JP2007308483A - Compound having fluoroisopropyl group as side chain and liquid crystal composition using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid crystal compound having low viscosity, appropriate optical anisotropy, appropriate dielectric anisotropy and excellent compatibility with other liquid crystal compounds; a liquid crystal composition containing the compound; and a liquid crystal display device containing the liquid crystal composition. <P>SOLUTION: The compound is represented by general formula (1), wherein R represents a 1-10C alkyl group; rings A<SP>1</SP>, A<SP>2</SP>and A<SP>3</SP>each independently represent 1,4-cyclohexylene or 1,4-cyclohexenylene, or 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl or decahydronaphthalene-2,6-diyl, Z<SP>1</SP>, Z<SP>2</SP>and Z<SP>3</SP>each independently represent a single bond, or a bonding group, e.g., -(CH<SB>2</SB>)<SB>2</SB>-, -CH<SB>2</SB>O-, -CH=CH-, -CF<SB>2</SB>O-, -(CH<SB>2</SB>)<SB>4</SB>-, -OCF<SB>2</SB>-, -CH<SB>2</SB>CH<SB>2</SB>CF<SB>2</SB>O-, -CH<SB>2</SB>CH<SB>2</SB>CH<SB>2</SB>O-, or -CH=CHCH<SB>2</SB>, Z<SP>4</SP>represents a single bond or -O-, and X represents hydrogen or fluorine. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a liquid crystal compound, a liquid crystal composition, and a liquid crystal display element. Specifically, the present invention relates to a liquid crystal compound having fluoroisopropyl, a liquid crystal composition containing this compound and having a nematic phase, and a liquid crystal display device containing this composition.

In the liquid crystal display element, the classification based on the operation mode of the liquid crystal includes PC (phase change), TN (twisted nematic), STN (super twisted nematic), BTN (Bistable twisted nematic), ECB (electrically controlled birefringence), OCB ( optically
compensated bend), IPS (in-plane switching), VA (vertical alignment), and the like. The classification based on the element driving method is PM (passive matrix) and AM (active matrix). PM (passive matrix) is classified into static and multiplex, and AM is classified into TFT (thin film transistor), MIM (metalinsulator metal), and the like.

  These devices contain a liquid crystal composition having appropriate physical properties. In order to improve the characteristics of the device, the composition preferably has appropriate physical properties. General physical properties necessary for the liquid crystal compound which is a component of the composition are as follows. (1) Chemical stability and physical stability. (2) High clearing point. The clearing point is a liquid crystal phase-isotropic phase transition temperature. (3) Low minimum temperature of the liquid crystal phase. The liquid crystal phase means a nematic phase, a smectic phase, or the like. (4) Small viscosity. (5) Appropriate optical anisotropy. (6) Appropriate dielectric anisotropy. A compound having a large dielectric anisotropy often has a large viscosity. (7) Large specific resistance.

  The composition is prepared by mixing many compounds. Therefore, the compound is preferably miscible with other compounds. Since the device may be used at a temperature below freezing point, a compound having good compatibility at a low temperature is preferable. A compound having a high clearing point or a low minimum temperature of the liquid crystal phase contributes to a wide temperature range of the nematic phase in the composition. Preferred compositions have low viscosity and optical anisotropy suitable for the device mode. The large dielectric anisotropy of the compound contributes to the low threshold voltage of the composition. With such a composition, an element having characteristics such as a wide usable temperature range, a short response time, a large contrast ratio, a small driving voltage, a small power consumption, and a large voltage holding ratio can be obtained. .

  Conventionally, heptafluoroisopropylbenzene (Non-patent Document 1) and 1-t-butyl-4-heptafluoroisopropyloxybenzene (Non-patent Document 2) are known as compounds having fluoroisopropyl. Few examples are known in which the compounds possessed are applied to liquid crystal display elements.

The Chemical Society of Japan, 1973, 2351-2356 Journal of Organic Chemical Synthesis 1983, 41, 48-63

One of the objects of the present invention is to provide, for example, general physical properties necessary for a compound, small viscosity, appropriate optical anisotropy, appropriate dielectric anisotropy, and excellent compatibility with other liquid crystal compounds. It is providing the liquid crystalline compound which has. Another object of the present invention is to provide, for example, a liquid crystal composition containing this compound and having a wide temperature range of a nematic phase, a small viscosity, a suitable optical anisotropy, and a low threshold voltage. . Another object of the present invention is to provide, for example, a liquid crystal display element containing these liquid crystal compositions and having a short response time, a small power consumption, a large contrast, and a high voltage holding ratio.

  The present invention provides the following compound, liquid crystal composition, and liquid crystal display device containing the liquid crystal composition.

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

[Where:
R is alkyl having 1 to 10 carbons, and any —CH ₂ — in the group may be replaced by —O—, —S—, —CO— or —CH═CH—;
Rings A ¹ , A ² and A ³ are, independently of one another, 1) or 2):
1) 1,4-cyclohexylene or 1,4-cyclohexylene cyclohexylene, any one of -CH ₂ present in the group - or more than one -CH ₂ nonadjacent - is - May be replaced by O-;
2) 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl or decahydronaphthalene-2,6-diyl, any one or two of 1,4-phenylene -CH = may be replaced by -N =;
In the group described in 1) or 2), one or more optional hydrogens are halogen, —C≡N, —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₃ , —OCHF ₂ or —OCH ₂ F May be replaced by;
L ¹ and L ² are independently of each other hydrogen or fluorine;
Z ¹ , Z ² and Z ³ are each independently a single bond, — (CH ₂ ) ₂ —, —CH ₂ O—, —CH═CH—, —CF ₂ O—, — (CH ₂ ) ₄ —. , —OCF ₂ —, —CH ₂ CH ₂ CF ₂ O—, —CH ₂ CH ₂ CH ₂ O—, —CH═CHCH ₂ O—, —CH═CH—CH ₂ CH ₂ —, —CH ₂ CO— , -COO-, -OCO-, -CF = CF- or -C≡C-;
Z ⁴ is a single bond or —O—;
X is hydrogen or fluorine;
m and n are each independently 0 or 1. ]

[2] R is alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons or alkoxy having 1 to 10 carbons;
The rings A ¹ , A ² and A ³ are independently of each other 1) or 2):
1) 1,4-cyclohexylene or 1,4-cyclohexylene cyclohexylene, any one of -CH ₂ present in the group - or more than one -CH ₂ nonadjacent - is - May be replaced by O-;
2) 1,4-phenylene or naphthalene-2,6-diyl, wherein any one or two -CH = of 1,4-phenylene may be replaced by -N =;
One or more hydrogens in the group described in 1) or 2) may be replaced by fluorine;
Z ¹ , Z ² and Z ³ are each independently a single bond, — (CH ₂ ) ₂ —, —CH ₂ O—, —CH═CH—, —CF ₂ O—, — (CH ₂ ) ₄ —. _{, -OCF 2 -, - CH 2} CH 2 CF 2 O -, - C
_{H 2 CH 2 CH 2 O -} , - CH = CHCH 2 O -, - CH = CHCH 2 CH 2 -, - CH 2 CO, a -COO- or -OCO-,
The compound according to [1].

[3] Rings A ¹ , A ² and A ³ are independently of each other, 1,4-cyclohexylene, 1,4-cyclohexenylene, 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 or pyridazine-2,5-diyl;
Z ¹ , Z ² and Z ³ are each independently a single bond, — (CH ₂ ) ₂ —, —CH ₂ O—, —CH═CH—, —CF ₂ O—, — (CH ₂ ) ₄ —. _{, -OCF 2 -, - CH 2} CH 2 CF 2 O -, - CH 2 CH 2 CH 2 O -, - CH = CHCH 2 O- or -CH = CHCH ₂ CH ₂ - is,
The compound according to [2].

[4] Rings A ¹ , A ² and A ³ are independently of each other, 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1, 4-phenylene, 2,5-difluoro-1,4-phenylene or 2,6-difluoro-1,4-phenylene;
Z ^1, Z ² and Z ³ are each independently a single _{bond, - (CH 2) 2 -} , - CH 2 O -, - CH = CH- or -CF ₂ O-,
The compound according to [2].

[5] A compound represented by any one of formulas (1-1) to (1-13).

Wherein R is alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons or alkoxy having 1 to 10 carbons;
L ¹ and L ² are independently of each other hydrogen or fluorine;
Z ⁴ is a single bond or —O—;
X is hydrogen or fluorine. )

[6] A compound represented by any one of formulas (1-14) to (1-45).

(In the formula, R is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons.)

[7] A liquid crystal composition comprising at least two compounds containing at least one compound according to any one of [1] to [6].
[8] The liquid crystal composition according to [7], comprising at least one compound selected from the group of compounds represented by formulas (2), (3) and (4).

[Wherein, R ¹ is alkyl having 1 to 10 carbon atoms, and any —CH ₂ — in the group may be replaced by —O— or —CH═CH—, and any hydrogen is fluorine. May be replaced;
Ring B and Ring D are independently of each other 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl or 1,4-phenylene in which any hydrogen may be replaced by fluorine;
Ring E is 1,4-cyclohexylene or 1,4-phenylene in which any hydrogen may be replaced by fluorine;
Z ⁵ and Z ⁶ are each independently — (CH ₂ ) ₂ —, — (CH ₂ ) ₄ —, —COO—, —CF ₂ O—, —OCF ₂ —, —CH═CH— or a single bond. Yes;
L ³ and L ⁴ are independently of each other hydrogen or fluorine;
X ¹ is fluorine, chlorine, —OCF ₃ , —OCHF ₂ , —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₂ CHF ₂ or —OCF ₂ CHFCF ₃ . ]

[9] The liquid crystal composition according to [7] or [8], containing at least one compound selected from the group of compounds represented by formulas (5) and (6).

[Wherein, R ² and R ³ are each independently alkyl having 1 to 10 carbon atoms, and any —CH ₂ — in the group may be replaced by —O— or —CH═CH—. Any hydrogen may be replaced by fluorine;
Ring G is 1,4-cyclohexylene, 1,4-phenylene, 1,3-dioxane-2,5-diyl or pyrimidine-2,5-diyl;
Ring J is 1,4-cyclohexylene, pyrimidine-2,5-diyl or 1,4-phenylene in which any hydrogen may be replaced by fluorine;
Z ⁷ is — (CH ₂ ) ₂ —, —COO—, —CF ₂ O—, —OCF ₂ — or a single bond;
L ⁵ , L ⁶ and L ⁷ are independently of each other hydrogen or fluorine;
X ² is —C≡N or —C≡C—C≡N;
b, c and d are each independently 0 or 1; ]

[10] containing at least one compound selected from the group of compounds represented by formula (7), formula (8), formula (9), formula (10) and formula (11), [7 ] The liquid crystal composition according to any one of [9].

