JP2020158503A - Liquid crystalline compound having dibenzothiophene ring, liquid crystal composition and liquid crystal display element - Google Patents

Abstract

To provide a liquid crystalline compound satisfying at least one of physical properties such as high stability to heat or light, a high clear point, a low minimum temperature of a liquid crystal phase, small viscosity, appropriate optical anisotropy, negatively large dielectric anisotropy, an appropriate elastic constant and good compatibility with other liquid crystalline compounds, a liquid crystal composition containing the compound, and a liquid crystal display element containing the composition.SOLUTION: The compound is represented by formula (1), and the liquid crystal composition contains the above compound. In the formula, R1 and R2 represent an alkyl having 1 to 16 carbon atoms, or the like; A1 to A2 represent 1,4-cyclohexylene or the like; Z1 and Z2 represent a single bond or the like; m1 and n1 represent 0, 1 or 2; W represents -S- or the like; X represents H or F; and Y1 to Y4 represent H or a methyl.SELECTED DRAWING: None

Description

The present invention relates to liquid crystal compounds, liquid crystal compositions, and liquid crystal display devices. More specifically, the present invention relates to a liquid crystal compound having a dibenzothiophene ring and a negative dielectric anisotropy, a liquid crystal composition containing this compound, and a liquid crystal display device containing this composition.

In liquid crystal display elements, classification based on the operation mode of liquid crystal molecules 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 driving 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.

A liquid crystal composition is enclosed in this device. The physical properties of this composition are related to the properties of the device. Examples of physical properties in the composition are stability to heat and light, temperature range of nematic phase, viscosity, optical anisotropy, dielectric anisotropy, resistivity, elastic constant and the like. The composition is prepared by mixing many liquid crystal compounds. The physical properties required for the compound are high stability to the environment such as water, air, heat and light, wide temperature range of liquid crystal phase, small viscosity, suitable optical anisotropy, large dielectric anisotropy, suitable elastic constant. , Good compatibility with other liquid crystal compounds, etc. Compounds with a high upper temperature limit of the nematic phase are preferred. Compounds having a low lower limit temperature in the liquid crystal phase such as the nematic phase and the smectic phase are preferable. Compounds with low viscosities contribute to the short response time of the device. The appropriate value of optical anisotropy depends on the mode of the device. In order to drive the device at a low voltage, a compound having a large positive or negative dielectric anisotropy is preferable. To prepare the composition, a compound having good compatibility with other liquid crystal compounds is preferable. Since the device may be used at a temperature below freezing, a compound having good compatibility at a low temperature is preferable.

So far, many liquid crystal compounds have been synthesized. Development of new liquid crystal compounds is still ongoing. This is because the new compound is expected to have good physical properties that the conventional compound does not have. This is because the novel compound may impart an appropriate balance to at least two physical properties in the composition.

Liquid crystal compounds having a dibenzothiophene ring are known. See Patent Documents 1 and 2. The compounds of this case differ from these compounds in that they have a methyl-substituted dibenzothiophene ring.

Japanese Unexamined Patent Publication No. 2015-206042 Japanese Unexamined Patent Publication No. 2016-199543

The first challenge is high stability to heat and light, high transparency (or high upper limit temperature of nematic phase), lower lower limit temperature of liquid crystal phase, low viscosity, proper optical anisotropy, negatively large dielectric constant difference. It is to provide a liquid crystal compound that satisfies at least one of physical properties such as anisotropy, an appropriate elastic constant, and good compatibility with other liquid crystal compounds. It is to provide a compound having good compatibility as compared with a similar compound. The second challenge is that it contains this compound and has high stability to heat and light, high upper limit temperature of nematic phase, lower lower limit temperature of nematic phase, small viscosity, proper optical anisotropy, negatively large dielectric constant difference. It is to provide a liquid crystal composition that satisfies at least one of physical properties such as anisotropy, a large specific resistance, and an appropriate elastic constant. The challenge is to provide a liquid crystal composition having an appropriate balance between at least two of these physical properties. A third challenge is a liquid crystal display that contains this composition and has a wide temperature range in which the device can be used, short response times, large voltage retention, low threshold voltage, large contrast ratio, small flicker rate, and long life. It is to provide an element.

式（１）において、
Ｒ^１およびＲ^２は独立して、水素、フッ素、塩素、または炭素数１から１６のアルキルであり、このアルキルにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＯＣＯＯ−、または−Ｓｉ（ＣＨ_３）_２−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素、塩素、−ＣＦ_３、または−Ｃ≡Ｎで置き換えられてもよく；
Ａ^１およびＡ^２は独立して、１，２−シクロプロピレン、１，３−シクロブチレン、１，３−シクロペンチレン、１，４−シクロヘキシレン、１，４−シクロヘキセニレン、１，４−シクロヘプチレン、１，５−シクロオクチレン、テトラヒドロピラン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、１，４−フェニレン、ピリジン−２，５−ジイル、ピリミジン−２，５−ジイル、デカヒドロナフタレン−２，６、−ジイル、テトラヒドロナフタレン−２，６−ジイル、またはナフタレン−２，６−ジイルであり、これらの基において、芳香環上の少なくとも１つの水素は、フッ素、塩素、−ＣＦ_３、−ＣＨＦ_２、−ＣＨ_２Ｆ、−ＯＣＦ_３、−ＯＣＨＦ_２、−ＯＣＨ_２Ｆ、または−Ｃ≡Ｎで置き換えられてもよく；
Ｚ^１およびＺ^２は独立して、単結合または炭素数１から６のアルキレンであり、１つの−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく、１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの二価基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；
ｍ^１およびｎ^１は独立して、０，１、または２であり、ｍ^１とｎ^１の和は、３以下であり；
Ｗは、−ＣＨ_２−、−ＣＦ_２−、−ＣＯ−、−Ｏ−、−Ｓ−、または−ＳＯ_２−であり；
Ｘは、水素またはフッ素であり；
Ｙ^１、Ｙ^２、Ｙ^３、およびＹ^４は独立して、水素またはメチルであり、Ｙ^１、Ｙ^２、Ｙ^３、およびＹ^４の少なくとも１つはメチルであり；Ｗが−Ｏ−であるとき、Ｙ^１、Ｙ^２、Ｙ^３、およびＹ^４の少なくとも２つはメチルである。 The present invention relates to a compound represented by the formula (1), a liquid crystal composition containing this compound, a liquid crystal display device containing this composition, and the like.

In equation (1)
R ¹ and R ² are independently hydrogen, fluorine, chlorine, or alkyl having 1 to 16 carbon atoms, in which at least one -CH ₂ − is -O-, -CO-, -COO. It may be replaced by −, −OCO−, −OCOO−, or −Si (CH ₃ ) ₂₋ , and at least one −CH ₂ CH ₂₋ is replaced by −CH = CH− or −C≡C−. In these groups, at least one hydrogen may be replaced by fluorine, chlorine, -CF ₃ , or -C≡N;
A ¹ and A ² are independently 1,2-cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4. -Cycloheptylene, 1,5-cyclooctylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, 1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2, 5-Diyl, decahydronaphthalene-2,6, -diyl, tetrahydronaphthalene-2,6-diyl, or naphthalene-2,6-diyl, in which at least one hydrogen on the aromatic ring is the hydrogen. It may be replaced with fluorine, chlorine, -CF ₃ , -CHF ₂ , -CH ₂ F, -OCF ₃ , -OCHF ₂ , -OCH ₂ F, or -C≡N;
Z ¹ and ^{Z 2} are independently a single bond or alkylene having 1 to 6 carbon atoms, one of _-CH 2 -, -O -, - CO -, - COO-, or replaced by -OCO- Alternatively, one −CH ₂ CH ₂₋ may be replaced by −CH = CH− or −C≡C−, and in these divalent groups, at least one hydrogen is replaced by fluorine or chlorine. May be;
m ¹ and n ¹ are independently 0, 1, or 2, and the sum of m ¹ and n ¹ is 3 or less;
W _{is, -CH 2 -, - CF 2} -, - CO -, - O -, - S-, or -SO ₂ - and is;
X is hydrogen or fluorine;
Y ¹ , Y ² , Y ³ , and Y ⁴ are independently hydrogen or methyl, and at least one of Y ¹ , Y ² , Y ³ , and Y ⁴ is methyl; W is -O-. At one time, at least two of Y ¹ , Y ² , Y ³ , and Y ⁴ are methyl.

The first advantages are high stability to heat and light, high transparency (or high upper limit temperature of nematic phase), lower lower limit temperature of liquid crystal phase, low viscosity, proper optical anisotropy, negatively large dielectric constant difference. It is to provide a liquid crystal compound that satisfies at least one of physical properties such as anisotropy, an appropriate elastic constant, and good compatibility with other liquid crystal compounds. It is to provide a compound having good compatibility as compared with a similar compound. The second advantage is that it contains this compound and has high stability to heat and light, high upper temperature limit of nematic phase, lower lower limit temperature of nematic phase, low viscosity, proper optical anisotropy, negatively large dielectric constant difference. It is to provide a liquid crystal composition that satisfies at least one of physical properties such as anisotropy, a large specific resistance, and an appropriate elastic constant. This advantage is to provide a liquid crystal composition having an appropriate balance between at least two of these physical properties. The third advantage is that the liquid crystal display contains this composition and has a wide temperature range in which the device can be used, short response time, large voltage retention, low threshold voltage, large contrast ratio, small flicker rate, and long life. It is to provide an element.

The usage of terms in this specification is as follows. The terms "liquid crystal compound", "liquid crystal composition", and "liquid crystal display element" may be abbreviated as "compound", "composition", and "element", respectively. 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 adjusting the physical properties of a composition such as upper limit temperature, lower limit temperature, viscosity, and dielectric anisotropy. It is a general term for compounds added for the purpose of This compound has a six-membered ring such as 1,4-cyclohexylene and 1,4-phenylene, and its molecular structure is rod-like. "Liquid crystal display element" is a general term for a liquid crystal display panel and a liquid crystal display module. The "polymerizable compound" is a compound added for the purpose of forming a polymer in the composition.

The liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. Additives are added to this composition for the purpose of further adjusting the physical properties. Additives such as polymerizable compounds, polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, UV absorbers, light stabilizers, heat stabilizers, dyes, and defoamers are added as needed. To. The liquid crystal compounds and additives are mixed in such a procedure. The ratio (content) of the liquid crystal compound is expressed as a weight percentage (% by weight) based on the weight of the liquid crystal composition containing no additive even when the additive is added. The ratio (addition amount) of the additive is expressed as a weight percentage (% by weight) based on the weight of the liquid crystal composition containing no additive. 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 "transparency point" is the transition temperature of the liquid crystal phase-isotropic phase in the liquid crystal compound. The "lower limit temperature of the liquid crystal phase" is the transition temperature of the solid-liquid crystal phase (smetic phase, nematic phase, etc.) in the liquid crystal compound. The "upper limit temperature of the nematic phase" is the transition temperature of the nematic phase-isotropic phase in the mixture or the liquid crystal composition of the liquid crystal compound and the mother liquid crystal, and may be abbreviated as the "upper limit temperature". The "lower limit temperature of the nematic phase" may be abbreviated as the "lower limit temperature". The expression "increase the dielectric anisotropy" means that when the composition has a positive dielectric anisotropy, its value increases positively, and the composition has a negative dielectric anisotropy. When it is a thing, it means that its value increases negatively. "Large voltage retention" means that the element has a large voltage retention not only at room temperature but also at a temperature close to the upper limit temperature at the initial stage, and after long-term use, it has a large voltage not only at room temperature but also at a temperature close to the upper limit temperature. It means having a retention rate. The characteristics of the composition or device may be examined before and after the aging test (including the accelerated deterioration test).

The compound represented by the formula (1) may be abbreviated as the compound (1). At least one compound selected from the group of compounds 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. These rules also apply to compounds represented by other formulas. In equations (1) to (15), symbols such as A ¹ , B ¹ , and C ¹ enclosed in hexagons correspond to rings such as ring A ¹ , ring B ¹ , and ring C ¹ , respectively. The hexagon represents a six-membered ring such as cyclohexane or benzene. The hexagon may represent a condensed ring such as naphthalene or a crosslinked ring such as adamantane.

In the chemical formulas of the component compounds, with symbols of terminal groups R ¹¹ to a plurality of compounds. In these compounds, two groups represented by any two R ¹¹ may be 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 R ¹² , R ¹³ , Z ¹¹ . In the compound (15), when i is 2, two rings ^{E 1} is present. The two two wherein the ring E ¹ represents the compound may be the same or different. When i is greater than 2, also apply to any two rings E ^1. This rule also applies to other symbols.

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 more than one, it means that 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 any'if any'A' is replaced by a'B'. If A'is replaced by'C', and any'A' is replaced by'D', then more than one'A'is'B','C', and / or'D' It means to include the case where it is replaced by at least two. For example, "alkyl in which at least one -CH _2- may be replaced with -O- or -CH = CH-" includes alkyl, alkoxy, alkoxyalkyl, alkoxy, 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.

"R ¹¹ and R ¹² are independently alkyls with 1 to 10 carbons or alkenyl with 2 to 10 carbons, in which at least one -CH ₂ − is replaced by -O-. Often, in these groups, at least one hydrogen may be replaced by fluorine. " In this expression, "in these groups" may be interpreted literally. In this expression, "these groups" means alkyl, alkenyl, alkoxy, alkenyloxy and the like. That is, "these groups" refers to all of the groups described prior to the term "in these groups". This common-sense interpretation also applies to the terms "in these monovalent groups" and "in these divalent groups". For example, "these monovalent groups" refers to all of the groups described prior to the term "in these monovalent groups".

In liquid crystal compounds, 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. 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.

