JP2008247890A - New compound having 2,2,2-bicyclooctane bonded with halogenated alkyl and liquid crystal composition using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid crystalline compound having general physical properties required for the compound, low viscosity, proper optical anisotropy, proper dielectric anisotropy and excellent compatibility with other liquid crystalline compounds. <P>SOLUTION: A compound represented by formula (1) is provided. For example, R is a 1-10C alkyl; ring A<SP>1</SP>, ring A<SP>2</SP>and ring A<SP>3</SP>are 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene or 1,3-dioxane-2,5-diyl; Z<SP>1</SP>, Z<SP>2</SP>and Z<SP>3</SP>are a single bond, -(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>-, -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-, -CH=CHCH<SB>2</SB>O-, -CH=CH-CH<SB>2</SB>CH<SB>2</SB>-, -CH<SB>2</SB>CO-, -COO-, -CF=CF-, or -C≡C-; Y is a 1-10C perfluoroalkyl; and m and n are 0 or 1. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a compound having 2,2,2-bicyclooctane having a halogenated alkyl group as a side chain and a liquid crystal composition. More specifically, it comprises a compound having 2,2,2-bicyclooctane bonded to a halogenated alkyl group, a liquid crystal composition containing the compound, and the liquid crystal composition.

  A display element using a liquid crystal compound (in this application, the term liquid crystal compound is used as a generic term for a compound that exhibits a liquid crystal phase and a compound that does not exhibit a liquid crystal phase but is useful as a component of a liquid crystal composition). Widely used in displays such as clocks, calculators and word processors. These display elements utilize the refractive index anisotropy and dielectric anisotropy of liquid crystal compounds.

  The liquid crystal phase includes a nematic liquid crystal phase, a smectic liquid crystal phase, and a cholesteric liquid crystal phase, and those using a nematic liquid crystal phase are most widely used. Display methods include dynamic scattering (DS) type, oriented phase deformation (DAP) type, guest / host (GH) type, twisted nematic (TN) type, super twisted nematic (STN) type, thin film transistor (TFT) type, There are a vertical alignment (VA) type, an in-plane switching (IPS) type, and the like.

  The liquid crystalline compounds used in these display systems exhibit a liquid crystal phase in a wide temperature range centered on room temperature, are sufficiently stable under the conditions in which the display element is used, and are sufficient to drive the display element. Although it must have characteristics, no single liquid crystal compound satisfying this condition has been found at present.

  Therefore, in reality, a liquid crystal composition having required characteristics is prepared by mixing several to several tens of liquid crystal compounds. These liquid crystal compositions are stable to moisture, light, heat and air that are usually present under the conditions in which the display element is used, are stable to electric fields and electromagnetic radiation, and are mixed. The compound is required to be chemically stable. In addition, the liquid crystal composition has various values of physical properties such as a refractive index anisotropy value (Δn) and a dielectric anisotropy value (Δε) depending on the display method and the shape of the display element. Is needed. Furthermore, it is important that the components in the liquid crystal composition have good solubility with each other.

  Mobile information terminal displays such as mobile PCs, PDAs, and mobile phones are required to be thin, lightweight, and have low power consumption. The transmissive displays that have been developed so far are disadvantageous in terms of low power consumption because they require a backlight, and the contrast is greatly reduced by scattered light due to surface reflection in bright places such as outdoors. There is. That is, the transmissive display does not have sufficient performance for use as a portable information terminal display. In order to solve this problem, a reflection type active matrix display that does not use a backlight (hereinafter, the active matrix display may be referred to as AM-LCD) has been developed.

  Reflective AM-LCDs are S. T.A. Light passes through the liquid crystal layer twice as reported by Wu et al. In SID97 Digest / 643. For this reason, the product (Δn · d) of the thickness (d) of the liquid crystal layer and the refractive index anisotropy value (Δn) of the liquid crystal must be set small. In the case of a conventional transmissive TN type liquid crystal composition for AM-LCD, the required Δn is about 0.075 to 0.120, but in the case of a reflective type liquid crystal composition for AM-LCD, 0.075 or less.

Conventionally, there are some synthesis report examples of compounds in which an alkyl halide is bonded to a 2,2,2-bicyclooctane ring (Non-Patent Document 1, Non-Patent Document 2, Non-Patent Document 3), but they are applied to liquid crystal display devices. There are few known examples.

J. Phys. Chem. A, 2006, 110, 10122-10129. J. Org. Chem., 1985, 50, 2551-2557. J. Org. Chem., 1982, 47, 2957-2966.

  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 formula (1).