[Wherein, R ⁴ is alkyl having 1 to 10 carbon atoms, and any —CH ₂ — in the group may be replaced by —O— or —CH═CH—, and any hydrogen is fluorine. May be replaced;
R ⁵ is fluorine or alkyl having 1 to 10 carbon atoms, and any —CH ₂ — in the group may be replaced with —O— or —CH═CH—, and any hydrogen is replaced with fluorine. May be;
Ring M and Ring P are independently of each other 1,4-cyclohexylene, 1,4-phenylene or decahydronaphthalene-2,6-diyl;
Z ⁸ and Z ⁹ are independently of each other — (CH ₂ ) ₂ —, —COO— or a single bond;
L ⁸ and L ⁹ are each independently hydrogen or fluorine, and at least one of L ⁸ and L ⁹ is fluorine. ]

[11] The system according to any one of [7] to [10], which contains at least one compound selected from the group of compounds represented by formula (12), formula (13), and formula (14). Liquid crystal composition.

[Wherein, R ⁶ and R ⁷ are each independently alkyl having 1 to 10 carbon atoms, and any —CH ₂ — in the group may be replaced by —O— or —CH═CH—. Any hydrogen may be replaced by fluorine;
Ring Q, Ring T and Ring U are each independently 1,4-cyclohexylene, pyrimidine-2,5-diyl or 1,4-phenylene in which any hydrogen may be replaced by fluorine;
Z ¹⁰ and Z ¹¹ are each independently —C≡C—, —COO—, — (CH ₂ ) ₂ —, —CH═CH— or a single bond. ]

[12] The liquid crystal composition according to any one of [7] to [11], wherein the compound according to any one of [1] to [6] is contained in an amount of 4 to 15% by weight based on the total weight of the composition. object.
[13] The liquid crystal composition according to any one of [7] to [12], further containing at least one optically active compound.
[14] A liquid crystal display device comprising the liquid crystal composition according to any one of [7] to [13].

  The compound of the present invention has, for example, general physical properties necessary for the compound, small viscosity, stability to heat, light, etc., appropriate optical anisotropy, appropriate dielectric anisotropy, and superiority to other liquid crystal compounds. Have compatibility. The liquid crystal composition of the present invention contains, for example, at least one of these compounds, and has a high maximum temperature of the nematic phase, a low minimum temperature of the nematic phase, a small viscosity, a suitable optical anisotropy, a low threshold value. Have voltage. The liquid crystal display device of the present invention contains, for example, this composition and has a wide temperature range in which it can be used, a short response time, a large contrast ratio, and a low driving voltage.

Terms used in this specification are as follows.
“Liquid crystal compound” is a generic term for 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 useful as a component of a liquid crystal composition.
A liquid crystal compound, a liquid crystal composition, and a liquid crystal display device may be abbreviated as “compound”, “composition”, and “device”, respectively. A liquid crystal display element is a general term for a liquid crystal display panel and a liquid crystal display module.
The upper limit temperature of the nematic phase is the phase transition temperature of the nematic phase-isotropic phase, and may simply be abbreviated as “upper limit temperature”. The lower limit temperature of the nematic phase may be simply abbreviated as “lower limit temperature”.
The compound represented by the formula (1) may be abbreviated as “compound (1)”. This abbreviation may also apply to compounds represented by formula (2) and the like.
In the formulas (1) to (14), symbols such as A, B, D, and E surrounded by hexagons correspond to the ring A, the ring B, the ring D, and the ring E, respectively.
The amount of the compound expressed as a percentage is a weight percentage (% by weight) based on the total weight of the composition.

“Arbitrary” indicates that not only the position but also the number is arbitrary, but the case where the number is 0 is not included. The expression that any A may be replaced by B, C, or D is in addition to any A being replaced by B, any A being replaced by C, and any A being replaced by D. Thus, it is meant to include the case where a plurality of A are replaced by at least two of B to D. For example, alkyl in which any —CH ₂ — may be replaced by —O— or —CH═CH— includes alkyl, alkenyl, alkoxy, alkoxyalkyl, alkoxyalkenyl, alkenyloxyalkyl, and the like. In the present invention, it is not preferable that two consecutive —CH ₂ — are replaced by —O— to form —O—O—. In addition, it is not preferable that —CH ₂ — at the terminal, which is not bonded to another group in alkyl, is replaced with —O—.
The present invention is further described below. In the following, preferred examples of the terminal group, ring, bonding group and the like in the compound (1) are also described.

1-1 Compound of the Present Invention The first aspect of the present invention relates to the compound (1).

In the formula (1), R is alkyl having 1 to 10 carbon atoms, and in this alkyl, arbitrary —CH ₂ — is replaced by —O—, —S—, —CO— or —CH═CH—. Also good. For example, in CH ₃ (CH ₂ ) ₃ —, examples in which any —CH ₂ — is replaced by —O— or —CH═CH— are CH ₃ (CH ₂ ) ₂ O—, CH ₃ —O—. _{(CH 2) 2 -, CH} 3 -O-CH 2 -O-, CH 2 = CH- (CH 2) 3 -, CH 3 -CH = CH- (CH 2) 2 -, CH 3 -CH = CH -CH ₂ O-, and the like.

Examples of such R are alkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, acyl, acylalkyl, acyloxy, acyloxyalkyl, alkoxycarbonyl, alkoxycarbonylalkyl, alkenyl, alkenyloxy, alkenyloxyalkyl, alkoxyalkenyl and the like. In these groups, straight chain is preferable to branch. Even when R is a branched group, it is preferable when it is optically active. The preferred configuration of —CH═CH— in alkenyl depends on the position of the double bond. _{-CH = CHCH 3, -CH = CHC} 2 H 5, -CH = CHC 3 H 7, -CH = CHC 4 H 9, -C 2 H 4 CH = CHCH 3, and -C ₂ H ₄ CH = CHC ₂ In alkenyl having a double bond at odd positions such as H ₅ , the trans configuration is preferable. -CH ₂ CH = CHCH _3, cis configuration in the alkenyl having an even position to the double bond, such as _{-CH 2 CH = CHC 2 H 5} , and -CH ₂ CH = CHC ₃ H ₇ are preferred.

The alkyl may be linear, branched or cyclic, and specific examples of alkyl include, for example, —CH ₃ , —C ₂ H ₅ , —C ₃ H ₇ , —C ₄ H ₉ , — _{C 5 H 11, -C 6 H} 13, -C 7 H 15, -C 8 H 17, is a -C ₉ H ₁₉ and -C ₁₀ H _21.

Specific examples of alkoxy include, for example, —OCH ₃ , —OC ₂ H ₅ , —OC ₃ H ₇ , —OC ₄ H ₉ , —OC ₅ H ₁₁ , —OC ₆ H ₁₃ and —OC ₇ H ₁₅ . is there.

The alkoxyalkyl may be linear or branched, and specific examples of alkoxyalkyl include, for example, —CH ₂ OCH ₃ , —CH ₂ OC ₂ H ₅ , —CH ₂ OC ₃ H ₇ , — (CH ₂ ) ₂ OCH ₃ , — (CH ₂ ) ₂ OC ₂ H ₅ , — (CH ₂ ) ₂ OC ₃ H ₇ , — (CH ₂ ) ₃ OCH ₃ , — (CH ₂ ) ₄ OCH ₃ , and — (CH ₂ ) ₅ OCH ₃ .

The alkenyl may be linear or branched, and specific examples of alkenyl include, for example, —CH═CH ₂ , —CH═CHCH ₃ , —CH ₂ CH═CH ₂ , —CH═CHC ₂ H _{5. , -CH 2 CH = CHCH 3,} - (CH 2) 2 CH = CH 2, -CH = CHC 3 H 7, -CH 2 CH = CHC 2 H 5, - (CH 2) 2 CH = CHCH 3, - _{(CH 2) 3 CH = CH} 2 and -CH = CH- (CH ₂₎ a ₂ -CH = CH _2.

Alkenyloxy may be linear or branched, and specific examples of alkenyloxy include, for example, —OCH ₂ CH═CH ₂ , —OCH ₂ CH═CHCH ₃ , and —OCH ₂ CH═CHC ₂ H. ₅ .

R is preferably alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, alkoxyalkyl having 2 to 10 carbons, or alkenyl having 2 to 10 carbons, alkyl having 1 to 10 carbons, or carbon 2 more preferably 10 alkenyl or alkoxy having 1 to 10 carbon _{atoms, -CH 3, -C 2 H 5} , -C 3 H 7, -C 4 H 9, -C 5 H 11, -C 6 H 13, _{-OCH 3, -OC 2 H 5,} -OC 3 H 7, -CH 2 OCH 3, -CH = CH 2, -CH = CHCH 3, - (CH 2) 2 CH = CH 2, and - (CH ₂ More preferably, ₂ CH = CHCH ₃ .

The rings A ¹ , A ² and A ³ in the formula (1) are, independently of each other, the following 1) or 2).
1) 1,4-cyclohexylene or 1,4-cyclohexylene cyclohexylene, any one of -CH ₂ present in the group - or more than one -CH ₂ nonadjacent - is - It may be replaced by O-.
2) 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl or decahydronaphthalene-2,6-diyl, any one or two of 1,4-phenylene -CH = may be replaced by -N =
In the group described in 1) or 2), one or more optional hydrogens are halogen, —C≡N, —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₃ , —OCHF ₂ or —OCH ₂ F It may be replaced with.

Preferably, the rings A ¹ , A ² and A ³ in the formula (1) are, independently of each other, the following 1) or 2).
1) 1,4-cyclohexylene or 1,4-cyclohexylene cyclohexylene, any one of -CH ₂ present in the group - or more than one -CH ₂ nonadjacent - is - It may be replaced by O-.
2) 1,4-phenylene or naphthalene-2,6-diyl, wherein any one or two -CH = of 1,4-phenylene may be replaced by -N = Hydrogen may be replaced by fluorine.

Specifically, preferable examples of the rings A ¹ , A ^2, and A ³ are represented by the following formulas (15-1) to (15-5) and (15-10) to (15-18). Group.

In the rings A ¹ , A ² and A ³ included in the range defined above, any hydrogen is halogen, —C≡N, —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₃ , —OCHF ₂ , or it may be replaced by -OCH ₂ F. Rings A ¹ and A ² in which any hydrogen is replaced by fluorine, chlorine, —C≡N, —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₃ , —OCHF ₂ , or —OCH ₂ F Specific examples are the following formulas (16-1) to (16-37).

Preferred examples of the rings A ¹ , A ² and A ³ are 1,4-cyclohexylene (15-1), 1,4-cyclohexenylene (15-10), (15-11), 1,3-dioxane. -2,5-diyl (15-4), (15-5), 1,4-phenylene (15-12), 2-fluoro-1,4-phenylene (16-1) (16-2), 2 , 3-Difluoro-1,4-phenylene (16-3), 2,5-difluoro-1,4-phenylene (16-5), 2,6-difluoro-1,4-phenylene (16-4) ( 16-6), 2,3,5-trifluoro-1,4-phenylene (16-7) (16-8), pyridine-2,5-diyl (15-13) (15-17), 3- Fluoropyridine-2,5-diyl (16-36) (16-37), pyrimidine-2,5-di Yl (15-14) (15-18) and pyridazine-2,5-diyl (15-16). The configuration of 1,4-cyclohexylene and 1,3-dioxane-2,5-diyl is preferably trans rather than cis. Since 1,3-dioxane-2,5-diyl is structurally identical to 4,6-dioxane-2,5-diyl, the latter was not exemplified. This rule also applies to the relationship between 2-fluoro-1,4-phenylene and 2,6-difluoro-1,4-phenylene.