式（１）において、
Ｒ^１およびＲ^２は独立して、水素、フッ素、塩素、または炭素数１から１６のアルキルであり、このアルキルにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＯＣＯＯ−、または−Ｓｉ（ＣＨ_３）_２−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素、塩素、−ＣＦ_３、または−Ｃ≡Ｎで置き換えられてもよく；
Ａ^１およびＡ^２は独立して、１，２−シクロプロピレン、１，３−シクロブチレン、１，３−シクロペンチレン、１，４−シクロヘキシレン、１，４−シクロヘキセニレン、１，４−シクロヘプチレン、１，５−シクロオクチレン、テトラヒドロピラン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、１，４−フェニレン、ピリジン−２，５−ジイル、ピリミジン−２，５−ジイル、デカヒドロナフタレン−２，６、−ジイル、テトラヒドロナフタレン−２，６−ジイル、またはナフタレン−２，６−ジイルであり、これらの基において、芳香環上の少なくとも１つの水素は、フッ素、塩素、−ＣＦ_３、−ＣＨＦ_２、−ＣＨ_２Ｆ、−ＯＣＦ_３、−ＯＣＨＦ_２、−ＯＣＨ_２Ｆ、または−Ｃ≡Ｎで置き換えられてもよく；
Ｚ^１およびＺ^２は独立して、単結合または炭素数１から６のアルキレンであり、１つの−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく、１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの二価基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；
ｍ^１およびｎ^１は独立して、０，１、または２であり、ｍ^１とｎ^１の和は、３以下であり；
Ｗは、−ＣＨ_２−、−ＣＦ_２−、−ＣＯ−、−Ｏ−、−Ｓ−、または−ＳＯ_２−であり；
Ｘは、水素またはフッ素であり；
Ｙ^１、Ｙ^２、Ｙ^３、およびＹ^４は独立して、水素またはメチルであり、Ｙ^１、Ｙ^２、Ｙ^３、およびＹ^４の少なくとも１つはメチルであり；Ｗが−Ｏ−であるとき、Ｙ^１、Ｙ^２、Ｙ^３、およびＹ^４の少なくとも２つはメチルである。 Item 1. A compound represented by the formula (1).

In equation (1)
R ¹ and R ² are independently hydrogen, fluorine, chlorine, or alkyl having 1 to 16 carbon atoms, in which at least one -CH ₂ − is -O-, -CO-, -COO. It may be replaced by −, −OCO−, −OCOO−, or −Si (CH ₃ ) ₂₋ , and at least one −CH ₂ CH ₂₋ is replaced by −CH = CH− or −C≡C−. In these groups, at least one hydrogen may be replaced by fluorine, chlorine, -CF ₃ , or -C≡N;
A ¹ and A ² are independently 1,2-cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4. -Cycloheptylene, 1,5-cyclooctylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, 1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2, 5-Diyl, decahydronaphthalene-2,6, -diyl, tetrahydronaphthalene-2,6-diyl, or naphthalene-2,6-diyl, in which at least one hydrogen on the aromatic ring is the hydrogen. It may be replaced with fluorine, chlorine, -CF ₃ , -CHF ₂ , -CH ₂ F, -OCF ₃ , -OCHF ₂ , -OCH ₂ F, or -C≡N;
Z ¹ and ^{Z 2} are independently a single bond or alkylene having 1 to 6 carbon atoms, one of _-CH 2 -, -O -, - CO -, - COO-, or replaced by -OCO- Alternatively, one −CH ₂ CH ₂₋ may be replaced by −CH = CH− or −C≡C−, and in these divalent groups, at least one hydrogen is replaced by fluorine or chlorine. May be;
m ¹ and n ¹ are independently 0, 1, or 2, and the sum of m ¹ and n ¹ is 3 or less;
W _{is, -CH 2 -, - CF 2} -, - CO -, - O -, - S-, or -SO ₂ - and is;
X is hydrogen or fluorine;
Y ¹ , Y ² , Y ³ , and Y ⁴ are independently hydrogen or methyl, and at least one of Y ¹ , Y ² , Y ³ , and Y ⁴ is methyl; W is -O-. At one time, at least two of Y ¹ , Y ² , Y ³ , and Y ⁴ are methyl.

Item 2. In the formula (1) described in Item 1,
R ¹ and R ² are independently hydrogen or alkyl having 1 to 14 carbon atoms, in which one or two -CH _2- may be replaced by -O-. CH ₂ CH ₂ − may be replaced by −CH = CH −, and in these groups at least one hydrogen may be replaced by fluorine;
A ¹ and A ² are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, 1,4- Phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, or naphthalene-2,6-diyl, in which at least one hydrogen on the aromatic ring may be replaced by fluorine. Often;
Z ¹ and Z ² are independently single-bonded, -COO-, -OCO-, -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF _2- , -CH ₂ CH _2- , _{-CF 2 CF 2 -, - CH} = CH -, - CF = CF -, - C≡C -, - (CH 2) 4 -, or _{-CH 2} CH = CHCH 2 - and is;
m ¹ and n ¹ are independently 0, 1, or 2, and the sum of m ¹ and n ¹ is 3 or less;
W is -CH _2- , -CO-, -S-, or -SO _2- ;
X is hydrogen or fluorine;
Item 2. The compound according to Item 1, wherein Y ¹ , Y ² , Y ³ , and Y ⁴ are independently hydrogen or methyl, and at least one of Y ¹ , Y ² , Y ³ , and Y ⁴ is methyl. ..

Item 3. In the formula (1) described in Item 1,
R ¹ and R ² are independently hydrogen or alkyl having 1 to 14 carbon atoms, in which one or two -CH _2- may be replaced by -O-. CH ₂ CH ₂ − may be replaced by −CH = CH −, and in these groups at least one hydrogen may be replaced by fluorine;
A ¹ and A ² are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, 1,4- Phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, or naphthalene-2,6-diyl, in which at least one hydrogen on the aromatic ring may be replaced by fluorine. Often;
Z ¹ and Z ² are independently single-bonded, -COO-, -OCO-, -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF _2- , -CH ₂ CH _2- , _{-CF 2 CF 2 -, - CH} = CH -, - CF = CF -, - C≡C -, - (CH 2) 4 -, or _{-CH 2} CH = CHCH 2 - and is;
m ¹ and n ¹ are independently 0, 1, or 2, and the sum of m ¹ and n ¹ is 3 or less;
W is -S-;
X is fluorine;
Item 1 or 2, wherein Y ¹ , Y ² , Y ³ , and Y ⁴ are independently hydrogen or methyl, and at least one of Y ¹ , Y ² , Y ³ , and Y ⁴ is methyl. Compound.

Item 4. In the formula (1) described in Item 1,
R ¹ and R ² are independently alkyls with 1 to 8 carbons, alkoxys with 1 to 8 carbons, or alkenyls with 2 to 8 carbons;
A ¹ and A ² are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, 1,4- Phenylene, 1,4-phenylene, pyridine-2,5-diyl, or pyrimidine-2,5-diyl in which one or two hydrogens have been replaced with fluorine;
Z ¹ and Z ² are independently single-bonded, -COO-, -OCO-, -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF _2- , -CH ₂ CH _2- , -CH = CH -, - C≡C-, or - _{(CH 2) 4} - a and;
m ¹ and n ¹ are independently 0, 1, or 2, and the sum of m ¹ and n ¹ is 3 or less;
W is -CH _2- , -CO-, or -S-;
X is hydrogen or fluorine;
Item 1 or 2, wherein Y ¹ , Y ² , Y ³ , and Y ⁴ are independently hydrogen or methyl, and at least one of Y ¹ , Y ² , Y ³ , and Y ⁴ is methyl. Compound.

Item 5. In the formula (1) described in Item 1,
R ¹ and R ² are independently alkyls with 1 to 8 carbons, alkoxys with 1 to 8 carbons, or alkenyls with 2 to 8 carbons;
A ¹ and A ² are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, 1,4- Phenylene, 1,4-phenylene, pyridine-2,5-diyl, or pyrimidine-2,5-diyl in which one or two hydrogens have been replaced with fluorine;
Z ¹ and Z ² are independently single-bonded, -COO-, -OCO-, -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF _2- , -CH ₂ CH _2- , -CH = CH -, - C≡C-, or - _{(CH 2) 4} - a and;
m ¹ and n ¹ are independently 0, 1, or 2, and the sum of m ¹ and n ¹ is 3 or less;
W is -S-;
X is fluorine;
Item 1 or 2, wherein Y ¹ , Y ² , Y ³ , and Y ⁴ are independently hydrogen or methyl, and at least one of Y ¹ , Y ² , Y ³ , and Y ⁴ is methyl. Compound.

Item 6. In the formula (1) described in Item 1,
R ¹ and R ² are independently alkyl with 1 to 5 carbons, alkoxy with 1 to 5 carbons, or alkenyl with 2 to 5 carbons;
A ¹ and A ² are independently 1,4-cyclohexylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,3-difluoro-1. , 4-Phenylene;
Z ¹ and Z ² are independently single-bonded, -CH ₂ O-, -OCH _2- , -CH ₂ CH _2- , or -CH = CH-;
m ¹ and n ¹ are independently 0, 1, or 2, and the sum of m ¹ and n ¹ is 3 or less;
W is -S-;
X is hydrogen or fluorine;
Item 1 or 2, wherein Y ¹ , Y ² , Y ³ , and Y ⁴ are independently hydrogen or methyl, and at least one of Y ¹ , Y ² , Y ³ , and Y ⁴ is methyl. Compound.

Item 7. In the formula (1) described in Item 1,
R ¹ and R ² are independently alkyl with 1 to 5 carbons, alkoxy with 1 to 5 carbons, or alkenyl with 2 to 5 carbons;
A ¹ and A ² are independently 1,4-cyclohexylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,3-difluoro-1. , 4-Phenylene;
Z ¹ and Z ² are independently single-bonded, -CH ₂ O-, -OCH _2- , -CH ₂ CH _2- , or -CH = CH-;
m ¹ and n ¹ are independently 0, 1, or 2, and the sum of m ¹ and n ¹ is 3 or less;
W is -S-;
X is fluorine;
Item 1 or 2, wherein Y ¹ , Y ² , Y ³ , and Y ⁴ are independently hydrogen or methyl, and at least one of Y ¹ , Y ² , Y ³ , and Y ⁴ is methyl. Compound.

式（１−ａ）から（１−ｉ）において、Ｒ^１およびＲ^２は独立して、炭素数１から５のアルキル、炭素数１から５のアルコキシ、または炭素数２から５のアルケニルであり；Ｙ^１、Ｙ^２、Ｙ^３、およびＹ^４は独立して、水素またはメチルであり、Ｙ^１、Ｙ^２、Ｙ^３、およびＹ^４の少なくとも１つはメチルである。 Item 8. Item 2. The compound according to Item 1, which is represented by any one of the formulas (1a) to (1i).

In formulas (1-a) to (1-i), R ¹ and R ² are independently alkyl with 1 to 5 carbon atoms, alkoxy with 1 to 5 carbon atoms, or alkenyl with 2 to 5 carbon atoms. ^{; Y 1, Y 2, Y} 3, and ^{Y 4} are independently hydrogen or ^methyl, Y ^1, Y 2, ^{Y 3,} and at least one of ^{Y 4} is methyl.

式（１ｊ）または（１ｋ）において、Ｒ^１およびＲ^２は独立して、炭素数１から５のアルキル、炭素数１から５のアルコキシ、または炭素数２から５のアルケニルである。 Item 9. Item 2. The compound according to Item 1, which is represented by the formula (1j) or (1k).

In formula (1j) or (1k), R ¹ and R ² are independently an alkyl having 1 to 5 carbon atoms, an alkoxy having 1 to 5 carbon atoms, or an alkenyl having 2 to 5 carbon atoms.

Item 10.
A liquid crystal composition containing at least one compound according to any one of Items 1 to 9.

式（２）から（４）において、
Ｒ^１１およびＲ^１２は独立して、炭素数１から１０のアルキルまたは炭素数２から１０のアルケニルであり、このアルキルおよびアルケニルにおいて、少なくとも１つの−ＣＨ_２−は−Ｏ−で置き換えられてもよく、これらの基において、少なくとも１つの水素はフッ素で置き換えられてもよく；
環Ｂ^１、環Ｂ^２、環Ｂ^３、および環Ｂ^４は独立して、１，４−シクロヘキシレン、１，４−フェニレン、２−フルオロ−１，４−フェニレン、２，５−ジフルオロ−１，４−フェニレン、またはピリミジン−２，５−ジイルであり；
Ｚ^１１、Ｚ^１２、およびＺ^１３は独立して、単結合、−ＣＯＯ−、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、または−Ｃ≡Ｃ−である。 Item 11. Item 2. The liquid crystal composition according to Item 10, further containing at least one compound selected from the compounds represented by the formulas (2) to (4).

In equations (2) to (4)
R ¹¹ and R ¹² are independently alkyls with 1 to 10 carbons or alkenyl with 2 to 10 carbons, in which at least one -CH ₂ − is replaced with -O-. Well, in these groups, at least one hydrogen may be replaced with 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, -COO-, -CH ₂ CH _2- , -CH = CH-, or -C≡C-.

式（５）から（１１）において、
Ｒ^１３、Ｒ^１４、およびＲ^１５は独立して、炭素数１から１０のアルキルまたは炭素数２から１０のアルケニルであり、このアルキルおよびアルケニルにおいて、少なくとも１つの−ＣＨ_２−は−Ｏ−で置き換えられてもよく、これらの基において、少なくとも１つの水素はフッ素で置き換えられてもよく、そしてＲ^１５は、水素またはフッ素であってもよく；
環Ｃ^１、環Ｃ^２、環Ｃ^３、および環Ｃ^４は独立して、１，４−シクロヘキシレン、１，４−シクロヘキセニレン、１，４−フェニレン、少なくとも１つの水素がフッ素で置き換えられた１，４−フェニレン、テトラヒドロピラン−２，５−ジイル、またはデカヒドロナフタレン−２，６−ジイルであり；
環Ｃ^５および環Ｃ^６は独立して、１，４−シクロヘキシレン、１，４−シクロヘキセニレン、１，４−フェニレン、テトラヒドロピラン−２，５−ジイル、またはデカヒドロナフタレン−２，６−ジイルであり；
Ｚ^１４、Ｚ^１５、Ｚ^１６、およびＺ^１７は独立して、単結合、−ＣＯＯ−、−ＣＨ_２Ｏ−、−ＯＣＦ_２−、−ＣＨ_２ＣＨ_２−、または−ＯＣＦ_２ＣＨ_２ＣＨ_２−であり；
Ｌ^１１およびＬ^１２は独立して、フッ素または塩素であり；
Ｓ^１１は、水素またはメチルであり；
Ｘは、−ＣＨＦ−または−ＣＦ_２−であり；
ｊ、ｋ、ｍ、ｎ、ｐ、ｑ、ｒ、およびｓは独立して、０または１であり、ｋ、ｍ、ｎ、およびｐの和は、１または２であり、ｑ、ｒ、およびｓの和は、０、１、２、または３であり、ｔは、１、２、または３である。 Item 12. Item 2. The liquid crystal composition according to Item 10 or 11, further containing at least one compound selected from the compounds represented by the formulas (5) to (11).

