized by fluorinating compound (26) with DAST ((diethylamino) sulfatrifluoride). See W. H. Bunnelle et al., J. Org. Chem. 1990, 55, 768. Compounds with -OCF _2- are also synthesized by this method.

Production of (IV) -CH = CH- Compound (22) is reacted with n-butyllithium and then DMF (N, N-dimethylformamide) to obtain aldehyde (27). Phosphorium salt (28) and potassium tert-butoxide are reacted to generate linylide, which is then reacted with aldehyde (27) to synthesize compound (1D). Since a cis form is produced depending on the reaction conditions, the cis form is isomerized to a trans form by a known method if necessary.

Production of (V)-(CH ₂ ) ₂ -The compound (1D) is hydrogenated in the presence of a palladium carbon catalyst to synthesize the compound (1E).

Production of (VI) -C≡C- After reacting compound (23) with 2-methyl-3-butin-2-ol in the presence of a catalyst of dichloropalladium and copper iodide, it is removed under basic conditions. Protect to obtain compound (29). Compound (29) is reacted with compound (22) in the presence of a catalyst of dichlorobis (triphenylphosphine) palladium and copper halide to synthesize compound (1F).

Production of (VII) -CH ₂ O- and -OCH _2- Compound (27) is reduced with sodium borohydride to obtain compound (30). This is brominated with hydrobromic acid to obtain compound (31). Compound (25) and compound (31) are reacted in the presence of potassium carbonate to synthesize compound (1G). Compounds with -OCH _2- are also synthesized by this method.

Production of (VIII) -CF = CF- Compound (23) is treated with n-butyllithium and then reacted with tetrafluoroethylene to obtain compound (32). Compound (22) is treated with n-butyllithium and then reacted with compound (32) to synthesize compound (1H).

(IX) Production of -CH = CHCO- and -COCH = CH- Compound (40) and compound (27) are subjected to an aldol condensation reaction in the presence of NaOH to synthesize compound (1I).

Formation of (X) -CH = CHCOO- and -OCOCH = CH-Cinnamic acid (41) and compound (25) in the presence of DCC (1,3-dicyclohexylcarbodiimide) and DMAP (4-dimethylaminopyridine) Dehydrate with to synthesize compound (1J).

Formation of (XI) -CH = CHCOS- and -SCOCCH = CH-Cinnamic acid (41) and compound (26) in the presence of DCC (1,3-dicyclohexylcarbodiimide) and DMAP (4-dimethylaminopyridine) Dehydrate with to synthesize compound (1K).

Production of (XII) -COS- and -SCO- The carboxylic acid (24) and the compound (26) are dehydrated in the presence of DCC (1,3-dicyclohexylcarbodiimide) and DMAP (4-dimethylaminopyridine) to form the compound. (1L) is synthesized.

2-2. Formation of rings A ¹ , A ² , A ³ and A ⁴ 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2-methyl-1 , 4-Phenanthrene, 2-Ethyl-1,4-Phenanthrene, Naphthalene-2,6-Diyl, Decahydronaphthalene-2,6-Diyl, 1,2,3,4-Tetrahydropyranphthalene-2,6-Diyl, Tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, perhydrocyclopenta [a] phenanthrene-3,17- For rings such as dioxane, 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta [a] phenanthrene-3,17-dioxane The starting material is commercially available or the synthetic method is well known.

2-3. Production of Linking Group Sp ¹ or Sp ² and Polymerizing Group P ¹ or P ² Preferred examples of the polymerizable group P ¹ or P ² are acrylic ester (1b), maleimide (1c), itaconic acid ester (1d). , Vinyl ester (1e), oxylanyl (1g), or vinyloxy (1h).

An example of a method for synthesizing a compound in which this polymerizable group is bonded to a ring with a linking group Sp ¹ or Sp ² is as follows. First, an example in which the linking group Sp ¹ or Sp ² is a single bond will be shown.

(1) Synthesis of compound having a single bond The method for synthesizing a compound having Sp ¹ or Sp ² having a single bond is as follows. In this scheme, MSG ¹ is a monovalent organic group having at least one ring. Compounds (1S) to (1X) correspond to compound (1). When the polymerizable group is an acrylate derivative, it is synthesized by esterification of the corresponding acrylic acid and HO-MSG ¹ . Vinyloxy is synthesized by etherification of HO-MSG ¹ and vinyl bromide. Oxylanyl is synthesized by oxidation of the terminal double bond. The maleimide group is synthesized by the reaction of an amino group with maleic anhydride. Itaconic acid esters are synthesized by esterification of the corresponding itaconic acid with HO-MSG ¹ . Vinyl ester is synthesized by transesterification reaction of vinyl acetate and HOOC-MSG ¹ .

The method for synthesizing a compound in which the linking group Sp ¹ or Sp ² is a single bond has been described above. Other methods for producing the linking group can be synthesized with reference to the method for synthesizing the linking groups Z ¹ , Z ² , Z ³ , Z ⁴ and Z ⁵ .

2-4. Synthesis example An example of a method for synthesizing compound (1) is as follows. In these compounds, MES is a mesogen group with at least one ring. The definitions of P ¹ , M ¹ , M ² , Sp ¹ , and Sp ² are the same as above.
Compound (51A) and compound (51B) can be synthesized according to a general organic synthesis method using commercially available or mesogen (MES) having an appropriate ring structure as a starting material.
When synthesizing a compound in which MES and Sp ¹ are linked by an ether bond, the compound (51A) is used as a starting material, and the compound is etherified with a base such as compound (52) and potassium hydroxide. (53A) can be obtained. When synthesizing a compound in which MES and Sp ¹ are linked by a single bond, a cross-coupling reaction is carried out using compound (52), a metal catalyst such as palladium, and a base starting from compound (51B). The compound (53B) can be obtained by carrying out the above. Compound (53A) or (53B) may, if necessary, induce compound (54A) or (54B) on which a protecting group such as TMS or THP is acted.
The compound (53A), (53B), (54A) or compound (54B) is then etherified again in the presence of a base such as compound (55) and potassium hydroxide to give compound (57A) or (54B). 57B) can be obtained. At this time, if the protecting group is allowed to act in the previous step, the protecting group is removed by a deprotection reaction.

Compound (1), of which P ² is a group represented by the formula (1b-3), can be synthesized from compound (57) by the following method. Compound (57) can be derived to compound (1Y) by performing an esterification reaction in the presence of compound (58), DCC and DMAP.

3. 3. Liquid crystal composition The liquid crystal composition according to the embodiment of the present invention contains compound (1) as a component A. The compound (1) can contribute to the control of the orientation of the liquid crystal molecules by the non-covalent interaction with the substrate of the device. This composition preferably contains compound (1) as component A and further contains a liquid crystal compound selected from the components B, C, D, and E shown below. Component B is compounds (2) to (4). Component C is compounds (5) to (7). Component D is compound (8). Component E is compounds (9) to (16). This composition may contain other liquid crystal compounds different from the compounds (2) to (16). When preparing this composition, it is preferable to select the components B, C, D, and E in consideration of the magnitude of positive or negative dielectric anisotropy. A composition with properly selected components has a high upper limit temperature, a lower lower limit temperature, a small viscosity, a suitable optical anisotropy (ie, a large optical anisotropy or a small optical anisotropy), and a large positive or negative modulus. It has anisotropy, high specific resistance, stability against heat or ultraviolet rays, and a suitable elastic constant (ie, a large elastic constant or a small elastic constant).

The preferred proportion of compound (1) is typically about 0.01% by weight or more, based on the weight of the liquid crystal composition to maintain high stability to UV light, to dissolve in the liquid crystal composition. Usually, it is about 10% by weight or less. A more preferred proportion is in the range of about 0.1% to about 5% by weight, based on the weight of the liquid crystal composition. The most preferred proportion is in the range of about 0.5% by weight to about 3% by weight, based on the weight of the liquid crystal composition.

Component B is a compound having two terminal groups such as alkyl. Preferred examples of the component B include compounds (2-1) to (2-11), compounds (3-1) to (3-19), and compounds (4-1) to (4-7). it can. In the compound of component B, R ¹¹ and R ¹² are independently an alkyl having 1 to 10 carbon atoms or an alkenyl having 2 to 10 carbon atoms, and in this alkyl or alkenyl, at least one -CH _2- is -O. It may be replaced with −, and at least one hydrogen may be replaced with fluorine.

Component B is a compound that is close to neutral because the absolute value of dielectric anisotropy is small. Compound (2) is mainly effective in reducing viscosity or adjusting optical anisotropy. The compounds (3) and (4) are effective in widening the temperature range of the nematic phase by increasing the upper limit temperature, or in adjusting the optical anisotropy.

As the content of component B is increased, the dielectric anisotropy of the composition decreases, but the viscosity decreases. Therefore, as long as the required value of the threshold voltage of the element is satisfied, the content is preferably large. When preparing a composition for a mode such as IPS or VA, the content of component B is preferably 30% by weight or more, more preferably 40% by weight or more, based on the weight of the liquid crystal composition.

Component C is a compound (5) to (7) having fluorine, chlorine or a fluorine-containing group at the right end. Preferred examples of the component C include compounds (5-1) to (5-16), compounds (6-1) to (6-120), and compounds (7-1) to (7-62). .. In the compound of component C, R ¹³ is an alkyl having 1 to 10 carbon atoms or an alkenyl having 2 to 10 carbon atoms, in which at least one -CH _2- may be replaced with -O-. , At least one hydrogen may be replaced with fluorine; X ¹¹ is fluorine, chlorine, -OCF ₃ , -OCHF ₂ , -CF ₃ , -CHF ₂ , -CH ₂ F, -OCF ₂ CHF ₂ , or. -OCF ₂ CHFCF ₃ .

Component C has a positive dielectric anisotropy and is extremely stable against heat, light, etc., and is therefore used when preparing a composition for modes such as IPS, FFS, and OCB. The content of component C is preferably in the range of 1% by weight to 99% by weight, preferably in the range of 10% by weight to 97% by weight, more preferably 40% by weight to 95% by weight, based on the weight of the liquid crystal composition. It is in the range of%. When the component C is added to a composition having a negative dielectric anisotropy, the content of the component C is preferably 30% by weight or less based on the weight of the liquid crystal composition. By adding the component C, it is possible to adjust the elastic constant of the composition and adjust the voltage-transmittance curve of the device.

Component D is compound (8) whose right terminal group is -C≡N or -C≡C-C≡N. Preferred examples of the component D include compounds (8-1) to (8-64). In the compound of component D, R ¹⁴ is an alkyl having 1 to 10 carbon atoms or an alkenyl having 2 to 10 carbon atoms, in which at least one -CH _2- may be replaced with -O-. , At least one hydrogen may be replaced by fluorine; X ¹² is -C ≡ N or -C ≡ C-C ≡ N.

Component D has a positive dielectric anisotropy and a large value, so it is mainly used when preparing a composition for a mode such as TN. By adding this component D, the dielectric anisotropy of the composition can be increased. The component D has the effect of widening the temperature range of the liquid crystal phase, adjusting the viscosity, or adjusting the optical anisotropy. Component D is also useful for adjusting the voltage-transmittance curve of the device.

When preparing a composition for a mode such as TN, the content of component D is preferably in the range of 1% by weight to 99% by weight, preferably from 10% by weight, based on the weight of the liquid crystal composition. It is in the range of 97% by weight, more preferably 40% by weight to 95% by weight. When the component D is added to a composition having a negative dielectric anisotropy, the content of the component D is preferably 30% by weight or less based on the weight of the liquid crystal composition. By adding the component D, it is possible to adjust the elastic constant of the composition and adjust the voltage-transmittance curve of the device.

Component E is compounds (9) to (16). These compounds have phenylene in which the lateral position is substituted with two fluorines or chlorine, such as 2,3-difluoro-1,4-phenylene.

Preferred examples of component E are compounds (9-1) to (9-8), compounds (10-1) to (10-17), compounds (11-1), compounds (12-1) to (12-). 3), compound (13-1) to (13-11), compound (14-1) to (14-3), compound (15-1) to (15-3) and compound (16-1) to (16-1). 16-3) can be mentioned. In the compound of component E, R ¹⁵ and R ¹⁶ are independently alkyl with 1 to 10 carbon atoms or alkenyl with 2 to 10 carbon atoms, in which at least one -CH _2- is -O. - may be replaced by at least one hydrogen may be replaced by fluorine; R ¹⁷ is hydrogen, fluorine, alkenyl alkyl of from 10 1 carbon atoms, or from 2 to 10 carbon atoms, the alkyl And in alkenyl, at least one -CH _2- may be replaced with -O- and at least one hydrogen may be replaced with fluorine.

Component E has a large negative dielectric anisotropy. Component E is used when preparing a composition for modes such as IPS, VA, PSA and the like. As the content of the component E is increased, the dielectric anisotropy of the composition becomes negatively large, but the viscosity becomes large. Therefore, as long as the required value of the threshold voltage of the element is satisfied, the content is preferably small. Considering that the dielectric anisotropy is about −5, the content of the component E is preferably 40% by weight or more based on the weight of the liquid crystal composition in order to drive the liquid crystal sufficiently.

Of the component E, the compound (9) is a bicyclic compound, and is therefore mainly effective in reducing the viscosity, adjusting the optical anisotropy, or increasing the dielectric anisotropy. Since the compounds (10) and (11) are tricyclic compounds, they have the effects of increasing the upper limit temperature, increasing the optical anisotropy, or increasing the dielectric anisotropy. The compounds (12) to (16) have the effect of increasing the dielectric anisotropy.

When preparing a composition for modes such as IPS, VA, PSA, the content of component E is preferably 40% by weight or more, more preferably 50% by weight, based on the weight of the liquid crystal composition. In the range of 95% by weight. When the component E is added to the composition having a positive dielectric anisotropy, the content of the component E is preferably 30% by weight or less based on the weight of the liquid crystal composition. By adding the component E, it is possible to adjust the elastic constant of the composition and adjust the voltage-transmittance curve of the device.

By properly combining the components B, C, D, and E described above, a high upper limit temperature, a lower lower limit temperature, a small viscosity, an appropriate optical anisotropy, a large positive or negative dielectric anisotropy, and a large A liquid crystal composition can be prepared that satisfies at least one of the properties such as specific resistance, high stability against ultraviolet rays, high stability against heat, and a large elastic constant. If necessary, liquid crystal compounds different from the components B, C, D, and E may be added.

The liquid crystal composition is prepared by a known method. For example, the constituent compounds are mixed and dissolved by heating. Additives may be added to this composition depending on the application. Examples of additives include polymerizable compounds other than the formulas (1) and (16), polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, and defoamers. For example, foaming agent. Such additives are well known to those of skill in the art and are described in the literature.