Wherein R is alkyl having 1 to 10 carbons, and any —CH ₂ — in the alkyl may be replaced by —O—, —S—, —CO— or —CH═CH—;
Ring A ¹ , Ring A ² and Ring A ³ are independently 1) or 2):
1) 1,4-cyclohexylene or 1,4-cyclohexenylene, and these one —CH ₂ — or two or more non-adjacent —CH ₂ — may be replaced by —O—. Often;
2) 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, or decahydronaphthalene-2,6-diyl, one of these 1,4-phenylene or Two -CH = may be replaced by -N =;
Any hydrogen in the group described in 1) or 2) is replaced with halogen, —C≡N, —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₃ , —OCHF _2, or —OCH ₂ F. May be;
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 —, _{-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 -, - CF = CF-, or -C≡C-;
Y is perfluoroalkyl having 1 to 10 carbon atoms;
m and n are independently 0 or 1.

[2] R is alkyl having 1 to 10 carbons, alkenyl having 2 to 11 carbons or alkoxy having 1 to 9 carbons;
Ring A ¹ , Ring A ² and Ring A ³ are independently the following 1) or 2):
1) 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, or 1,3-dioxane-2,5-diyl;
2) 1,4-phenylene, naphthalene-2,6-diyl, pyridine-2,5-diyl, or pyrimidine-2,5-diyl;
Any hydrogen in the group described in 2) may be replaced by fluorine;
Z ¹ , Z ² and Z ³ are independently a single bond, — (CH ₂ ) ₂ —, —CH ₂ O—, —CH═CH—, — (CH ₂ ) ₄ —, —CH ₂ CH ₂ CH ₂ O—, —CH═CHCH ₂ CH ₂ —, or —COO—,
The compound according to item [1].

[3] R is alkyl having 1 to 10 carbons, alkenyl having 2 to 11 carbons or alkoxy having 1 to 5 carbons;
Ring A ¹ , Ring A ² and Ring A ³ are independently 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, pyridine-2,5-diyl, 3-fluoropyridine-2,5-diyl, or pyrimidine-2,5-diyl;
Z ¹ , Z ² and Z ³ are each independently a single bond, — (CH ₂ ) ₂ —, —CH ₂ O—, —CH═CH—, — (CH ₂ ) ₄ —, or —COO—. ,
The compound according to item [1].

[4] R is alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons or alkoxy having 1 to 5 carbons;
Ring A ¹ , Ring A ² and Ring A ³ are independently 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 independently a single bond, — (CH ₂ ) ₂ —, —CH ₂ O—, or —CH═CH—.
The compound according to item [1].

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

は、１，４−フェニレン、または１つ〜２つの水素がフッ素で置き換えられた１，４−フェニレンであり、；
Ｚ^３は単結合であり；
Ｙは−ＣＦ_３である。 In the formula, R is alkyl having 1 to 10 carbons or alkenyl having 2 to 5 carbons;

Is 1,4-phenylene, or 1,4-phenylene in which one to two hydrogens are replaced by fluorine;
Z ³ is a single bond;
Y is -CF _3.

式中、Ｒは炭素数１〜５のアルキルである。 [6] A compound represented by any one of formulas (1-7) to (1-9).

In the formula, R is alkyl having 1 to 5 carbon atoms.

  [7] A liquid crystal composition comprising two or more components, comprising at least one compound according to any one of items [1] to [6].

[8] The liquid crystal composition according to item [7], containing as a component at least one compound selected from the group of compounds represented by formulas (2), (3), and (4).

In the formula, R ³ is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in alkyl and alkenyl, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be —O—. May be replaced by;
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 ;
Ring A ¹ , Ring A ² and Ring A ³ are independently 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, 1-pyran-2,5. -Diyl or 1,4-phenylene in which any hydrogen may be replaced by fluorine;
Z ¹ and Z ² are independently — (CH ₂ ) ₂ —, — (CH ₂ ) ₄ —, —COO—, —CF ₂ O—, —OCF ₂ —, —CH═CH—, —C≡. C—, —CH ₂ O—, or a single bond;
L ¹ and L ² are independently hydrogen or fluorine.

[9] The liquid crystal composition according to item [7], further containing at least one compound selected from the group of compounds represented by formula (5).

In the formula, R ⁴ is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in alkyl and alkenyl, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be —O—. May be replaced by;
X ² is —C≡N or —C≡C—C≡N;
Ring B ¹ , Ring B ² and Ring B ³ are independently 1,4-cyclohexylene, 1,4-phenylene, 1,3-dioxane-2,5- in which any hydrogen may be replaced by fluorine Diyl, 1-pyran-2,5-diyl, or pyrimidine-2,5-diyl;
Z ³ is — (CH ₂ ) ₂ —, —COO—, —CF ₂ O—, —OCF ₂ —, —C≡C—, —CH ₂ O—, or a single bond;
L ³ and L ⁴ are independently hydrogen or fluorine;
q is independently 0, 1 or 2, and r is independently 0 or 1.

[10] Item [7] containing at least one compound selected from the group of compounds represented by formulas (6), (7), (8), (9) and (10) as one component ] The liquid crystal composition as described in.