In equations (5) to (11)
R ¹³ , R ¹⁴ , and R ¹⁵ are independently alkyls with 1 to 10 carbon atoms or alkenyl with 2 to 10 carbon atoms, in which at least one -CH ₂ − is -O-. It may be replaced, in these groups, at least one hydrogen may be replaced by fluorine, and R ¹⁵ may be hydrogen or fluorine;
Ring C ¹ , Ring C ² , Ring C ³ , and Ring C ⁴ independently replace 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, at least one hydrogen with fluorine. 1,4-Phenylene, tetrahydropyran-2,5-diyl, or decahydronaphthalene-2,6-diyl;
Ring ^{C 5} and ring ^{C 6} are each independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl or decahydronaphthalene, 2,6 -Jeil;
^{Z 14, Z 15, Z 16} , and ^{Z 17} are independently a single _{bond, -COO -, - CH 2 O} -, - OCF 2 -, - CH 2 CH 2 -, or -OCF ₂ CH ₂ CH ₂ -And;
L ¹¹ and L ¹² 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.

式（１２）から（１４）において、
Ｒ^１６は炭素数１から１０のアルキルまたは炭素数２から１０のアルケニルであり、このアルキルおよびアルケニルにおいて、少なくとも１つの−ＣＨ_２−は−Ｏ−で置き換えられてもよく、これらの基において、少なくとも１つの水素はフッ素で置き換えられてもよく；
Ｘ^１１は、フッ素、塩素、−ＣＦ_３、−ＣＨＦ_２、−ＣＨ_２Ｆ、−ＯＣＦ_３、−ＯＣＨＦ_２、−ＯＣＦ_２ＣＨＦ_２、または−ＯＣＦ_２ＣＨＦＣＦ_３であり；
環Ｄ^１、環Ｄ^２、および環Ｄ^３は独立して、１，４−シクロヘキシレン、１，４−フェニレン、少なくとも１つの水素がフッ素で置き換えられた１，４−フェニレン、テトラヒドロピラン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、またはピリミジン−２，５−ジイルであり；
Ｚ^１８、Ｚ^１９、およびＺ^２０は独立して、単結合、−ＣＯＯ−、−ＣＨ_２Ｏ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、または−（ＣＨ_２）_４−であり；
Ｌ^１３およびＬ^１４は独立して、水素またはフッ素である。 Item 13. Item 6. The liquid crystal composition according to any one of Items 10 to 12, further containing at least one compound selected from the compounds represented by the formulas (12) to (14).

In equations (12) to (14)
R ¹⁶ 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-in these alkyl and alkenyl, in these groups. At least one hydrogen may be replaced with fluorine;
X ¹¹ is fluorine, chlorine, -CF ₃ , -CHF ₂ , -CH ₂ F, -OCF ₃ , -OCHF ₂ , -OCF ₂ CHF ₂ , or -OCF ₂ CHFCF ₃ ;
Rings D ¹ , Ring D ² , and Ring D ³ are independently 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylene, tetrahydropyran-2 in which at least one hydrogen is replaced by fluorine. , 5-Diyl, 1,3-dioxane-2,5-Diyl, or pyrimidine-2,5-Diyl;
Z ¹⁸ , Z ¹⁹ and Z ²⁰ are independently single-bonded, -COO-, -CH ₂ O-, -CF ₂ O-, -OCF _2- , -CH ₂ CH _2- , -CH = CH- , -C≡C-, or - _{(CH 2) 4} - a and;
L ¹³ and L ¹⁴ are independently hydrogen or fluorine.

式（１５）において、
Ｒ^１７は炭素数１から１０のアルキルまたは炭素数２から１０のアルケニルであり、このアルキルおよびアルケニルにおいて、少なくとも１つの−ＣＨ_２−は−Ｏ−で置き換えられてもよく、これらの基において、少なくとも１つの水素はフッ素で置き換えられてもよく；
Ｘ^１２は−Ｃ≡Ｎまたは−Ｃ≡Ｃ−Ｃ≡Ｎであり；
環Ｅ^１は、１，４−シクロヘキシレン、１，４−フェニレン、少なくとも１つの水素がフッ素で置き換えられた１，４−フェニレン、テトラヒドロピラン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、またはピリミジン−２，５−ジイルであり；
Ｚ^２１は、単結合、−ＣＯＯ−、−ＣＨ_２Ｏ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＨ_２ＣＨ_２−、または−Ｃ≡Ｃ−であり；
Ｌ^１５およびＬ^１６は独立して、水素またはフッ素であり；
ｉは、１、２、３、または４である。 Item 14. Item 6. The liquid crystal composition according to any one of Items 10 to 13, further containing at least one compound selected from the compounds represented by the formula (15).

In equation (15)
R ¹⁷ 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 by -O-, and in these groups, At least one hydrogen may be replaced by fluorine;
X ¹² is -C ≡ N or -C ≡ C-C ≡ N;
Ring E ¹ is 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced with fluorine, tetrahydropyran-2,5-diyl, 1,3-dioxane-2. , 5-Dioxane, or pyrimidine-2,5-Dioxane;
Z ²¹ is a single bond, -COO-, -CH ₂ O-, -CF ₂ O-, -OCF _2- , -CH ₂ CH _2- , or -C ≡ C-;
L ¹⁵ and L ¹⁶ are independently hydrogen or fluorine;
i is 1, 2, 3, or 4.

Item 15. A liquid crystal display device containing the liquid crystal composition according to any one of Items 10 to 14.

The present invention also includes the following items. (A) The above composition further comprising at least one optically active compound and / or polymerizable compound. (B) The composition described above further comprising at least one antioxidant and / or UV absorber.

The present invention also includes the following items. (C) One selected from the group of polymerizable compounds, polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, dyes, and defoamers. The above composition further comprising two or at least three additives. (D) The upper limit temperature of the nematic phase is 70 ° C. or higher, the optical anisotropy at a wavelength of 589 nm (measured at 25 ° C.) is 0.08 or higher, and the dielectric anisotropy at a frequency of 1 kHz (measured at 25 ° C.). ) Is -2 or less, the above composition.

The present invention also includes the following items. (E) A device containing the above composition and having a mode of PC, TN, STN, ECB, OCB, IPS, VA, FFS, FPA, or PSA. (F) AM device containing the above composition. (G) A transmissive device containing the above composition. (H) Use of the above composition as a composition having a nematic phase. (I) Use as an optically active composition by adding an optically active compound to the above composition.

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) Compound (1) is characterized by having a dibenzothiophene skeleton. Y ¹ , Y ² , Y ³ , and Y ⁴ are independently hydrogen (-H) or methyl (-CH ₃ ), and at least one of Y ¹ , Y ² , Y ³ , and Y ⁴ is methyl. Is. That is, compound (1) has a methyl-substituted dibenzothiophene ring. The definition of the symbol of compound (1) is as described in Item 1.

This compound has a negative dielectric anisotropy. This compound is extremely physically and chemically stable under the conditions in which the device is normally used, and has good compatibility with other liquid crystal compounds. Compositions containing this compound are stable under the conditions in which the device is commonly used. When the composition is stored at a low temperature, the compound is less likely to precipitate as crystals (or smectic phase). This compound has the general physical properties required for the components of the composition, appropriate optical anisotropy, and large dielectric anisotropy.

Terminal groups (R ¹ and R ² ), rings (A ¹ and A ² ), binding groups (Z ¹ and Z ² ), cross-linking groups (W), and substituents (X and Y ¹ to Y) in compound (1). A preferable example of ⁴ ) is as follows. This example also applies to the sub-formula of compound (1). In compound (1), the physical properties can be arbitrarily adjusted by appropriately combining these groups. Because large difference is not in the physical properties of the compound, the compound (1) is, ^{2 H} (deuterium), an isotope such as ^{13 C} may contain more than the amount of natural abundance.

In formula (1), R ¹ and R ² are independently hydrogen, fluorine, chlorine, or alkyl having 1 to 16 carbon atoms, in which at least one -CH ₂ − is -O-, It may be replaced by −CO−, −COO−, −OCO−, −OCOO−, or −Si (CH ₃ ) ₂₋ , and at least one −CH ₂ CH ₂₋ is −CH = CH− or − In these groups, at least one hydrogen may be replaced with fluorine, chlorine, -CF ₃ , or -C ≡ N.

Preferred R ¹ or R ² are hydrogen, alkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, alkylthio, alkylthioalkoxy, acyl, acylalkyl, acyloxy, acyloxyalkyl, alkoxycarbonyl, alkoxycarbonylalkyl, alkenyl, alkenyloxy, alkenyloxyalkyl. , Alkoxyalkenyl, alkynyl, alkynyloxy, silaalkyl, or disilaalkyl. In these groups, at least one hydrogen may be replaced with fluorine or chlorine. This example contains a group in which at least two hydrogens have been replaced with both fluorine and chlorine. Groups in which at least one hydrogen has been replaced with fluorine alone are even more preferred. Of these groups, straight chains are preferred over branched chains. Even if R ¹ or R ² is a branched chain, it is preferable when it has an asymmetric center and is optically active.

式（Ｇ１）から式（Ｇ４）において、Ｒ^３は、炭素数１から１２のアルキルであり、このアルキルにおいて、１つまたは２つの−ＣＨ_２−は、−Ｏ−で置き換えられてもよく、１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよい。好ましいＲ^３は、アルキルである。具体的なＲ^３は、メチルまたはエチルである。このような基を有する化合物は、光学活性であってもよく、またはラセミ体であってもよい。 When R ¹ or R ² has a methyl (-CH ₃ ), this methyl may be replaced by a group represented by the formulas (G1) to (G4).

In formulas (G1) to (G4), R ³ is an alkyl having 1 to 12 carbon atoms, in which one or two -CH _2- may be replaced by -O-. One −CH ₂ CH ₂₋ may be replaced by −CH = CH−, and in these groups at least one hydrogen may be replaced by fluorine or chlorine. Preferred ^{R 3} is alkyl. Specific R ³ is methyl or ethyl. The compound having such a group may be optically active or may be racemic.

More preferred R ¹ or R ² are alkyl, alkoxy, alkoxyalkyl, alkenyl, monofluoroalkyl, polyfluoroalkyl, monofluoroalkoxy, or polyfluoroalkoxy. In addition, polyfluoroalkyl and polyfluoroalkoxy include perfluoroalkyl and perfluoroalkoxy, respectively. Particularly preferred R ¹ or R ² is alkyl, alkoxy, or alkenyl.

The preferred configuration of -CH = CH- in alkenyl depends on the position of the double bond. Trans-configuration is preferred for alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl, 3-hexenyl. The cis configuration is preferred for alkenyl such as 2-butenyl, 2-pentenyl, 2-hexenyl.

Specific R ¹ or R ² are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, methoxymethyl, methoxyethyl, methoxy. Propyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, propoxymethyl, butoxymethyl, pentoxymethyl, vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl , 3-Pentenyl, 4-Pentenyl, 2-propenyloxy, 2-butenyloxy, 2-pentenyloxy, 1-propynyl, or 1-pentenyl.

Specific R ¹ or R ² is 2-fluoroethyl, 3-fluoropropyl, 2,2,2-trifluoroethyl, 2-fluorovinyl, 2,2-difluorovinyl, 2-fluoro-2-vinyl, It is also 3-fluoro-1-propenyl, 3,3,3-trifluoro-1-propenyl, 4-fluoro-1-propenyl, or 4,4-difluoro-3-butenyl.

More preferred R ¹ or R ² are methyl, ethyl, propyl, butyl, pentyl, methoxy, ethoxy, propoxy, butoxy, pentyloxy, methoxymethyl, ethoxymethyl, propoxymethyl, vinyl, 1-propenyl, 2-propenyl, 1 -Butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 2-propenyloxy, 2-butenyloxy, or 2-pentenyloxy. The most preferred R ¹ or R ² are methyl, ethyl, propyl, butyl, pentyl, methoxy, ethoxy, propoxy, methoxymethyl, vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl.

In formula (1), A ¹ and A ² are independently 1,2-cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,4-cyclohexyl. Senilene, 1,4-cycloheptylene, 1,5-cyclooctylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, 1,4-phenylene, pyridine-2,5- Diyl, pyrimidine-2,5-diyl, decahydronaphthalene-2,6, -diyl, tetrahydronaphthalene-2,6-diyl, or naphthalene-2,6-diyl, on the aromatic ring in these groups. At least one hydrogen may be replaced with fluorine, chlorine, -CF ₃ , -CHF ₂ , -CH ₂ F, -OCF ₃ , -OCHF ₂ , -OCH ₂ F, or -C ≡ N.

Preferred A ¹ or A ² are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, 1,4-phenylene, 2-Fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, 2,3 5-Trifluoro-1,4-phenylene, pyridine-2,5-diyl, 3-fluoropyridine-2,5-diyl, pyrimidine-2,5-diyl, decahydronaphthalene-2,6-diyl, 1, It is 2,3,4-tetrahydronaphthalene-2,6-diyl, or naphthalene-2,6-diyl. The configuration of 1,4-cyclohexylene and 1,3-dioxane-2,5-diyl is preferably trans over cis.

More preferred A ¹ or A ² are 1,4-cyclohexylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4. -Phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyridine-2,5-diyl, or pyrimidine- 2,5-Dioxane. Particularly preferred A ¹ or A ² is 1,4-cyclohexylene or 1,4-phenylene.