The polymerizable compound is added for the purpose of forming a polymer in the liquid crystal composition. A polymer is produced in the liquid crystal composition by irradiating ultraviolet rays with a voltage applied between the electrodes to copolymerize the polymerizable compound and the compound (1). At this time, the compound (1) is immobilized in a state in which the polar group interacts with the surface of the glass (or metal oxide) substrate in a non-covalent bond. As a result, the ability to control the orientation of the liquid crystal molecules is further improved, and at the same time, the compound (1) does not leak into the liquid crystal composition. Further, since an appropriate pretilt can be obtained even on the substrate surface of glass (or metal oxide), a liquid crystal display element having a short response time and a large voltage holding ratio can be obtained.

Preferred examples of the polymerizable compound are acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxylane, oxetane), and vinyl ketone. More preferred examples are compounds having at least one acryloyloxy and compounds having at least one methacryloyloxy. More preferred examples also include compounds having both acryloyloxy and methacryloyloxy.

More preferred examples of the polymerizable compounds are compounds (M-1) to (M-17). In compounds (M-1) to (M-17), R ²⁵ to R ³¹ are independently hydrogen or methyl; s, v, and x are independently 0 or 1; t and u. Are independently integers from 1 to 10; L ²¹ to L ²⁶ are independently hydrogen or fluorine, and L ²⁷ and L ²⁸ are independently hydrogen, fluorine, or methyl.

The polymerizable compound can be rapidly polymerized by adding a polymerization initiator. By optimizing the reaction temperature, the amount of residual polymerizable compound can be reduced. Examples of photoradical polymerization initiators are TPO, 1173, and 4265 from BASF's DaroCure series and 184,369,500,651,784,819,907,1300,1700,1800,1850 from the Irgacure series. , And 2959.

Additional examples of photoradical polymerization initiators include 4-methoxyphenyl-2,4-bis (trichloromethyl) triazine, 2- (4-butoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole, 9-Phenylaclysine, 9,10-benzphenazine, benzophenone / Michler's ketone mixture, hexaarylbiimidazole / mercaptobenzimidazole mixture, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, benzyl Dimethylketal, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2,4-diethylxanthone / p-dimethylaminomethyl benzoate mixture, benzophenone / methyltriethanolamine mixture Is.

After adding a photoradical polymerization initiator to the liquid crystal composition, polymerization can be carried out by irradiating ultraviolet rays with an electric field applied. However, unreacted polymerization initiators or degradation products of the polymerization initiators may cause display defects such as image burn-in on the device. In order to prevent this, photopolymerization may be carried out without adding a polymerization initiator. The preferred wavelength of the emitted light is in the range of 150 nm to 500 nm. More preferred wavelengths are in the range of 250 nm to 450 nm, and most preferred wavelengths are in the range of 300 nm to 400 nm.

A compound that is a component A when a compound (1) having a thioester (-COS-, -SCO-) or a thiocinnamic acid ester (-CH = CHCOS-, -SCOCH = CH-) as a binding group is mixed with the composition. The main effects of (1) on the properties of the composition are as follows. This compound (1) is arranged in a certain direction at the molecular level when the Fries rearrangement or photodimerization is caused by polarized light. Therefore, the thin film prepared from the polar compound orients the liquid crystal molecules in the same manner as the alignment film such as polyimide.

In the case of the compound (1) having an aromatic thioester and having a polymerizable group, the aromatic thioester site is photodecomposed by irradiation with ultraviolet light to form radicals, which causes photofries rearrangement. ..
In the optical Fries rearrangement, photodecomposition of the aromatic thioester moiety occurs when the polarization direction of the polarized ultraviolet light and the long axis direction of the aromatic thioester moiety are the same direction. After photolysis, it recombines and tautomerization produces thiol groups in the molecule. It is considered that this thiol group causes an interaction between the substrate interfaces and makes it easier for polar compounds to be adsorbed on the substrate interface side with anisotropy. Further, since it has a polymerizable group, the compound (1) that has reacted along the direction of polarized light by polymerization is immobilized without losing its directionality. A thin film capable of orienting liquid crystal molecules can be prepared by utilizing this property. In order to prepare this thin film, linearly polarized light is suitable for the ultraviolet rays to be irradiated. First, the compound (1), which is a polar compound, is added to the liquid crystal composition in the range of 0.1% by weight to 10% by weight, and the composition is heated to dissolve the polar compound. This composition is injected into a device that does not have an alignment film. Next, the polar compound is subjected to photofries rearrangement and polymerized by irradiating the element with linearly polarized light while heating it.
The polar compounds rearranged with optical fries are arranged in a certain direction, and the thin film formed after polymerization has a function as a liquid crystal alignment film.

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

The optically active compound has the effect of preventing reverse twisting by inducing a helical structure in the liquid crystal molecule to give the required twist angle. The spiral pitch can be adjusted by adding an optically active compound. Two or more optically active compounds may be added for the purpose of adjusting the temperature dependence of the spiral pitch. Preferred examples of the optically active compound include the following compounds (Op-1) to (Op-18). In compound (Op-18), ring J is 1,4-cyclohexylene or 1,4-phenylene, and R ²⁸ is an alkyl having 1 to 10 carbon atoms.

Antioxidants are effective in maintaining a large voltage retention rate. Preferred examples of the antioxidants include the following compounds (AO-1) and (AO-2); IRGANOX 415, IRGANOX 565, IRGANOX 1010, IRGANOX 1035, IRGANOX 3114, and IRGANOX 1098 (trade name: BASF). be able to. The ultraviolet absorber is effective for preventing a decrease in the upper limit temperature. Preferred examples of the UV absorber are benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Specific examples include the following compounds (AO-3) and (AO-4); TINUVIN 329, TINUVIN P, TINUVIN 326, TINUVIN 234, TINUVIN 213, TINUVIN 400, TINUVIN 328, and TINUVIN 99-2 (trade name: BASF). ); And 1,4-diazabicyclo [2.2.2] octane (DABCO) can be mentioned.

A light stabilizer such as amine with steric hindrance is preferable in order to maintain a large voltage holding ratio. Preferred examples of the light stabilizer include the following compounds (AO-5) and (AO-6); TINUVIN 144, TINUVIN 765, and TINUVIN 770DF (trade name: BASF). A heat stabilizer is also effective for maintaining a large voltage holding ratio, and a preferable example thereof is IRGAFOS 168 (trade name: BASF). Defoamers are effective in preventing foaming. Preferred examples of the defoaming agent are dimethyl silicone oil, methyl phenyl silicone oil and the like.

In compound (AO-1), R ⁴⁰ is an alkyl having 1 to 20 carbon atoms, an alkoxy having 1 to 20 carbon atoms, -COOR ⁴¹ , or -CH ₂ CH ₂ COOR ⁴¹ , where R ⁴¹ has 1 carbon atom. To 20 alkyl. In compounds (AO-2) and (AO-5), R ⁴² is an alkyl having 1 to 20 carbon atoms. In compound (AO-5), R ⁴³ is hydrogen, methyl, or O ^· (oxygen radical), ring G is 1,4-cyclohexylene or 1,4-phenylene, z is 1, 2, Or 3.

4. Liquid crystal display element The liquid crystal composition has an operation mode such as PC, TN, STN, OCB, PSA, and can be used for a liquid crystal display element driven by an active matrix method. This composition has an operation mode such as PC, TN, STN, OCB, VA, and IPS, and can also be used for a liquid crystal display element driven by a passive matrix method. These elements can be applied to any type of reflective type, transmissive type, and semitransparent type.

This composition consists of an NCAP (nematic curvilinear aligned phase) element produced by microencapsulating a nematic liquid crystal, a polymer dispersed liquid crystal display element (PDLCD) produced by forming a three-dimensional network polymer in the liquid crystal, and a polymer. It can also be used for network liquid crystal display elements (PNLCD). When the amount of the polymerizable compound added is about 10% by weight or less based on the weight of the liquid crystal composition, a PSA mode liquid crystal display device is produced. The preferred proportion of the polymerizable compound is in the range of about 0.1% by weight to about 2% by weight, based on the weight of the liquid crystal composition. A more preferred proportion is in the range of about 0.2% by weight to about 1.0% by weight, based on the weight of the liquid crystal composition. The PSA mode element can be driven by a drive system such as an active matrix or a passive matrix. Such an element can be applied to any type of reflective type, transmissive type, and semitransparent type. By increasing the amount of the polymerizable compound added, a device in the polymer dispersed mode can also be manufactured.

In a polymer-supported orientation type device, the polymer contained in the composition orients the liquid crystal molecules. Compound (1), which is a polar compound, assists in arranging liquid crystal molecules. That is, compound (1) can be used instead of the alignment film. An example of a method for manufacturing such an element is as follows.
An element having two substrates called an array substrate and a color filter substrate is prepared. This substrate has no alignment film. At least one of the substrates has an electrode layer. Liquid crystal compounds are mixed to prepare a liquid crystal composition. A polymerizable compound and a compound (1) which is a polar compound are added to this composition. Additional additives may be added as needed. This composition is injected into the device. Light is applied to this element. Ultraviolet rays are preferred. The polymerizable compound is polymerized by light irradiation. By this polymerization, a composition containing a polymer is produced, and an element having a PSA mode is produced.

The method of manufacturing the element will be explained. The first is a step of adding the compound (1), which is a polar compound, to the liquid crystal composition, and heating and dissolving the composition at a temperature higher than the upper limit temperature. The second is a step of injecting this composition into the liquid crystal display element. The third is a step of irradiating polarized ultraviolet rays while the liquid crystal composition is heated to a temperature higher than the upper limit temperature. Compound (1), which is a polar compound, undergoes photo-Fries rearrangement or photodimerization by linearly polarized light, and at the same time, polymerization also proceeds. The polymer of compound (1) is formed and immobilized on the substrate as a thin film. Since this polymer is arranged in a certain direction at the molecular level, the thin film has a function as a liquid crystal alignment film. By this method, a liquid crystal display element having no alignment film such as polyimide can be manufactured.

In this procedure, the polar compound (1) is unevenly distributed on the substrate because the polar groups interact with the surface of the substrate. The compound (1) orients the liquid crystal molecules by irradiation with polarized ultraviolet rays, and at the same time, the polymerizable compound is polymerized by the ultraviolet rays, so that a polymer maintaining this orientation is produced. The effect of this polymer further stabilizes the orientation of the liquid crystal molecules, thus shortening the response time of the device. Since the burn-in of the image is a malfunction of the liquid crystal molecules, the burn-in is also improved at the same time by the effect of this polymer. In particular, since the compound (1) according to the embodiment of the present invention is a polymerizable polar compound, the liquid crystal molecules are oriented and copolymerized with other polymerizable compounds. As a result, the polar compound does not leak into the liquid crystal composition, so that a liquid crystal display element having a large voltage holding ratio can be obtained.

The present invention will be described in more detail with reference to Examples (including synthesis examples and device usage examples). The present invention is not limited by these examples. The present invention includes a mixture of the composition of Example 1 and the composition of Example 2. The present invention also includes a mixture prepared by mixing at least two of the compositions of Examples.
1. 1. Example of compound (1)

Compound (1) was synthesized by the procedure shown in Example 1 and the like. Unless otherwise stated, the reaction was carried out in a nitrogen atmosphere. The synthesized compound was identified by a method such as NMR analysis. The characteristics of the compound (1), the liquid crystal compound, the composition, and the device were measured by the following methods.

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

Gas chromatograph analysis: A GC-2010 type gas chromatograph manufactured by Shimadzu Corporation was used for the measurement. As the column, a capillary column DB-1 (length 60 m, inner diameter 0.25 mm, film thickness 0.25 μm) manufactured by Agilent Technologies Inc. was used. Helium (1 ml / min) was used as the carrier gas. The temperature of the sample vaporization chamber was set to 300 ° C., and the temperature of the detector (FID) portion was set to 300 ° C. The sample was dissolved in acetone to prepare a 1% by weight solution, and 1 μl of the obtained solution was injected into the sample vaporization chamber. A GC Solution system manufactured by Shimadzu Corporation was used as the recorder.

HPLC analysis: Prominence (LC-20AD; SPD-20A) manufactured by Shimadzu Corporation was used for the measurement. As the column, YMC-Pack ODS-A (length 150 mm, inner diameter 4.6 mm, particle diameter 5 μm) manufactured by YMC was used. The eluate used was an appropriate mixture of acetonitrile and water. As the detector, a UV detector, an RI detector, a CORONA detector and the like were appropriately used. When a UV detector was used, the detection wavelength was 254 nm. The sample was prepared to dissolve in acetonitrile to form a 0.1% by weight solution, and 1 μL of this solution was introduced into the sample chamber. As a recorder, C-R7Aplus manufactured by Shimadzu Corporation was used.

Ultraviolet-visible spectroscopic analysis: For the measurement, PharmaSpec UV-1700 manufactured by Shimadzu Corporation was used. The detection wavelength was 190 nm to 700 nm. The sample was prepared by dissolving it in acetonitrile to form a solution of 0.01 mmol / L, and placed in a quartz cell (optical path length 1 cm) for measurement.

Measurement sample: When measuring the phase structure and transition temperature (transparency point, melting point, polymerization initiation temperature, etc.), the compound itself was used as a sample.

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

(1) Phase structure A sample was placed on a hot plate (FP-52 type hot stage manufactured by Mettler) of a melting point measuring device equipped with a polarizing microscope. The phase state and its change were observed with a polarizing microscope while heating this sample at a rate of 3 ° C./min to identify the type of phase.

(2) Transition temperature (° C)
For the measurement, a scanning calorimeter manufactured by PerkinElmer, a Diamond DSC system, or a high-sensitivity differential scanning calorimeter manufactured by SSI Nanotechnology, X-DSC7000 was used. The temperature of the sample was raised and lowered at a rate of 3 ° C./min, and the start point of the endothermic peak or the exothermic peak accompanying the phase change of the sample was determined by extrapolation to determine the transition temperature. The melting point and polymerization initiation temperature of the compound were also measured using this device. The temperature at which a compound transitions from a solid to a liquid crystal phase such as a smectic phase or a nematic phase may be abbreviated as "lower limit temperature of the liquid crystal phase". The temperature at which a compound transitions from the liquid crystal phase to a liquid may be abbreviated as "transparency point".

The crystal was represented as C. When the types of crystals can be distinguished, they are represented as C ₁ and C ₂ , respectively. The smectic phase was represented as S and the nematic phase was represented as N. Among the smectic phase, a smectic A phase, a smectic B phase, if can be distinguished in the smectic C phase, or a smectic F phase, respectively _S _A, S B, expressed as _{S C} or _{S F,.} The liquid (isotropic) was represented as I. The transition temperature is expressed as, for example, "C 50.0 N 100.0 I". This indicates that the transition temperature from the crystal to the nematic phase is 50.0 ° C. and the transition temperature from the nematic phase to the liquid is 100.0 ° C.