In the formula, R ⁵ and R ⁶ are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, any hydrogen may be replaced by fluorine, and any — CH ₂ — may be replaced by —O—;
Ring C ¹ , Ring C ² , Ring C ³ and Ring C ⁴ are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4- Phenylene, 6-pyran-2,5-diyl or decahydro-2,6-naphthalene;
Z ⁴ , Z ⁵ , Z ⁶ and Z ⁷ are independently — (CH ₂ ) ₂ —, —COO—, —CH ₂ O—, —OCF ₂ —, —OCF ₂ (CH ₂ ) ₂ —, or A bond;
L ⁵ and L ⁶ are independently fluorine or chlorine;
j, k, l, m and n are each independently 0 or 1, and k + l + m + n is 1 or 2.

[11] The liquid crystal composition according to item [7], containing at least one compound selected from the group of compounds represented by formulas (11), (12) and (13) as one component.

In the formula, R ⁷ and R ⁸ are each independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in this alkyl and alkenyl, any hydrogen may be replaced by fluorine, and any — CH ₂ — may be replaced by —O—;
Ring D ¹ , Ring D ² and Ring D ³ are independently 1,4-cyclohexylene, pyrimidine-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro- 1,4-phenylene or 2,5-difluoro 1,4-phenylene;
Z ⁸ and Z ⁹ are independently —C≡C—, —COO—, — (CH ₂ ) ₂ —, —CH═CH—, or a single bond.

  [12] The liquid crystal composition according to item [8], further comprising at least one compound selected from the group of compounds represented by formula (5) according to item [9].

  [13] The item [8], further comprising at least one compound selected from the group of compounds represented by each of the general formulas (11), (12), and (13) described in item [11] Liquid crystal composition.

  [14] The item [9], further comprising at least one compound selected from the group of compounds represented by each of the general formulas (11), (12), and (13) described in item [11] Liquid crystal composition.

  [15] The item [10], further comprising at least one compound selected from the group of compounds represented by each of the general formulas (11), (12), and (13) described in item [11] Liquid crystal composition.

  [16] The liquid crystal composition according to any one of items [7] to [15], further containing at least one optically active compound.

  [17] The liquid crystal composition according to any one of items [7] to [16], comprising at least one antioxidant and / or ultraviolet absorber.

  [18] A liquid crystal display device comprising the liquid crystal composition according to any one of items [7] to [17].

  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 element may be abbreviated as “compound”, “composition”, and “element”, 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 with —O— to become —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 by —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, examples of groups in which any —CH ₂ — in CH ₃ (CH ₂ ) ₃ — 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, -C 9 H 19, and a _-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} It is.

The alkoxyalkyl may be linear or branched, and specific examples of alkoxyalkyl include —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 is 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.

The 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 11 carbons, alkyl having 1 to 10 carbons, or carbon 2 to 11 alkenyl or is more preferably an alkoxy having 1 to 9 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 , or — (CH More preferably, ₂ ) ₂ CH═CHCH ₃ .

Ring A ¹ , ring A ² and ring A ³ in formula (1) are independently the following 1) or 2).
1) 1,4-cyclohexylene or 1,4-cyclohexylene cyclohexylene, of any one of these groups -CH ₂ - or non-adjacent two or more -CH ₂ - by -O- It may be replaced.
2) 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl or decahydronaphthalene-2,6, -diyl, and any one of 1,4-phenylene One or two —CH═ may be replaced by —N═,
Any hydrogen in the group described in 1) or 2) is replaced with halogen, —C≡N, —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₃ , —OCHF ₂ , or —OCH ₂ F. May be

Preferably, ring A ¹ , ring A ² and ring A ³ in formula (1) are independently the following 1) or 2).
1) 1,4-cyclohexylene or 1,4-cyclohexenylene, and these one —CH ₂ — or two or more non-adjacent —CH ₂ — may be replaced by —O—. Good.
2) 1,4-phenylene or naphthalene-2,6-diyl, wherein one or two —CH═ of 1,4-phenylene may be replaced by —N═, and any hydrogen is replaced by fluorine May be.

Specifically, preferred examples of ring A ¹ , ring A ² and ring A ³ are groups represented by the following formulas (15-1) to (15-11).

In ring A ¹ , ring A ² and ring A ³ included in the range defined above, any hydrogen is halogen, —C≡N, —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₃ , — It may be replaced with OCHF ₂ or —OCH ₂ F.

Preferred examples of ring A ¹ , ring A ² and ring A ³ include 1,4-cyclohexylene (15-1), tetrahydropyran 2,5-diyl (15-2) (15-3), 1,3- Dioxane-2,5-diyl (15-4) (15-5), 1,4-cyclohexenylene (15-10), (15-11), 1,4-phenylene (15-12), pyridine- 2,5-diyl (15-13) and pyrimidine-2,5-diyl (15-14) (15-15), in which case the upper limit temperature is relatively high. 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 ring A ¹ , ring A ² and ring A ³ are 1,4-cyclohexylene, tetrahydropyran 2,5-diyl, 1,3-dioxane 2,5-diyl, 1,4-phenylene, and Pyrimidine-2,5-diyl, in which case the dielectric anisotropy is relatively large.