In formula (1), Z ¹ and Z ² are independently single-bonded or alkylene with 1 to 6 carbon atoms, and one -CH _2- is -O-, -CO-, -COO-, or. It may be replaced by −OCO−, one −CH ₂ CH ₂₋ may be replaced by −CH = CH− or −C≡C−, and in these divalent groups, at least one hydrogen is present. , Fluorine or chlorine may be replaced.

Specific examples of Z ¹ or Z ² are single bond, -O-, -COO-, -OCO-, -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF ₂ -,- CH ₂ CH _2- , -CH = CH-, -CF = CH-, -CH = CF-, -CF = CF-, -C≡C-, -CH ₂ CO-, -COCH ₂ -,-(CH) _{2) 4 -, - CH 2} CH = CHCH 2 -, - (CH 2) 2 COO -, - (CH 2) 2 OCO -, - OCO (CH 2) 2 -, - COO (CH 2) 2 -, -(CH ₂ ) ₂ CF ₂ O-,-(CH ₂ ) ₂ OCF _2- , -OCF ₂ (CH ₂ ) _2- , -CF ₂ O (CH ₂ ) ₂ -,-(CH ₂ ) ₃ O- , Or −O (CH ₂ ) ₃₋ . Trans is preferred over cis for the configuration of double bonds of binding groups such as −CH = CH−, −CF = CF−, −CH = CH−CH ₂ O−, and −OCH ₂ −CH = CH−. ..

Preferred Z ¹ or Z ² are single bonds, -O-, -COO-, -OCO-, -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF _2- , -CH ₂ CH ₂ -, - CH = CH -, - CF = CF -, - C≡C-, or - _{(CH 2) 4} - a. More preferred Z ¹ or Z ² are single bonds, -COO-, -OCO-, -CF ₂ O-, -OCF _2- , -CH = CH-, -CH ₂ CH _2- , or -C ≡ C-. Is. The most preferred Z ¹ or Z ² is a single bond.

In formula (1), m ¹ and n ¹ are independently 0, 1, or 2, and the sum of m ¹ and n ¹ is 3 or less. When counting the dibenzothiophene ring as one ring, this compound has one to four rings. A compound in which the sum of m ¹ and n ¹ is 0 or 1 has good compatibility with other liquid crystal compounds and has a low viscosity. A compound having a sum of m and n of 2 or 3 has a high upper limit temperature and a wide temperature range of the liquid crystal phase.

In the formula (1), W _{is, -CH 2 -, - CF 2} -, - CO -, - O -, - S-, or -SO ₂ - is. Preferred Ws are -CF _2- , -O-, -S- ,. More preferable Ws are -O- and -S-. A particularly preferable W is −S−.

In formula (1), X is hydrogen or fluorine. Preferred X is fluorine.

In the formula ^{(1), Y 1, Y} 2, Y 3, and ^{Y 4} are independently hydrogen or ^methyl, Y ^1, Y 2, ^{Y 3,} and at least one of ^{Y 4} is methyl; when W is ^{-O-, Y 1, Y 2,} Y 3, and at least two ^{Y 4} is methyl.

Physical properties such as optical anisotropy and dielectric anisotropy can be arbitrarily adjusted by appropriately selecting the terminal group, ring, bonding group, substituent, number of rings, etc. of compound (1). is there. The effects of these types of groups on the physical properties of compound (1) will be described below.

In compound (1), when the terminal group (R ¹ or R ² ) is linear, the temperature range of the liquid crystal phase is wide and the viscosity is low. When R ¹ or R ² is a branched chain, the compatibility with other liquid crystal compounds is good. Compounds whose terminal groups are optically active groups are useful as chiral dopants. By adding this compound to the composition, it is possible to prevent the reverse twisted domain generated in the device. Compounds whose terminal groups are not optically active groups are useful as components of the composition. When the terminal group is alkenyl, the preferred configuration depends on the position of the double bond. Alkenyl compounds with a preferred configuration have a high upper temperature limit or a wide temperature range of the liquid crystal phase. Mol. Cryst. Liq. Cryst., 1985, 131, 109 and Mol. Cryst. Liq. Cryst., 1985, 131, 327 have detailed explanations.

Ring A ¹ or A ² may have at least one hydrogen substituted with fluorine or chlorine 1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, or pyridazine-3,6 -When it is diyl, the optical anisotropy is large. When this ring is 1,4-cyclohexylene, 1,4-cyclohexenylene or 1,3-dioxane-2,5-diyl, the optical anisotropy is small.

When at least one ring is 1,4-cyclohexylene, the upper limit temperature is high and the optical anisotropy is small. When at least one ring is 1,4-phenylene, the optical anisotropy is relatively large and the oriental order parameter is large. When at least two rings are 1,4-phenylene, the optical anisotropy is large, the temperature range of the liquid crystal phase is wide, and the upper limit temperature is high.

Bonding group Z ¹ or Z ² is single bond, -O-, -CH ₂ O-, -CF ₂ O-, -OCF _2- , -CH ₂ CH _2- , -CH = CH-, -CF = CF- , or - _{(CH 2) 4} - is when the viscosity is small. The viscosity is smaller when the binding group is a single bond, -OCF _2- , -CF ₂ O-, -CH ₂ CH _2- , or -CH = CH-. When the binding group is −CH = CH−, the temperature range of the liquid crystal phase is wide, and the elastic constant ratio K ₃₃ / K ₁₁ (K ₃₃ : bend elastic constant, K ₁₁ : spray elastic constant) is large. When the binding group is −C≡C−, the optical anisotropy is large.

When compound (1) has one or two rings, the viscosity is low. When compound (1) has four or five rings, the upper limit temperature is high. As described above, a compound having necessary physical properties can be obtained by appropriately selecting the type of terminal group, ring, and bonding group, and the number of rings. Therefore, compound (1) is useful as a component of compositions used in devices having modes such as PC, TN, STN, ECB, OCB, IPS, and VA. Compound (1) is suitable for devices having modes such as VA, IPS, and PSA.

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. The methods for introducing the required terminal groups, rings and binding groups into the starting material are "Organic Syntheses" (John Wiley & Sons, Inc.) and "Organic Reactions" (John Wiley & Sons). , Inc.), "Comprehensive Organic Synthesis" (Pergamon Press), "New Experimental Chemistry Course" (Maruzen), etc.

2-1. Generation of Binding Group Z First, a scheme is shown with respect to the method of generating binding groups Z ¹ and Z ² . Next, the reactions described in the scheme according to the methods (1) to (11) will be described. In this scheme, MSG ¹ (or MSG ² ) is a monovalent organic group. The monovalent organic groups represented by the plurality of MSG ¹ (or MSG ² ) used in the scheme may be the same or different. Compounds (1A) to (1J) correspond to compound (1).

(1) Generation of single bond A compound by reacting an arylboric acid (21) synthesized by a known method with a halide (22) in the presence of a catalyst such as carbonate and tetrakis (triphenylphosphine) palladium. (1A) is synthesized. This compound (1A) is prepared by reacting a halide (23) synthesized by a known method with n-butyllithium and then zinc chloride, and in the presence of a catalyst such as dichlorobis (triphenylphosphine) palladium. It is also synthesized by reacting (22).

(2) Production of -COO- The halide (23) is reacted with n-butyllithium and then carbon dioxide to obtain a carboxylic acid (24). Compound (1B) is synthesized by dehydrating compound (25) and carboxylic acid (24) synthesized by a known method in the presence of DDC (1,3-dicyclohexylcarbodiimide) and DMAP (4-dimethylaminopyridine). To do.

(3) Production of -CF ₂ O- The compound (1B) is treated with a sulfurizing agent such as Lawesson's reagent to obtain a thionoester (26). The thionoester (26) is fluorinated with a hydrogen fluoride pyridine complex and NBS (N-bromosuccinimide) to synthesize compound (1C). See M. Kuroboshi et al., Chem. Lett., 1992, 827. Compound (1C) is also synthesized by fluorinating thionoester (26) with DAST ((diethylamino) sulfatrifluoride). See WH Bunnelle et al., J. Org. Chem. 1990, 55, 768. It is also possible to generate this binding group by the method described in Peer. Kirsch et al., Angew. Chem. Int. Ed. 2001, 40, 1480.

(4) Production of -CH = CH- The halide (22) is treated with n-butyllithium and then reacted with DMF (N, N-dimethylformamide) to obtain an aldehyde (28). The phosphonium salt (27) synthesized by a known method is treated with a base such as potassium t-butoxide to generate phosphorus irid. This phosphorus irid is reacted with aldehyde (28) 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.

(5) -CH ₂ CH _2- Production Compound (1E) is synthesized by hydrogenating compound (1D) in the presence of a catalyst such as palladium carbon.

(6)-Production of-(CH ₂ ) ₄ -A compound having- (CH ₂ ) _2- CH = CH- is prepared by using a phosphonium salt (29) instead of the phosphonium salt (27) and following the method of method (4). obtain. This is catalytically hydrogenated to synthesize compound (1F).

(7) -CH ₂ CH = CHCH _2- Formation A compound according to the method (4), using a phosphonium salt (30) instead of the phosphonium salt (27) and an aldehyde (31) instead of the aldehyde (28). (1G) is synthesized. Since a trans form is produced depending on the reaction conditions, the trans form is isomerized to a cis form by a known method if necessary.

(8) Production of -C≡C- After reacting the halide (23) with 2-methyl-3-butyne-2-ol in the presence of a catalyst of dichloropalladium and copper halide, under basic conditions. Deprotection with to give compound (32). In the presence of a catalyst of dichloropalladium and copper halide, compound (32) is reacted with a halide (22) to synthesize compound (1H).

(9) Production of -CF = CF- The halide (23) is treated with n-butyllithium and then reacted with tetrafluoroethylene to obtain compound (33). The halide (22) is treated with n-butyllithium and then reacted with compound (33) to synthesize compound (1I).

(10) Production of −OCH _2- The aldehyde (28) is reduced with a reducing agent such as sodium borohydride to obtain compound (34). The compound (34) is bromide with hydrobromic acid or the like to obtain a bromide (35). In the presence of a base such as potassium carbonate, the bromide (35) is reacted with the compound (36) to synthesize the compound (1J).

Generation of (11)-(CF ₂ ) _2-
Diketone (-COCO-) was fluorinated with sulfur tetrafluoride in the presence of a hydrogen fluoride catalyst according to the method described in J. Am. Chem. Soc., 2001, 123, 5414.-(CF ₂ ). Obtain a compound having _2- .

2-2. Ring formation Next, the formation method for rings A ¹ and A ² will be described. 1,4-Cyclohexylene, 1,3-dioxane-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, pyridine-2 For rings such as, 5-dioxane, pyrimidine-2,5-dioxane, starting materials are commercially available, or production methods are well known. Therefore, the compounds (64), (67), and (71) shown below will be described.

Decahydronaphthalene-2,6-dione (64) is a starting point for compounds having decahydronaphthalene-2,6-diyl. This compound (64) can be obtained by catalytically reducing diol (63) with ruthenium oxide in the presence of ruthenium oxide and further oxidizing with chromium oxide according to the method described in JP-A-2000-239564. This compound is converted to compound (1) by a usual method.

The structural units of 2,3- (bistrifluoromethyl) phenylene are synthesized by the method described in Org. Lett., 2000, 2 (21), 3345. Aniline (66) is synthesized by reacting furan (65) with 1,1,1,4,4,4-hexafluoro-2-butin at a high temperature in a Diels-Alder type reaction. This compound is subjected to a Sandmeyer-type reaction according to the method described in Org. Synth. Coll., Vol. 2, 1943, 355 to obtain iodide (67). This compound is converted to compound (1) by a usual method.

The structural unit of 2-difluoromethyl-3-fluorophenylene is synthesized by the following method. The hydroxyl group of compound (68) is protected with an appropriate protecting group to obtain compound (69). P means protecting group. Compound (69) is allowed to act on s-butyllithium, followed by reaction with N, N-dimethylformamide (DMF) to give aldehyde (70). This compound is fluorinated with diethylaminosulfatrifluoride (DAST) and subsequently deprotected to give phenol (71). This compound is converted to compound (1) by a usual method.

2-3. Generation of Methyl-Substituted Dibenzothiophene Ring A method for producing a methyl-substituted dibenzothiophene ring is described in Synthesis Example 1.

3. 3. Liquid crystal composition 3-1. Component Compound The liquid crystal composition of the present invention will be described. This composition contains at least one compound (1) as a component (a). The composition may contain two or more compounds (1). The component of the composition may be only compound (1). It is preferable that the composition contains at least one of the compound (1) in the range of 1% by weight to 99% by weight in order to exhibit good physical properties. In a composition having a negative dielectric anisotropy, the preferred proportion of compound (1) is in the range of 5% by weight to 60% by weight. In the composition having a positive dielectric anisotropy, the preferable ratio of the compound (1) is 30% by weight or less.

This composition contains compound (1) as component (a). It is preferable that this composition further contains a liquid crystal compound selected from the components (b) to (e) shown in Table 1. When preparing this composition, it is preferable to select the components (b) to (e) in consideration of the positive and negative of the dielectric anisotropy and the magnitude. This composition may contain a liquid crystal compound different from the compounds (1) to (15). The composition does not have to contain such liquid crystal compounds.

The 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). be able to. In these compounds, R ¹¹ and R ¹² are independently alkyls with 1 to 10 carbon atoms or alkenyl with 2 to 10 carbon atoms, in which at least one -CH _2- is -O-. At least one hydrogen may be replaced with fluorine in these groups.

Component (b) has a small dielectric anisotropy. The dielectric anisotropy of component (b) is close to zero. Compound (2) has the effect of lowering the viscosity or adjusting the optical anisotropy. Compounds (3) and (4) have the effect of widening the temperature range of the nematic phase or adjusting the optical anisotropy by raising the upper limit temperature.

As the proportion of the component (b) increases, the viscosity of the composition decreases, but the dielectric anisotropy 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 proportion of the component (b) is preferably 30% by weight or more, more preferably 40% by weight or more.