(3) Upper limit temperature of nematic phase (T _NI or NI; ° C)
The 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 at which a part of the sample changed from the nematic phase to the isotropic liquid was measured. The upper limit temperature of the nematic phase may be abbreviated as "upper limit temperature". When the sample was a mixture of compound (1) and mother liquid crystal, it was indicated by the _TNI symbol. When the sample is a mixture of compound (1) and compounds such as components B, C and D, it is indicated by the symbol NI.

(4) Minimum Temperature of a Nematic Phase _{(T C;} ° C.)
A sample having a nematic phase was stored in a freezer at 0 ° C., −10 ° C., −20 ° C., −30 ° C., and −40 ° C. for 10 days, and then the liquid crystal phase was observed. For example, _TC was described as ≤-20 ° _C when the sample remained in the nematic phase at −20 ° C. and changed to a crystalline or smectic phase at −30 ° C. The lower limit temperature of the nematic phase may be abbreviated as "lower limit temperature".

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

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

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

The method of measuring the characteristics may differ between a sample with a positive dielectric anisotropy and a sample with a negative dielectric anisotropy. The measuring method when the dielectric anisotropy is positive is described in Items (8a) to (12a). When the dielectric anisotropy is negative, it is described in the items (8b) to (12b).

(8a) Viscosity (rotational viscosity; γ1; measured at 25 ° C.; mPa · s)
Positive Permittivity Anisotropy: Measurements were made according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). The sample was placed in a TN device having a twist angle of 0 degrees and a distance (cell gap) between the two glass substrates of 5 μm. A stepwise application was applied to this device in 0.5 V increments in the range of 16 V to 19.5 V. After no application for 0.2 seconds, application was repeated under the conditions of only one square wave (square pulse; 0.2 seconds) and no application (2 seconds). The peak current and peak time of the transient current generated by this application were measured. These measurements and M.I. The value of rotational viscosity was obtained from the paper by Imai et al., Calculation formula (8) on page 40. The value of the dielectric anisotropy required for this calculation was obtained by the method described below using the device whose rotational viscosity was measured.

(8b) Viscosity (rotational viscosity; γ1; measured at 25 ° C.; mPa · s)
Negative Permittivity Anisotropy: Measurements were made according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). The sample was placed in a VA element having a distance (cell gap) of 20 μm between the two glass substrates. A stepwise application was applied to this device in the range of 39 to 50 volts in 1 volt increments. After no application for 0.2 seconds, application was repeated under the conditions of only one square wave (square pulse; 0.2 seconds) and no application (2 seconds). The peak current and peak time of the transient current generated by this application were measured. These measurements and M.I. The value of rotational viscosity was obtained from the paper by Imai et al., Calculation formula (8) on page 40. For the dielectric anisotropy required for this calculation, the value measured in the section of dielectric anisotropy below was used.

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

(9b) Dielectric constant anisotropy (Δε; measured at 25 ° C)
Negative permittivity anisotropy: The value of permittivity anisotropy was calculated from the equation Δε ＝ ε∥－ε⊥. The permittivity (ε∥ and ε⊥) was measured as follows.
1) Measurement of permittivity (ε∥): A solution of octadecyltriethoxysilane (0.16 mL) in ethanol (20 mL) was applied to a well-washed glass substrate. After rotating the glass substrate with a spinner, it was heated at 150 ° C. for 1 hour. A sample was placed in a VA element in which the distance (cell gap) between the two glass substrates was 4 μm, and this element was sealed with an adhesive that cures with ultraviolet rays. A sine wave (0.5 V, 1 kHz) was applied to this device, and after 2 seconds, the permittivity (ε∥) of the liquid crystal molecule in the long axis direction was measured.
2) Measurement of permittivity (ε⊥): A polyimide solution was applied to a well-cleaned glass substrate. After firing this glass substrate, the obtained alignment film was subjected to a rubbing treatment. The sample was placed in a TN element in which the distance (cell gap) between the two glass substrates was 9 μm and the twist angle was 80 degrees. A sine wave (0.5 V, 1 kHz) was applied to this device, and after 2 seconds, the permittivity (ε⊥) of the liquid crystal molecule in the minor axis direction was measured.

(10a) Elastic constant (K; measured at 25 ° C; pN)
Positive permittivity anisotropy: An HP4284A LCR meter manufactured by Yokogawa Hewlett-Packard Co., Ltd. was used for the measurement. The sample was placed in a horizontally oriented element in which the distance (cell gap) between the two glass substrates was 20 μm. A charge of 0 to 20 volts was applied to this device, and the capacitance and applied voltage were measured. Fit the measured capacitance (C) and applied voltage (V) values using the "Liquid Crystal Device Handbook" (Nikkan Kogyo Shimbun), formulas (2.98) and formula (2.11) on page 75. Then, the values of K ₁₁ and K ₃₃ were obtained from the equation (2.99). Next, K ₂₂ was calculated using the values of K ₁₁ and K ₃₃ obtained earlier in the formula (3.18) on page 171. The elastic constant K is represented by the average value of K ₁₁ , K _22, and K ₃₃ thus obtained.

(10b) Elastic constants (K ₁₁ and K ₃₃ ; measured at 25 ° C; pN)
Negative permittivity anisotropy: An EC-1 type elastic constant measuring instrument manufactured by Toyo Corporation was used for the measurement. The sample was placed in a vertically oriented element in which the distance (cell gap) between the two glass substrates was 20 μm. A charge of 20 to 0 volts was applied to this device, and the capacitance and applied voltage were measured. The values of capacitance (C) and applied voltage (V) are fitted using the formulas (2.98) and (2.11) on page 75 of the "Liquid Crystal Device Handbook" (Nikkan Kogyo Shimbun). , The value of the elastic constant was obtained from the equation (2.10).

(11a) Threshold voltage (Vth; measured at 25 ° C; V)
Positive permittivity anisotropy: An LCD5100 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source was a halogen lamp. The sample was placed in a normally white mode TN element in which the distance (cell gap) between the two glass substrates was 0.45 / Δn (μm) and the twist angle was 80 degrees. The voltage (32 Hz, square wave) applied to this device was gradually increased by 0.02 V from 0 V to 10 V. At this time, the element was irradiated with light from the vertical direction, and the amount of light transmitted through the element was measured. A voltage-transmittance curve was created in which the transmittance was 100% when the amount of light was maximum and the transmittance was 0% when the amount of light was minimum. The threshold voltage is expressed as the voltage when the transmittance reaches 90%.

(11b) Threshold voltage (Vth; measured at 25 ° C; V)
Negative permittivity anisotropy: An LCD5100 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source was a halogen lamp. A sample is placed in a VA element in normally black mode in which the distance (cell gap) between two glass substrates is 4 μm and the rubbing direction is anti-parallel, and an adhesive that cures this element with ultraviolet rays is applied. Sealed using. The voltage (60 Hz, square wave) applied to this device was gradually increased by 0.02 V from 0 V to 20 V. At this time, the element was irradiated with light from the vertical direction, and the amount of light transmitted through the element was measured. A voltage-transmittance curve was created in which the transmittance was 100% when the amount of light was maximum and the transmittance was 0% when the amount of light was minimum. The threshold voltage is expressed as the voltage when the transmittance reaches 10%.

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

(12b) Response time (τ; measured at 25 ° C; ms)
Negative permittivity anisotropy: An LCD5100 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source was a halogen lamp. The low-pass filter was set to 5 kHz. The sample was placed in a normally black mode PVA element in which the distance between the two glass substrates (cell gap) was 3.2 μm and the rubbing direction was antiparallel. This element was sealed with an UV curable adhesive. A voltage slightly exceeding the threshold voltage was applied to this device for 1 minute, and then 23.5 mW / cm ² ultraviolet rays were irradiated for 8 minutes while applying a voltage of 5.6 V. A square wave (60 Hz, 10 V, 0.5 seconds) was applied to this device. At this time, the element was irradiated with light from the vertical direction, and the amount of light transmitted through the element was measured. It was considered that the transmittance was 100% when the amount of light was maximum, and the transmittance was 0% when the amount of light was minimum. The response time was expressed as the time required for the transmittance to change from 90% to 10% (fall time; fall time; millisecond).

Raw material Solmix (registered trademark) A-11 is a mixture of ethanol (85.5%), methanol (13.4%) and isopropanol (1.1%), and was obtained from Japan Alcohol Trading Co., Ltd.

[Synthesis Example 1]
Synthesis of compound (No. 1)

First step Compound (T-1) (10.00 g), compound (T-2) (17.01 g), DMAP (1.30 g), and dichloromethane (150 ml) were placed in a reactor and cooled to 0 ° C. .. DCC (12.00 g) was added thereto, and the mixture was stirred for 12 hours while returning to room temperature. After filtering the insoluble material, the reaction mixture was poured into water and the aqueous layer was extracted with dichloromethane. The organic layer was washed with water and dried over anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, ethyl acetate: toluene = 1:19) to obtain compound (T-3) (9.98 g; 41%). As the compound (T-2), a commercially available product (4-([6- (acrylolyloxy) oxy) benzoic acid) can be obtained from, for example, Sigma-Aldrich.

Second step Compound (T-3) (5.00 g), Compound (T-4) (2.68 g), Copper iodide (0.21 g), Pd (PPh ₃ ) ₄ (0.4 g), THF ( 50 ml) and triethylamine (50 ml) were taken in a container and stirred overnight in a nitrogen atmosphere. The reaction mixture was poured into water, extracted with toluene, washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give a light brown solid. This solid is used as a solution, purified by silica gel column chromatography (volume ratio, ethyl acetate: toluene = 1: 4), and reprecipitated with heptane to compound (No. 1) (3.00 g; 45%). Got

The NMR analysis values of the obtained compound (No. 1) are as follows.
¹ H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 8.02 (d, 2H), 7.59 (d, 2H), 7.51 (d, 2H), 7.50 (d, 2H) , 6.97 (d, 2H), 6.92 (d, 2H), 6.46 (dd, 1H), 6.45 (dd, 1H), 6.19 (dd, 1H), 6.14 ( dd, 1H), 5.88 (dd, 1H), 5.87 (dd, 1H), 4.56 (t, 2H), 4.27 (t, 2H), 4.20 (t, 2H), 4.07 (t, 2H), 1.86 (quint, 2H), 1.75 (quint, 2H), 1.55 (quint, 2H), 1.49 (quint, 2H).

The physical properties of compound (No. 1) were as follows.
Transition temperature (° C): C 83.1 I Polymerization temperature (° C): 212.8

[Synthesis Example 2]
Synthesis of compound (No. 2)

First step Compound (T-5) (0.50 g), compound (T-2) (1.47 g), DMAP (0.06 g), and dichloromethane (100 ml) were placed in a reactor and cooled to 0 ° C. .. DCC (1.04 g) was added thereto, and the mixture was stirred for 12 hours while returning to room temperature. After filtering the insoluble material, the reaction mixture was poured into water and the aqueous layer was extracted with dichloromethane. The organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, the residue was purified by silica gel chromatography (volume ratio, ethyl acetate: toluene = 1: 4), and reprecipitated with heptane to compound (No. 2) (0.92 g; 52). %) Was obtained.

The NMR analysis values of the obtained compound (No. 2) are as follows.
^{1 1} H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 8.04 (d, 4H), 7.71 (d, 4H), 7.62 (d, 4H), 6.98 (d, 4H) , 6.43 (dd, 2H), 6.17 (dd, 2H), 5.85 (dd, 2H), 4.21 (t, 2H), 4.07 (t, 2H), 1.86 ( Quant, 4H), 1.75 (quint, 4H), 1.55 (quint, 4H), 1.49 (quint, 4H).

The physical properties of compound (No. 2) were as follows.
Transition temperature (° C): C 124.8 I Polymerization temperature (° C): 127.7

[Synthesis Example 3]
Synthesis of compound (No. 617)

First step Compound (T-6) (25.0 g) and THF (200 ml) were placed in a reactor and cooled to −60 ° C. or lower. Se-BuLi (1M hexane solution) (75 ml) was added dropwise thereto while maintaining a temperature of −60 ° C. or lower, and the mixture was then stirred for 1 hour. Sulfur (2.5 g) was added thereto, and the mixture was stirred for 30 minutes, returned to room temperature, and further stirred for 1 hour. Compound (T-7) was slowly added thereto, and the mixture was stirred for 1 hour. The reaction mixture was poured into water and the aqueous layer was extracted with toluene. The organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (volume ratio, ethyl acetate: toluene = 3:10) to give compound (T-8) (14.9 g; 38%). The compound (T-6) and the compound (T-7) are known substances, and those skilled in the art can easily obtain a synthetic method.

Second step Compound (T-8) (16.4 g), PPTS (pyridinium pyridinium paratoluene sulfonic acid) (4.1 g), THF (150 ml) and MeOH (150 ml) were taken in a container and placed at 40 ° C. The mixture was stirred for 4 hours. The reaction mixture was poured into water, extracted with ethyl acetate, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give a light brown solid. This solid was used as a solution and purified by silica gel column chromatography (volume ratio, ethyl acetate: toluene = 1: 3) to obtain compound (T-9) (13.1 g; 89%).

Step 3 Compound (T-9) (12.6 g), methacrylic acid (3.0 g), DMAP (0.99 g), and dichloromethane (250 ml) were placed in a reactor and cooled to 0 ° C. DCC (7.19 g) was added thereto, and the mixture was stirred for 12 hours while returning to room temperature. After filtering the insoluble material, the reaction mixture was poured into water and the aqueous layer was extracted with dichloromethane. The organic layer was washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (toluene) to give compound (T-10) (10.64 g; 71%).

Step 4 Compound (T-10) (10.1 g), Compound (T-11) (3.2 g), Copper iodide (0.35 g), Pd (PPh ₃ ) ₄ (1.08 g), THF ( 100 ml) and triethylamine (50 ml) were taken in a container and stirred overnight in a nitrogen atmosphere. The reaction mixture was poured into water, extracted with toluene, washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give a light brown solid. This solid is made into a solution, purified by silica gel column chromatography (volume ratio, ethyl acetate: heptane = 1: 1), and reprecipitated with heptane to compound (T-12) (6.72 g; 63%). Got

Step 5 Compound (T-12) (6.72 g), compound (T-13) (1.37 g), DMAP (0.29 g), and dichloromethane (134 ml) were placed in a reactor and cooled to 0 ° C. .. DCC (3.15 g) was added thereto, and the mixture was stirred for 12 hours while returning to room temperature. After filtering the insoluble material, the reaction mixture was poured into water and the aqueous layer was extracted with dichloromethane. The organic layer was washed with water and dried over anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, ethyl acetate: toluene = 19: 1) to obtain compound (No. 617) (6.93 g; 85%).