The most preferred examples of ring A ¹ , ring A ² and ring A ³ are 1,4-cyclohexylene, tetrahydropyran 2,5-diyl, and 1,3-dioxane 2,5-diyl, in this case optical Anisotropy is relatively small.

Z ¹ , Z ² and Z ³ in formula (1) are 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-, or -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-, Alternatively, -OCO- is more preferable because the temperature of the liquid crystal phase is relatively wide. 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 —, —CH _2. In the case of CH ₂ CF ₂ O—, —CH ₂ CH ₂ CH ₂ O—, —CH═CHCH ₂ O—, or —CH═CH—CH ₂ CH ₂ —, it is relatively stable and hardly deteriorates. Further preferred. ^Further, Z 1, ^{Z 2} and ^{Z 3} are a single _{bond, - (CH 2) 2 -} , - CH 2 O -, - CF 2 O-, and -CH = CH- relatively optically anisotropic in the case of Is most preferable since it is relatively small.
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.

Y in Formula (1) is a C1-C10 perfluoroalkyl.
M and n in Formula (1) are independently 0 or 1.

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 , ring A ² , ring A ³ , Z ¹ , Z ² , Z ³ and Y of compound (1), physical properties such as optical anisotropy and dielectric anisotropy Can be arbitrarily adjusted. The effects of the types of R, ring A ¹ , ring A ² , ring A ³ , Z ¹ , Z ² , Z ³ and Y ^{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.

Ring A ¹ , Ring A ² and Ring A ³ in Formula (1) are 1,4-phenylene, pyridine-2,5-diyl or 1,3-dioxane-2,5 in which any hydrogen is replaced by halogen -When it is diyl, the dielectric anisotropy is relatively large. Ring A ¹ , Ring A ² and A ³ may be 1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, or pyridazine-3, where any hydrogen may be replaced by halogen When it is 6-diyl, the optical anisotropy is relatively large. Ring A ¹ , Ring A ² and Ring A ³ are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydrofuran-2,5-diyl, or 1,3-dioxane-2,5-diyl. Sometimes the optical anisotropy is relatively small.

When ring A ¹ , ring A ² and ring A ³ are 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 ring A ² is 1,4-phenylene, the optical anisotropy is relatively large and the orientational order parameter is relatively large. When any of ring A ¹ , ring A ² and ring A ³ is 1,4-phenylene, the optical anisotropy is relatively large, the temperature range of the liquid crystal phase is relatively wide, and the maximum temperature is compared. High.

Z ¹ , Z ² and Z ³ are a single bond, — (CH ₂ ) ₂ —, —CH ₂ O—, —CF ₂ O—, —CH═CH—, —CF═CF—, or — (CH ₂ ). ₄ - 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—, — (CH ₂ ) ₄ —, they are chemically relatively stable. Therefore, it is relatively difficult to cause deterioration.

  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 type of R, ring A ¹ , ring A ² , ring A ³ , Z ¹ , Z ² and Z ³ and the number of rings. it can. 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 Examples of Compound (1) Preferred examples of compound (1) are compounds (1-1) to (1-6). More preferred examples of compound (1) are compounds (1-7) to (1-9). More specific examples are compounds (1-10) to (1-104) shown in Example 5 described later.

式中、Ｒは炭素数１〜１０のアルキル、または炭素数２〜５のアルケニルであり；
Ｚ^３は単結合であり；
Ｙは−ＣＦ_３である。

In the formula, R is alkyl having 1 to 10 carbons or alkenyl having 2 to 5 carbons;
Z ³ is a single bond;
Y is -CF _3.

式中、Ｒは炭素数１〜５のアルキルである。

In the formula, R is alkyl having 1 to 5 carbon atoms.

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 the 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 a single bond A compound obtained by reacting an arylboric acid (16) with a compound (17) synthesized by a known method in the presence of a catalyst such as an aqueous carbonate solution and tetrakis (triphenylphosphine) palladium. Synthesize (1A). This compound (1A) is obtained by reacting compound (18) 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— The compound (18) is reacted with n-butyllithium and subsequently with carbon dioxide to obtain a carboxylic acid (19). Compound having —COO— by dehydrating compound (19) and phenol (20) synthesized by a known method in the presence of DCC (1,3-dicyclohexylcarbodiimide) and DMAP (4-dimethylaminopyridine) Synthesize (1B).

(III) Formation with —CF ₂ O— Compound (21) is obtained by treating compound (1B) with a sulfurizing agent such as Lawesson's reagent. Compound (21) is fluorinated with hydrogen fluoride pyridine complex and NBS (N-bromosuccinimide) to synthesize compound (1C) having —CF ₂ O—. See M. Kuroboshi et al., Chem. Lett., 1992, 827. Compound (1C) can also be synthesized by fluorinating compound (21) with (diethylamino) sulfur trifluoride (DAST). See WH Bunnelle et al., J. Org. Chem. 1990, 55, 768. It is also possible to generate this linking group by the method described in Peer. Kirsch et al., Anbew. Chem. Int. Ed. 2001, 40, 1480.