The component (c) is a compound (5) to (11). These compounds have phenylene in which the lateral position is substituted with two halogens, such as 2,3-difluoro-1,4-phenylene. Preferred examples of the component (c) are compounds (5-1) to (5-8), compounds (6-1) to (6-17), compounds (7-1), and compounds (8-1) to ( 8-3), compounds (9-1) to (9-11), compounds (10-1) to (10-3), and compounds (11-1) to (11-3) can be mentioned. In these compounds, R ¹³ , R ¹⁴ , and R ¹⁵ are independently alkyls with 1 to 10 carbon atoms or alkenyl with 2 to 10 carbon atoms, and in these alkyl and alkenyl at least one -CH _2- may be replaced by -O-, in these groups, at least one hydrogen may be replaced by fluorine, and R ¹⁵ may be hydrogen or fluorine.

The component (c) has a large negative dielectric anisotropy. Ingredient (c) is used when preparing compositions for modes such as IPS, VA, PSA. As the proportion of the component (c) is increased, the dielectric anisotropy of the composition increases negatively, but the viscosity increases. 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 ratio is preferably 40% by weight or more in order to drive the voltage sufficiently.

Since the compound (5) of the component (c) is a bicyclic compound, it has the effects of lowering the viscosity, adjusting the optical anisotropy, or increasing the dielectric anisotropy. Since the compounds (5) and (6) are tricyclic compounds, they have the effects of increasing the upper limit temperature, increasing the optical anisotropy, or increasing the dielectric anisotropy. The compounds (8) to (11) have the effect of increasing the dielectric anisotropy.

When preparing a composition for a mode such as IPS, VA, PSA, the proportion of the component (c) is preferably 40% by weight or more, more preferably in the range of 50% by weight to 95% by weight. .. When the component (c) is added to a composition having a positive dielectric anisotropy, the proportion of the component (c) is preferably 30% by weight or less. 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 a compound having a halogen or fluorine-containing group at the right end. Preferred examples of the component (d) include compounds (12-1) to (12-16), compounds (13-1) to (13-116), and compounds (14-1) to (14-59). Can be done. In these compounds, R ¹⁶ is an alkyl with 1 to 10 carbons or an alkenyl with 2 to 10 carbons, in which at least one -CH ₂ − may be replaced with -O-. In these groups, 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 .

The component (d) has a positive dielectric anisotropy and very good stability to heat and light, and is therefore used when preparing a composition for modes such as IPS, FFS, and OCB. The proportion of the component (d) 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, and more preferably in the range of 40% by weight to 95% by weight. When the component (d) is added to a composition having a negative dielectric anisotropy, the proportion of the component (d) is preferably 30% by weight or less. 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.

The component (e) is compound (15) having a right terminal group of −C≡N or −C≡C−C≡N. Preferred examples of the component (e) include compounds (15-1) to (15-64). In these compounds, R ¹⁷ is an alkyl with 1 to 10 carbons or an alkenyl with 2 to 10 carbons, in which at least one -CH ₂ − may be replaced with -O-. In these groups, at least one hydrogen may be replaced with fluorine. X ¹² is −C≡N or −C≡C−C≡N.

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

When preparing a composition for a mode such as TN, the proportion of the component (e) 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, and further. It is preferably in the range of 40% by weight to 95% by weight. When the component (e) is added to a composition having a negative dielectric anisotropy, the proportion of the component (e) is preferably 30% by weight or less. By adding the component (e), it becomes possible to adjust the elastic constant of the composition and adjust the voltage-transmittance curve of the device.

By combining the compound appropriately selected from the above components (b) to (e) and the compound (1), high stability to heat and light, high upper limit temperature, lower lower limit temperature, small viscosity, appropriate optical anisotropy Directionality (ie, large optical anisotropy or small optical anisotropy), positive or negative modulus anisotropy, large specific resistance, appropriate elastic constant (ie, large elastic constant or small elastic constant), etc. A liquid crystal composition satisfying at least one of the physical properties can be prepared. Devices containing such compositions have a wide temperature range in which the device can be used, short response times, high voltage retention, low threshold voltage, high contrast ratio, low flicker rate, and long lifetime.

If the element is used for a long time, flicker may occur on the display screen. The flicker rate (%) can be expressed by (| brightness when a positive voltage is applied-brightness when a negative voltage is applied |) / average brightness) × 100. An element having a flicker rate in the range of 0% to 1% is less likely to cause flicker on the display screen even if the element is used for a long time. This flicker is related to image burn-in and is presumed to be caused by the potential difference between the positive and negative frames when driven by alternating current. The composition containing the compound (1) is also useful for reducing the occurrence of flicker.

3-2. Additives 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 are polymerizable compounds, polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, dyes, defoamers and the like. Such additives are well known to those of skill in the art and are described in the literature.

In a liquid crystal display device having a PSA (polymer sustained alignment) mode, the composition contains a polymer. The polymerizable compound is added for the purpose of forming a polymer in the composition. A polymer is produced in the composition by irradiating ultraviolet rays with a voltage applied between the electrodes to polymerize the polymerizable compound. By this method, an appropriate pre-tilt is achieved, so that an element having a short response time and improved image burn-in is produced.

Preferred examples of polymerizable compounds are acrylates, methacrylates, vinyl compounds, vinyloxy compounds, propenyl ethers, epoxy compounds (oxylane, oxetane), and vinyl ketones. 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 are compounds (M-1) to (M-18). In these compounds, R ²⁵ to R ³¹ are hydrogen or methyl; R ³² , R ³³ , and R ³⁴ are independently hydrogen or alkyl having 1 to 5 carbon atoms, R ³² , R ³³ , And at least one of R ³⁴ is an alkyl having 1 to 5 carbon atoms; v, w, and x are independently 0 or 1; u and y are independently integers from 1 to 10. .. L ²¹ to L ²⁶ are hydrogen or fluorine; 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 conditions, 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-Phenylaclysin, 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.

Polymerization can be carried out by adding a photoradical polymerization initiator to the liquid crystal composition and then irradiating it with ultraviolet rays while applying an electric field. 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.

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 a necessary 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. * Marks represent asymmetric carbon.

Antioxidants are effective in maintaining a large voltage retention. Preferred examples of the antioxidants include the following compounds (AO-1) and (AO-2); Irganox415, Irganox565, Irganox1010, Irganox1035, Irganox3114, and Irganox1098 (trade name; BASF). 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, and specific examples thereof include the following compounds (AO-3) and (AO-4); Tinuvin 328, and Tinuvin 99-2 (trade name; BASF); and 1,4-diazabicyclo [2.2.2] octane (DABCO) can be mentioned.

Light stabilizers such as amines with steric hindrance are preferred for maintaining high voltage retention. Preferred examples of light stabilizers are the following compounds (AO-5), (AO-6), and (AO-7); Tinuvin 144, Tinuvin 765, and Tinuvin 770DF (trade name; BASF); LA-77Y and LA- 77G (trade name; ADEKA Corporation) can be mentioned. A heat stabilizer is also effective for maintaining a large voltage holding ratio, and Irgafos 168 (trade name; BASF) can be mentioned as a preferable example. Dichroic dyes such as azo dyes, anthraquinone dyes, etc. are added to the composition to accommodate devices in GH (guest host) mode. 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 carbons, an alkoxy having 1 to 20 carbons, -COOR ⁴¹ , or -CH ₂ CH ₂ COOR ⁴¹ , where R ⁴¹ has 1 carbon. To 20 alkyl. In compounds (AO-2) and (AO-5), R ⁴² is an alkyl having 1 to 20 carbon atoms. In the compound ^{(AO-5), R 43} is hydrogen, methyl, or O ^·, (oxygen radicals); ring ^{G 1} is 1,4-cyclohexylene or 1,4-phenylene; Compound (AO-7 ), Ring G ² is 1,4-cyclohexylene, 1,4-phenylene, or 1,4-phenylene in which at least one hydrogen is replaced with fluorine; compounds (AO-5) and (AO-7). ), 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 is also suitable for NCAP (nematic curvilinear aligned phase) devices, where the composition is microencapsulated. This composition can also be used in a polymer-dispersed liquid crystal display device (PDLCD) and a polymer network liquid crystal display device (PNLCD). In these compositions, a large amount of the polymerizable compound is added. On the other hand, when the proportion of the polymerizable compound is 10% by weight or less based on the weight of the liquid crystal composition, a PSA mode liquid crystal display element is manufactured. The preferred proportion is in the range of 0.1% by weight to 2% by weight. A more preferable ratio is in the range of 0.2% by weight to 1.0% by weight. The PSA mode element can be driven by a drive system such as an active matrix system or a passive matrix system. Such an element can be applied to any type of reflective type, transmissive type, and semitransparent type.

1. 1. Examples of Compound (1) The present invention will be described in more detail by way of examples. The present invention is not limited by the examples, as the examples are typical. Compound (1) was synthesized by the following procedure. The synthesized compound was identified by a method such as NMR analysis. The physical properties of the compound or composition and the characteristics of 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 measured at room temperature, 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.

Mass spectrometry: A QP-2010 Ultra type gas chromatograph mass spectrometer 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., the temperature of the ion source was set to 200 ° C., the ionization voltage was set to 70 eV, and the emission current was set to 150 uA. The sample was dissolved in acetone to prepare a 1% by weight solution, and 1 μl of the solution was injected into the sample vaporization chamber. A GCM Solution system manufactured by Shimadzu Corporation was used as the recorder.

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) 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: A HarmaSpec UV-1700 manufactured by Shimadzu Corporation was used for the measurement. 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 start temperature, etc.), the compound itself was used as a sample. When measuring physical properties such as the upper limit temperature, viscosity, optical anisotropy, and dielectric anisotropy of the nematic phase, a mixture of the compound and the mother liquid crystal was used as a sample.

When a sample in which the compound was mixed with the mother liquid crystal was used, the measurement was performed as follows. A sample was prepared by mixing 15% by weight of the compound and 85% by weight of the mother liquid crystal. Extrapolated values were calculated from the measured values of this sample according to the following equation, and these values are described. <Extrapolation value> = (100 x <measured value of sample>-<measured value of mother liquid crystal> x <measured value of mother liquid crystal>) / <weight% of compound>

When crystals (or smectic phase) are precipitated at this ratio at 25 ° C., the ratio of the compound to the mother liquid crystal is 10% by weight: 90% by weight, 5% by weight: 95% by weight, 1% by weight: 99% by weight. The physical properties of the sample were measured at a rate at which the crystals (or smectic phase) did not precipitate at 25 ° C. Unless otherwise specified, the ratio of the compound to the mother liquid crystal is 15% by weight: 85% by weight.

When the dielectric anisotropy of the compound was zero or positive, the following mother liquid crystal (A) was used. The ratio of each component was expressed in% by weight.

When the dielectric anisotropy of the compound was zero or negative, the following mother liquid crystal (B) was used. The ratio of each component was expressed in% by weight.

Measurement method: The physical properties were measured by the following method. Many of these are described in the JEITA standard (JEITA ED-2521B), which is deliberated and enacted by the Japan Electronics and Information Technology Industries Association (JEITA). A modified method was also used. 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.): A scanning calorimeter manufactured by PerkinElmer, Diamond DSC system, or a high-sensitivity differential scanning calorimeter manufactured by SII Nanotechnology, X-DSC7000 was used for the measurement. 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 of the compound and the polymerization initiation temperature 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 crystals can be distinguished into two types, each is represented as C ₁ or C ₂ . The smectic phase was represented as S and the nematic phase was represented as N. Smectic A phase, a smectic B phase, a smectic C phase, and if can be distinguished phases such as smectic F phase, represented respectively _{S A,} S B, _{S C,} and the _{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) Compatibility of compounds: A sample in which a mother liquid crystal and a compound are mixed so that the ratio of the compound is 20% by weight, 15% by weight, 10% by weight, 5% by weight, 3% by weight, or 1% by weight. Was prepared. Samples were placed in glass bottles and stored in a freezer at -10 ° C or -20 ° C for a period of time. It was observed whether the nematic phase of the sample was maintained or whether crystals (or smectic phase) were precipitated. The conditions under which the nematic phase was maintained were used as a measure of compatibility. The proportion of compounds and the temperature of the freezer may be changed as needed.

(4) Upper limit temperature of nematic phase (T _NI or NI; ° C.): A sample was placed on a hot plate of a melting point measuring device equipped with a polarizing microscope and heated at a rate of 1 ° C./min. The temperature at which a part of the sample changed from the nematic phase to the isotropic liquid was measured. When the sample was a mixture of compound (1) and mother liquid crystal, it was indicated by the _TNI symbol. When the sample was a mixture of compound (1) and a compound selected from compounds (2) to (15), it was indicated by the symbol NI. The upper limit temperature of the nematic phase may be abbreviated as "upper limit temperature".

(5) Minimum Temperature of a Nematic Phase _{(T C;} ° C.): A sample having a nematic phase was put in a glass bottle, 0 ℃, -10 ℃, -20 ℃, -30 ℃, and -40 ℃ for 10 days in a freezer After storage, 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".

(6) 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.

(7) Optical anisotropy (refractive index anisotropy; measured at 25 ° C.; Δn): The measurement was carried out using light having a wavelength of 589 nm and using an Abbe refractometer with a polarizing plate 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 of Δn = n‖−n⊥.

(8) Specific resistance (ρ; measured at 25 ° C; Ωcm): 1.0 mL of the sample was injected into a container equipped with an electrode. 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 equation. (Specific resistance) = {(voltage) x (electric capacity of container)} / {(DC current) x (vacuum permittivity)}.

(9) Voltage retention rate (VHR-1; measured at 25 ° C.;%): The TN element used for the measurement had a polyimide alignment film, and the distance (cell gap) between the two glass substrates was 5 μm. .. This device was sealed with an adhesive that cures with ultraviolet light after the sample was placed. A pulse voltage (60 microseconds at 5 V) was applied to this device to charge it. The decaying voltage was measured with a high-speed voltmeter for 16.7 milliseconds, and the area A between the voltage curve and the horizontal axis in a unit period was determined. Area B was the area when there was no attenuation. The voltage holding ratio is expressed as a percentage of the area A with respect to the area B.