More preferred examples of the rings A ¹ , A ² and A ³ include 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyridine-2,5-diyl, and pyrimidine-2,5 -Diyl.

Most preferred examples of the rings A ¹ , A ² and A ³ are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene and 2,6-difluoro-1,4-phenylene.

Z ¹ , Z ² and Z ³ in formula (1) are each independently a single bond, — (CH ₂ ) ₂ —, —CH ₂ O—, —CF ₂ O—, —OCF ₂ —, —CH═CH -, - CF = CF -, - C≡C -, - (CH 2) 4 -, - (CH 2) 2 CF 2 O -, - CH 2 CH 2 CH 2 O -, - CH = CHCH 2 O- _{, -CH = CH-CH 2 CH} 2 -, - CH 2 CO -, - COO -, - OCO -, - a CF = CF-. Z ¹ , Z ² and Z ³ are a single bond, — (CH ₂ ) ₂ —, —CH ₂ O—, —CH═CH—, —CF ₂ O—, — (CH ₂ ) ₄ —, —OCF _{2. -, - CH 2 CH 2 CF} 2 O -, - CH 2 CH 2 CH 2 O -, - CH = CHCH 2 O -, - CH = CHCH 2 CH 2 -, - CH 2 CO, -COO- or -OCO- is more preferable. Z ¹ , Z ² and Z ³ are a single bond, — (CH ₂ ) ₂ —, —CH ₂ O—, —CH═CH—, —CF ₂ O—, — (CH ₂ ) ₄ —, —OCF _{2. -, - CH 2 CH 2 CF} 2 O -, - CH 2 CH 2 CH 2 O -, - CH = CHCH 2 O- or -CH = CHCH ₂ CH ₂ - is more preferred. Z ¹ , Z ² and Z ³ are most preferably a single bond, — (CH ₂ ) ₂ —, —CH ₂ O—, —CF ₂ O—, —OCF ₂ — and —CH═CH—.
In these bonds, the configuration regarding the double bond of the bonding group such as —CH═CH—, —CF═CF—, —CH═CH—CH ₂ O—, and —OCH ₂ —CH═CH— is cis Trans is preferred over.

Z ⁴ in the formula (1) is a single bond or —O—. Among these, -O- is preferable.
X in Formula (1) is hydrogen or fluorine. Among these, fluorine is preferable.
L ¹ and L ² in the formula (1) are hydrogen or fluorine. Among these, fluorine is preferable.
M and n are independently 0 or 1, but it is preferable that m and n are not 0 at the same time.

1-2 Properties of Compound of the Present Invention and Preparation Method Thereof The compound (1) of the present invention will be described in more detail.
This compound is extremely physically and chemically stable under the conditions under which the device is normally used, and is compatible with other liquid crystal compounds. A composition containing this compound is stable under conditions in which the device is normally used. Even when the composition is stored at a low temperature, the compound does not precipitate as crystals (or a smectic phase). This compound has general physical properties necessary for the compound, appropriate optical anisotropy, and appropriate dielectric anisotropy. Compound (1) has a large positive dielectric anisotropy. A compound having a large dielectric anisotropy is useful as a component for lowering the threshold voltage of the composition.

By appropriately selecting R, ring A ¹ , A ² and A ³ , Z ¹ , Z ² , Z ³ and Z ⁴ of compound (1), physical properties such as optical anisotropy and dielectric anisotropy can be obtained. It is possible to adjust arbitrarily. The influence of the types of R, rings A ¹ , A ² and A ³ , Z ¹ , Z ² , Z ³ and Z ^{4 on} the physical properties of compound (1) will be described below.

When R in formula (1) is linear, the temperature range of the liquid crystal phase is wide and the viscosity is small. When R is a branched chain, the compatibility with other liquid crystal compounds is good. A compound in which R is an optically active group is useful as a chiral dopant. By adding this compound to the composition, a reverse twisted domain generated in the device can be prevented. A compound in which R is not an optically active group is useful as a component of the composition. When R is alkenyl, the preferred configuration depends on the position of the double bond. An alkenyl compound having a preferred configuration has a high maximum temperature 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 descriptions.

1,4-phenylene, pyridine-2,5-diyl or 1,3-dioxane-2,5-diyl in which rings A ¹ , A ² and A ³ in formula (1) are optionally substituted with halogen Is relatively large in dielectric anisotropy. Rings A ¹ , A ² and A ³ are 1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, or pyridazine-3,6 where any hydrogen may be replaced by halogen -When diyl, the optical anisotropy is relatively large. When rings A ¹ , A ² and A ³ are 1,4-cyclohexylene, 1,4-cyclohexenylene or 1,3-dioxane-2,5-diyl, the optical anisotropy is relatively small.

When the two rings A ¹ , A ² and A ³ are all 1,4-cyclohexylene, the maximum temperature is relatively high, the optical anisotropy is relatively small, and the viscosity is relatively small. When at least one ring A ¹ or A ² is 1,4-phenylene, the optical anisotropy is relatively large and the orientational order parameter is relatively large. When any two rings A ¹ , A ² and A ³ are all 1,4-phenylene, the optical anisotropy is relatively large, the temperature range of the liquid crystal phase is relatively wide, and the upper limit temperature is Relatively high.

Z ¹ , Z ² and Z ³ are a single bond, — (CH ₂ ) ₂ —, —CH ₂ O—, —CF ₂ O—, —OCF ₂ —, —CH═CH—, —CF═CF—, or - (CH _{2) 4} - a time is relatively small viscosity at. When Z ¹ , Z ² and Z ³ are a single bond, — (CH ₂ ) ₂ —, —OCF ₂ —, —CF ₂ O—, or —CH═CH—, the viscosity is smaller. When Z ¹ , Z ² and Z ³ are —CH═CH—, the temperature range of the liquid crystal phase is relatively wide, and the elastic constant ratio K ₃₃ / K ₁₁ (K ₃₃ : bend elastic constant, K ₁₁ : splay elasticity) (Constant) is relatively large. When Z ¹ , Z ² and Z ³ are —C≡C—, the optical anisotropy is relatively large. When Z ¹ , Z ² and Z ³ are a single bond, — (CH ₂ ) ₂ —, —CH ₂ O—, —CF ₂ O—, —OCF ₂ —, — (CH ₂ ) ₄ — It is relatively stable and relatively difficult to deteriorate.

  When the compound (1) has two rings, the viscosity is relatively small. When the compound (1) has a tricycle, the maximum temperature is relatively high. When compound (1) has a tetracycle, the maximum temperature is even higher.

As described above, a compound having desired physical properties can be obtained by appropriately selecting the types of R, rings A ¹ , A ² , A ³ , Z ¹ , Z ² and Z ³ and the number of rings. Therefore, the compound (1) is useful as a component of a composition used for devices such as PC, TN, STN, ECB, OCB, IPS, and VA.

1-3 Specific Example of Compound (1) Preferred examples of compound (1) are compounds (1-1) to (1-13). More preferred examples of compound (1) are compounds (1-14) to (1-45). More specific examples are the compounds (1-46) to (1-204) shown in Example 5 in the Examples described later.

Wherein R is alkyl having 1 to 10 carbons, or alkenyl having 2 to 10 carbons, or alkoxy having 1 to 10 carbons;
L ¹ and L ² are independently of each other hydrogen or fluorine;
Z ⁴ is a single bond or —O—;
X is hydrogen or fluorine. )

(In the formula, R is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons.)

1-4 Synthesis of Compound (1) Next, a synthesis method of the compound (1) will be described. Compound (1) can be synthesized by appropriately combining techniques in organic synthetic chemistry. Methods for introducing the desired end groups, rings and linking groups into the starting materials are Organic Syntheses (John Wiley & Sons, Inc), Organic Reactions (John Wiley & Sons, Inc), Comprehensive・ It is described in organic synthesis (Comprehensive Organic Synthesis, Pergamon Press), new experimental chemistry course (Maruzen).

1-4-1 One example of a method for forming the bonding group Z ^1, Z ² and Z ³ in the bonding group Z ^1, wherein the compound that generates a Z ² and Z ³ (1) are as follows scheme. In this scheme, MSG ¹ or MSG ² is a monovalent organic group having at least one ring. A 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).

(I) Formation of Single Bond A compound obtained by reacting arylboric acid (21) with compound (22) synthesized by a known method in the presence of a carbonate aqueous solution and a catalyst such as tetrakis (triphenylphosphine) palladium. Synthesize (1A). This compound (1A) is obtained by reacting compound (23) synthesized by a known method with n-butyllithium and then with zinc chloride, and in the presence of a catalyst such as dichlorobis (triphenylphosphine) palladium. ) Is also reacted.

(II) Formation of —COO— and —OCO— The compound (23) is reacted with n-butyllithium and subsequently with carbon dioxide to obtain a carboxylic acid (24). Compound having —COO— by dehydrating compound (24) and phenol (25) synthesized by a known method in the presence of DDC (1,3-dicyclohexylcarbodiimide) and DMAP (4-dimethylaminopyridine) Synthesize (1B). A compound having —OCO— is also synthesized by this method.

(III) Formation of —CF ₂ O— and —OCF ₂ — Compound (1B) is treated with a sulfurizing agent such as Lawesson's reagent to obtain compound (26). The compound (26) is fluorinated with a hydrogen fluoride pyridine complex and NBS (N-bromosuccinimide) to synthesize a compound (1C) having —CF ₂ O—. See M. Kuroboshi et al., Chem. Lett., 1992, 827. Compound (1C) can also be synthesized by fluorinating compound (26) with (diethylamino) sulfur trifluoride (DAST). See WH Bunnelle et al., J. Org. Chem. 1990, 55, 768. A compound having —OCF ₂ — is also synthesized by this method. These linking groups can also be generated by the method described in Peer. Kirsch et al., Anbew. Chem. Int. Ed. 2001, 40, 1480.

(IV) Formation of —CH═CH— The compound (23) is treated with n-butyllithium and then reacted with formamide such as N, N-dimethylformamide (DMF) to obtain the aldehyde (28). A phosphoryl ylide generated by treating a phosphonium salt (27) synthesized by a known method with a base such as potassium tert-butoxide is reacted with an aldehyde (28) to synthesize a compound (1D). Since a cis isomer is generated depending on the reaction conditions, the cis isomer is isomerized to a trans isomer by a known method as necessary.

(V) Formation of — (CH ₂ ) ₂ — Compound (1D) is synthesized by hydrogenating compound (1D) in the presence of a catalyst such as palladium carbon.

(VI) Formation of — (CH ₂ ) ₄ — A compound having — (CH ₂ ) ₂ —CH═CH— is prepared by using the phosphonium salt (29) instead of the phosphonium salt (27) and according to the method of the item (IV). obtain. This is catalytically hydrogenated to synthesize compound (1F).