(IV) Formation of —CH═CH— The compound (18) is treated with n-butyllithium and then reacted with formamide such as N, N-dimethylformamide (DMF) to obtain the aldehyde (23). A phosphoryl ylide generated by treating a phosphonium salt (22) synthesized by a known method with a base such as potassium tert-butoxide is reacted with an aldehyde (238) 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 (1E) 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 obtained by using the phosphonium salt (24) instead of the phosphonium salt (22) 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 (18) with 2-methyl-3-butyn-2-ol in the presence of a catalyst of dichlorobistriphenylphosphine palladium and copper halide, basic Deprotection under conditions gives compound (25). Compound (1G) is synthesized by reacting compound (25) with compound (17) in the presence of a catalyst of dichlorobistriphenylphosphine palladium and copper halide.

(VIII) Formation of —CF═CF— The compound (18) is treated with n-butyllithium and then reacted with tetrafluoroethylene to obtain the compound (26). Compound (17) is treated with n-butyllithium and then reacted with compound (26) to synthesize compound (1H).

(IX) Formation of —CH ₂ O— or —OCH ₂ — Compound (23) is obtained by reducing compound (23) with a reducing agent such as sodium borohydride. This is halogenated with hydrobromic acid or the like to obtain compound (28). Compound (1J) is synthesized by reacting compound (28) with compound (20) in the presence of potassium carbonate or the like.

1-4-2 Method for synthesizing ring A ¹ , ring A ² and ring A ³ 1,4-cyclohexanone, 1,3-dioxane-2,5-diyl, 1,4-phenylene, 2-fluoro-1, Regarding the rings such as 4-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. It has been. Therefore, the synthesis of the following compounds (31) and (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 (32) is protected with an appropriate protecting group to obtain compound (33). P means a protecting group, for example, Me group. Compound (33) is allowed to react with sec-butyllithium and subsequently reacted with N, N-dimethylformamide (DMF) to obtain aldehyde (34). This compound is fluorinated with dimethylaminosulfur trifluoride (DAST) followed by deprotection to give phenol (35). This compound is converted into the compound (1) by a general method of synthetic organic chemistry. Incidentally, Q ² in the above is a group represented by the following formula.

式中、環Ａ^３、Ｚ^３、およびＹは、式（１）において定義された意味と同一である。

In the formula, rings A ³ , Z ³ and Y have the same meaning as defined in formula (1).

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 compounds (37) and (38) as starting materials Synthesis of compounds (37) and (38) as 2,2,2-bicyclooctane ring derivatives as starting materials A method will be described.

Synthesis method of (37) and (38) which is a starting material when Y is —CF ₃

  Synthesized from ethyl acrylate according to J. Org. Chem., 1982, 47, 2957-2966. (36) according to J. Org. Chem., 1985, 50, 1079-1087. (37) or (38) Is obtained.

  Synthesis method of (41) and (42) as starting materials when Y is an alkyl halide having 2 to 10 carbon atoms

(36) synthesized above was prepared according to J. Org. Chem., 1988, 53, 5259-5266. And Journal of the Chemical Society of Japan, 1973, 2351-2356 (Rf = C _n F _{2n + 1} ) (41) or (42) is obtained.

1-4-3-2 Method for Synthesizing Compound (1) from Compound (43) or (44) A method for synthesizing (1) from compound (38) or (42) as a starting material will be described.
Compound (1) can be synthesized from compound (38) or (42) as a starting material by using a general method in organic synthetic chemistry.
The general synthesis examples (A) to (C) for synthesizing the compound (1) are shown below.
(A) Method for synthesizing compound (45) when ring A ³ is cyclohexylene and Z ³ is a single bond, or when Z ³ is alkylene and Y is alkyl halide

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

式中、Ｒ、環Ａ^１、環Ａ^２、環Ａ^３、Ｚ^１、Ｚ^２、Ｚ^３、ｍ、およびｎは、式（１）において定義された意味と同一である。

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

  As shown in Scheme 1 above, a cyclohexanone derivative (43) or a carbonyl derivative (44) is first prepared according to a method of organic synthetic chemistry, and a Grignard reaction, acid using an appropriate Grignard reagent (38), (42) is prepared. The dehydration reaction by hydrogenation and the hydrogen reduction using a Pd catalyst are sequentially performed, and then recrystallization is performed as necessary, or the alcohol is converted into FITS reagent or Angew described in Journal of Organic Chemical Synthesis 1983, 41, 48-63. Chem. Int. Ed., 2000, 39, 4216-4235. By fluorination, the compound (45) can be synthesized.