(10) Voltage retention rate (VHR-2; measured at 80 ° C.;%): The voltage retention rate was measured by the above method except that the voltage retention rate was measured at 80 ° C. instead of 25 ° C. The results obtained are indicated by the symbol VHR-2.

(11) Flicker rate (measured at 25 ° C.;%): A multimedia display tester 3298F manufactured by Yokogawa Electric Corporation was used for the measurement. The light source was an LED. The sample was placed in an FFS element in a normally black mode in which the distance (cell gap) between the two glass substrates was 3.5 μm and the rubbing direction was antiparallel. The device was sealed with an UV curable adhesive. A voltage was applied to this device, and the voltage at which the amount of light transmitted through the device was maximized was measured. While applying this voltage to the element, the sensor unit was brought close to the element and the displayed flicker rate was read.

The method for measuring physical properties may differ between a sample having a positive dielectric anisotropy and a sample having a negative dielectric anisotropy. The measuring method when the dielectric anisotropy is positive is described in measurement (12a) to measurement (16a). When the dielectric anisotropy was negative, it was described in measurement (12b) to measurement (16b).

(12a) Viscosity (rotational viscosity; γ1; measured at 25 ° C.; mPa · s; sample with positive dielectric anisotropy): Measured by M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995) was followed. 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 of 16 V to 19.5 V was applied to this device in 0.5 V increments. After no application for 0.2 seconds, application was repeated under the conditions of only one square wave (rectangular 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. Rotational viscosity values were obtained from the paper by Imai et al., Equation (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.

(12b) Viscosity (rotational viscosity; γ1; measured at 25 ° C; mPa · s; sample with negative dielectric anisotropy): The measurement was performed by M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995) was followed. The sample was placed in a VA element having a distance (cell gap) between two glass substrates of 20 μm. A stepwise application of 39 V to 50 V was applied to this device in 1 V increments. After no application for 0.2 seconds, application was repeated under the conditions of only one square wave (rectangular 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. Rotational viscosity values were obtained from the paper by Imai et al., Equation (8) on page 40. The permittivity anisotropy required for this calculation was measured in the section of permittivity anisotropy below.

(13a) Permittivity anisotropy (Δε; measured at 25 ° C; sample with positive permittivity anisotropy): The distance (cell gap) between the two glass substrates is 9 μm, and the twist angle is 80 degrees. A sample was placed in a TN element. 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⊥.

(13b) Permittivity anisotropy (Δε; measured at 25 ° C; sample with 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.

(14a) Elastic constant (K; measured at 25 ° C.; pN; sample with positive dielectric anisotropy): An HP4284A type 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. An electric charge of 0 V to 20 V was applied to this device, and the capacitance (C) and the applied voltage (V) were measured. These measured values were fitted using the equation (2.98) and equation (2.11) on page 75 of "Liquid Crystal Device Handbook" (Nikkan Kogyo Shimbun), and the equation (2.99). The values of K ₁₁ and K ₃₃ were obtained from. Next, K ₂₂ was calculated using the values of K ₁₁ and K ₃₃ obtained earlier in the equation (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.

(14b) Elastic constants (K ₁₁ and K ₃₃ ; measured at 25 ° C; pN; sample with negative dielectric anisotropy): An EC-1 type elastic constant measuring instrument manufactured by Toyo Technica Co., Ltd. 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. An electric charge of 20 V to 0 V was applied to this device, and the capacitance (C) and the applied voltage (V) were measured. These values are fitted using the equation (2.98) and equation (2.11) on page 75 of the "Liquid Crystal Device Handbook" (Nikkan Kogyo Shimbun), and from the equation (2.10). The value of the elastic constant was obtained.

(15a) Threshold voltage (Vth; measured at 25 ° C.; V; sample with positive dielectric 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%.

(15b) Threshold voltage (Vth; measured at 25 ° C.; V; sample with negative dielectric 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%.

(16a) Response time (τ; measured at 25 ° C.; ms; sample with positive dielectric 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.

(16b) Response time (τ; measured at 25 ° C.; ms; sample with negative dielectric 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 (cell gap) between the two glass substrates was 3.2 μm and the rubbing direction was antiparallel. The device 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).

[Synthesis Example 1]
Synthesis of compound (1a-1)

[First Step] Synthesis of Compound (1a-a) THF (100 g, 518.16 mmol) was added to a suspension in which THF (100 ml) was added to magnesium (12.594 g, 518.16 mmol). The solution dissolved in (150 ml) was added dropwise at 20 ° C to 40 ° C. Thirty minutes after the completion of the dropping, the mixture was ice-cooled, CuI (4.93 g, 25.91 mmol) was added, and a solution of methyl iodide (73.547 g, 518.16 mmol) in THF (100 ml) was added at 0 ° C. to 0 ° C. It was added dropwise at 10 ° C. After stirring overnight at room temperature, the mixture was poured into a saturated aqueous solution of ammonium chloride (300 ml) and extracted with pentane (100 ml × 3). The extract was washed with brine (50 ml x 2), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by atmospheric distillation (100-105 ° C.) to give compound (1a-a) (45.0 g, 68%) as a pale pink oil.

Second step: Synthesis of compound (1ab) s-Butyllithium (191.48 ml, 204) in a solution of compound (1a-a) (25.000 g, 195.13 mmol) in THF (500 ml) at −70 ° C. or lower. .88 mmol) was added dropwise. After 1 hour, trimethylbolate (21.290 g, 204.88 mmol) was added dropwise. After stirring overnight at room temperature, 2NHCl (100 ml) was added and then extracted with ethyl acetate (100 ml x 3). The extract was washed with brine (50 ml x 2), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained crude crystals were washed with heptane to obtain compound (1ab) (30.0 g, 89%) as colorless crystals.

Third step: Synthesis of compound (1ac) 2-bromo-6-fluoro in a suspension of sodium hydride (26.865 g, 615.71 mmol) (55%) and THF (270 ml) under ice cooling. A solution of phenol (98.0 g, 513.09 mmol) in THF (500 ml) was added dropwise. After 1 hour, a solution of chloromethyl methyl ether (MOMCl; 52.180 g, 615.71 mmol) in THF (250 ml) was added dropwise. After stirring overnight at room temperature, the mixture was poured into ice water (1000 ml) and extracted with ethyl acetate (300 ml x 3). The extract was washed with brine (200 ml x 2), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel chromatography (toluene) to give compound (15-e) (16.5 g, 95%) as colorless crystals. Purification by silica gel chromatography (toluene: heptane = 1: 1) gave 1-bromo-3-fluoro-2-methoxymethyl (1a-c) (117.68 g, 98%) as a colorless oil.

Fourth step: Synthesis of compound (1ad) Compound (1ab) (24.578 g, 142.95 mmol), 1-bromo-3-fluoro-2-methoxymethyl (4-c) (28.0 g,). 119.12 mmol), Pd-132 (0.253 g, 0.360 mmol), potassium carbonate (32.927 g, 238.24 mmol), tetrabutylammonium bromide (9.601 g, 29.780 mmol) toluene (120 ml), isopropyl alcohol. A mixture of (120 ml) and water (60 ml) was heated and stirred for 4 hours. It was poured into water (200 ml) and separated into an organic layer and an aqueous layer. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography (toluene: heptane = 3: 1) to give compound (1ad) (33.62 g, 89%) as colorless crystals.

Fifth step: Synthesis of compound (1a-e) 6N-HCl (60 ml) was added to a solution of compound (1ad) (30.0 g, 106.28 mmol) in THF (200 ml), and the mixture was stirred at room temperature. After 24 hours, the reaction mixture was extracted with ethyl acetate (100 mlx3). The extract was washed with brine (50 ml x 2), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel chromatography (toluene) to give compound (1ae) (29 g, 99%) as colorless crystals.

Sixth Step: Synthesis of Compound (1af) Pyridine (26.250 g, 331.85 mmol) in a solution of compound (1a-e) (26.35 g, 58.46 mmol) in methylene chloride (300 ml) under ice-cooling. , Trifluoromethanesphonic anhydride (34.329 g, 121.68 mmol) was added. After stirring overnight at room temperature, it was poured into water (300 ml) to separate the organic layer and the aqueous layer. The aqueous layer was further extracted with methylene chloride (100 ml x 3). The combined organic layer was washed with brine (50 ml x 2) and saturated aqueous sodium hydrogen carbonate (50 ml x 2), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel chromatography (toluene: heptane = 4: 1) to give compound (1af) (32.3 g, 79%) as colorless crystals.

Step 7: Synthesis of compound (1a-g) Compound (1a-f) (32.3 g, 87.23 mmol), ethyl 3-mercaptopropionate (11.706 g, 87.23 mmol), N, N-diisopropylethylamine (DIPEA; 12.402 g, 95.96 mmol), 1,1'-bis (diphenylphosphino) ferrocene (dppf; 0.967 g, 1.74 mmol), tris (dibenzylideneacetone) dipalladium (0) (0. A mixture of 799 g, 0.87 mmol) and toluene (100 ml) was heated to reflux. After 6 hours, it was poured into water and extracted with toluene (100 ml x 2). The extract was washed with brine (50 ml x 2), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel chromatography (toluene) to give compound (1 ag) (29 g, 94%) as colorless crystals.

Eighth step: Synthesis of compound (1ah) t-butoxypotassium (11.779 g, 104.97 mmol) is added to a solution of compound (1a-g) (31 g, 87.47 mmol) in THF (100 ml) and heated to reflux. did. After 8 hours, it was poured into water and extracted with toluene (100 ml x 3). The extract was washed with brine (50 ml x 2), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel chromatography (toluene) to give compound (1ah) (16.85 g, 82%) as colorless crystals.

9th step: Synthesis of compound (1a-i) s-Butyllithium (67.22 ml, 71.93 mmol) (1.) In a solution of compound (1a-h) (16.85 g, 71.93 mmol) in THF (300 ml). 07 mol / l) was added dropwise at −70 ° C. or lower. After 1 hour, a solution of trimethylbolate (7.474 g, 71.93 mmol) in THF (10 ml) was added dropwise below −70 ° C. After 1 hour, the temperature was returned to room temperature, and then acetic acid (8.639 g, 143.85 mmol) was added dropwise. After 30 minutes, 30% hydrogen peroxide solution (4.893 g, 143.85 mmol) was added dropwise. After stirring overnight at room temperature, it was poured into water (200 ml) and extracted with ethyl acetate (100 ml x 3). The extract was washed with brine (50 ml x 2), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel chromatography (toluene: ethyl acetate = 3: 1) to give compound (1a-i) (15 g, 83%) as colorless crystals.

Step 10: Synthesis of compound (1a-j) Potassium carbonate (8.934 g, 63.93 mmol) in a solution of compound (1a-i) (8.00 g, 31.97 mmol) in N, N-dimethylformamide (100 ml). ), Ethyl iodide (5.983 g, 38.36 mmol) was added, and the mixture was heated and stirred at 70 to 80 ° C. After 3 hours, the temperature was returned to room temperature, poured into water (100 ml), and extracted with ethyl acetate (100 ml x 3). The extract was washed with brine (50 ml x 2), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel chromatography (toluene: ethyl acetate = 4: 1) to give compound (1a-j) (7.1 g, 80%) as colorless crystals.

Step 11: Synthesis of compound (1ak) s-Butyllithium (36.27 ml, 38.80 mmol) (1) in a solution of compound (1a-j) (9.0 g, 32.34 mmol) in THF (200 ml). .07 mol / l) was added dropwise at −70 ° C. or lower. After 1 hour, a solution of trimethylborate (4.032 g, 38.80 mmol) in THF (10 ml) was added dropwise below −70 ° C. After 1 hour, the temperature was returned to room temperature, and then acetic acid (3.884 g, 64.67 mmol) was added dropwise. After 30 minutes, 30% hydrogen peroxide solution (7.333 g, 64.67 mmol) was added dropwise. After stirring overnight at room temperature, the mixture was poured into water (100 ml) and extracted with ethyl acetate (100 ml x 3). The extract was washed with brine (50 ml x 2), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel chromatography (toluene: ethyl acetate = 9: 1) to give compound (1ak) (7.10 g, 75%) as colorless crystals.

Step 12: Synthesis of compound (1a-l) Potassium carbonate (6.668 g, 48.246 mmol) in a solution of compound (1ak) (7.10 g, 24.123 mmol) in N, N-dimethylformamide (100 ml). ), Iodine propane (5.327 g, 28.948 mmol) was added, and the mixture was heated and stirred at 70 to 80 ° C. After 3 hours, the temperature was returned to room temperature, poured into water (100 ml), and extracted with ethyl acetate (100 ml x 3). The extract was washed with brine (50 ml x 2), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel chromatography (toluene: ethyl acetate = 4: 1) to give compound (1a-l) (8.0 g, 95%) as colorless crystals.

^{1 1} H-NMR (CDCl ₃ , ppm): δ1.00 (3H, t, J = 7.4Hz), 1.47 (3H, t, J = 7.0Hz), 1.50-1.58 (2H) , M), 1.77-1.82 (2H, m), 2.39 (3H, s), 4.12 (2H, t, J = 6.3Hz), 4.18 (2H, q, J) = 7.4Hz,), 7.06 (1H, dd, J = 8.0, 8.3Hz,), 7.51 (1H, s), 7.7 (d, 1H, J = 8.5Hz) ..

¹⁹ F-NMR (δppm; CDCl3): -133.02 (s, 1F), 136.27 (d, J = 8.5Hz, 1F).

[Comparative Example 1]
The compound (1a-1) synthesized in Synthesis Example 1 was compared with a similar compound shown in Table 2. Compound A was selected as a similar compound. Compound A is the ninth compound described in JP-A-2015-206042 (Patent Document 1), page 144, Example M1. Compound (1a-1) has methyl on the benzene ring, while compound A has no methyl.

Compound (1a-1): T _NI : 32.3 ° C., Δn: 0.1803. Compound A: T _NI : 78.3 ° C., Δn: 0.2103.