The NMR analysis values of the obtained compound (No. 617) are as follows.
¹ H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 7.87 (s, 1H), 7.82 (d, 1H), 7.55 (d, 1H), 7.50 (d, 2H) , 7.39 (d, 2H), 6.97 (d, 2H), 6.92 (d, 2H), 6.10 (s, 1H), 5.78 (dd, 1H), 5.55 ( t, 1H), 5.38 (dd, 1H), 4.61 (t, 2H), 4.28 (t, 2H), 4.16 (t, 2H), 4.00 (t, 2H), 2.57 (s, 3H), 1.95 (s, 3H), 1.82 (quint, 2H), 1.72 (quint, 2H), 1.55 (quint, 2H), 1.47 (quint) , 2H).

The physical properties of compound (No. 617) were as follows.
Transition temperature (° C): C 72.25 I Polymerization temperature (° C): 118.8

[Synthesis Example 4]
Synthesis of compound (No. 618) In Synthesis Example 3, compound (T-14) is used instead of compound (T-6), and compound (T-15) is used instead of compound (T-7). (No. 618) was obtained. The compound (T-14) can be easily synthesized by referring to the method for synthesizing the compound (T-6). In addition, compound (T-15) is a known substance.

The NMR analysis values of the obtained compound (No. 618) are as follows.
¹ H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 8.15 (d, 2H), 7.62 (d, 2H), 7.51 (d, 2H), 7.31 (d, 1H) , 7.05 (s, 1H), 7.03 (d, 1H), 6.92 (d, 2H), 6.10 (s, 1H), 5.67 (dd, 1H), 5.55 ( t, 1H), 5.38 (dd, 1H), 4.61 (t, 2H), 4.28 (t, 2H), 4.15 (t, 2H), 2.90 (t, 2H), 2.40 (s, 3H), 1.95 (s, 3H), 1.67 (quint, 2H), 1.66 (quint, 2H), 1.50 (quint, 2H), 1.43 (quint) , 2H).

The physical properties of compound (No. 618) were as follows.
Transition temperature (° C): C 59.74 I Polymerization temperature (° C): 154.6

As a specific example of compound (1), the following compound can be synthesized in addition to the compound shown in the synthesis example according to the synthesis method described in the synthesis example.

2. Example of device use The compounds in the example of use are represented by symbols based on the definitions in Table 2 below. In Table 2, the configuration for 1,4-cyclohexylene is trans. The number in parentheses after the symbol corresponds to the compound number. The symbol (-) means other liquid crystal compounds. The proportion (percentage) of the liquid crystal compound is a weight percentage (% by weight) based on the weight of the liquid crystal composition. Finally, the characteristic values of the composition are summarized.

1. 1. The composition to which the polar compound was added was injected into the device having no raw material alignment film. After irradiating with linearly polarized light, the orientation of the liquid crystal molecules in this device was confirmed. First, the raw materials will be described. The raw material was appropriately selected from the composition (M1) to the composition (M41) and the compound (No. 1) to the compound (No. 618) such as the compound (1). The composition is as follows.

[Composition (M1)]
3-HB (2F, 3F) -O2 (9-1) 10%
5-HB (2F, 3F) -O2 (9-1) 7%
2-BB (2F, 3F) -O2 (9-3) 7%
3-BB (2F, 3F) -O2 (9-3) 7%
3-B (2F, 3F) B (2F, 3F) -O2 (9-7) 3%
2-HHB (2F, 3F) -O2 (10-1) 5%
3-HHB (2F, 3F) -O2 (10-1) 10%
2-HBB (2F, 3F) -O2 (10-7) 8%
3-HBB (2F, 3F) -O2 (10-7) 10%
2-HH-3 (2-1) 14%
3-HB-O1 (2-5) 5%
3-HHB-1 (3-1) 3%
3-HHB-O1 (3-1) 3%
3-HHB-3 (3-1) 4%
2-BB (F) B-3 (3-6) 4%
NI = 73.2 ° C; Tc <-20 ° C; Δn = 0.113; Δε = -4.0; Vth = 2.18V; η = 22.6mPa · s.

[Composition (M2)]
3-HB (2F, 3F) -O4 (9-1) 6%
3-H2B (2F, 3F) -O2 (9-4) 8%
3-H1OB (2F, 3F) -O2 (9-5) 4%
3-BB (2F, 3F) -O2 (9-3) 7%
2-HHB (2F, 3F) -O2 (10-1) 7%
3-HHB (2F, 3F) -O2 (10-1) 7%
3-HH2B (2F, 3F) -O2 (10-4) 7%
5-HH2B (2F, 3F) -O2 (10-4) 4%
2-HBB (2F, 3F) -O2 (10-7) 5%
3-HBB (2F, 3F) -O2 (10-7) 5%
4-HBB (2F, 3F) -O2 (10-7) 6%
2-HH-3 (2-1) 12%
1-BB-5 (2-8) 12%
3-HHB-1 (3-1) 4%
3-HHB-O1 (3-1) 3%
3-HBB-2 (3-4) 3%
NI = 82.8 ° C; Tc <-30 ° C; Δn = 0.118; Δε = -4.4; Vth = 2.13V; η = 22.5mPa · s.

[Composition (M3)]
3-HB (2F, 3F) -O2 (9-1) 7%
5-HB (2F, 3F) -O2 (9-1) 7%
3-BB (2F, 3F) -O2 (9-3) 8%
3-HHB (2F, 3F) -O2 (10-1) 5%
5-HHB (2F, 3F) -O2 (10-1) 4%
3-HH1OB (2F, 3F) -O2 (10-5) 4%
2-BB (2F, 3F) B-3 (11-1) 5%
2-HBB (2F, 3F) -O2 (10-7) 3%
3-HBB (2F, 3F) -O2 (10-7) 8%
4-HBB (2F, 3F) -O2 (10-7) 5%
5-HBB (2F, 3F) -O2 (10-7) 8%
3-HH-V (2-1) 27%
3-HH-V1 (2-1) 6%
V-HHB-1 (3-1) 3%
NI = 78.1 ° C; Tc <-30 ° C; Δn = 0.107; Δε = -3.2; Vth = 2.02V; η = 15.9 mPa · s.

[Composition (M4)]
3-HB (2F, 3F) -O2 (9-1) 10%
5-HB (2F, 3F) -O2 (9-1) 10%
3-H2B (2F, 3F) -O2 (9-4) 8%
5-H2B (2F, 3F) -O2 (9-4) 8%
2-HBB (2F, 3F) -O2 (10-7) 6%
3-HBB (2F, 3F) -O2 (10-7) 8%
4-HBB (2F, 3F) -O2 (10-7) 7%
5-HBB (2F, 3F) -O2 (10-7) 7%
3-HDhB (2F, 3F) -O2 (10-3) 5%
3-HH-4 (2-1) 14%
V-HHB-1 (3-1) 10%
3-HBB-2 (3-4) 7%
NI = 88.5 ° C; Tc <-30 ° C; Δn = 0.108; Δε = -3.8; Vth = 2.25V; η = 24.6mPa · s; VHR-1 = 99.1%; VHR -2 = 98.2%; VHR-3 = 97.8%.

[Composition (M5)]
3-HB (2F, 3F) -O2 (9-1) 7%
3-HB (2F, 3F) -O4 (9-1) 8%
3-H2B (2F, 3F) -O2 (9-4) 8%
3-BB (2F, 3F) -O2 (9-3) 10%
2-HHB (2F, 3F) -O2 (10-1) 4%
3-HHB (2F, 3F) -O2 (10-1) 7%
3-HHB (2F, 3F) -1 (10-1) 6%
2-HBB (2F, 3F) -O2 (10-7) 6%
3-HBB (2F, 3F) -O2 (10-7) 6%
4-HBB (2F, 3F) -O2 (10-7) 5%
5-HBB (2F, 3F) -O2 (10-7) 4%
3-HEB (2F, 3F) B (2F, 3F) -O2 (16-1) 3%
3-H1OCro (7F, 8F) -5 (13-2) 3%
3-HDhB (2F, 3F) -O2 (10-3) 5%
3-HH-O1 (2-1) 5%
1-BB-5 (2-8) 4%
V-HHB-1 (3-1) 4%
5-HB (F) BH-3 (4-2) 5%
NI = 81.1 ° C; Tc <-30 ° C; Δn = 0.119; Δε = -4.5; Vth = 1.69V; η = 31.4mPa · s.

[Composition (M6)]
3-HB (2F, 3F) -O4 (9-1) 15%
3-HBB (2F, 3F) -O2 (10-7) 8%
4-HBB (2F, 3F) -O2 (10-7) 5%
5-HBB (2F, 3F) -O2 (10-7) 7%
3-dhBB (2F, 3F) -O2 (10-9) 5%
3-chB (2F, 3F) -O2 (16-2) 7%
2-HchB (2F, 3F) -O2 (16-3) 8%
5-HH-V (2-1) 18%
7-HB-1 (2-5) 5%
V-HHB-1 (3-1) 7%
V2-HHB-1 (3-1) 7%
3-HBB (F) B-3 (4-5) 8%
NI = 98.8 ° C; Tc <-30 ° C; Δn = 0.111; Δε = -3.2; Vth = 2.47V; η = 23.9mPa · s.

[Composition (M7)]
3-H2B (2F, 3F) -O2 (9-4) 18%
5-H2B (2F, 3F) -O2 (9-4) 17%
3-HHB (2F, 3Cl) -O2 (10-12) 5%
3-HBB (2F, 3Cl) -O2 (10-13) 8%
5-HBB (2F, 3Cl) -O2 (10-13) 7%
3-HDhB (2F, 3F) -O2 (10-3) 5%
3-HH-V (2-1) 11%
3-HH-VFF (2-1) 7%
F3-HH-V (2-1) 10%
3-HHEH-3 (3-13) 4%
3-HB (F) HH-2 (4-7) 4%
3-HHEBH-3 (4-6) 4%
NI = 77.5 ° C; Tc <-30 ° C; Δn = 0.084; Δε = -2.6; Vth = 2.43V; η = 22.8mPa · s.

[Composition (M8)]
3-HB (2F, 3F) -O2 (9-1) 8%
3-H2B (2F, 3F) -O2 (9-4) 10%
3-BB (2F, 3F) -O2 (9-3) 10%
2O-BB (2F, 3F) -O2 (9-3) 3%
2-HHB (2F, 3F) -O2 (10-1) 4%
3-HHB (2F, 3F) -O2 (10-1) 7%
2-HHB (2F, 3F) -1 (10-1) 5%
2-BB (2F, 3F) B-3 (11-1) 6%
2-BB (2F, 3F) B-4 (11-1) 6%
2-HBB (2F, 3F) -O2 (10-7) 4%
3-HBB (2F, 3F) -O2 (10-7) 7%
3-HH1OCro (7F, 8F) -5 (13-6) 4%
3-HDhB (2F, 3F) -O2 (10-3) 6%
3-dhBB (2F, 3F) -O2 (10-9) 4%
3-HH-V (2-1) 11%
1-BB-5 (2-8) 5%
NI = 70.6 ° C; Tc <-20 ° C; Δn = 0.129; Δε = -4.3; Vth = 1.69V; η = 27.0 mPa · s.

[Composition (M9)]
3-HB (2F, 3F) -O4 (9-1) 14%
3-H1OB (2F, 3F) -O2 (9-5) 3%
3-BB (2F, 3F) -O2 (9-3) 10%
2-HHB (2F, 3F) -O2 (10-1) 7%
3-HHB (2F, 3F) -O2 (10-1) 7%
3-HH1OB (2F, 3F) -O2 (10-5) 6%
2-HBB (2F, 3F) -O2 (10-7) 4%
3-HBB (2F, 3F) -O2 (10-7) 6%
4-HBB (2F, 3F) -O2 (10-7) 4%
3-HH-V (2-1) 14%
1-BB-3 (2-8) 3%
3-HHB-1 (3-1) 4%
3-HHB-O1 (3-1) 4%
V-HBB-2 (3-4) 4%
1-BB (F) B-2V (3-6) 6%
5-HBBH-1O1 (4-1) 4%
NI = 93.0 ° C; Tc <-30 ° C; Δn = 0.123; Δε = -4.0; Vth = 2.27V; η = 29.6 mPa · s.

[Composition (M10)]
3-HB (2F, 3F) -O4 (9-1) 6%
3-H2B (2F, 3F) -O2 (9-4) 8%
3-H1OB (2F, 3F) -O2 (9-5) 5%
3-BB (2F, 3F) -O2 (9-3) 10%
2-HHB (2F, 3F) -O2 (10-1) 7%
3-HHB (2F, 3F) -O2 (10-1) 7%
5-HHB (2F, 3F) -O2 (10-1) 7%
2-HBB (2F, 3F) -O2 (10-7) 4%
3-HBB (2F, 3F) -O2 (10-7) 7%
5-HBB (2F, 3F) -O2 (10-7) 6%
3-HH-V (2-1) 11%
1-BB-3 (2-8) 6%
3-HHB-1 (3-1) 4%
3-HHB-O1 (3-1) 4%
3-HBB-2 (3-4) 4%
3-B (F) BB-2 (3-8) 4%
NI = 87.6 ° C; Tc <-30 ° C; Δn = 0.126; Δε = -4.5; Vth = 2.21V; η = 25.3 mPa · s.

[Composition (M11)]
3-HB (2F, 3F) -O4 (9-1) 6%
3-H2B (2F, 3F) -O2 (9-4) 8%
3-H1OB (2F, 3F) -O2 (9-5) 4%
3-BB (2F, 3F) -O2 (9-3) 7%
2-HHB (2F, 3F) -O2 (10-1) 6%
3-HHB (2F, 3F) -O2 (10-1) 10%
5-HHB (2F, 3F) -O2 (10-1) 8%
2-HBB (2F, 3F) -O2 (10-7) 5%
3-HBB (2F, 3F) -O2 (10-7) 7%
5-HBB (2F, 3F) -O2 (10-7) 5%
2-HH-3 (2-1) 12%
1-BB-3 (2-8) 6%
3-HHB-1 (3-1) 3%
3-HHB-O1 (3-1) 4%
3-HBB-2 (3-4) 6%
3-B (F) BB-2 (3-8) 3%
NI = 93.0 ° C; Tc <-20 ° C; Δn = 0.124; Δε = −4.5; Vth = 2.22V; η = 25.0 mPa · s.