(VII) Formation of -C≡C- After reacting compound (23) with 2-methyl-3-butyn-2-ol in the presence of a catalyst of dichloropalladium and copper halide, under basic conditions Deprotection yields compound (30). Compound (1G) is synthesized by reacting compound (30) with compound (22) in the presence of a catalyst of dichloropalladium and copper halide.

(VIII) Formation of —CF═CF— The compound (23) is treated with n-butyllithium and then reacted with tetrafluoroethylene to obtain the compound (31). Compound (22) is treated with n-butyllithium and then reacted with compound (31) to synthesize compound (1H).

(IX) Formation of —CH ₂ O— or —OCH ₂ — Compound (32) is obtained by reducing compound (28) with a reducing agent such as sodium borohydride. This is halogenated with hydrobromic acid or the like to obtain compound (33). Compound (1J) is synthesized by reacting compound (33) with compound (25) in the presence of potassium carbonate or the like.

1-4-2 Method for synthesizing rings A ¹ , A ² and A ³ 1,4-cyclohexanone, 1,3-dioxane-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4- For rings such as phenylene, 2,3-difluoro-1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, starting materials are commercially available or synthetic methods are well known. Yes. Therefore, the synthesis of the following compound (38) and compound (42) will be described.
(Synthesis of Compound (38))

The structural unit of 2,3-bistrifluoromethylphenylene is synthesized by the method described in the literature of Org. Lett., 2000, 2 (21), 3345. Aniline (37) is synthesized by reacting furan (36) with 1,1,1,4,4,4-hexafluoro-2-butyne at a high temperature in a Diels-Alder type reaction. From this compound, an iodide (38) is obtained by a Sand-Meier type reaction according to the method described in Org. Synth. Coll., Vol. 2, 1943,355. This compound is converted into the compound (1) by a general method of synthetic organic chemistry.
(Synthesis of Compound (42))

The structural unit of 2-difluoromethyl-3-fluorophenylene is synthesized by the following method. The hydroxyl group of compound (39) is protected with an appropriate protecting group to obtain compound (40). P ¹ means a protecting group, for example methyl. Compound (40) is allowed to react with sec-butyllithium and subsequently reacted with N, N-dimethylformamide (DMF) to obtain aldehyde (41). This compound is fluorinated with dimethylaminosulfur trifluoride (DAST) followed by deprotection to give phenol (42). This compound is converted into the compound (1) by a general method of synthetic organic chemistry. Q ² in the above is a group represented by the following formula.

(In the formula, A ³ , Z ³ , L ¹ and L ² have the same meaning as defined in formula (1). P ² is a protecting group.)
P ² is, for example, benzyl.

1-4-3 Method for Synthesizing Compound Represented by Formula (1) There are a plurality of methods for synthesizing compound (1), and an example is shown here.
1-4-3-1 Method for synthesizing compound (52) as starting material A method for synthesizing the compound (52) as starting material will be described.
The compound (52), which is a starting material represented by the following formula (52), can be synthesized by using a general method in the above synthesis method and organic synthetic chemistry.
The general synthesis examples (A) to (C) for synthesizing the compound (52) are shown below.

(A) Method for synthesizing compound (52) when A ³ is cyclohexylene and Z ³ is a single bond, or when Z ³ is alkylene

In the present specification, Q ¹ is a group represented by the following formula.

(In the formula, R, A ¹ , A ² , A ³ , Z ¹ , Z ² , Z ³ , m, and n have the same meaning as defined in Formula (1).)

  As shown in Scheme 1 above, first, a cyclohexanone derivative (50a) or a carbonyl derivative (50b) is prepared according to a method of synthetic organic chemistry, and a Grignard reaction using an appropriate Grignard reagent (51), a dehydration reaction with an acid, The compound (52) can be synthesized by sequentially performing hydrogen reduction using a Pd catalyst and a Pd catalyst, and then performing an isomerization reaction as necessary. Bn represents benzyl.

(B-1) Method for synthesizing compound (52) when A ³ is phenylene, pyrimidine, etc. and Z ³ is a single bond

(B-2) Synthesis method of compound (52) when A ³ is phenylene, pyrimidine or the like and Z ³ is alkenylene

(B-3) Synthesis method of compound (52) when A ³ is phenylene, pyrimidine or the like and Z ³ is alkylene

(B-4) Synthesis method of compound (52) when A ³ is phenylene, pyrimidine, etc. and Z ³ is alkynylene

(B-5) Synthesis method of compound (52) when A ³ is phenylene, pyrimidine, etc. and Z ³ is — (CH ₂ ) O—

(In the formula, R, A ¹ , A ² , A ³ , Z ¹ , Z ² , Z ³ , m, and n have the same meaning as defined in Formula (1).)

  As shown in the above Scheme 2 or Scheme 3-6, first, compound (53a) or compound (53b) is prepared according to the method of organic synthetic chemistry, for example, coupling reaction with compounds (51) to (51e), etc. Or a method of performing Williamson etherification with a phenol derivative (55) or the like, can be easily derived into the compound (52).

(C) Synthesis method of compound (52) when Z ³ is —CF ₂ O—

(In the formula, R, A ¹ , A ² , Z ¹ , Z ² , m and n have the same meaning as defined in formula (1).)

As shown in Scheme 7 above, the compound (53c) is first prepared according to the method of synthetic organic chemistry, esterified with a phenol derivative (55) and the like, and then the synthesis scheme (III) of the linking group described above Can be easily derived into the compound (52).

1-4-3-2 Method for synthesizing compound (1) from compound (52)
(A) Synthesis method of compound (57) when Z ⁴ is a single bond Scheme 8 in which compound (52) is derived to compound (57) is shown.

  The compound (52b) is treated with butyllithium and then reacted with iodine to obtain an iodine body (56). Thereafter, the compound (57) is obtained by reacting copper and perfluoroisopropyl iodide in N, N-dimethylformamide (DMF) by the method described in Journal of Chemical Society of Japan, 1973, 2351-2356.

(B) Synthesis method of compound (58) when Z ⁴ is —O— Scheme 9 in which the compound (52) is derived to the compound (58) is shown.

  Compound (52c) is reacted with perfluoroisopropylphenyliodonium trifluoromethanesulfonate (FITS-3i) described in Journal of Organic Chemistry Synthesis 1983, 41, 48-63 and pyridine in dichloromethane. 58). Compound (52c) can be synthesized from compound (52b) by the method described above.

2 Composition of the Present Invention The second aspect of the present invention is a composition containing a compound represented by the formula (1), and is preferably a liquid crystal composition that can be used for a liquid crystal material. The component of the composition may be only a plurality of compounds selected from the compound (1), but may contain at least one compound selected from the compounds (1) in a proportion of 1 to 99% by weight. preferable. In addition to the compound (1), this composition preferably further contains a component selected from the group of the compounds (2) to (14). When preparing the composition of the present invention, it is preferable to select components in consideration of the dielectric anisotropy of the compound (1).

  A preferred composition containing the compound (1) having a positive dielectric anisotropy and a relatively large amount contains at least one compound selected from the group consisting of the compounds (2), (3) and (4). Another preferred composition contains at least one compound selected from the group of compounds (5) and (6). Another preferred composition contains at least two compounds selected from each of these two groups. These compositions are a group of compounds (12), (13) and (14) for the purpose of adjusting the temperature range, viscosity, optical anisotropy, dielectric anisotropy, threshold voltage and the like of the liquid crystal phase. It may further contain at least one compound selected from These compositions may further contain at least one compound selected from the group of the compounds (7) to (11) for the purpose of further adjusting physical properties. In addition, these compositions may further contain other liquid crystal compounds and compounds such as additives for the purpose of adapting to AM-TN devices, STN devices and the like.

A preferred composition containing the compound (1) having a relatively small dielectric anisotropy contains at least one compound selected from the group of the compounds (2), (3) and (4). Another preferred composition contains at least one compound selected from the group of compounds (5) and (6). Another preferred composition contains at least two compounds selected from each of the two such groups. These compositions are a group of compounds (12), (13) and (14) for the purpose of adjusting the temperature range, viscosity, optical anisotropy, dielectric anisotropy, threshold voltage and the like of the liquid crystal phase. It may further contain at least one compound selected from This composition may further contain at least one compound selected from the group of the compounds (7) to (11) for the purpose of further adjusting physical properties. In addition, this composition is an AM-TN device, STN.
For the purpose of adapting to a device, etc., other liquid crystalline compounds and additives may be further contained.
Another preferred composition contains at least one compound selected from the group of compounds (7) to (11). The composition may further contain at least one compound selected from the group of compounds (12), (13) and (14). This composition may further contain at least one compound selected from the group of the compounds (2) to (6) for the purpose of further adjusting the physical properties. This composition may further contain compounds such as other liquid crystal compounds and additives for the purpose of adapting to VA devices and the like.

  Compounds (2), (3) and (4) have a positive dielectric anisotropy and are relatively large, and are therefore mainly used in compositions for AM-TN devices. In this composition, the total amount of the compounds (2), (3) and (4) is preferably 1 to 99% by weight, and more preferably 10 to 97% by weight. Moreover, it is especially preferable that the said range is 40 to 95 weight%. When the compound (12), (13) or (14) is further added to this composition, the preferred addition amount of these compounds (12), (13) or (14) is 60% by weight or less, and 40% by weight. % Or less is more preferable.

  Since the compounds (5) and (6) have a positive dielectric anisotropy and are very large, they are mainly used in compositions for STN devices. In this composition, the total amount of the compounds (5) and (6) is preferably 1 to 99% by weight, and more preferably 10 to 97% by weight. Moreover, it is especially preferable that the said range is 40 to 95%. When the compound (12), (13) or (14) is further added to this composition, the preferred addition amount of these compounds (12), (13) or (14) is 60% by weight or less, and 40% by weight. % Or less is more preferable.

  Since the compounds (7), (8), (9), (10), and (11) have a negative dielectric anisotropy, they are mainly used in compositions for VA devices. The total of these compounds (7), (8), (9), (10), and (11) is preferably 80% by weight or less, and more preferably 40-80% by weight. When the compound (12), (13) or (14) is further added to this composition, the preferred addition amount of these compounds (12), (13) or (14) is 60% by weight or less, and 40% by weight. % Or less is more preferable.

The dielectric anisotropy of the compounds (12), (13) and (14) is relatively small. The compound (12) is mainly used for the purpose of adjusting the viscosity or optical anisotropy. Compounds (13) and (14) are mainly used for the purpose of increasing the maximum temperature to widen the temperature range of the liquid crystal phase or adjusting the optical anisotropy.
Increasing the amounts of compounds (12), (13) and (14) increases the threshold voltage of the composition and decreases the viscosity. Therefore, a large amount may be used as long as the threshold voltage requirement of the composition is satisfied.