According to the measurement (3), the compatibility between the compound (1a-1) and the compound A was measured. The sample (20% by weight) was dissolved in the mother liquid crystal (B) (80% by weight), stored in a freezer at −10 ° C., and whether or not crystals were precipitated was observed every 24 hours. The results are summarized in Table 2. Crystals of Compound A were precipitated within 1 day. On the other hand, the compound (1a-1) did not precipitate crystals for 4 days. From this result, it was found that the compound (1a-1) had better compatibility.

It is possible to synthesize the compounds shown below by referring to the method described in the synthesis example and the section “2. Synthesis of compound (1)”.

Examples of the composition are shown below. The present invention includes a mixture of Use Example 1 and Use Example 2. The present invention also includes a mixture of at least two of the compositions of Examples. The component compounds are represented by symbols based on the definitions in Table 3 below. In Table 3, the configuration for 1,4-cyclohexylene is trans. The number in parentheses after the symbolized compound represents the chemical formula to which the compound belongs. The symbol (-) means a liquid crystal compound different from the compounds (1) to (15). The proportion (percentage) of the liquid crystal compound is a weight percentage (% by weight) based on the weight of the liquid crystal composition containing no additives. Finally, the physical property values of the composition are summarized. The physical properties were measured according to the method described above, and the measured values were described as they were (without extrapolation).

[Usage example 1]
2O-dbt (1F, 3Me, 8F) -O46 6%
1-BB-3 (2-8) 7%
1-BB-5 (2-8) 7%
2-BTB-1 (2-10) 3%
3-HHB-1 (3-1) 7%
3-HHB-O1 (3-1) 5%
3-HHB-3 (3-1) 12%
3-HHB-F (13-1) 3%
2-HHB (F) -F (13-2) 6%
3-HHB (F) -F (13-2) 6%
5-HHB (F) -F (13-2) 6%
3-HHB (F, F) -F (13-3) 6%
3-HHEB-F (13-10) 5%
5-HHEB-F (13-10) 4%
2-HB-C (15-1) 5%
3-HB-C (15-1) 12%
NI = 92.1 ° C; η = 20.3 mPa · s; Δn = 0.113; Δε = 4.2.

[Usage example 2]
2O-dbt (1F, 4Me, 8F) -O48%
3-HH-4 (2-1) 11%
7-HB-1 (2-5) 3%
5-HB-O2 (2-5) 4%
5-HBB (F) B-2 (4-5) 6%
5-HBB (F) B-3 (4-5) 5%
3-HB-CL (12-2) 9%
3-HHB (F, F) -F (13-3) 3%
3-HBB (F, F) -F (13-24) 26%
5-HBB (F, F) -F (13-24) 25%

[Usage example 3]
2O-dbt (1F, 3Me, 8F) -O4 3%
1V2-HH-1 (2-1) 3%
1V2-HH-3 (2-1) 4%
7-HB (F, F) -F (12-4) 3%
2-HHB (F) -F (13-2) 10%
3-HHB (F) -F (13-2) 8%
5-HHB (F) -F (13-2) 10%
2-HBB-F (13-22) 4%
3-HBB-F (13-22) 4%
5-HBB-F (13-22) 3%
2-HBB (F) -F (13-23) 7%
3-HBB (F) -F (13-23) 9%
5-HBB (F) -F (13-23) 16%
3-HBB (F, F) -F (13-24) 6%
5-HBB (F, F) -F (13-24) 10%
NI = 83.2 ° C; η = 26.1 mPa · s; Δn = 0.113; Δε = 5.3.

[Usage example 4]
2O-dbt (1F, 4Me, 8F) -O4 10%
2-HH-3 (2-1) 3%
3-HH-4 (2-1) 10%
1O1-HBBH-5 (4-1) 3%
5-HB-CL (12-2) 14%
3-HHB-F (13-1) 3%
3-HHB-CL (13-1) 3%
4-HHB-CL (13-1) 3%
3-HHB (F) -F (13-2) 10%
4-HHB (F) -F (13-2) 8%
5-HHB (F) -F (13-2) 8%
7-HHB (F) -F (13-2) 7%
5-HBB (F) -F (13-23) 4%
3-HHBB (F, F) -F (14-6) 2%
4-HHBB (F, F) -F (14-6) 3%
5-HHBB (F, F) -F (14-6) 3%
3-HH2BB (F, F) -F (14-15) 3%
4-HH2BB (F, F) -F (14-15) 3%

[Usage example 5]
2O-dbt (1F, 3Me, 8F) -O4 4%
V-HBB-2 (3-4) 9%
1O1-HBBH-4 (4-1) 4%
1O1-HBBH-5 (4-1) 4%
3-HHB (F, F) -F (13-3) 8%
3-H2HB (F, F) -F (13-15) 8%
4-H2HB (F, F) -F (13-15) 7%
5-H2HB (F, F) -F (13-15) 8%
3-HBB (F, F) -F (13-24) 11%
5-HBB (F, F) -F (13-24) 18%
3-H2BB (F, F) -F (13-27) 9%
5-HHBB (F, F) -F (14-6) 4%
3-HH2BB (F, F) -F (14-15) 3%
5-HHEBB-F (14-17) 3%
NI = 105.2 ° C.; η = 34.0 mPa · s; Δn = 0.125; Δε = 7.5.

[Usage example 6]
2O-dbt (1F, 4Me, 8F) -O4 3%
5-HBBH-3 (4-1) 3%
3-HB (F) BH-3 (4-2) 4%
5-HB-F (12-2) 12%
6-HB-F (12-2) 9%
7-HB-F (12-2) 6%
2-HHB-OCF3 (13-1) 5%
3-HHB-OCF3 (13-1) 6%
4-HHB-OCF3 (13-1) 7%
5-HHB-OCF3 (13-1) 6%
3-HHB (F, F) -OCF2H (13-3) 4%
3-HHB (F, F) -OCF3 (13-3) 5%
3-HH2B-OCF3 (13-4) 5%
5-HH2B-OCF3 (13-4) 4%
3-HH2B (F) -F (13-5) 4%
3-HBB (F) -F (13-23) 10%
5-HBB (F) -F (13-23) 7%

[Usage example 7]
2O-dbt (1F, 3Me, 8F) -O4 4%
2-HH-5 (2-1) 5%
3-HH-4 (2-1) 4%
5-B (F) BB-2 (3-8) 4%
5-HB-CL (12-2) 8%
3-HHB (F, F) -F (13-3) 10%
3-HHEB (F, F) -F (13-12) 9%
4-HHEB (F, F) -F (13-12) 6%
5-HHEB (F, F) -F (13-12) 5%
3-HBB (F, F) -F (13-24) 15%
5-HBB (F, F) -F (13-24) 10%
2-HBEB (F, F) -F (13-39) 5%
3-HBEB (F, F) -F (13-39) 5%
5-HBEB (F, F) -F (13-39) 5%
3-HHBB (F, F) -F (14-6) 5%
NI = 78.8 ° C.; η = 25.4 mPa · s; Δn = 0.109; Δε = 8.4.

[Usage example 8]
2O-dbt (1F, 4Me, 8F) -O49 9%
V2-HHB-1 (3-1) 4%
3-HB-CL (12-2) 5%
5-HB-CL (12-2) 3%
3-HHB-OCF3 (13-1) 4%
5-HHB (F) -F (13-2) 4%
V-HHB (F) -F (13-2) 4%
3-H2HB-OCF3 (13-13) 4%
5-H2HB (F, F) -F (13-15) 4%
5-H4HB-OCF3 (13-19) 13%
5-H4HB (F, F) -F (13-21) 8%
3-H4HB (F, F) -CF3 (13-21) 7%
5-H4HB (F, F) -CF3 (13-21) 9%
2-H2BB (F) -F (13-26) 6%
3-H2BB (F) -F (13-26) 9%
3-HBEB (F, F) -F (13-39) 7%

[Usage example 9]
2O-dbt (1F, 3Me, 8F) -O4 4%
3-HH-4 (2-1) 10%
3-HH-5 (2-1) 5%
3-HB-O2 (2-5) 13%
3-HHB-1 (3-1) 8%
3-HHB-O1 (3-1) 7%
5-HB-CL (12-2) 15%
7-HB (F, F) -F (12-4) 3%
2-HHB (F) -F (13-2) 8%
3-HHB (F) -F (13-2) 5%
5-HHB (F) -F (13-2) 6%
3-HHB (F, F) -F (13-3) 6%
3-H2HB (F, F) -F (13-15) 4%
4-H2HB (F, F) -F (13-15) 6%
NI = 73.2 ° C.; η = 16.5 mPa · s; Δn = 0.079; Δε = 2.3.

[Usage example 10]
2O-dbt (1F, 4Me, 8F) -O4 3%
3-HH-4 (2-1) 8%
3-HH-5 (2-1) 9%
3-HHB-3 (3-1) 12%
5-HB-CL (12-2) 5%
7-HB (F) -F (12-3) 5%
2-HHB (F, F) -F (13-3) 5%
3-HHB (F, F) -F (13-3) 7%
3-HHEB-F (13-10) 7%
5-HHEB-F (13-10) 7%
3-HHEB (F, F) -F (13-12) 10%
4-HHEB (F, F) -F (13-12) 5%
3-GHB (F, F) -F (13-109) 5%
4-GHB (F, F) -F (13-109) 6%
5-GHB (F, F) -F (13-109) 6%

[Usage example 11]
2O-dbt (1F, 3Me, 8F) -O45%
2O-dbt (1F, 4Me, 8F) -O4 4%
3-HH-VFF (2-1) 3%
5-HH-VFF (2-1) 23%
2-BTB-1 (2-10) 8%
3-HHB-1 (3-1) 4%
VFF-HHB-1 (3-1) 8%
VFF2-HHB-1 (3-1) 11%
3-H2BTB-2 (3-17) 7%
3-H2BTB-3 (3-17) 5%
3-H2BTB-4 (3-17) 4%
3-HB-C (15-1) 13%
1V2-BEB (F, F) -C (15-15) 5%

[Usage example 12]
2O-dbt (1F, 4Me, 8F) -O45 5%
3-HH-V (2-1) 32%
3-HH-V1 (2-1) 3%
5-HH-V (2-1) 3%
3-HHB-1 (3-1) 5%
V-HHB-1 (3-1) 5%
2-BB (F) B-3 (3-6) 5%
3-HHEH-5 (3-13) 4%
1V2-BB-F (12-1) 4%
3-BB (F, F) XB (F, F) -F (13-97) 10%
3-BB (2F, 3F) XB (F, F) -F (13-114) 3%
3-HHBB (F, F) -F (14-6) 3%
3-HBBXB (F, F) -F (14-32) 3%
5-HB (F) B (F, F) XB (F, F) -F (14-41) 5%
3-BB (F) B (F, F) XB (F, F) -F (14-47) 3%
4-BB (F) B (F, F) XB (F, F) -F (14-47) 4%
5-BB (F) B (F, F) XB (F, F) -F (14-47) 3%

[Usage example 13]
2O-dbt (1F, 3Me, 8F) -O45%
3-HH-V (2-1) 27%
3-HH-V1 (2-1) 6%
V-HH-V1 (2-1) 6%
3-HHB-1 (3-1) 5%
V-HHB-1 (3-1) 4%
1-BB (F) B-2V (3-6) 4%
3-HHEH-5 (3-13) 3%
1V2-BB-F (12-1) 3%
3-BB (F, F) XB (F, F) -F (13-97) 5%
3-HHXB (F, F) -CF3 (13-100) 3%
3-GB (F, F) XB (F, F) -F (13-113) 4%
3-GB (F) B (F, F) -F (13-116) 3%
3-HHBB (F, F) -F (14-6) 4%
3-BB (F) B (F, F) XB (F, F) -F (14-47) 3%
4-BB (F) B (F, F) XB (F, F) -F (14-47) 7%
5-BB (F) B (F, F) XB (F, F) -F (14-47) 3%
3-GB (F) B (F, F) XB (F, F) -F (14-57) 5%
NI = 81.4 ° C; η = 17.6 mPa · s; Δn = 0.111; Δε = 6.7.

[Usage example 14]
2O-dbt (1F, 4Me, 8F) -O4 3%
3-HH-V (2-1) 32%
3-HH-V1 (2-1) 5%
3-HHB-1 (3-1) 4%
V-HHB-1 (3-1) 5%
3-HBB-2 (3-4) 3%
V2-BB (F) B-1 (3-6) 4%
3-HHEH-3 (3-13) 3%
3-HHEH-5 (3-13) 3%
1V2-BB-F (12-1) 3%
3-BB (F, F) XB (F, F) -F (13-97) 4%
3-GB (F, F) XB (F, F) -F (13-113) 3%
3-HHBB (F, F) -F (14-6) 3%
3-HBB (F, F) XB (F, F) -F (14-38) 4%
3-BB (F) B (F, F) XB (F) -F (14-46) 3%
4-BB (F) B (F, F) XB (F, F) -F (14-47) 3%
5-BB (F) B (F, F) XB (F, F) -F (14-47) 3%
3-GB (F) B (F, F) XB (F, F) -F (14-57) 5%
4-GB (F) B (F, F) XB (F, F) -F (14-57) 3%
5-GB (F) B (F, F) XB (F, F) -F (14-57) 4%

[Usage example 15]
2O-dbt (1F, 3Me, 8F) -O4 4%
3-HH-V (2-1) 30%
3-HH-V1 (2-1) 5%
3-HHB-1 (3-1) 4%
V-HHB-1 (3-1) 4%
V2-BB (F) B-1 (3-6) 4%
3-HHEH-5 (3-13) 3%
3-HHEBH-3 (4-6) 4%
1V2-BB-F (12-1) 4%
3-BB (F) B (F, F) -F (13-69) 3%
3-BB (F, F) XB (F, F) -F (13-97) 5%
3-HHBB (F, F) -F (14-6) 3%
5-HB (F) B (F, F) XB (F, F) -F (14-41) 4%
4-BB (F) B (F, F) XB (F, F) -F (14-47) 5%
5-BB (F) B (F, F) XB (F, F) -F (14-47) 3%
2-dhBB (F, F) XB (F, F) -F (14-50) 2%
3-dhBB (F, F) XB (F, F) -F (14-50) 4%
3-GBB (F) B (F, F) -F (14-55) 3%
4-GBB (F) B (F, F) -F (14-55) 3%
3-BB (F, F) XB (F) B (F, F) -F (14-56) 3%
NI = 83.2 ° C; η = 21.7 mPa · s; Δn = 0.106; Δε = 5.3.