(B-1) Method for synthesizing compound (47) when ring A ³ is phenylene, pyrimidine, etc., Z ³ is a single bond, and Y is an alkyl halide

(B-2) Synthesis method of compound (49) when ring A ³ is phenylene, pyrimidine, etc., Z ³ is alkenylene and Y is alkyl halide

(B-3) Method for synthesizing compound (50) when ring A ³ is phenylene, pyrimidine, etc., Z ³ is alkynylene, and Y is an alkyl halide

  As shown above, the compound (48) can be easily derived into the compound (50) by first preparing the compound (48) according to a method of organic synthetic chemistry and performing a coupling reaction.

(C) Synthesis method of compound (52) when Z ³ is —CF ₂ O— and Y is an alkyl halide

式中、Ｒ、環Ａ^１、環Ａ^２、Ｚ^１、Ｚ^２、ｍ、およびｎは、式（１）において定義された意味と同一である。

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

  First, a compound (51) is prepared according to a method of organic synthetic chemistry, and is esterified with a compound (37) or (41) which is a 2,2,2, -bicyclooctane ring derivative as a starting material. By using the synthesis scheme (III) of the linking group described above, the compound (52) can be easily derived.

2 Composition of the Present Invention The compound of the present invention is superior in compatibility with other liquid crystal materials, has a low viscosity, and has a wide liquid crystal temperature range as compared with known compounds having the same structure. Moreover, compared with a similar compound, it has a low threshold voltage and a relatively low viscosity. Furthermore, the compound of the present invention is sufficiently stable physically and chemically under the conditions in which a liquid crystal display device is normally used, and is extremely excellent as a constituent component of a nematic liquid crystal composition, and a liquid crystal composition for TN type, STN type and TFT type. It can be suitably used as a constituent of a product.

  The liquid crystal composition of the present invention needs to contain the compound represented by the formula (1) of the present invention as Component A. The composition of only component A or a composition of component A and other components not specifically indicated in the present specification may be used, but components B, C, D and E shown below for component A are as follows. The liquid crystal composition (a), (b), (c), (d), (e) of the present invention having various characteristics can be provided by adding a component selected from the above.

  The component added to component A was selected from the group consisting of at least one compound selected from the group consisting of formulas (2), (3) and (4) and / or the group consisting of formula (5). Component C consisting of at least one compound and / or Component D consisting of at least one compound selected from the group consisting of formulas (6), (7), (8), (9) and (10) A mixture thereof is preferred [liquid crystal compositions (b), (c) and (d)].

Further, by mixing component E consisting of at least one compound selected from the group consisting of formulas (11), (12) and (13), threshold voltage, liquid crystal phase temperature range, refractive index anisotropy value The dielectric anisotropy value and viscosity can be adjusted [the liquid crystal composition (e)].
In addition, each component of the liquid crystal composition used in the present invention is not greatly different in physical properties even if it is an analog composed of an isotope element of each element.

  Among the components B, formulas (2-1) to (2-15) are preferable examples of the compound represented by the formula (2), and formulas (3-1) to (2) are preferable examples of the compound represented by the formula (3). Formulas (4-1) to (4-52) can be cited as preferred examples of the compound represented by (3-112) and the formula (4), respectively.

式中、Ｒ^３、Ｘ¹は前記と同じ意味である。

In the formula, R ³ and X ¹ have the same meaning as described above.

Since the compounds represented by the formulas (2) to (4), that is, the component B, have a positive dielectric anisotropy value and are very excellent in thermal stability and chemical stability, a liquid crystal for TFT is used. Used when preparing a composition. The content of component B in the liquid crystal composition of the present invention is suitably in the range of 1 to 99% by weight, preferably in the range of 10 to 97% by weight, more preferably 40 to 95%, based on the total weight of the liquid crystal composition. It is in the range of wt%. The viscosity can be adjusted by further containing a compound (component E) represented by formulas (11) to (13).
Preferred examples of the compound represented by formula (5), that is, component C, include formulas (5-1) to (5-62).

式中、Ｒ^４およびＸ²は前記と同じ意味である。

In the formula, R ⁴ and X ² have the same meaning as described above.

These compounds represented by the formula (5), that is, the component C, are mainly used when preparing liquid crystal compositions for STN and TN because the dielectric anisotropy value is positive and the value is very large. By containing this component C, the threshold voltage of the composition can be reduced. Further, the viscosity, the refractive index anisotropy value, and the liquid crystal phase temperature range can be expanded. It can also be used to improve steepness.
When preparing a liquid crystal composition for STN or TN, the content of component C can be in the range of 0.1 to 99.9% by weight, preferably in the range of 10 to 97% by weight, more preferably It is in the range of 40 to 95% by weight. Moreover, the threshold voltage, the liquid crystal phase temperature range, the refractive index anisotropy value, the dielectric anisotropy value, the viscosity, and the like can be adjusted by mixing the components described later.