Specific examples of preferable compounds in the compounds (2) to (14) are the compounds (2-1) to (2-9), the compounds (3-1) to (3-97), and the compounds (4-1) to (14), respectively. (4-33), compounds (5-1) to (5-56), compounds (6-1) to (6-3), compounds (7-1) to (7-4), compound (8-1) ) To (8-6), compounds (9-1) to (9-4), compound (10-1), compound (11-1), compounds (12-1) to (12-11), compound ( 13-1) to (13-21) and compounds (14-1) to (14-6). In these compounds, the meanings of the symbols R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , X ¹ , and X ² are the same as those in each of the compounds (2) to (14) described above. The meaning of these symbols is the same.

  The composition of the present invention containing compound (1) is prepared by a known method. For example, it can be prepared by mixing compounds that are predetermined components and dissolving them by heating. Moreover, you may adjust the physical property of a composition by adding an appropriate additive to a composition. Such additives are well known to those skilled in the art. A composition for a GH device may be prepared by adding a dichroic dye which is a compound such as merocyanine, styryl, azo, azomethine, azoxy, quinophthalone, anthraquinone, and tetrazine. On the other hand, a chiral dopant is added for the purpose of inducing a helical structure of the liquid crystal to give a necessary twist angle. Examples of the chiral dopant are the following optically active compounds (Op-1) to (Op-13).

  A chiral dopant can be added to the composition of the present invention to adjust the pitch of twist. A preferred pitch for TN elements and TN-TFT elements is in the range of 40-200 μm. A preferred pitch for STN elements is in the range of 6-20 μm. A preferred pitch for the BTN device is in the range of 1.5-4 μm. Chiral dopants can be added so that they can be applied to the preferred pitch range of these various devices. In general, for PC device applications, a relatively large amount of chiral dopant is added to the composition of the present invention. Further, at least two chiral dopants may be added for the purpose of adjusting the temperature dependence of the pitch.

3. The liquid crystal display element of this invention The 3rd aspect of this invention is related with the liquid crystal display element using the composition of this invention.
The shape of the spacer constituting the liquid crystal display element is preferably a square, a rectangle, a circle or an ellipse when viewed from directly above. In the case of a rectangle or an ellipse, the major axis direction is horizontal or orthogonal to the rubbing direction. It is preferable. Moreover, the beads conventionally used in the resin coating can be dispersed and fixed for use. Also, a photosensitive resin composition is applied on a glass substrate, patterned in the same manner, leaving the composition only in the peripheral part of the substrate, and assembling a liquid crystal cell so that another substrate is opposed thereto, and crimping, By baking, the composition can be incorporated into a liquid crystal element as a sealing material. Furthermore, you may form the film | membrane which performs an orientation process on this resin coating film.

  The liquid crystal display element of the present invention can be prepared, for example, by aligning the positions of the upper and lower element substrates formed as described above, press-bonding, and combining them by heat treatment, and then injecting the composition of the present invention to seal the injection port. Produced by stopping. Alternatively, after the composition of the present invention is dispersed on the liquid crystal element substrate, the substrates may be overlapped and sealed so as not to leak the liquid crystal display element. In this way, the composition of the present invention can be present in a liquid crystal display device.

  Specifically, the composition of the present invention can be used for liquid crystal display elements such as PC, TN, STN, BTN, ECB, OCB, IPS, and VA. These liquid crystal display elements may be driven by PM or AM. A NCAP (nematic curvilinear aligned phase) element produced by microencapsulating the composition of the present invention, or a PD (polymer dispersed) element in which a three-dimensional network polymer is formed in the composition, for example, PN (polymer network) It can also be used for devices.

  Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited by these examples. Further, the structure of the obtained compound was identified by nuclear magnetic resonance spectrum, mass spectrum and the like.

Example 1 Synthesis of Compound (1-001) A compound represented by the following formula (1-001), which is one example of the compound (1), was synthesized.

  Compound (1-001) was synthesized according to the following scheme 11.

  A compound (1-001a) (11.382 g) synthesized according to a conventional method, perfluoroisopropyl iodide (manufactured by Tokyo Chemical Industry) (7.209 g) and copper (8.820 g) were dissolved in a DMF (80 ml) solvent under a nitrogen atmosphere. After that, the mixture was stirred with heating in a sealed tube at 130-140 ° C. for 12 hours. The reaction product was filtered to remove copper, diluted with water (80 ml), extracted twice with toluene (100 ml), washed with water in the usual manner, and then concentrated, and the residue was subjected to silica gel column chromatography. Purification by chromatography isolated compound (1-001) (4.267 g).

The physicochemical properties of the obtained compound (1-001) are shown below.
¹ H-NMR (CDCl ₃ , ppm): δ 0.83-1.46 (18H, m), 1.72-1.94 (8H, m), 2.47-2.53 (1H, m), 7.31 (2H, d, J = 8.2Hz ), 7.50 (2H, d, J = 8.2Hz).
¹⁹ F (CDCl ₃ , ppm): δ-76.2 (6F, d), -182.8 (1F, dq).

Example 2 Synthesis of Compound (1-002) A compound represented by the following formula (1-002), which is one example of the compound (1), was synthesized.

  Compound (1-002) was synthesized according to the following scheme.

(First stage)
The bromo compound (1-002a) (30 g) synthesized according to a conventional method was added dropwise to a suspension obtained by adding THF (5 ml) to a commercially available magnesium ribbon (2.87 g). 30 minutes after the completion of dropping, a solution obtained by diluting a ketone body (26.596 g) synthesized according to a conventional method with THF (50 ml) was dropped at 20 ° C. or lower. After stirring at room temperature overnight, the reaction mixture was ice-cooled and quenched with saturated ammonium chloride, extracted three times with toluene (200 ml), washed with water by a conventional method, and then concentrated. Subsequently, the obtained residue was dissolved in toluene (500 ml) without isolation, p-toluenesulfonic acid monohydrate (1.0 g) was added, and the mixture was heated to reflux for 4 hours. The reaction mixture was cooled to room temperature, washed with saturated aqueous sodium hydrogen carbonate (100 ml) and water (100 ml), and concentrated. The residue was purified by silica gel column chromatography to give compound (1-002b) (16. 7 g) was isolated.

(Second stage)
The benzyl compound (15.0 g) was dissolved in a mixed solvent (1: 1) of toluene-methanol (400 ml), and 5% Pd / C (Pd: C = 5 wt%: 95 wt%) (1.0 g) was added. And stirred for 3 days under a hydrogen atmosphere. The reaction solution was filtered to remove Pd / C, then concentrated and purified by silica gel column chromatography to isolate compound (1-002c) (11.599 g).
Next, in a nitrogen atmosphere, aluminum chloride (2.6 g) was added to a cyclohexane (300 ml) solution of the alcohol (11.0 g), and the mixture was heated and stirred at 40 ° C. for 10 hours. The reaction solution was poured into water (400 ml), extracted twice with toluene (200 ml), washed with water by a conventional method, then concentrated, and the residue was purified by silica gel column chromatography to give compound (1-002d ) (8.0 g) was isolated.

(Third stage)
After dissolving the alcohol (2.5 g) in methylene chloride (100 ml), pyridine (0.675 ml) and perfluoroisopropylphenyliodonium trifluoromethanesulfonate (FITS-3i) (manufactured by Tokyo Chemical Industry) (4.325 g) ) And stirred at room temperature for 4 hours. The reaction solution was washed with water by a conventional method and then concentrated, and then the residue was purified by silica gel column chromatography to isolate compound (1-002) (529 mg).

The physicochemical properties of the obtained compound (1-002) are shown below.
¹ H-NMR (CDCl ₃ , ppm): δ 0.82-1.42 (18H, m), 1.72-1.91 (8H, m), 2.41-2.47 (1H, m), 7.02 (2H, d, J = 7.2 Hz ), 7.18 (2H, d, J = 7.2Hz).
¹⁹ F (CDCl ₃ , ppm): δ-78.8 (6F, d), -135.6 (1F, dq)
MS: 468 (M ⁺ )

Example 3 Synthesis of Compound (1-003) A compound represented by the following formula (1-003), which is one example of the compound (1), was synthesized.

  Compound (1-003) was synthesized according to the following scheme.

(First stage)
A commercially available bromo compound (38.3 g) was added dropwise to a suspension obtained by adding THF (20 ml) to a commercially available magnesium ribbon (5.67 g). 30 minutes after the completion of dropping, a solution obtained by diluting a ketone body (43.3 g) synthesized according to a conventional method with THF (50 ml) was added dropwise at 20 ° C. or lower. After stirring at room temperature overnight, the reaction mixture was ice-cooled and quenched with saturated ammonium chloride, extracted three times with toluene (200 ml), washed with water by a conventional method, and then concentrated. Subsequently, the obtained residue was dissolved in toluene (500 ml) without isolation, p-toluenesulfonic acid monohydrate (1.0 g) was added, and the mixture was heated to reflux for 4 hours. The reaction mixture was cooled to room temperature, washed with saturated aqueous sodium hydrogencarbonate (100 ml) and water (100 ml), and concentrated. The residue was purified by silica gel column chromatography to give compound (1-003a) (49. 5 g) was isolated.

(Second stage)
The benzyl compound (67.5 g) was dissolved in a mixed solvent (1: 1) of toluene-methanol (600 ml), 5% Pd / C (1.0 g) was added, and the mixture was stirred under a hydrogen atmosphere for 3 days. The reaction solution was filtered to remove Pd / C, then concentrated and purified by silica gel column chromatography to isolate compound (1-003b) (67.0 g).
Next, in a nitrogen atmosphere, potassium t-butoxy (4.69 g) was added to a solution of alcohol (11.0 g) in N-methylpyrrolidone (250 ml), and the mixture was heated and stirred at 50 ° C. for 6 hours. The reaction solution was poured into water (600 ml), extracted four times with toluene (300 ml), washed with water by a conventional method, then concentrated, and the residue was purified by silica gel column chromatography to give compound (1-003c ) (30.0 g) was isolated.
Next, n-butyllithium (1.57 mol / l) (28.621 ml) was added dropwise to a THF (100 ml) solution of the difluoro compound (12.0 g) in a nitrogen atmosphere at −70 ° C. or lower and stirred for 30 minutes. Subsequently, trimethyl borate (5.01 ml) was added dropwise at −70 ° C. or lower and stirred overnight at room temperature, then quenched with 3N hydrochloric acid, extracted twice with ethyl acetate (100 ml), washed with water by a conventional method, After concentration, the residue was washed with heptane to isolate compound (1-003d) (11.7 g).

(Third stage)
Boronic acid (8.2 g) was dissolved in THF (100 ml), and then 30% aqueous hydrogen peroxide (5
. 10 ml) was added and stirred at 50-60 ° C. for 6 hours. The reaction product was quenched with an aqueous sodium sulfite solution, extracted three times with toluene (100 ml), washed with water by a conventional method, and then concentrated. The residue was purified by silica gel column chromatography to give compound (1-003e ) (2.89 g) was isolated.
Next, the alcohol (2.89 g) was dissolved in methylene chloride (150 ml), and then pyridine (0.687 ml) and perfluoroisopropylphenyliodonium trifluoromethanesulfonate (FITS-3i) (manufactured by Tokyo Chemical Industry) ( 4.50 g) was added and stirred at room temperature for 4 hours. The reaction solution was washed with water by a conventional method and then concentrated, and then the residue was purified by silica gel column chromatography to isolate compound (1-003) (1.40 g).