[Composition (M12)]
3-HB (2F, 3F) -O2 (9-1) 7%
5-HB (2F, 3F) -O2 (9-1) 7%
3-BB (2F, 3F) -O2 (9-3) 8%
3-HHB (2F, 3F) -O2 (10-1) 4%
5-HHB (2F, 3F) -O2 (10-1) 5%
3-HH1OB (2F, 3F) -O2 (10-5) 5%
2-BB (2F, 3F) B-3 (11-1) 4%
2-HBB (2F, 3F) -O2 (10-7) 3%
3-HBB (2F, 3F) -O2 (10-7) 8%
4-HBB (2F, 3F) -O2 (10-7) 5%
5-HBB (2F, 3F) -O2 (10-7) 8%
3-HH-V (2-1) 33%
V-HHB-1 (3-1) 3%
NI = 76.4 ° C; Tc <-30 ° C; Δn = 0.104; Δε = -3.2; Vth = 2.06V; η = 15.6 mPa · s.

[Composition (M13)]
2-H1OB (2F, 3F) -O2 (9-5) 6%
3-H1OB (2F, 3F) -O2 (9-5) 4%
3-BB (2F, 3F) -O2 (9-3) 3%
2-HH1OB (2F, 3F) -O2 (10-5) 14%
2-HBB (2F, 3F) -O2 (10-7) 7%
3-HBB (2F, 3F) -O2 (10-7) 11%
5-HBB (2F, 3F) -O2 (10-7) 9%
2-HH-3 (2-1) 5%
3-HH-VFF (2-1) 30%
1-BB-3 (2-8) 5%
3-HHB-1 (3-1) 3%
3-HBB-2 (3-4) 3%
NI = 78.3 ° C; Tc <-20 ° C; Δn = 0.103; Δε = -3.2; Vth = 2.17V; η = 17.7mPa · s.

[Composition (M14)]
3-HB (2F, 3F) -O2 (9-1) 5%
5-HB (2F, 3F) -O2 (9-1) 7%
3-BB (2F, 3F) -O2 (9-3) 8%
3-HHB (2F, 3F) -O2 (10-1) 5%
5-HHB (2F, 3F) -O2 (10-1) 4%
3-HH1OB (2F, 3F) -O2 (10-5) 5%
2-BB (2F, 3F) B-3 (11-1) 4%
2-HBB (2F, 3F) -O2 (10-7) 3%
3-HBB (2F, 3F) -O2 (10-7) 9%
4-HBB (2F, 3F) -O2 (10-7) 4%
5-HBB (2F, 3F) -O2 (10-7) 8%
3-HH-V (2-1) 27%
3-HH-V1 (2-1) 6%
V-HHB-1 (3-1) 5%
NI = 81.2 ° C; Tc <-20 ° C; Δn = 0.107; Δε = -3.2; Vth = 2.11V; η = 15.5 mPa · s.

[Composition (M15)]
3-H2B (2F, 3F) -O2 (9-4) 7%
3-HHB (2F, 3F) -O2 (10-1) 8%
3-HH1OB (2F, 3F) -O2 (10-5) 5%
2-BB (2F, 3F) B-3 (11-1) 7%
2-BB (2F, 3F) B-4 (11-1) 7%
3-HDhB (2F, 3F) -O2 (10-3) 3%
5-HDhB (2F, 3F) -O2 (10-3) 4%
2-HchB (2F, 3F) -O2 (16-3) 8%
4-HH-V (2-1) 15%
3-HH-V1 (2-1) 6%
1-HH-2V1 (2-1) 6%
3-HH-2V1 (2-1) 4%
V2-BB-1 (2-8) 5%
1V2-BB-1 (2-8) 5%
3-HHB-1 (3-1) 6%
3-HB (F) BH-3 (4-2) 4%
NI = 88.7 ° C; Tc <-30 ° C; Δn = 0.115; Δε = -1.9; Vth = 2.82V; η = 17.3mPa · s.

[Composition (M16)]
V2-H2B (2F, 3F) -O2 (9-4) 8%
V2-H1OB (2F, 3F) -O4 (9-5) 4%
3-BB (2F, 3F) -O2 (9-3) 7%
2-HHB (2F, 3F) -O2 (10-1) 7%
3-HHB (2F, 3F) -O2 (10-1) 7%
3-HH2B (2F, 3F) -O2 (10-4) 7%
5-HH2B (2F, 3F) -O2 (10-4) 4%
V-HH2B (2F, 3F) -O2 (10-4) 6%
V2-HBB (2F, 3F) -O2 (10-7) 5%
V-HBB (2F, 3F) -O2 (10-7) 5%
V-HBB (2F, 3F) -O4 (10-7) 6%
2-HH-3 (2-1) 12%
1-BB-5 (2-8) 12%
3-HHB-1 (3-1) 4%
3-HHB-O1 (3-1) 3%
3-HBB-2 (3-4) 3%
NI = 89.9 ° C; Tc <-20 ° C; Δn = 0.122; Δε = -4.2; Vth = 2.16V; η = 23.4 mPa · s.

[Composition (M17)]
3-HB (2F, 3F) -O2 (9-1) 3%
V-HB (2F, 3F) -O2 (9-1) 3%
V2-HB (2F, 3F) -O2 (9-1) 5%
5-H2B (2F, 3F) -O2 (9-4) 5%
V2-BB (2F, 3F) -O2 (9-3) 3%
1V2-BB (2F, 3F) -O2 (9-3) 3%
3-HHB (2F, 3F) -O2 (10-1) 6%
V-HHB (2F, 3F) -O2 (10-1) 6%
V-HHB (2F, 3F) -O4 (10-1) 5%
V2-HHB (2F, 3F) -O2 (10-1) 4%
V2-BB (2F, 3F) B-1 (11-1) 4%
V2-HBB (2F, 3F) -O2 (10-7) 5%
V-HBB (2F, 3F) -O2 (10-7) 4%
V-HBB (2F, 3F) -O4 (10-7) 5%
V-HHB (2F, 3Cl) -O2 (10-12) 3%
3-HH-V (2-1) 27%
3-HH-V1 (2-1) 6%
V-HHB-1 (3-1) 3%
NI = 77.1 ° C; Tc <-20 ° C; Δn = 0.101; Δε = −3.0; Vth = 2.04V; η = 13.9 mPa · s.

[Composition (M18)]
V-HB (2F, 3F) -O2 (9-1) 10%
V2-HB (2F, 3F) -O2 (9-1) 10%
2-H1OB (2F, 3F) -O2 (9-5) 3%
3-H1OB (2F, 3F) -O2 (9-5) 3%
2O-BB (2F, 3F) -O2 (9-3) 3%
V2-BB (2F, 3F) -O2 (9-3) 8%
V2-HHB (2F, 3F) -O2 (10-1) 5%
2-HBB (2F, 3F) -O2 (10-7) 3%
3-HBB (2F, 3F) -O2 (10-7) 3%
V-HBB (2F, 3F) -O2 (10-7) 6%
V-HBB (2F, 3F) -O4 (10-7) 8%
V-HHB (2F, 3Cl) -O2 (10-12) 7%
3-HH-4 (2-1) 14%
V-HHB-1 (3-1) 10%
3-HBB-2 (3-4) 7%
NI = 75.9 ° C; Tc <-20 ° C; Δn = 0.114; Δε = -3.9; Vth = 2.20V; η = 24.7mPa · s.

[Composition (M19)]
2-H1OB (2F, 3F) -O2 (9-5) 7%
3-H1OB (2F, 3F) -O2 (9-5) 11%
3-HH1OB (2F, 3F) -O2 (10-5) 8%
2-HBB (2F, 3F) -O2 (10-7) 3%
3-HBB (2F, 3F) -O2 (10-7) 9%
5-HBB (2F, 3F) -O2 (10-7) 7%
V-HBB (2F, 3F) -O2 (10-7) 8%
3-HDhB (2F, 3F) -O2 (10-3) 3.5%
2-HH-3 (2-1) 21%
3-HH-4 (2-1) 5%
3-HB-O2 (2-5) 2.5%
1-BB-3 (2-8) 4%
3-HHB-1 (3-1) 1.5%
3-HBB-2 (3-4) 9.5%
NI = 80.8 ° C; Tc <-20 ° C; Δn = 0.108; Δε = -3.8; Vth = 2.02V; η = 19.8 mPa · s.

[Composition (M20)]
2-H1OB (2F, 3F) -O2 (9-5) 5.5%
2-BB (2F, 3F) -O2 (9-3) 11%
2-HH1OB (2F, 3F) -O2 (10-5) 13%
3-HH1OB (2F, 3F) -O2 (10-5) 15.5%
3-HBB (2F, 3F) -O2 (10-7) 9%
2-HH-3 (2-1) 25%
3-HH-4 (2-1) 3%
3-HBB-2 (3-4) 14%
5-B (F) BB-2 (3-8) 4%
NI = 85.3 ° C; Tc <-20 ° C; Δn = 0.109; Δε = -3.6; Vth = 2.06V; η = 20.9mPa · s.

[Composition (M21)]
V-HB (2F, 3F) -O2 (9-1) 7%
V-2BB (2F, 3F) -O2 (9-3) 10%
V-HHB (2F, 3F) -O1 (10-1) 7%
V-HHB (2F, 3F) -O2 (10-1) 9%
V-2HHB (2F, 3F) -O2 (10-1) 8%
3-HH2B (2F, 3F) -O2 (10-4) 9%
V-HBB (2F, 3F) -O2 (10-7) 7%
V-HBB (2F, 3F) -O4 (10-7) 7%
2-HH-3 (2-1) 9%
3-HH-4 (2-1) 3%
3-HH-V (2-1) 15%
3-HH-V1 (2-1) 6%
1V2-HH-3 (2-1) 3%
NI = 87.5 ° C; Tc <-20 ° C; Δn = 0.100; Δε = -3.4; Vth = 2.25V; η = 16.6 mPa · s.

[Composition (M22)]
3-HHXB (F, F) -F (6-100) 6%
3-BB (F, F) XB (F, F) -F (6-97) 13%
3-HHBB (F, F) -F (7-6) 4%
4-HHBB (F, F) -F (7-6) 5%
3-HBBXB (F, F) -F (7-32) 3%
3-BB (F) B (F, F) XB (F) -F (7-46) 2%
4-BB (F) B (F, F) XB (F, F) -F (7-47) 8%
5-BB (F) B (F, F) XB (F, F) -F (7-47) 7%
3-HH-V (2-1) 44%
V-HHB-1 (3-1) 6%
2-BB (F) B-3 (3-6) 2%
NI = 79.8 ° C; Tc <-30 ° C; Δn = 0.106; Δε = 8.5; Vth = 1.45V; η = 11.6 mPa · s; γ1 = 60.0 mPa · s.

[Composition (M23)]
5-HXB (F, F) -F (5-13) 3%
3-HHXB (F, F) -F (6-100) 3%
3-HHXB (F, F) -CF3 (6-100) 3%
3-HGB (F, F) -F (6-103) 3%
3-HB (F) B (F, F) -F (6-50) 5%
3-BB (F, F) XB (F, F) -F (6-97) 6%
3-HHBB (F, F) -F (7-6) 6%
5-BB (F) B (F, F) XB (F) B (F, F) -F (-)
2%
3-BB (2F, 3F) XB (F, F) -F (6-114) 4%
3-B (2F, 3F) BXB (F, F) -F (6-115) 5%
3-HHB (F, F) XB (F, F) -F (7-29) 4%
3-HB-CL (5-2) 3%
3-HHB-OCF3 (6-1) 3%
3-HH-V (2-1) 22%
3-HH-V1 (2-1) 10%
5-HB-O2 (2-5) 5%
3-HHEH-3 (3-13) 3%
3-HBB-2 (3-4) 7%
5-B (F) BB-3 (3-8) 3%
NI = 71.2 ° C; Tc <-20 ° C; Δn = 0.099; Δε = 6.1; Vth = 1.74V; η = 13.2 mPa · s; γ1 = 59.3 mPa · s.

[Composition (M24)]
5-HXB (F, F) -F (5-13) 6%
3-HHXB (F, F) -F (6-100) 6%
V-HB (F) B (F, F) -F (6-50) 5%
3-HHB (F) B (F, F) -F (7-9) 7%
2-BB (F) B (F, F) XB (F) -F (7-47) 3%
3-BB (F) B (F, F) XB (F) -F (7-47) 3%
4-BB (F) B (F, F) XB (F) -F (7-47) 4%
5-HB-CL (5-2) 5%
2-HH-5 (2-1) 8%
3-HH-V (2-1) 10%
3-HH-V1 (2-1) 7%
4-HH-V (2-1) 10%
4-HH-V1 (2-1) 8%
5-HB-O2 (2-5) 7%
4-HHEH-3 (3-13) 3%
1-BB (F) B-2V (3-6) 3%
1O1-HBBH-3 (4-1) 5%
NI = 78.5 ° C; Tc <-20 ° C; Δn = 0.095; Δε = 3.4; Vth = 1.50V; η = 8.4mPa · s; γ1 = 54.2mPa · s.

[Composition (M25)]
3-HHEB (F, F) -F (6-12) 5%
3-HHXB (F, F) -F (6-100) 7%
5-HBEB (F, F) -F (6-39) 5%
3-BB (F, F) XB (F, F) -F (6-97) 10%
2-HHB (F) B (F, F) -F (7-9) 3%
3-HB (2F, 3F) BXB (F, F) -F (7-58) 3%
3-BB (2F, 3F) BXB (F, F) -F (7-59) 2%
5-HHB (F, F) XB (F, F) -F (7-29) 6%
2-HH-3 (2-1) 8%
3-HH-V (2-1) 20%
3-HH-V1 (2-1) 7%
4-HH-V (2-1) 6%
5-HB-O2 (2-5) 5%
V2-B2BB-1 (3) 3%
3-HHEBH-3 (4-6) 5%
3-HHEBH-5 (4-6) 5%
NI = 90.3 ° C; Tc <-20 ° C; Δn = 0.089; Δε = 5.5; Vth = 1.65V; η = 13.6 mPa · s; γ1 = 60.1 mPa · s.

[Composition (M26)]
3-BB (F, F) XB (F, F) -F (6-97) 12%
3-HHBB (F, F) -F (7-6) 5%
4-HHBB (F, F) -F (7-6) 4%
3-HBBXB (F, F) -F (7-32) 3%
3-BB (F) B (F, F) XB (F) -F (7-46) 3%
3-BB (F) B (F, F) XB (F, F) -F (7-47) 3%
4-BB (F) B (F, F) XB (F, F) -F (7-47) 5%
5-BB (F) B (F, F) XB (F, F) -F (7-47) 4%
2-HH-3 (2-1) 6%
3-HH-5 (2-1) 6%
3-HH-V (2-1) 25%
3-HH-VFF (2-1) 6%
5-HB-O2 (2-5) 7%
V-HHB-1 (3-1) 6%
V-HBB-2 (3-4) 5%
NI = 78.3 ° C; Tc <-20 ° C; Δn = 0.107; Δε = 7.0; Vth = 1.55V; η = 11.6mPa · s; γ1 = 55.6mPa · s.