Component D consisting of at least one compound selected from the group consisting of formulas (6) to (8) and (10) has a dielectric anisotropy used in a vertical alignment mode (VA mode) and the like. This is a preferred component when preparing a negative liquid crystal composition of the present invention.
Preferable examples of the compound (component D) represented by the formulas (6) to (8) and (10) are the formulas (6-1) to (6-5) and (7-1) to (7-9), respectively. ), (8-1) to (8-3), and (10-1) to (10-11).

式中、Ｒ^５，Ｒ^６は前記と同じ意味である。

In the formula, R ⁵ and R ⁶ have the same meaning as described above.

  These compounds of component D are mainly used in liquid crystal compositions for VA mode having a negative dielectric anisotropy value. Increasing the content lowers the threshold voltage of the composition, but increases the viscosity. Therefore, it is preferable to reduce the content as long as the required value of the threshold voltage is satisfied. However, since the absolute value of the dielectric anisotropy value is about 5, if the content is less than 40% by weight, voltage driving may not be possible.

  Since the compound represented by the formula (6) among the component D is a bicyclic compound, there is mainly an effect of adjusting the threshold voltage, adjusting the viscosity, or adjusting the refractive index anisotropy value. Further, since the compounds represented by the formulas (7) and (8) are tricyclic compounds, the clearing point is increased, the nematic range is increased, the threshold voltage is decreased, and the refractive index anisotropy value is increased. The effect such as enlarging is obtained.

  When preparing the composition for VA mode, the content of component D is preferably 40% by weight or more, more preferably 50 to 95% by weight, based on the total amount of the composition. Further, by mixing the component D, it is possible to control the elastic constant and control the voltage transmittance curve of the composition. When component D is mixed with a composition having a positive dielectric anisotropy value, the content is preferably 30% by weight or less based on the total amount of the composition.

  Preferable examples of the compound (component E) represented by the formulas (11), (12) and (13) are the formulas (11-1) to (11-11) and (12-1) to (12-18), respectively. And (13-1) to (13-6).

式中、Ｒ^７およびＲ^８は前記と同じ意味である。

In the formula, R ⁷ and R ⁸ have the same meaning as described above.

  The compound (component E) represented by the formulas (11) to (13) is a compound having a small absolute value of dielectric anisotropy and close to neutrality. The compound represented by the formula (11) is mainly effective in adjusting the viscosity or the refractive index anisotropy value, and the compounds represented by the formulas (12) and (13) are nematic such as increasing the clearing point. It has the effect of widening the range or adjusting the refractive index anisotropy value.

  Increasing the content of the compound represented by Component E increases the threshold voltage of the liquid crystal composition and decreases the viscosity. Therefore, as long as the required value of the threshold voltage of the liquid crystal composition is satisfied, the content is More is desirable. When preparing a liquid crystal composition for TFT, the content of component E is preferably 60% by weight or less, more preferably 40% by weight or less based on the total amount of the composition. When preparing a liquid crystal composition for STN or TN, the content of component E is preferably 70% by weight or less, more preferably 60% by weight or less, based on the total amount of the composition.

The liquid crystal composition of the present invention preferably contains at least one kind of the compound represented by the formula (1) of the present invention in a proportion of 0.1 to 99% by weight in order to develop excellent characteristics.
The liquid crystal composition of the present invention is generally prepared by a known method, for example, a method of dissolving necessary components at a high temperature. Further, additives well known to those skilled in the art are added depending on the application, for example, the liquid crystal composition (f) of the present invention containing an optically active compound as described below, and the GH type to which a dye is added. A liquid crystal composition can be prepared. Usually, additives are well known to those skilled in the art and are described in detail in the literature.

The liquid crystal composition (f) of the present invention can further contain one or more optically active compounds in the liquid crystal composition of the present invention described above.
A known chiral dopant is added as an optically active compound. This chiral dopant has the effect of inducing the helical structure of the liquid crystal to adjust the necessary twist angle and preventing reverse twist. Examples of the chiral dopant include the following optically active compounds (Op-1) to (Op-13).

  In the liquid crystal composition (f) of the present invention, these optically active compounds are usually added to adjust the twist pitch. The twist pitch is preferably adjusted in the range of 40 to 200 μm in the case of a liquid crystal composition for TFT and TN. If it is the liquid crystal composition for STN, it is preferable to adjust to the range of 6-20 micrometers. In the case of the bistable TN (Bistable TN) mode, it is preferably adjusted to a range of 1.5 to 4 μm. Two or more optically active compounds may be added for the purpose of adjusting the temperature dependence of the pitch.

The liquid crystal composition of the present invention can be obtained as a GH type liquid crystal composition by adding a dichroic dye such as merocyanine, styryl, azo, azomethine, azoxy, quinophthalone, anthraquinone, and tetrazine. It can also be used.
In addition, the liquid crystal composition of the present invention includes NCAP produced by encapsulating nematic liquid crystal, and polymer dispersed liquid crystal display element (PDLCD) produced by forming a three-dimensional network polymer in liquid crystal, for example, a polymer. It can be used as a liquid crystal composition for birefringence control (ECB) type and DS type as well as for network liquid crystal display elements (PNLCD).