The physicochemical properties of the obtained compound (1-003) are shown below.
¹ H-NMR (CDCl ₃ , ppm): δ 0.84-1.39 (18H, m), 1.71-1.91 (8H, m), 2.39-2.45 (1H, m), 6.82 (2H, d, J = 9.1 Hz ).
¹⁹ F (CDCl ₃ , ppm): δ-80.2 (6F, m), -125.0 (2F, m), -140.4 (1F, m).

Example 4 Synthesis of Compound (1-004) A compound represented by the following formula (1-004), which is one example of the compound (1), was synthesized.

  Compound (1-004) was synthesized according to the following scheme.

(First stage)
Toluene (80 ml) was added to commercially available triphenylphosphine (1.920 g) and Pd (Ph ₃ P) ₂ Cl (2.568 g), and the mixture was heated to reflux. After 1 hour, boronic acid (20 g), bromo compound (21.340 g), potassium carbonate (25.280 g), and tetrabutylammonium bromide (9.828 g) were added to the suspension, and the mixture was heated to reflux again. After 2 hours, the reaction solution was cooled to room temperature, extracted three times with toluene (200 ml), washed with water by a conventional method, then concentrated, and then the residue was purified by silica gel column chromatography to obtain compound (1 -004a) (25.0 g) was isolated.
Next, sec-butyllithium (1.00 mol / l) (60.717 ml) was added dropwise to a THF (200 ml) solution of the fluoro compound (10.30 g) at −70 ° C. or less and stirred for 60 minutes. Subsequently, a solution of iodine (14.640 g) dissolved in THF (100 ml) was added dropwise at −70 ° C. or lower and stirred at room temperature. After overnight, diluted with toluene (300 ml), washed with water by a conventional method, and then concentrated. The residue was purified by silica gel column chromatography to obtain compound (1-004b) (8.0 g). Isolated.

(Second stage)
Iodine (18.3 g), boronic acid (10.194 g) synthesized according to a conventional method, tetrabutylammonium boronide (4.336 g), potassium carbonate (14.870 g), 5% Pd / C (3.66 g) Ethanol (100 ml), toluene (100 ml) and water (20 ml) were added and the mixture was heated to reflux for 4 hours. The reaction solution was returned to room temperature, and the solution from which Pd / C was removed was extracted twice with toluene (200 ml), washed with water by a conventional method, then concentrated, and the residue was purified by silica gel column chromatography. Compound (1-004c) (11.0 g) was isolated.
Next, n-butyllithium (1.57 mol / l) was added dropwise at −70 ° C. or lower to a THF (100 ml) solution of the difluoro compound (11.0 g) in a nitrogen atmosphere, and the mixture was stirred for 30 minutes. Subsequently, trimethyl borate (5.01 ml) was added dropwise at −70 ° C. or lower and stirred overnight at room temperature, then quenched with 3N hydrochloric acid, extracted twice with ethyl acetate (100 ml), washed with water by a conventional method, After concentration, the residue was washed with ethyl acetate to isolate compound (1-004d) (9.0 g).

(Third stage)
Boronic acid (8.50 g) was dissolved in THF (100 ml), 30% aqueous hydrogen peroxide (5.206 ml) was added, and the mixture was stirred at 50-60 ° C. for 6 hr. The reaction product was quenched with an aqueous sodium sulfite solution, extracted with toluene (100 ml) three times with toluene, washed with water by a conventional method, and then concentrated. The residue was purified by silica gel column chromatography to give compound (1 -004e) (2.89 g) was isolated.
Next, after dissolving the alcohol form (0.344 g) in methylene chloride (150 ml), pyridine (0.687 ml) and perfluoroisopropylphenyliodonium trifluoromethanesulfonate (FITS-3i) (manufactured by Tokyo Chemical Industry) ( 4.50 g) was added and stirred at room temperature for 4 hours. The reaction solution was washed with water by a conventional method and then concentrated, and then the residue was purified by silica gel column chromatography to isolate compound (1-004) (0.110 g).

The physicochemical properties of the obtained compound (1-004) are shown below.
¹ H-NMR (CDCl ₃ , ppm): δ 0.98 (3H, t, J = 7.4 Hz), 1.63-1.73 (2H, m), 2.64 (2H, t, J = 7.4 Hz), 7.24-7.26 ( 2H, m), 7.28 (2H, d, J = 8.1Hz), 7.39-7.47 (3H, m),
7.52 (2H, d, J = 8.1Hz). ¹⁹ F (CDCl ₃ , ppm): δ-80.1 (6F, m), -117.7 (1H, m), -124.0 (2F, m), -140.2 (1F , m).

Example 5 Synthesis of Compound (1-005) A compound represented by the following formula (1-005), which is one example of the compound (1), was synthesized.

  Compound (1-005) was synthesized according to the following scheme.

(First stage)
Commercially available dinitrobenzene (5.0 g), tetrabutylammonium fluoride trihydrate (46.920 g) and 1,1,1,3,3,3-hexafluoro-2-propanol (4.930 ml) ) Was dissolved in N, N-dimethylformamide (300 ml) and stirred at room temperature for 24 hours. The reaction solution was adjusted to pH 3 to 4 with dilute hydrochloric acid, extracted three times with ether (100 ml), washed with water by a conventional method, then concentrated, and the residue was purified by silica gel column chromatography to give a compound ( 1-005a) (3.0 g) was isolated.

  Next, the nitro compound (1-005a) (3.0 g) was dissolved in a mixed solvent (1: 1) of toluene-sol mix (50 ml), 5% Pd / C (300 mg) was added, and the mixture was added under a hydrogen atmosphere. Stir overnight. The reaction solution was filtered to remove Pd / C, then concentrated and purified by silica gel column chromatography to isolate compound (1-005b) (2.420 g).

(Second stage)
The amino compound (1-005b) (2.040 g) was dissolved in concentrated hydrochloric acid (12.024 ml) and heated and stirred at 50 to 55 ° C. After 1 hour, the suspension was cooled to −5 ° C., and a solution of sodium nitrite (624 mg) dissolved in water (8.299 ml) was added dropwise at 0 ° C. or lower. After stirring at 0 ° C. for 30 minutes, a solution of potassium iodide (2.637 g) in water (11.030 ml) was added dropwise and stirred overnight at room temperature. The reaction solution was extracted three times with toluene (30 ml), washed with an aqueous sodium sulfite solution, an aqueous potassium hydroxide solution, and water according to a conventional method, then concentrated, and the residue was purified by silica gel column chromatography to give a compound. (1-005c) (1.890 g) was isolated.

Iodine (1-005c) (1.700 g), boronic acid (1.356 g) synthesized according to a conventional method, tetrabutylammonium boronamide (0.371 g), potassium carbonate (1.270 g) 5% Pd / C (0 .340 g) was added to a mixture of ethanol (40 ml), toluene (40 ml) and water (8 ml), and the mixture was heated to reflux for 4 hours. The reaction solution was returned to room temperature, and the solution from which Pd / C had been removed was extracted twice with toluene (40 ml), washed with water by a conventional method, then concentrated, and the residue was purified by silica gel column chromatography. Compound (1-005) (1.600 g) was isolated.

The physicochemical properties of the obtained compound (1-005) are shown below.
¹ H-NMR (CDCl ₃ , ppm): δ 0.90 (3H, t, J = 7.2 Hz), 1.02-1.10 (2H, m), 1.21-1.36 (9H, m), 1.44-1.52 (2H, m), 1.87-1.93 (4H, m), 2.48-2.53 (1H, m), 4.83 (1H, Septet), 7.11-7.14 (2H, m), 7.27-7.29 (2H, m), 7.46-7.47 ( 2H m), 7.55 (2H, dd, J = 11.4Hz J = 2.6Hz),
¹⁹ F (CDCl ₃ , ppm): δ-74.03 and -74.05 (3F x 2, sx 2).

[Example 6]
Based on Examples 1 to 5 and the synthesis method described above, Compound (1-46) to Compound (1-204), which are examples of Compound (1) of the present invention, are synthesized.

Next, typical composition examples of the present invention containing the compound (1) of the present invention are shown below.
In the measurement of physical property values, there are three methods: a method using a compound alone as a sample, a method using a compound mixed with mother liquid crystals as a sample, and a method using a composition as a sample as it is.
When the compound is mixed with the mother liquid crystal, the following method is taken. The sample is prepared by mixing 15% by weight of compound and 85% by weight of mother liquid crystals. The physical property value of the compound is calculated from the value obtained by the measurement by extrapolation.
Extrapolated value = (measured value of sample−0.85 × measured value of mother liquid crystal) /0.15.
When the smectic phase (or crystal) is precipitated at 25 ° C. at this ratio, the ratio of the compound and the mother liquid crystal is changed in the order of 10 mass%: 90 mass%, 5 mass%, 1 mass%: 99 mass%.
The physical property value was measured according to the method described later.

(Composition Example 1)
Four compounds were mixed to prepare a composition A (mother liquid crystal) having a nematic phase. The four compounds are 4- (4-propylcyclohexyl) benzonitrile (24% by weight), 4- (4-pentylcyclohexyl) benzonitrile (36% by weight), 4- (4-heptylcyclohexyl) benzonitrile (25% by weight). %), And 4- (4-pentylcyclohexyl) -4′-cyanobiphenyl (15% by weight).
The physical properties of composition A were as follows. Upper limit temperature (NI) = 71.7 ℃; viscosity _{(η 20) = 27.0mPa · s} ; optical anisotropy (Δn) = 0.137; dielectric anisotropy (Δε) = 11.0.
The composition example 1 was prepared by adding the compound (1-001) described in the example 1 to the composition A. Specifically, Compound (1-001) was added at 10% by weight based on Composition Example 1 to prepare Composition Example 1 of the present invention. As a result of measuring the physical property values of Composition Example 1, the maximum temperature (NI) = 148.7 ° C .; the optical anisotropy (Δn) = 0.157; and the dielectric anisotropy (Δε) = 22.6. .

(Composition Example 2)
The composition example 2 was prepared by adding the compound (1-002) synthesized in the example 2 to the composition A described in the composition example 1. Specifically, the compound (1-002) was added so that it might be 10 weight% with respect to the composition example 2, and the composition example 2 of this invention was prepared. As a result of measuring the physical property values of Composition Example 2, the maximum temperature (NI) = 79.7 ° C .; the optical anisotropy (Δn) = 0.077; and the dielectric anisotropy (Δε) = 7.6. .

(Composition Example 3)
The composition example 3 was prepared by adding the compound (1-003) synthesized in the example 3 to the composition A described in the composition example 1. Specifically, the compound (1-003) was added so that it might be 15 weight% with respect to the composition example 3, and the composition example 3 of this invention was prepared. As a result of measuring the physical property values of Composition Example 3, the maximum temperature (NI) = 75.7 ° C .; the optical anisotropy (Δn) = 0.077; and the dielectric anisotropy (Δε) = 11.3. .