[Composition (M27)]
3-HHXB (F, F) -F (6-100) 3%
3-BBXB (F, F) -F (6-91) 3%
3-BB (F, F) XB (F, F) -F (6-97) 8%
3-HHBB (F, F) -F (7-6) 5%
4-HHBB (F, F) -F (7-6) 4%
3-BB (F) B (F, F) XB (F, F) -F (7-47) 3%
4-BB (F) B (F, F) XB (F, F) -F (7-47) 6%
5-BB (F) B (F, F) XB (F, F) -F (7-47) 5%
3-HH-V (2-1) 30%
3-HH-V1 (2-1) 5%
3-HHB-O1 (3-1) 2%
V-HHB-1 (3-1) 5%
2-BB (F) B-3 (3-6) 6%
F3-HH-V (2-1) 15%
NI = 80.4 ° C; Tc <-20 ° C; Δn = 0.106; Δε = 5.8; Vth = 1.40V; η = 11.6mPa · s; γ1 = 61.0mPa · s.

[Composition (M28)]
3-HGB (F, F) -F (6-103) 3%
5-GHB (F, F) -F (6-109) 4%
3-GB (F, F) XB (F, F) -F (6-113) 5%
3-BB (F) B (F, F) -CF3 (6-69) 2%
3-HHBB (F, F) -F (7-6) 4%
3-GBB (F) B (F, F) -F (7-55) 2%
2-dhBB (F, F) XB (F, F) -F (7-50) 4%
3-GB (F) B (F, F) XB (F, F) -F (7-57) 3%
3-HGB (F, F) XB (F, F) -F (-) 5%
7-HB (F, F) -F (5-4) 3%
2-HH-3 (2-1) 14%
2-HH-5 (2-1) 4%
3-HH-V (2-1) 26%
1V2-HH-3 (2-1) 5%
1V2-BB-1 (2-8) 3%
2-BB (F) B-3 (3-6) 3%
3-HB (F) HH-2 (4-7) 4%
5-HBB (F) B-2 (4-5) 6%
NI = 78.4 ° C; Tc <-20 ° C; Δn = 0.094; Δε = 5.6; Vth = 1.45V; η = 11.5mPa · s; γ1 = 61.7mPa · s.

[Composition (M29)]
3-HBB (F, F) -F (6-24) 5%
5-HBB (F, F) -F (6-24) 4%
3-BB (F) B (F, F) -F (6-69) 3%
3-BB (F) B (F, F) XB (F, F) -F (7-47) 3%
4-BB (F) B (F, F) XB (F, F) -F (7-47) 5%
3-BB (F, F) XB (F) B (F, F) -F (7-60) 3%
5-BB (F) B (F, F) XB (F) B (F, F) -F (-)
4%
3-HH2BB (F, F) -F (7-15) 3%
4-HH2BB (F, F) -F (7-15) 3%
2-HH-5 (2-1) 8%
3-HH-V (2-1) 25%
3-HH-V1 (2-1) 7%
4-HH-V1 (2-1) 6%
5-HB-O2 (2-5) 5%
7-HB-1 (2-5) 5%
VFF-HHB-O1 (3-1) 8%
VFF-HHB-1 (3-1) 3%
NI = 80.0 ° C; Tc <-20 ° C; Δn = 0.101; Δε = 4.6; Vth = 1.71V; η = 11.0 mPa · s; γ1 = 47.2 mPa · s.

[Composition (M30)]
3-HHB (F, F) -F (6-3) 8%
3-GB (F) B (F) -F (6-116) 2%
3-GB (F) B (F, F) -F (6-117) 3%
3-BB (F, F) XB (F, F) -F (6-97) 8%
3-GB (F) B (F, F) XB (F, F) -F (7-57) 6%
5-GB (F) B (F, F) XB (F, F) -F (7-57) 5%
3-HH-V (2-1) 30%
3-HH-V1 (2-1) 10%
1V2-HH-3 (2-1) 8%
3-HH-VFF (2-1) 8%
V2-BB-1 (2-8) 2%
5-HB (F) BH-3 (4-2) 5%
5-HBBH-3 (4-1) 5%
NI = 78.6 ° C; Tc <-20 ° C; Δn = 0.088; Δε = 5.6; Vth = 1.85V; η = 13.9mPa · s; γ1 = 66.9mPa · s.

[Composition (M31)]
3-HHEB (F, F) -F (6-12) 4%
5-HHEB (F, F) -F (6-12) 3%
3-HBEB (F, F) -F (6-39) 3%
5-HBEB (F, F) -F (6-39) 3%
3-BB (F) B (F, F) -F (6-69) 3%
3-GB (F) B (F, F) XB (F, F) -F (7-57) 5%
4-GB (F) B (F, F) XB (F, F) -F (7-57) 5%
5-HB-CL (2-5) 5%
3-HHB-OCF3 (3-1) 4%
3-HHB (F, F) XB (F, F) -F (7-29) 5%
5-HHB (F, F) XB (F, F) -F (7-29) 3%
3-HGB (F, F) XB (F, F) -F (-) 5%
2-HH-5 (2-1) 3%
3-HH-5 (2-1) 5%
3-HH-V (2-1) 24%
4-HH-V (2-1) 5%
1V2-HH-3 (2-1) 5%
3-HHEH-3 (3-13) 5%
5-B (F) BB-2 (3-8) 3%
5-B (F) BB-3 (3-8) 2%
NI = 82.9 ° C; Tc <-20 ° C; Δn = 0.093; Δε = 6.9; Vth = 1.50V; η = 16.3 mPa · s; γ1 = 65.2 mPa · s.

[Composition (M32)]
3-HHXB (F, F) -F (6-100) 9%
3-HBB (F, F) -F (6-24) 3%
3-BB (F) B (F, F) -F (6-69) 4%
3-BB (F) B (F, F) -CF3 (6-69) 4%
3-BB (F, F) XB (F, F) -F (6-97) 5%
3-GBB (F) B (F, F) -F (7-55) 3%
4-GBB (F) B (F, F) -F (7-55) 4%
3-HH-V (2-1) 25%
3-HH-V1 (2-1) 10%
5-HB-O2 (2-5) 10%
7-HB-1 (2-5) 5%
V2-BB-1 (2-8) 3%
3-HHB-1 (3-1) 4%
1V-HBB-2 (3-4) 5%
5-HBB (F) B-2 (4-5) 6%
NI = 79.6 ° C; Tc <-20 ° C; Δn = 0.111; Δε = 4.7; Vth = 1.86V; η = 9.7mPa · s; γ1 = 49.9mPa · s.

[Composition (M33)]
3-BB (F, F) XB (F, F) -F (6-97) 14%
5-BB (F) B (F, F) XB (F, F) -F (7-47) 7%
7-HB (F, F) -F (5-4) 6%
2-HH-5 (2-1) 5%
3-HH-V (2-1) 30%
3-HH-V1 (2-1) 3%
3-HH-VFF (2-1) 10%
3-HHB-1 (3-1) 4%
3-HHB-3 (3-1) 5%
3-HHB-O1 (3-1) 3%
1-BB (F) B-2V (3-6) 3%
3-HHEBH-3 (4-6) 3%
3-HHEBH-4 (4-6) 4%
3-HHEBH-5 (4-6) 3%
NI = 83.0 ° C; Tc <-20 ° C; Δn = 0.086; Δε = 3.8; Vth = 1.94V; η = 7.5 mPa · s; γ1 = 51.5 mPa · s.

[Composition (M34)]
3-HBB (F, F) -F (6-24) 5%
5-HBB (F, F) -F (6-24) 4%
3-BB (F) B (F, F) -F (6-69) 3%
3-BB (F) B (F, F) XB (F, F) -F (7-47) 3%
4-BB (F) B (F, F) XB (F, F) -F (7-47) 5%
3-BB (F, F) XB (F) B (F, F) -F (7-60) 3%
5-BB (F) B (F, F) XB (F) B (F, F) -F (-)
4%
3-HH2BB (F, F) -F (7-15) 3%
4-HH2BB (F, F) -F (7-15) 3%
2-HH-5 (2-1) 8%
3-HH-V (2-1) 28%
4-HH-V1 (2-1) 7%
5-HB-O2 (2-5) 2%
7-HB-1 (2-5) 5%
VFF-HHB-O1 (3-1) 8%
VFF-HHB-1 (3-1) 3%
2-BB (2F, 3F) B-3 (11-1) 4%
3-HBB (2F, 3F) -O2 (10-7) 2%
NI = 81.9 ° C; Tc <-20 ° C; Δn = 0.109; Δε = 4.8; Vth = 1.75V; η = 13.3 mPa · s; γ1 = 57.4 mPa · s.

[Composition (M35)]
3-HHEB (F, F) -F (6-12) 4%
3-HBEB (F, F) -F (6-39) 3%
5-HBEB (F, F) -F (6-39) 3%
3-BB (F) B (F, F) -F (6-69) 3%
3-HBBXB (F, F) -F (7-32) 6%
4-GBB (F, F) XB (F, F) -F (7-61) 2%
5-GBB (F, F) XB (F, F) -F (7-61) 2%
3-GB (F) B (F, F) XB (F, F) -F (7-57) 5%
4-GB (F) B (F, F) XB (F, F) -F (7-57) 5%
5-HHB (F, F) XB (F, F) -F (7-29) 3%
5-HEB (F, F) -F (5-10) 3%
5-HB-CL (5-2) 2%
3-HHB-OCF3 (6-1) 4%
3-HH-5 (2-1) 4%
3-HH-V (2-1) 21%
3-HH-V1 (2-1) 3%
4-HH-V (2-1) 4%
1V2-HH-3 (2-1) 6%
5-B (F) BB-2 (3-8) 3%
5-B (F) BB-3 (3-8) 2%
3-HB (2F, 3F) -O2 (9-1) 3%
3-BB (2F, 3F) -O2 (9-3) 2%
3-HHB (2F, 3F) -O2 (10-1) 4%
F3-HH-V (2-1) 3%
NI = 78.2 ° C; Tc <-20 ° C; Δn = 0.101; Δε = 6.7; Vth = 1.45V; η = 17.8 mPa · s; γ1 = 67.8 mPa · s.

[Composition (M36)]
3-HHB (F, F) -F (6-3) 10%
3-HHXB (F, F) -F (6-100) 2%
3-GHB (F, F) -F (6-109) 5%
3-BB (F) B (F, F) -F (6-69) 6%
3-BB (F, F) XB (F, F) -F (6-97) 14%
4-BB (F) B (F, F) XB (F, F) -F (7-47) 10%
5-BB (F) B (F, F) XB (F, F) -F (7-47) 6%
2-HH-3 (2-1) 5%
3-HH-4 (2-1) 11%
3-HH-O1 (2-1) 5%
5-HB-O2 (2-5) 8%
3-HHB-1 (3-1) 6%
3-HHB-3 (3-1) 6%
3-HHB-O1 (3-1) 6%
NI = 77.6 ° C; Tc <-20 ° C; Δn = 0.109; Δε = 10.6; Vth = 1.34V; η = 22.6 mPa · s; γ1 = 92.4 mPa · s.

[Composition (M37)]
3-HBB-F (6-22) 3%
3-BB (F, F) XB (F) -OCF3 (6-96) 3%
3-HHB (F) -F (6-2) 3%
3-HGB (F, F) -F (6-103) 3%
5-GHB (F, F) -F (6-109) 3%
3-HBB (F, F) -F (6-24) 4%
3-BB (F, F) XB (F, F) -F (6-97) 5%
3-HHBB (F, F) -F (7-6) 5%
3-HBBXB (F, F) -F (7-32) 5%
3-BBVFFXB (F, F) -F (6-119) 8%
3-HH-V (2-1) 39%
1-HH-V1 (2-1) 3%
1-HH-2V1 (2-1) 4%
3-HHEH-5 (3-13) 3%
1-BB (F) B-2V (3-6) 3%
3-HHEBH-3 (4-6) 3%
5-HBB (F) B-2 (4-5) 3%
NI = 85.2 ° C; Tc <-20 ° C; Δn = 0.102; Δε = 4.1; γ1 = 43.0 mPa · s.

[Composition (M38)]
3-HHBB (F) -F (7-5) 3%
2-HHEB (F, F) -F (6-12) 3%
5-BB (F) B (F, F) -F (6-69) 7%
3-HHB (F) B (F, F) -F (7-9) 3%
3-GB (F) B (F, F) XB (F, F) -F (7-57) 3%
3-BB (F, F) XB (F) B (F, F) -F (7-60) 3%
3-HHVFFXB (F, F) -F (6-120) 5%
3-BBVFFXB (F, F) -F (6-119) 5%
3-HBBVFFXB (F, F) -F (7-62) 3%
2-HH-5 (2-1) 5%
3-HH-V (2-1) 20%
5-HH-V (2-1) 12%
3-HH-V1 (2-1) 4%
4-HH-V1 (2-1) 5%
2-HH-2V1 (2-1) 3%
1-BB-3 (2-8) 3%
V2-BB (F) B-1 (3-6) 5%
V2-B (F) BB-1 (3-8) 5%
3-HB (F) HH-5 (4-7) 3%
NI = 85.8 ° C; Tc <-20 ° C; Δn = 0.115; Δε = 4.2; γ1 = 41.4 mPa · s.

[Composition (M39)]
3-BB (F) XB (F) B (F, F) -F (7-60) 5%
3-HGB (F, F) -F (6-103) 3%
5-GHB (F, F) -F (6-109) 4%
3-GB (F, F) XB (F, F) -F (6-113) 5%
3-HHBB (F, F) -F (7-6) 4%
2-dhBB (F, F) XB (F, F) -F (7-50) 4%
3-GB (F) B (F, F) XB (F, F) -F (7-57) 3%
3-HGB (F, F) XB (F, F) -F (7) 5%
7-HB (F, F) -F (5-4) 3%
2-HH-3 (2-1) 14%
2-HH-5 (2-1) 4%
3-HH-V (2-1) 26%
1V2-HH-3 (2-1) 5%
1V2-BB-1 (2-8) 3%
2-BB (F) B-3 (3-6) 3%
3-HB (F) HH-2 (4-7) 4%
5-HBB (F) B-2 (4-5) 5%
NI = 78.4 ° C; Tc <-20 ° C; Δn = 0.094; Δε = 5.6; Vth = 1.45V; η = 11.5mPa · s; γ1 = 61.7mPa · s.