[Usage example 16]
2O-dbt (1F, 4Me, 8F) -O47%
3-HH-V (2-1) 31%
3-HH-V1 (2-1) 3%
3-HHB-1 (3-1) 4%
V-HHB-1 (3-1) 4%
V2-BB (F) B-1 (3-6) 3%
3-HHEH-5 (3-13) 3%
1V2-BB-F (12-1) 3%
3-BB (F) B (F, F) -CF3 (13-69) 3%
3-BB (F, F) XB (F, F) -F (13-97) 4%
3-HHXB (F, F) -F (13-100) 5%
3-GB (F, F) XB (F, F) -F (13-113) 3%
3-GB (F) B (F) -F (13-115) 3%
3-HHBB (F, F) -F (14-6) 4%
5-HB (F) B (F, F) XB (F, F) -F (14-41) 3%
3-GB (F) B (F, F) XB (F, F) -F (14-57) 3%
3-GBB (F, F) XB (F, F) -F (14-58) 3%
4-GBB (F, F) XB (F, F) -F (14-58) 4%
5-GBB (F, F) XB (F, F) -F (14-58) 3%
3-GB (F) B (F) B (F) -F (14-59) 4%

The liquid crystal composition containing the compound (1) can be used for a liquid crystal monitor, a liquid crystal television, or the like.

Claims (15)

A compound represented by the formula (1).

In equation (1)
R ¹ and R ² are independently hydrogen, fluorine, chlorine, or alkyl having 1 to 16 carbon atoms, in which at least one -CH ₂ − is -O-, -CO-, -COO. It may be replaced by −, −OCO−, −OCOO−, or −Si (CH ₃ ) ₂₋ , and at least one −CH ₂ CH ₂₋ is replaced by −CH = CH− or −C≡C−. In these groups, at least one hydrogen may be replaced by fluorine, chlorine, -CF ₃ , or -C≡N;
A ¹ and A ² are independently 1,2-cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4. -Cycloheptylene, 1,5-cyclooctylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, 1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2, 5-Diyl, decahydronaphthalene-2,6, -diyl, tetrahydronaphthalene-2,6-diyl, or naphthalene-2,6-diyl, in which at least one hydrogen on the aromatic ring is the hydrogen. It may be replaced with fluorine, chlorine, -CF ₃ , -CHF ₂ , -CH ₂ F, -OCF ₃ , -OCHF ₂ , -OCH ₂ F, or -C≡N;
Z ¹ and ^{Z 2} are independently a single bond or alkylene having 1 to 6 carbon atoms, one of _-CH 2 -, -O -, - CO -, - COO-, or replaced by -OCO- Alternatively, one −CH ₂ CH ₂₋ may be replaced by −CH = CH− or −C≡C−, and in these divalent groups, at least one hydrogen is replaced by fluorine or chlorine. May be;
m ¹ and n ¹ are independently 0, 1, or 2, and the sum of m ¹ and n ¹ is 3 or less;
W _{is, -CH 2 -, - CF 2} -, - CO -, - O -, - S-, or -SO ₂ - and is;
X is hydrogen or fluorine;
Y ¹ , Y ² , Y ³ , and Y ⁴ are independently hydrogen or methyl, and at least one of Y ¹ , Y ² , Y ³ , and Y ⁴ is methyl; W is -O-. At one time, at least two of Y ¹ , Y ² , Y ³ , and Y ⁴ are methyl. In the formula (1) according to claim 1,
R ¹ and R ² are independently hydrogen or alkyl having 1 to 14 carbon atoms, in which one or two -CH _2- may be replaced by -O-. CH ₂ CH ₂ − may be replaced by −CH = CH −, and in these groups at least one hydrogen may be replaced by fluorine;
A ¹ and A ² are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, 1,4- Phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, or naphthalene-2,6-diyl, in which at least one hydrogen on the aromatic ring may be replaced by fluorine. Often;
Z ¹ and Z ² are independently single-bonded, -COO-, -OCO-, -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF _2- , -CH ₂ CH _2- , _{-CF 2 CF 2 -, - CH} = CH -, - CF = CF -, - C≡C -, - (CH 2) 4 -, or _{-CH 2} CH = CHCH 2 - and is;
m ¹ and n ¹ are independently 0, 1, or 2, and the sum of m ¹ and n ¹ is 3 or less;
W is -CH _2- , -CO-, -S-, or -SO _2- ;
X is hydrogen or fluorine;
The ^{first aspect of claim 1} , wherein Y ¹ , Y ² , Y ³ , and Y ⁴ are independently hydrogen or methyl, and at least one of Y ¹ , Y ² , Y ³ , and Y ⁴ is methyl. Compound. In the formula (1) according to claim 1,
R ¹ and R ² are independently hydrogen or alkyl having 1 to 14 carbon atoms, in which one or two -CH _2- may be replaced by -O-. CH ₂ CH ₂ − may be replaced by −CH = CH −, and in these groups at least one hydrogen may be replaced by fluorine;
A ¹ and A ² are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, 1,4- Phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, or naphthalene-2,6-diyl, in which at least one hydrogen on the aromatic ring may be replaced by fluorine. Often;
Z ¹ and Z ² are independently single-bonded, -COO-, -OCO-, -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF _2- , -CH ₂ CH _2- , _{-CF 2 CF 2 -, - CH} = CH -, - CF = CF -, - C≡C -, - (CH 2) 4 -, or _{-CH 2} CH = CHCH 2 - and is;
m ¹ and n ¹ are independently 0, 1, or 2, and the sum of m ¹ and n ¹ is 3 or less;
W is -S-;
X is fluorine;
In claim ¹ or ² , Y ¹ , Y ² , Y ³ , and Y ⁴ are independently hydrogen or methyl, and at least one of Y ¹ , Y ² , Y ³ , and Y ⁴ is methyl. The compound described. In the formula (1) according to claim 1,
R ¹ and R ² are independently alkyls with 1 to 8 carbons, alkoxys with 1 to 8 carbons, or alkenyls with 2 to 8 carbons;
A ¹ and A ² are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, 1,4- Phenylene, 1,4-phenylene, pyridine-2,5-diyl, or pyrimidine-2,5-diyl in which one or two hydrogens have been replaced with fluorine;
Z ¹ and Z ² are independently single-bonded, -COO-, -OCO-, -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF _2- , -CH ₂ CH _2- , -CH = CH -, - C≡C-, or - _{(CH 2) 4} - a and;
m ¹ and n ¹ are independently 0, 1, or 2, and the sum of m ¹ and n ¹ is 3 or less;
W is -CH _2- , -CO-, or -S-;
X is hydrogen or fluorine;
In claim ¹ or ² , Y ¹ , Y ² , Y ³ , and Y ⁴ are independently hydrogen or methyl, and at least one of Y ¹ , Y ² , Y ³ , and Y ⁴ is methyl. The compound described. In the formula (1) according to claim 1,
R ¹ and R ² are independently alkyls with 1 to 8 carbons, alkoxys with 1 to 8 carbons, or alkenyls with 2 to 8 carbons;
A ¹ and A ² are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, 1,4- Phenylene, 1,4-phenylene, pyridine-2,5-diyl, or pyrimidine-2,5-diyl in which one or two hydrogens have been replaced with fluorine;
Z ¹ and Z ² are independently single-bonded, -COO-, -OCO-, -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF _2- , -CH ₂ CH _2- , -CH = CH -, - C≡C-, or - _{(CH 2) 4} - a and;
m ¹ and n ¹ are independently 0, 1, or 2, and the sum of m ¹ and n ¹ is 3 or less;
W is -S-;
X is fluorine;
In claim ¹ or ² , Y ¹ , Y ² , Y ³ , and Y ⁴ are independently hydrogen or methyl, and at least one of Y ¹ , Y ² , Y ³ , and Y ⁴ is methyl. The compound described. In the formula (1) according to claim 1,
R ¹ and R ² are independently alkyl with 1 to 5 carbons, alkoxy with 1 to 5 carbons, or alkenyl with 2 to 5 carbons;
A ¹ and A ² are independently 1,4-cyclohexylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,3-difluoro-1. , 4-Phenylene;
Z ¹ and Z ² are independently single-bonded, -CH ₂ O-, -OCH _2- , -CH ₂ CH _2- , or -CH = CH-;
m ¹ and n ¹ are independently 0, 1, or 2, and the sum of m ¹ and n ¹ is 3 or less;
W is -S-;
X is hydrogen or fluorine;
In claim ¹ or ² , Y ¹ , Y ² , Y ³ , and Y ⁴ are independently hydrogen or methyl, and at least one of Y ¹ , Y ² , Y ³ , and Y ⁴ is methyl. The compound described. In the formula (1) according to claim 1,
R ¹ and R ² are independently alkyl with 1 to 5 carbons, alkoxy with 1 to 5 carbons, or alkenyl with 2 to 5 carbons;
A ¹ and A ² are independently 1,4-cyclohexylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,3-difluoro-1. , 4-Phenylene;
Z ¹ and Z ² are independently single-bonded, -CH ₂ O-, -OCH _2- , -CH ₂ CH _2- , or -CH = CH-;
m ¹ and n ¹ are independently 0, 1, or 2, and the sum of m ¹ and n ¹ is 3 or less;
W is -S-;
X is fluorine;
In claim ¹ or ² , Y ¹ , Y ² , Y ³ , and Y ⁴ are independently hydrogen or methyl, and at least one of Y ¹ , Y ² , Y ³ , and Y ⁴ is methyl. The compound described. The compound according to claim 1, which is represented by any one of the formulas (1a) to (1i).

In the formula ^{(1a) (1i), R} 1 and ^{R 2} are each independently alkyl having 1 to 5 carbon atoms, alkenyl alkoxy of 1 to 5 carbon atoms, or a carbon number of 2 ^{5; Y} 1, Y ^{2, Y 3,} and ^{Y 4} are independently hydrogen or ^methyl, Y ^1, Y 2, ^{Y 3,} and at least one of ^{Y 4} is methyl. The compound according to claim 1, which is represented by the formula (1j) or (1k).

In formula (1j) or (1k), R ¹ and R ² are independently an alkyl having 1 to 5 carbon atoms, an alkoxy having 1 to 5 carbon atoms, or an alkenyl having 2 to 5 carbon atoms. A liquid crystal composition containing at least one compound according to any one of claims 1 to 9. The liquid crystal composition according to claim 10, further comprising at least one compound selected from the compounds represented by the formulas (2) to (4).

In equations (2) to (4)
R ¹¹ and R ¹² are independently alkyls with 1 to 10 carbons or alkenyl with 2 to 10 carbons, in which at least one -CH ₂ − is replaced with -O-. Well, in these groups, at least one hydrogen may be replaced with 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, -COO-, -CH ₂ CH _2- , -CH = CH-, or -C≡C-. The liquid crystal composition according to claim 10 or 11, further comprising at least one compound selected from the compounds represented by the formulas (5) to (11).

In equations (5) to (11)
R ¹³ , R ¹⁴ , and R ¹⁵ are independently alkyls with 1 to 10 carbon atoms or alkenyl with 2 to 10 carbon atoms, in which at least one -CH ₂ − is -O-. It may be replaced, in these groups, at least one hydrogen may be replaced by fluorine, and R ¹⁵ may be hydrogen or fluorine;
Ring C ¹ , Ring C ² , Ring C ³ , and Ring C ⁴ independently replace 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, at least one hydrogen with fluorine. 1,4-Phenylene, tetrahydropyran-2,5-diyl, or decahydronaphthalene-2,6-diyl;
Ring ^{C 5} and ring ^{C 6} are each independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl or decahydronaphthalene, 2,6 -Jeil;
^{Z 14, Z 15, Z 16} , and ^{Z 17} are independently a single _{bond, -COO -, - CH 2 O} -, - OCF 2 -, - CH 2 CH 2 -, or -OCF ₂ CH ₂ CH ₂ -And;
L ¹¹ and L ¹² 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 10 to 12, further containing at least one compound selected from the compounds represented by the formulas (12) to (14).

In equations (12) to (14)
R ¹⁶ 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-in these alkyl and alkenyl, in these groups. At least one hydrogen may be replaced with fluorine;
X ¹¹ is fluorine, chlorine, -CF ₃ , -CHF ₂ , -CH ₂ F, -OCF ₃ , -OCHF ₂ , -OCF ₂ CHF ₂ , or -OCF ₂ CHFCF ₃ ;
Rings D ¹ , Ring D ² , and Ring D ³ are independently 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylene, tetrahydropyran-2 in which at least one hydrogen is replaced by fluorine. , 5-Diyl, 1,3-dioxane-2,5-Diyl, or pyrimidine-2,5-Diyl;
Z ¹⁸ , Z ¹⁹ and Z ²⁰ are independently single-bonded, -COO-, -CH ₂ O-, -CF ₂ O-, -OCF _2- , -CH ₂ CH _2- , -CH = CH- , -C≡C-, or - _{(CH 2) 4} - a and;
L ¹³ and L ¹⁴ are independently hydrogen or fluorine. The liquid crystal composition according to any one of claims 10 to 13, further comprising at least one compound selected from the compounds represented by the formula (15).

In equation (15)
R ¹⁷ 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 by -O-, and in these groups, At least one hydrogen may be replaced by fluorine;
X ¹² is -C ≡ N or -C ≡ C-C ≡ N;
Ring E ¹ is 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced with fluorine, tetrahydropyran-2,5-diyl, 1,3-dioxane-2. , 5-Dioxane, or pyrimidine-2,5-Dioxane;
Z ²¹ is a single bond, -COO-, -CH ₂ O-, -CF ₂ O-, -OCF _2- , -CH ₂ CH _2- , or -C ≡ C-;
L ¹⁵ and L ¹⁶ are independently hydrogen or fluorine;
i is 1, 2, 3, or 4. A liquid crystal display device containing the liquid crystal composition according to any one of claims 10 to 14.