(Composition Example 4)
A composition example 4 was prepared by adding the compound (1-004) synthesized in the example 4 to the composition A described in the composition example 1. Specifically, the compound (1-004) was added at 5% by weight with respect to the composition example 4 to prepare composition example 4 of the present invention. As a result of measuring the physical property values of Composition Example 4, the maximum temperature (NI) = 57.7 ° C .; the optical anisotropy (Δn) = 0.157; and the dielectric anisotropy (Δε) = 17.4. .

(Composition Example 5)
A composition example 5 was prepared by adding the compound (1-005) synthesized in the example 5 to the composition A described in the composition example 1. Specifically, the compound (1-005) was added so that it might be 15 weight% with respect to the composition example 5, and the composition example 5 of this invention was prepared. As a result of measuring the physical property values of Composition Example 5, the maximum temperature (NI) = 43 ° C .; the optical anisotropy (Δn) = 0.097; and the dielectric anisotropy (Δε) = 11.6.

(Composition Examples 6-18)
Furthermore, about the typical composition examples 6-18 of this invention containing a compound (1), the compound which is a component of the composition, its quantity (weight%), and the physical-property value were shown.
The compounds included in each composition example were indicated by the symbols of the left terminal group, the linking group, the ring structure, and the right terminal group according to the conventions in Table 1. The configuration of 1,4-cyclohexylene and 1,3-dioxane-2,5-diyl is trans. When there is no terminal group symbol, it means that the terminal group is hydrogen.

Moreover, the physical property value of each composition example was measured and shown. Specifically, the upper limit temperature of the nematic phase (NI; ° C.), the lower limit temperature of the nematic phase (T _C ; ° C.), the compatibility of the compound, the viscosity (η; measured at 20 ° C .; mPa · s), optical anisotropy (Refractive index anisotropy; Δn; measured at 25 ° C.), dielectric anisotropy (Δε; measured at 25 ° C.) and threshold voltage (Vth; measured at 25 ° C .; V) . The physical property values were measured in accordance with the method described in Standard of Electronic Industries Association of Japan, EIAJ / ED-2521A, or a modified method thereof, specifically as follows. .

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

Minimum temperature of nematic phase (T _C ; ° C.): A sample having a nematic phase is stored in a freezer at 0 ° C., −10 ° C., −20 ° C., −30 ° C., and −40 ° C. Observed. For example, when the sample remains in a nematic phase at −20 ° C. and changes to a crystal (or smectic phase) at −30 ° C., T _C is described as ≦ −20 ° C. The lower limit temperature of the nematic phase may be abbreviated as “lower limit temperature”.

  Compound compatibility: A mother liquid crystal having a nematic phase was prepared by mixing several compounds having a similar structure. A composition in which the compound to be measured and this mother liquid crystal were mixed was obtained. An example of the mixing ratio is 15% compound and 85% mother liquid crystal. This composition was stored at a low temperature such as −20 ° C. and −30 ° C. for 30 days. It was observed whether a part of this composition was changed to a crystal (or smectic phase). The mixing ratio and storage temperature were changed as necessary. From the measurement results, the conditions under which crystals (or smectic phases) precipitate and the conditions under which crystals (or smectic phases) do not precipitate were determined. These conditions are a measure of compatibility.

  Viscosity (η; measured at 20 ° C .; mPa · s): An E-type rotational viscometer was used to measure the viscosity.

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

Dielectric Anisotropy (Δε; measured at 25 ° C.): When the sample was a compound, the compound was mixed with an appropriate composition, and then the dielectric anisotropy was measured. The dielectric anisotropy of the compound is an extrapolated value.
1) Composition having a positive dielectric anisotropy: A sample was placed in a liquid crystal cell in which the distance (gap) between two glass substrates was about 9 μm and the twist angle was 80 degrees. 20 volts was applied to the cell, and the dielectric constant (ε 率) in the major axis direction of the liquid crystal molecules was measured. 0.5 V was applied, and the dielectric constant (ε⊥) in the minor axis direction of the liquid crystal molecules was measured. The value of dielectric anisotropy was calculated from the equation: Δε = ε∥−ε⊥.
2) Composition having a negative dielectric anisotropy: A sample was placed in a liquid crystal cell treated in a homeotropic alignment, and 0.5 volt was applied to measure the dielectric constant (ε ボ ル ト). A sample was put in a liquid crystal cell treated to homogeneous alignment, and a dielectric constant (ε⊥) was measured by applying 0.5 volts. The value of dielectric anisotropy was calculated from the equation: Δε = ε∥−ε⊥.

Threshold voltage (Vth; measured at 25 ° C .; V): When the sample was a compound, the threshold voltage was measured after mixing the compound with an appropriate composition. The threshold voltage of the compound is an extrapolated value.
1) A composition having a positive dielectric anisotropy: a normally white mode (normally white mode) in which a distance (gap) between two glass substrates is (0.5 / Δn) μm and a twist angle is 80 degrees.
A sample was put in a liquid crystal display element in white mode). Δn is a value of optical anisotropy measured by the above method. A rectangular wave having a frequency of 32 Hz was applied to this element. The voltage of the rectangular wave was increased and the value of the voltage when the transmittance of light passing through the element reached 90% was measured.
2) Composition having a negative dielectric anisotropy: For a normally black mode liquid crystal display element in which the distance (gap) between two glass substrates is about 9 μm and is processed in a homeotropic alignment. A sample was placed. A rectangular wave having a frequency of 32 Hz was applied to this element. The voltage of the rectangular wave was raised, and the value of the voltage when the transmittance of light passing through the element reached 10% was measured.

  Helical pitch (measured at 20 ° C .; μm): Kano's wedge cell method was used to measure the helical pitch. A sample was injected into a Kano wedge-shaped cell, and the distance (a; unit: μm) between disclination lines observed from the cell was measured. The helical pitch (P) was calculated from the formula P = 2 · a · tan θ. θ is an angle between two glass plates in the wedge-shaped cell.

(Composition Example 6)
3-HHB-IF7 10%

2-BEB (F) -C 5%
3-BEB (F) -C 4%
4-BEB (F) -C 12%
1V2-BEB (F, F) -C 16%
3-HB-O2 4%
3-HH-4 3%
3-HHB-F 3%
3-HHB-1 4%
3-HHB-O1 4%
3-HBEB-F 4%
3-HHEB-F 7%
5-HHEB-F 7%
3-H2BTB-2 4%
3-H2BTB-3 4%
3-H2BTB-4 4%
3-HB (F) TB-2 5%

NI = 83.5 ° C .; Δn = 0.140; Δε = 28.8; Vth = 0.96V.

(Composition Example 7)
3-HHB (F) B (F, F) -OIF7 5%
3-HHXB (F, F) -OIF7 5%

2-HB-C 5%
3-HB-C 10%
3-HB-O2 15%
2-BTB-1 3%
3-HHB-F 8%
3-HHB-1 4%
3-HHB-O1 5%
3-HHB-3 14%
3-HHEB-F 4%
5-HHEB-F 4%
2-HHB (F) -F 4%
3-HHB (F) -F 4%
5-HHB (F) -F 5%
3-HHB (F, F) -F 5%

(Composition Example 8)
3-HHB-IF7 3%
3-HHB-OIF7 5%
3-HHB (F, F) -OIF7 5%

3-BEB (F) -C 8%
3-HB-C 8%
V-HB-C 8%
1V-HB-C 8%
3-HB-O2 3%
3-HH-2V 10%
3-HH-2V1 6%
V2-HHB-1 7%
3-HHB-1 5%
3-HHEB-F 7%
3-H2BTB-2 6%
3-H2BTB-3 6%
3-H2BTB-4 5%

NI = 90.7 ° C .; Δn = 0.130; Δε = 9.3; Vth = 1.60V.

(Composition Example 9)
3-HHB-OIF7 5%
3-HHB (F, F) -OIF7 5%

5-BEB (F) -C 5%
V-HB-C 11%
5-PyB-C 6%
4-BB-3 6%
3-HH-2V 10%
5-HH-V 11%
V-HHB-1 7%
V2-HHB-1 10%
3-HHB-1 9%
1V2-HBB-2 10%
3-HHEBH-3 5%

NI = 92.6 ° C .; Δn = 0.113; Δε = 5.5; Vth = 1.90V.

(Composition Example 10)
3-HHB (F, F) -OIF7 5%
2-BB (F, F) XB (F, F) -OIF7 5%

1V2-BEB (F, F) -C 6%

3-HB-C 18%
2-BTB-1 10%
5-HH-VFF 20%
3-HHB-1 4%
VFF-HHB-1 8%
VFF2-HHB-1 11%
3-H2BTB-2 5%
3-H2BTB-3 4%
3-H2BTB-4 4%

(Composition Example 11)
3-HHB-IF7 5%
3-HHB (F, F) -OIF7 5%

5-HB-CL 16%
3-HH-4 12%
3-HH-5 4%
3-HHB-F 4%
3-HHB-CL 3%
4-HHB-CL 4%
3-HHB (F) -F 8%
4-HHB (F) -F 6%
5-HHB (F) -F 6%
7-HHB (F) -F 6%
5-HBB (F) -F 4%
1O1-HBBH-5 3%
3-HHBB (F, F) -F 2%
4-HHBB (F, F) -F 3%
5-HHBB (F, F) -F 3%
3-HH2BB (F, F) -F 3%
4-HH2BB (F, F) -F 3%

NI = 109.2 ° C .; Δn = 0.090; Δε = 4.1; Vth = 2.19V.
The pitch when 0.25 part of Op05 was added to 100 parts of the composition was 60.0 μm.

(Composition Example 12)
3-HHB (F, F) -OIF7 5%
2-BB (F, F) XB (F) -OIF7 6%

3-HHB (F, F) -F 9%
3-H2HB (F, F) -F 8%
4-H2HB (F, F) -F 8%
5-H2HB (F, F) -F 8%
3-HBB (F, F) -F 20%
5-HBB (F, F) -F 15%
3-H2BB (F, F) -F 5%
5-HHBB (F, F) -F 3%
5-HHEBB-F 3%
3-HH2BB (F, F) -F 2%
1O1-HBBH-4 4%
1O1-HBBH-5 4%

(Composition Example 13)
3-HHB-IF7 5%
3-HHB-OIF7 5%
3-BB (F) B (F, F) -OIF7 5%

5-HB-F 12%
6-HB-F 9%
7-HB-F 6%
2-HHB-OCF3 6%
3-HHB-OCF3 6%
4-HHB-OCF3 6%
5-HHB-OCF3 4%
3-HH2B-OCF3 4%
5-HH2B-OCF3 4%
3-HHB (F, F) -OCF2H 4%
3-HHB (F, F) -OCF3 5%
3-HH2B (F) -F 3%
3-HBB (F) -F 5%
5-HBB (F) -F 5%
5-HBBH-3 3%
3-HB (F) BH-3 3%

(Composition Example 14)
3-HHB-IF7 7%
3-HHB-OIF7 5%

5-HB-CL 11%
3-HH-4 8%
3-HHB-1 5%
3-HHB (F, F) -F 6%
3-HBB (F, F) -F 13%
5-HBB (F, F) -F 10%
3-HHEB (F, F) -F 10%
4-HHEB (F, F) -F 3%
5-HHEB (F, F) -F 3%
2-HBEB (F, F) -F 3%
3-HBEB (F, F) -F 5%
5-HBEB (F, F) -F 3%
3-HHBB (F, F) -F 8%

NI = 79.4 ° C .; Δn = 0.097; Δε = 8.2; Vth = 1.59V.