[Composition (M40)]
3-HBB (F, F) -F (6-24) 5%
5-HBB (F, F) -F (6-24) 4%
3-BB (F) B (F, F) XB (F, F) -F (7-47) 3%
4-BB (F) B (F, F) XB (F, F) -F (7-47) 5%
3-BB (F, F) XB (F) B (F, F) -F (7-60) 10%
3-HH2BB (F, F) -F (7-15) 3%
4-HH2BB (F, F) -F (7-15) 3%
2-HH-5 (2-1) 4%
3-HH-V (2-1) 25%
3-HH-V1 (2-1) 10%
4-HH-V1 (2-1) 7%
5-HB-O2 (2-5) 5%
7-HB-1 (2-5) 5%
VFF-HHB-O1 (3-1) 8%
VFF-HHB-1 (3-1) 3%
NI = 79.3 ° C; Tc <-20 ° C; Δn = 0.099; Δε = 5.0; Vth = 1.64V; η = 10.4 mPa · s; γ1 = 44.7 mPa · s.

[Composition (M41)]
3-GBXB (F) B (F, F) -F (7) 5%
3-HHB (F, F) -F (6-3) 7%
3-GB (F) B (F) -F (6-116) 2%
3-GB (F) B (F, F) -F (6-117) 3%
3-BB (F, F) XB (F, F) -F (6-97) 7%
3-GB (F) B (F, F) XB (F, F) -F (7-57) 4%
5-GB (F) B (F, F) XB (F, F) -F (7-57) 5%
3-HH-V (2-1) 30%
3-HH-V1 (2-1) 10%
1V2-HH-3 (2-1) 8%
3-HH-VFF (2-1) 8%
V2-BB-1 (2-8) 2%
5-HB (F) BH-3 (4-2) 4%
5-HBBH-3 (4-1) 5%
NI = 79.7 ° C; Tc <-20 ° C; Δn = 0.091; Δε = 5.7; Vth = 1.83V; η = 14.9 mPa · s; γ1 = 69.3 mPa · s.

2. Orientation of liquid crystal molecules Usage Examples 1 to 7
(Sample preparation)
2. Compound (No. 1) as compound (1) in the composition (M1) is 0.1% by weight, 0.3% by weight, 0.5% by weight, 1.0% by weight, 3.0% by weight, 5. 0 wt%, in a proportion of 10.0 wt%, as an ^antioxidant, was added compound ^{R 40} is n- heptyl and (AO-1) in a proportion of 150 ppm. When the mixture was heated and stirred at 100 ° C., then returned to room temperature and left for one week, these mixtures were completely dissolved without precipitation of crystals or the like.
(Manufacturing of element)
These mixtures were injected at 90 ° C. into an IPS device without an alignment film. Since these mixtures showed an isotropic phase at 90 ° C., it means that these mixtures were injected above the upper limit temperature of the nematic phase. While heating the IPS element at 90 ° C., the element is aligned by irradiating the element with polarized ultraviolet rays having peaks at wavelengths of 313 nm, 335 nm and 365 nm for a certain period of time from the normal direction, and the orientation is improved. Irradiation was continued until.
(Irradiation conditions for polarized ultraviolet rays)
-The illuminance at a wavelength of 313 nm is 3 mW / cm ² . The measurement was performed using UIT-150 and UVD-S313 manufactured by Ushio, Inc.
-A USH-250BY manufactured by Ushio, Inc. was used as the ultraviolet irradiation lamp.
-The exposure machine unit used was ML-251A / B manufactured by Ushio, Inc.
-Polarized ultraviolet rays were formed using a wire grid polarizer (ProFlux UVT260A manufactured by Polatechno Co., Ltd.).
(Method of confirming orientation)
Set the element in a polarizing microscope in which the polarizer and the analyzer are arranged orthogonally to the polarization axis of linearly polarized light, and irradiate this element with light from below to check for light leakage. Was observed. If the light did not pass through the element, it was determined that the orientation was "good". When the light passing through the element was observed, it was judged that the orientation was "poor" and the irradiation was insufficient.
(Evaluation of ease of orientation)
The irradiation time was changed from 1 minute to 60 minutes, and the orientation at each irradiation time was confirmed. Irradiation was stopped when the orientation was good. The irradiation time until the orientation becomes good is summarized in Table 3 below.

Usage example 8 to usage example 28
Using a composition (M1), as an ^antioxidant, it was added compound ^{R 40} is n- heptyl and (AO-1) in a proportion of 150 ppm, was mixed in the ratio shown compound (1) in Table 3 below. Others were operated in the same manner as in Usage Example 1. The irradiation time was measured by the same method as in Example 1. The results are summarized in Table 3 below. The mixture of Examples 8 to 28 also showed an isotropic phase at 90 ° C.

Table 3

In Use Examples 1 to 28, when the compositions used were changed to M2 to M41 and the same operations were performed for each, there was no significant change in the irradiation time.

The composition (M1) to the composition (M41) and the compound (No. 1) to the compound (No. 618) were appropriately selected from the composition (1), and the same operation was performed. In each case, the irradiation time was within 10 minutes.

Comparative Examples 1 to 21
Compound (A-1-1-1), compound (S-1) described in Patent Document 3 and compound (S-2) described in Patent Document 2 are designated as compound (1) at the ratios shown in Table 4 below. It was mixed with the composition (M1), and the irradiation time was evaluated by the same operation as in the example of use. The mixture of Comparative Examples 1 to 21 also showed an isotropic phase at 90 ° C.
As a result, as compared with the compound according to the embodiment of the present invention, in any of the compounds, good orientation was not obtained at the longest irradiation time of 10 minutes in the use example, and good orientation was confirmed. The time was more than 30 minutes. Moreover, when the same evaluation was performed using the compositions (M2) to (M41), the tendency was the same as that when the composition (M1) was used.

Table 4

In the example of use, the composition and the type and amount of the compound (1), which is a polar compound, were changed, but there was no undissolved residue or precipitation, and no light leakage of the device was observed within 10 minutes of irradiation. This result indicates that the orientation is good even if the device does not have an alignment film such as polyimide, and all the liquid crystal molecules are arranged in a certain direction. On the other hand, in the comparative example, light leakage of the element was observed in the irradiation within 30 minutes, and the orientation was not good. Therefore, by using the compound (1) according to the embodiment of the present invention, it can be used in light irradiation for a short time or with low energy, thereby shortening the tact time and reducing the damage caused by the light irradiation of the mother liquid crystal. can do. Further, by using the liquid crystal composition according to the embodiment of the present invention, at least one characteristic of a wide temperature range in which the device can be used, a short response time, a high voltage retention rate, a low threshold voltage, a large contrast ratio, and a long life can be obtained. The liquid crystal display element to have is obtained. In addition, the high upper temperature of the nematic phase, the lower lower temperature of the nematic phase, small viscosity, proper optical anisotropy, negatively large permittivity anisotropy, large specific resistance, high stability to ultraviolet rays, high stability to heat A liquid crystal display element having a liquid crystal composition satisfying at least one of the above characteristics can be obtained.

The liquid crystal composition according to the embodiment of the present invention can be used for a liquid crystal monitor, a liquid crystal television, or the like.

Claims

A compound represented by the formula (1).

In equation (1)
a and b are independently 0, 1 or 2, 0 ≦ a + b ≦ 3, and so on.
Ring A 1 , Ring A 2 , Ring A 3 and Ring A 4 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, Decahydronaphthrene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine- 2,5-diyl, pyridine-2,5-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, perhydrocyclopenta [a] phenanthrene-3,17 -Diyl, or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta [a] phenanthrene-3,17-diyl, In these rings, at least one hydrogen is fluorine, chlorine, alkyl with 1 to 12 carbon atoms, alkenyl with 2 to 12 carbon atoms, alkoxy with 1 to 11 carbon atoms, alkenyloxy with 2 to 11 carbon atoms, -Sp. It may be replaced by 1- P 1 or -Sp 2- P 2 , and in these groups at least one hydrogen may be replaced by fluorine or chlorine.
When a is 2, two rings A 1 may be different when b is 2, two rings A 4 may be different;
Z 1 , Z 2 , Z 3 , Z 4 and Z 5 are independently single-bonded or alkylenes with 1 to 10 carbon atoms, in which at least one -CH 2- is -O-,-. It may be replaced by S-, -CO-, -COO-, -OCO-, or -OCOO-, and at least one- (CH 2 ) 2 -is -CH = CH- or -C≡C-. It may be replaced, in which at least one hydrogen may be replaced with fluorine or chlorine. However, at least one of Z 2 , Z 3 , or Z 4 is -COS-, -SCO-, -CH = CHCOS-, or -SCOCH = CH-, and Z 2 , Z 3 , or Z. -COS- and -OCO- or -SCO- and -COO- are never simultaneously present in the 4, when a is 2, two Z 1 may be different when b is 2, the two Z 5 may be different;
Sp 1 and Sp 2 are independently single-bonded or alkylene with 1 to 10 carbon atoms, in which at least one -CH 2- is -O-, -CO-, -COO-, -OCO. -Or -OCOO- may be replaced, and at least one- (CH 2 ) 2- may be replaced by -CH = CH- or -C≡C-, at least 1 in these groups. One hydrogen may be replaced with fluorine or chlorine,
If multiple Sp 1 or Sp 2 are present, it may be different from each;
P 1 and P 2 are independent groups represented by any of the formulas (1b) to (1h), and when a plurality of P 1 or P 2 are present, they may be different from each other;

In equations (1b) to (1h),
M 1 , M 2 , M 3 and M 4 are independently hydrogen, fluorine, chlorine, alkyl with 1 to 5 carbon atoms, or alkyl with 1 to 5 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. And X 1 is O or S;
R 2 is hydrogen, fluorine, chlorine, or an alkyl having 1 to 5 carbon atoms, in which at least one hydrogen may be replaced by fluorine or chlorine, and at least one -CH 2- is -O-. May be replaced with;
R 3 , R 4 , R 5 , R 6 and R 7 are independently hydrogen or alkyl with 1 to 15 carbon atoms, in which at least one -CH 2- is -O- or-. It may be replaced by S-, at least one- (CH 2 ) 2 -may be replaced by -CH = CH- or -C≡C-, and in these groups, at least one hydrogen is fluorine. Alternatively, it may be replaced with chlorine.
In equation (1)
a and b are independently 0, 1 or 2, and 0 ≦ a + b ≦ 2.
Ring A 1 , Ring A 2 , Ring A 3 and Ring A 4 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, Decahydronaphthrene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine- 2,5-diyl, pyridine-2,5-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, perhydrocyclopenta [a] phenanthrene-3,17 -Diyl, or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta [a] phenanthrene-3,17-diyl, In these rings, at least one hydrogen is fluorine, chlorine, alkyl with 1 to 12 carbon atoms, alkenyl with 2 to 12 carbon atoms, alkoxy with 1 to 11 carbon atoms, alkenyloxy with 2 to 11 carbon atoms, -Sp. It may be replaced by 1- P 1 or -Sp 2- P 2 , in these groups at least one hydrogen may be replaced by fluorine or chlorine, and when a is 2, two rings A 1 may be different when b is 2, two rings a 4 may be different;
Z 1 , Z 2 , Z 3 , Z 4 and Z 5 are independently single-bonded,-(CH 2 ) 2- , -C ≡ C-, -C ≡ C-C ≡ C-, -COO-, -OCO-, -CF 2 O-, -OCF 2- , -CH 2 O-, -OCH 2- , -CF = CF-, -CH = CHCOO-, -OCOCH = CH-, -CH = CH-, -CH = CHCO-, -COCH = CH-, -COS-, -SCO-, -CH = CHCOS-, or -SCOCH = CH-, provided that at least in Z 2 , Z 3 , or Z 4. One is -COS-, -SCO-, -CH = CHCOS-, or -SCOCH = CH-, and in Z 2 , Z 3 , or Z 4 , -COS- and -OCO- or -SCO- and- COO-does not exist at the same time;
When a is 2, two Z 1 may be different, the two Z 5 may be different;
Sp 1 and Sp 2 are independently a single bond or alkylene having 1 to 10 carbon atoms, in the alkylene, at least one of -CH 2 -, -O -, - COO-, or substituted with -OCO- At least one of-(CH 2 ) 2 -may be replaced by -CH = CH-, and in these groups, at least one hydrogen may be replaced by fluorine or chlorine. If multiple Sp 1 or Sp 2 there may be different from each;
P 1 and P 2 are independent groups represented by any of the formulas (1b) to (1h), and when a plurality of P 1 or P 2 are present, they may be different from each other;

In equations (1b) to (1h),
M 1 , M 2 , M 3 and M 4 are independently hydrogen, fluorine, chlorine, alkyl with 1 to 5 carbon atoms, or alkyl with 1 to 5 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. And X 1 is O or S;
R 2 is hydrogen, fluorine, chlorine, or an alkyl having 1 to 5 carbon atoms, in which at least one hydrogen may be replaced by fluorine or chlorine, and at least one -CH 2- is -O-. May be replaced with;
R 3 , R 4 , R 5 , R 6 and R 7 are independently hydrogen or alkyl with 1 to 15 carbon atoms, in which at least one -CH 2- is -O- or-. It may be replaced by S-, at least one- (CH 2 ) 2 -may be replaced by -CH = CH- or -C≡C-, and in these groups, at least one hydrogen is fluorine. The compound according to claim 1, which may be replaced with chlorine.
The compound according to claim 1 or 2, which is represented by any one of formulas (1-1) to (1-3).

In equations (1-1) to (1-3),
Ring A 1 , Ring A 2 , Ring A 3 and Ring A 4 are independent, 1,4-cyclohexylene, 1,4-phenylene, naphthalene-2,6-diyl, pyrimidine-2,5-diyl, Pyridine-2,5-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, or anthracene-2,6-diyl, in which at least one hydrogen is fluorine, chlorine, Replaced by alkyl with 1 to 12 carbons, alkenyl with 2 to 12 carbons, alkoxy with 1 to 11 carbons, alkenyloxy with 2 to 11 carbons, -Sp 1- P 1 or -Sp 2- P 2. at best, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine, when a is 2, two rings a 1 may be different when b is 2, 2 One of the rings a 4 may be different;
Z 2 , Z 3 and Z 4 are independently single-bonded,-(CH 2 ) 2- , -C ≡ C-, -C ≡ C-C ≡ C-, -COO-, -OCO-, -CF 2 O -, - OCF 2 - , - CH 2 O -, - OCH 2 -, - CF = CF -, - CH = CHCOO -, - OCOCH = CH -, - CH = CH -, - CH = CHCO-, -COCH = CH -, - COS - , - SCO -, - CH = CHCOS-, or -SCOCH = a CH-, provided that at least one among Z 2, Z 3 or Z 4, are,-COS -, - SCO -, - CH = CHCOS-, or -SCOCH = a CH-, Z 2, Z 3, or in Z 4 -COS- and -OCO- or -SCO- and -COO- simultaneous presence Never;
Sp 1 and Sp 2 are independently single-bonded or alkylene with 1 to 10 carbon atoms, in which at least one -CH 2- is -O-, -COO-, -OCOO-, or-. It may be replaced by OCO-, at least one- (CH 2 ) 2 -may be replaced by -CH = CH-, and in these groups at least one hydrogen is replaced by fluorine or chlorine. at best, when a plurality of Sp 1 or Sp 2 are present, it may be different from each;
P 1 and P 2 are independent groups represented by any of the formulas (1b) to (1h), and when a plurality of P 1 or P 2 are present, they may be different from each other;

In equations (1b) to (1h),
M 1 , M 2 , M 3 and M 4 are independently hydrogen, fluorine, chlorine, alkyl with 1 to 5 carbon atoms, or alkyl with 1 to 5 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. And X 1 is O or S;
R 2 is hydrogen, fluorine, chlorine, or an alkyl having 1 to 5 carbon atoms, in which at least one hydrogen may be replaced by fluorine or chlorine, and at least one -CH 2- is -O-. May be replaced with;
R 3 , R 4 , R 5 , R 6 , and R 7 are independently hydrogen, or alkyl with 1 to 15 carbon atoms, in which at least one -CH 2- is -O- or It may be replaced by —S—, at least one − (CH 2 ) 2 − may be replaced by −CH = CH− or −C≡C−, and in these groups, at least one hydrogen It may be replaced with fluorine or chlorine.
In equations (1-1) to (1-3),
Ring A 1 , Ring A 2 , Ring A 3 and Ring A 4 are independently 1,4-cyclohexylene, 1,4-phenylene, naphthalene-2,6-diyl, fluorene-2,7-diyl, Or phenanthrene-2,7-diyl, in these rings at least one hydrogen is fluorine, chlorine, alkyl with 1 to 12 carbons, alkenyl with 2 to 12 carbons, alkoxy with 1 to 11 carbons, It may be replaced by alkenyloxy with 2 to 11 carbon atoms, -Sp 1- P 1 , or -Sp 2- P 2 ;
Z 2 , Z 3 and Z 4 are independently single-bonded,-(CH 2 ) 2- , -C ≡ C-C ≡ C-, -C ≡ C-, -COO-, -OCO-, -CH = CHCOO-, -OCOCH = CH-, -CH = CH-, -CH = CHCO-, -COCH = CH-, -COS-, -SCO-, -CH = CHCOS-, or -SCOCH = CH-. However, at least one of Z 2 , Z 3 , or Z 4 is -COS-, -SCO-, -CH = CHCOS-, or -SCOCH = CH-, and is Z 2 , Z 3 , or. never -COS- and the -OCO- or -SCO- and -COO- are present simultaneously in the Z 4;
Sp 1 and Sp 2 are independently single-bonded or alkylene with 1 to 10 carbon atoms, in which at least one -CH 2- is -O-, -COO-, -OCOO-, or-. It may be replaced by OCO-, and at least one- (CH 2 ) 2 -may be replaced by -CH = CH-, and if multiple Sp 1 or Sp 2 are present, each is different. Well;
P 1 and P 2 are independently represented by any of the formula (1b), the formula (1c), the formula (1d), or the formula (1e), and there are a plurality of P 1 or P 2. If so, each may be different;

In equations (1b) to (1e),
M 1 , M 2 , M 3 and M 4 are independently hydrogen, fluorine, chlorine, alkyl with 1 to 5 carbon atoms, or alkyl with 1 to 5 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. And X 1 is O or S;
R 2 is hydrogen, fluorine, chlorine, or an alkyl having 1 to 5 carbon atoms, in which at least one hydrogen may be replaced by fluorine or chlorine, and at least one -CH 2- is -O-. May be replaced with;
R 3 , R 4 , R 5 and R 6 are independently hydrogen or alkyl with 1 to 15 carbon atoms, in which at least one -CH 2- is -O- or -S-. It may be replaced, and at least one- (CH 2 ) 2 -may be replaced by -CH = CH- or -C≡C-, in which at least one hydrogen is fluorine or chlorine. The compound according to claim 3, which may be replaced.
In equations (1-1) to (1-3),
Ring A 1 , Ring A 2 , Ring A 3 and Ring A 4 are independent, 1,4-cyclohexylene, 1,4-phenylene, naphthalene-2,6-diyl, fluorene-2,7-diyl, Alternatively, it may be phenanthrene-2,7-diyl, in which at least one hydrogen may be replaced with fluorine, chlorine, methyl, or ethyl;
Z 2 , Z 3 and Z 4 are independently single-bonded,-(CH 2 ) 2- , -C ≡ C-C ≡ C-, -C ≡ C-, -COO-, -OCO-, -CH = CHCOO-, -OCOCH = CH-, -CH = CH-, -CH = CHCO-, -COCH = CH-, -COS-, -SCO-, -CH = CHCOS-, or -SCOCH = CH-. However, at least one of Z 2 , Z 3 , or Z 4 is -COS-, -SCO-, -CH = CHCOS-, or -SCOCH = CH-, and is Z 2 , Z 3 , or. never -COS- and the -OCO- or -SCO- and -COO- are present simultaneously in the Z 4;
Sp 1 and Sp 2 are independently single-bonded or alkylene with 1 to 10 carbon atoms, in which at least one -CH 2- is -O-, -COO-, -OCOO-, or-. It may be replaced by OCO-, and at least one- (CH 2 ) 2 -may be replaced by -CH = CH-, and if multiple Sp 1 or Sp 2 are present, each is different. Well;
P 1 and P 2 are each independently formula (1b-1), (1b -2), (1b-3), (1b-4), formula (1b-5), (1c -1), (1d -1), (1d-2) or (1e-1) in a group represented by the X 2, X 3, X 4 , X 5 and X 6 claim 3 is O or S independently The compound described.
In claim 3 , in the compound represented by the formulas (1-1) to (1-3), any one of Z 2 , Z 3 , or Z 4 is -COS- or -SCO-. The compound described.
The compound according to any one of claims 1 to 6, which is represented by any one of the following formulas.

P 1 and P 2 are each independently formula (1b-1), (1b -2), (1b-3), (1b-4), formula (1b-5), (1c -1), (1d -1), a group represented by (1d-2) or (1e-1), where X 2 , X 3 , X 4 , X 5 and X 6 are independently O or S;
Sp 1 and Sp 2 are independently single bonds or alkylenes having 1 to 10 carbon atoms, in which at least one -CH 2- is -O-, -COO-, -OCOO-, or-. It may be replaced by OCO-, and at least one- (CH 2 ) 2- may be replaced by -CH = CH-;
In partial structures other than P 1 , P 2 , Sp 1 and Sp 2 , at least one hydrogen may be replaced with fluorine, chlorine, methyl, or ethyl.
In the formulas (1-1-1) to (1-1-7), (1-2-1) to (1-2-14), (1-3-1), or (1-3-2) In the compounds represented, Sp 1 and Sp 2 are independently alkylenes having 1 to 10 carbon atoms, in which at least one -CH 2- is -O-, -COO-, -OCOO-. , Or the compound according to claim 7, wherein the −OCO— may be replaced, and at least one − (CH 2 ) 2 − may be substituted with −CH = CH−.
A liquid crystal composition containing at least one of the compounds according to any one of claims 1 to 8.
The liquid crystal composition according to claim 9, further comprising at least one compound selected from the group of compounds represented by formulas (2) to (4).

In equations (2) to (4),
R 11 and R 12 are independently alkyl with 1 to 10 carbon atoms or alkenyl with 2 to 10 carbon atoms, even if at least one -CH 2- is replaced with -O- in the alkyl and alkenyl. Well, at least one hydrogen may be replaced by fluorine;
Ring B 1 , Ring B 2 , Ring B 3 , and Ring B 4 are independent, 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro-. 1,4-phenylene, or pyrimidine-2,5-diyl;
Z 11 , Z 12 , and Z 13 are independently single-bonded,-(CH 2 ) 2- , -CH = CH-, -C≡C-, or -COO-.
The liquid crystal composition according to claim 9 or 10, further comprising at least one compound selected from the group of compounds represented by formulas (5) to (7).

In equations (5) to (7),
R 13 is an alkyl having 1 to 10 carbon atoms or an alkenyl having 2 to 10 carbon atoms, in which at least one -CH 2- may be replaced with -O-, and at least one hydrogen is. May be replaced with fluorine;
X 11 is fluorine, chlorine, -OCF 3 , -OCHF 2 , -CF 3 , -CHF 2 , -CH 2 F, -OCF 2 CHF 2 , or -OCF 2 CHFCF 3 ;
Ring C 1 , Ring C 2 , and Ring C 3 are independently 1,4-cyclohexylene, 1,4-phenylene, where at least one hydrogen may be replaced by fluorine, tetrahydropyran-2,5-diyl. , 1,3-dioxane-2,5-diyl, or pyrimidine-2,5-diyl;
Z 14 , Z 15 and Z 16 are independently single-bonded,-(CH 2 ) 2- , -CH = CH-, -C≡C-, -COO-, -CF 2 O-, -OCF 2 -, - CH 2 O -, - CF = CF -, - CH = CF- or - (CH 2) 4 - a and;
L 11 and L 12 are independently hydrogen or fluorine.
The liquid crystal composition according to any one of claims 9 to 11, further containing at least one compound selected from the group of compounds represented by the formula (8).

In equation (8)
R 14 is an alkyl having 1 to 10 carbon atoms or an alkenyl having 2 to 10 carbon atoms, in which at least one -CH 2- may be replaced with -O-, and at least one hydrogen is. May be replaced with fluorine;
X 12 is -C≡N or -C≡C-C≡N;
Ring D 1 is independently 1,4-cyclohexylene, 1,4-phenylene in which at least one hydrogen may be replaced by fluorine, tetrahydropyran-2,5-diyl, 1,3-dioxane-2, 5-dioxane, or pyrimidine-2,5-dioxane;
Z 17 is independently a single bond, - (CH 2) 2 - , - C≡C -, - COO -, - CF 2 O -, - OCF 2 -, or -CH 2 O-;
L 13 and L 14 are independently hydrogen or fluorine;
i is 1, 2, 3, or 4.
The liquid crystal composition according to any one of claims 9 to 12, further comprising at least one compound selected from the group of compounds represented by the formulas (9) to (15).

In equations (9) to (15),
R 15 and R 16 are independently alkyls with 1 to 10 carbon atoms or alkenyl with 2 to 10 carbon atoms, even if at least one -CH 2- is replaced with -O- in the alkyl and alkenyl. Well, at least one hydrogen may be replaced by fluorine;
R 17 is hydrogen, fluorine, an alkyl having 1 to 10 carbon atoms, or an alkenyl having 2 to 10 carbon atoms, in which at least one -CH 2- may be replaced with -O-. , At least one hydrogen may be replaced by fluorine;
Ring E 1 , Ring E 2 , Ring E 3 , and Ring E 4 may independently replace 1,4-cyclohexylene, 1,4-cyclohexenylene, and at least one hydrogen with fluorine 1, 4-Phenylene, tetrahydropyran-2,5-diyl, or decahydronaphthalene-2,6-diyl;
Rings E 5 and E 6 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, or decahydronaphthalene-2,6. -Jeil;
Z 18, Z 19, Z 20 , and Z 21 are independently a single bond, - (CH 2) 2 - , - COO -, - CH 2 O -, - OCF 2 -, or -OCF 2 CH 2 CH 2- is;
L 15 and L 16 are independently fluorine or chlorine;
S 11 is hydrogen or methyl;
X is -CHF- or -CF 2- ;
j, k, m, n, p, q, r, and s are independently 0 or 1, and the sum of k, m, n, and p is 1 or 2, q, r, and The sum of s is 0, 1, 2, or 3, and t is 1, 2, or 3.
The liquid crystal composition according to any one of claims 9 to 13, which contains at least one polymerizable compound selected from the group of compounds represented by the formula (16).

In equation (16)
Rings F and I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidine-2-yl, or pyridine. -2-yl, in these rings at least one hydrogen is fluorine, chlorine, alkyl with 1 to 12 carbon atoms, or at least one hydrogen is alkyl with 1 to 12 carbon atoms with fluorine or chlorine replaced. May be replaced with;
Ring G is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, Naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene- 2,7-Diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in these rings. , At least one hydrogen is replaced with fluorine, chlorine, alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms, or alkyl with 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. May;
Z 22 and Z 23 are independently single bonds or alkylenes with 1 to 10 carbon atoms, in which at least one -CH 2- is -O-, -CO-, -COO-, or-. It may be replaced by OCO-, and at least one- (CH 2 ) 2- is -CH = CH-, -C (CH 3 ) = CH-, -CH = C (CH 3 )-, or -C. It may be replaced by (CH 3 ) = C (CH 3 )-and at least one hydrogen in these groups may be replaced by fluorine or chlorine;
P 11, P 12, and P 13 are independently a polymerizable group selected from the group of radicals represented by the formula (P-1) by the formula (P-5);

M 11 , M 12 , and M 13 are independently hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or alkyl having 1 to 5 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine;
Sp 11 , Sp 12 , and Sp 13 are independently single bonds or alkylenes with 1 to 10 carbon atoms, in which at least one -CH 2- is -O-, -COO-, -OCO. -Or -OCOO- may be replaced, and at least one- (CH 2 ) 2- may be replaced with -CH = CH- or -C≡C-, at least 1 in these groups. One hydrogen may be replaced with fluorine or chlorine;
u is 0, 1, or 2;
f, g, and h are independently 0, 1, 2, 3, or 4, and the sum of f, g, and h is greater than or equal to 2.
The liquid crystal composition according to any one of claims 9 to 14, which contains at least one polymerizable compound selected from the group of compounds represented by formulas (16-1) to (16-27). ..

In equations (16-1) to (16-27),
P 11 , P 12 , and P 13 are independently polymerizable groups selected from the group of groups represented by the formulas (P-1) to (P-3), wherein M 11 , M. 12, and M 13 are independently hydrogen, fluorine, alkyl of C 1 -C 5 alkyl or at least one hydrogen is from 1 carbon atoms is replaced by fluorine or chlorine, 5;

Sp 11 , Sp 12 , and Sp 13 are independently single bonds or alkylenes with 1 to 10 carbon atoms, in which at least one -CH 2- is -O-, -COO-, -OCO. -Or -OCOO- may be replaced, and at least one- (CH 2 ) 2- may be replaced with -CH = CH- or -C≡C-, at least 1 in these groups. One hydrogen may be replaced with fluorine or chlorine.
At least one of a polymerizable compound other than the formulas (1) and (16), a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, and an antifoaming agent. The liquid crystal composition according to any one of claims 9 to 15, further comprising one.
A liquid crystal display device containing the liquid crystal composition according to any one of claims 9 to 16.