(Composition Example 15)
3-HHB-IF7 5%
3-BB (F) B (F, F) -OIF7 5%

3-HB-CL 6%
5-HB-CL 4%
3-HHB-OCF3 5%
3-H2HB-OCF3 5%
5-H4HB-OCF3 12%
V-HHB (F) -F 5%
3-HHB (F) -F 5%
5-HHB (F) -F 5%
3-H4HB (F, F) -CF3 8%
5-H4HB (F, F) -CF3 10%
5-H2HB (F, F) -F 5%
5-H4HB (F, F) -F 7%
2-H2BB (F) -F 3%
3-H2BB (F) -F 5%
3-HBEB (F, F) -F 5%

(Composition Example 16)
3-HHB (F, F) -OIF7 5%
3-BB (F) B (F, F) -OIF7 5%
3-HHXB (F, F) -OIF7 5%

5-HB-CL 17%
7-HB (F, F) -F 3%
3-HH-4 10%
3-HH-5 5%
3-HB-O2 8%
3-HHB-1 8%
3-HHB-O1 5%
2-HHB (F) -F 4%
3-HHB (F) -F 5%
5-HHB (F) -F 4%
3-HHB (F, F) -F 6%
3-H2HB (F, F) -F 5%
4-H2HB (F, F) -F 5%

(Composition Example 17)
3-HHB (F, F) -OIF7 10%

5-HB-CL 3%
7-HB (F) -F 7%
3-HH-4 9%
3-HH-EMe 13%
3-HHEB-F 8%
5-HHEB-F 8%
3-HHEB (F, F) -F 10%
4-HHEB (F, F) -F 5%
4-HB (F, F) -F 5%
5-HB (F, F) -F 6%
2-H2B (F, F) -F 4%
3-H2B (F, F) -F 5%
5-HB (F, F) -F 7%

NI = 79.7 ° C .; Δn = 0.065; Δε = 6.7; Vth = 1.73 V.

(Composition Example 18)
3-HHB-OIF7 10%

3-HH-4 8%
3-HHB-1 6%
3-HHB (F, F) -F 10%
3-H2HB (F, F) -F 9%
3-HBB (F, F) -F 10%
3-BB (F, F) XB (F, F) -F 30%
1O1-HBBH-5 7%
2-HHBB (F, F) -F 3%
3-HHBB (F, F) -F 3%
3-HH2BB (F, F) -F 4%

NI = 86.3 ° C .; Δn = 0.111; Δε = 11.1; Vth = 1.30V.

  By using the compound of the present invention and the composition containing the compound as a liquid crystal display composition, a liquid crystal display element having a wide temperature range, a short response time, a large contrast ratio, and a low driving voltage can be produced.

Claims (14)

The compound represented by General formula (1).

[Where:
R is alkyl having 1 to 10 carbons, and any —CH ₂ — in the group may be replaced by —O—, —S—, —CO— or —CH═CH—;
Rings A ¹ , A ² and A ³ are, independently of one another, 1) or 2):
1) 1,4-cyclohexylene or 1,4-cyclohexylene cyclohexylene, any one of -CH ₂ present in the group - or more than one -CH ₂ nonadjacent - is - May be replaced by O-;
2) 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl or decahydronaphthalene-2,6-diyl, any one or two of 1,4-phenylene -CH = may be replaced by -N =;
In the group described in 1) or 2), one or more optional hydrogens are halogen, —C≡N, —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₃ , —OCHF ₂ or —OCH ₂ F May be replaced by;
L ¹ and L ² are independently of each other hydrogen or fluorine;
Z ¹ , Z ² and Z ³ are each independently a single bond, — (CH ₂ ) ₂ —, —CH ₂ O—, —CH═CH—, —CF ₂ O—, — (CH ₂ ) ₄ —. , —OCF ₂ —, —CH ₂ CH ₂ CF ₂ O—, —CH ₂ CH ₂ CH ₂ O—, —CH═CHCH ₂ O—, —CH═CH—CH ₂ CH ₂ —, —CH ₂ CO— , -COO-, -OCO-, -CF = CF- or -C≡C-;
Z ⁴ is a single bond or —O—;
X is hydrogen or fluorine;
m and n are each independently 0 or 1. ] R is alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons or alkoxy having 1 to 10 carbons;
The rings A ¹ , A ² and A ³ are independently of each other 1) or 2):
1) 1,4-cyclohexylene or 1,4-cyclohexylene cyclohexylene, any one of -CH ₂ present in the group - or more than one -CH ₂ nonadjacent - is - May be replaced by O-;
2) 1,4-phenylene or naphthalene-2,6-diyl, wherein any one or two -CH = of 1,4-phenylene may be replaced by -N =;
One or more hydrogens in the group described in 1) or 2) may be replaced by fluorine;
Z ¹ , Z ² and Z ³ are each independently a single bond, — (CH ₂ ) ₂ —, —CH ₂ O—, —CH═CH—, —CF ₂ O—, — (CH ₂ ) ₄ —. _{, -OCF 2 -, - CH 2} CH 2 CF 2 O -, - CH 2 CH 2 CH 2 O -, - CH = CHCH 2 O -, - CH = CHCH 2 CH 2 -, - CH 2 CO, -COO- or -OCO-.
The compound of claim 1. Rings A ¹ , A ² and A ³ are independently of each other 1,4-cyclohexylene, 1,4-cyclohexenylene, 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 or pyridazine-2,5-diyl;
Z ¹ , Z ² and Z ³ are each independently a single bond, — (CH ₂ ) ₂ —, —CH ₂ O—, —CH═CH—, —CF ₂ O—, — (CH ₂ ) ₄ —. _{, -OCF 2 -, - CH 2} CH 2 CF 2 O -, - CH 2 CH 2 CH 2 O -, - CH = CHCH 2 O- or -CH = CHCH ₂ CH ₂ - is,
The compound according to claim 2. Rings A ¹ , A ² and A ³ are independently of each other 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene 2,5-difluoro-1,4-phenylene or 2,6-difluoro-1,4-phenylene;
Z ^1, Z ² and Z ³ are each independently a single _{bond, - (CH 2) 2 -} , - CH 2 O -, - CH = CH- or -CF ₂ O-,
The compound according to claim 2. A compound represented by any one of formulas (1-1) to (1-13).

Wherein R is alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons or alkoxy having 1 to 10 carbons;
L ¹ and L ² are independently of each other hydrogen or fluorine;
Z ⁴ is a single bond or —O—;
X is hydrogen or fluorine. ) A compound represented by any one of formulas (1-14) to (1-45):

(In the formula, R is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons.)   A liquid crystal composition comprising at least two compounds containing at least one compound according to any one of claims 1 to 6. The liquid crystal composition according to claim 7, comprising at least one compound selected from the group of compounds represented by formulas (2), (3), and (4).

[Wherein, R ¹ is alkyl having 1 to 10 carbon atoms, and any —CH ₂ — in the group may be replaced by —O— or —CH═CH—, and any hydrogen is fluorine. May be replaced;
Ring B and Ring D are independently of each other 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl or 1,4-phenylene in which any hydrogen may be replaced by fluorine;
Ring E is 1,4-cyclohexylene or 1,4-phenylene in which any hydrogen may be replaced by fluorine;
Z ⁵ and Z ⁶ are each independently — (CH ₂ ) ₂ —, — (CH ₂ ) ₄ —, —COO—, —CF ₂ O—, —OCF ₂ —, —CH═CH— or a single bond. Yes;
L ³ and L ⁴ are independently of each other hydrogen or fluorine;
X ¹ is fluorine, chlorine, —OCF ₃ , —OCHF ₂ , —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₂ CHF ₂ or —OCF ₂ CHFCF ₃ . ] The liquid crystal composition according to claim 7 or 8, comprising at least one compound selected from the group of compounds represented by formulas (5) and (6).

[Wherein, R ² and R ³ are each independently alkyl having 1 to 10 carbon atoms, and any —CH ₂ — in the group may be replaced by —O— or —CH═CH—. Any hydrogen may be replaced by fluorine;
Ring G is 1,4-cyclohexylene, 1,4-phenylene, 1,3-dioxane-2,5-diyl or pyrimidine-2,5-diyl;
Ring J is 1,4-cyclohexylene, pyrimidine-2,5-diyl or 1,4-phenylene in which any hydrogen may be replaced by fluorine;
Z ⁷ is — (CH ₂ ) ₂ —, —COO—, —CF ₂ O—, —OCF ₂ — or a single bond;
L ⁵ , L ⁶ and L ⁷ are independently of each other hydrogen or fluorine;
X ² is —C≡N or —C≡C—C≡N;
b, c and d are each independently 0 or 1; ] It contains at least one compound selected from the group of compounds represented by each of formula (7), formula (8), formula (9), formula (10) and formula (11). The liquid crystal composition according to any one of the above.

[Wherein, R ⁴ is alkyl having 1 to 10 carbon atoms, and any —CH ₂ — in the group may be replaced by —O— or —CH═CH—, and any hydrogen is fluorine. May be replaced;
R ⁵ is fluorine or alkyl having 1 to 10 carbon atoms, and any —CH ₂ — in the group may be replaced with —O— or —CH═CH—, and any hydrogen is replaced with fluorine. May be;
Ring M and Ring P are independently of each other 1,4-cyclohexylene, 1,4-phenylene or decahydronaphthalene-2,6-diyl;
Z ⁸ and Z ⁹ are independently of each other — (CH ₂ ) ₂ —, —COO— or a single bond;
L ⁸ and L ⁹ are each independently hydrogen or fluorine, and at least one of L ⁸ and L ⁹ is fluorine. ] The liquid crystal composition according to any one of claims 7 to 10, comprising at least one compound selected from the group of compounds represented by formula (12), formula (13) and formula (14). object.

[Wherein, R ⁶ and R ⁷ are each independently alkyl having 1 to 10 carbon atoms, and any —CH ₂ — in the group may be replaced by —O— or —CH═CH—. Any hydrogen may be replaced by fluorine;
Ring Q, Ring T and Ring U are each independently 1,4-cyclohexylene, pyrimidine-2,5-diyl or 1,4-phenylene in which any hydrogen may be replaced by fluorine;
Z ¹⁰ and Z ¹¹ are each independently —C≡C—, —COO—, — (CH ₂ ) ₂ —, —CH═CH— or a single bond. ]   The liquid crystal composition according to any one of claims 7 to 11, wherein the compound according to any one of claims 1 to 6 is contained in an amount of 4 to 15% by weight based on the total weight of the composition.   The liquid crystal composition according to any one of claims 7 to 12, further comprising at least one optically active compound.   The liquid crystal display element containing the liquid-crystal composition as described in any one of Claims 7-13.