  Hereinafter, the present invention will be described in more detail with reference to examples. In each example, C is a crystal, SA is a smectic A phase, SB is a smectic B phase, SX is a smectic phase whose phase structure has not been analyzed, N is a nematic phase, and I is an isotropic phase. All the units of phase transition temperature are shown in ° C.

  Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited by these examples. Moreover, since the structure of the obtained compound was identified by a nuclear magnetic resonance spectrum, a mass spectrum, etc., an analysis method is demonstrated first.

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

  GC analysis: GC-14B type gas chromatograph made by Shimadzu Corporation was used as a measuring apparatus. As the column, a capillary column CBP1-M25-025 (length 25 m, inner diameter 0.22 mm, film thickness 0.25 μm) manufactured by Shimadzu Corporation; dimethylpolysiloxane; nonpolar) was used as the stationary liquid phase. Helium was used as the carrier gas, and the flow rate was adjusted to 1 ml / min. The temperature of the sample vaporizing chamber was set to 300 ° C., and the temperature of the detector (FID) portion was set to 300 ° C.

  The sample was dissolved in toluene to prepare a 1% by weight solution, and 1 μl of the resulting solution was injected into the sample vaporization chamber. As a recorder, a C-R6A type Chromatopac manufactured by Shimadzu Corporation or an equivalent thereof was used. The obtained gas chromatogram shows the peak retention time and peak area value corresponding to the component compounds.

  As a sample dilution solvent, for example, chloroform or hexane may be used. In addition, as columns, Agilent Technologies Inc. capillary column DB-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm), Agilent Technologies Inc. HP-1 (length 30 m, inner diameter 0) .32 mm, film thickness 0.25 μm), Rtx-1 from Restek Corporation (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm), BP-1 from SGE International Pty. Ltd (length 30 m, inner diameter) 0.32 mm, film thickness of 0.25 μm) or the like may be used.

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

Samples for measuring physical property values of liquid crystal compounds, etc. There are two types of samples for measuring the physical property values of liquid crystal compounds: when the compound itself is used as a sample, and when the compound is mixed with mother liquid crystals as a sample.

In the latter case using a sample in which a compound is mixed with mother liquid crystals, the measurement is performed by the following method. First, 15% by weight of the obtained liquid crystal compound and 85% by weight of the mother liquid crystal are mixed to prepare a sample. Then, an extrapolated value is calculated from the measured value of the obtained sample according to the extrapolation method shown in the following equation. This extrapolated value is taken as the physical property value of this compound.

  <Extrapolated value> = (100 × <Measured value of sample> − <Weight% of mother liquid crystal> × <Measured value of mother liquid crystal>) / <Weight% of liquid crystal compound>

  Even when the ratio between the liquid crystal compound and the mother liquid crystal is this ratio, when the smectic phase or crystal is precipitated at 25 ° C., the ratio between the liquid crystal compound and the mother liquid crystal is 10% by weight: 90% by weight, 5% by weight. %: 95% by weight, 1% by weight: 99% by weight, and the physical properties of the sample were measured with a composition in which the smectic phase or crystals did not precipitate at 25 ° C., and extrapolated according to the above formula. This is taken as the physical property value of the liquid crystal compound.

There are various types of mother liquid crystals used for measurement. For example, the composition (% by weight) of the mother liquid crystals A is as follows.
Mother liquid crystal A:

Method for measuring physical property values of liquid crystal compounds, etc. The physical property values were measured by the method described later. Many of these measurement methods are the methods described in the Standard of Electric Industries Association of Japan EIAJ / ED-2521A or a modified method thereof. Moreover, TFT was not attached to the TN element used for the measurement.

  Among the measured values, when the liquid crystal compound itself was used as a sample, the obtained value was described as experimental data. When a mixture of a liquid crystal compound and mother liquid crystals was used as a sample, values obtained by extrapolation were described as experimental data.

Phase structure and phase transition temperature (° C.): Measurement was performed by the following methods (1) and (2).
(1) A compound is placed on a hot plate (Mettler FP-52 type hot stage) equipped with a polarizing microscope, and the phase state and its change are observed with a polarizing microscope while heating at a rate of 3 ° C./min. , Identified the type of liquid crystal phase.
(2) Using a scanning calorimeter DSC-7 system or Diamond DSC system manufactured by PerkinElmer Inc., the temperature is raised and lowered at a rate of 3 ° C./min, and the end point of the endothermic peak or exothermic peak accompanying the phase change of the sample is excluded. The phase transition temperature was determined by onset.

Hereinafter, the crystal is expressed as C, and when the crystal can be distinguished, it is expressed as C ₁ or C ₂ , respectively. Further, the smectic phase is represented as S and the nematic phase is represented as N. The liquid (isotropic) was designated as I. In the smectic phase, when the smectic B phase or the smectic A phase can be distinguished, they are represented as S _B or S _A , respectively. As a representation of the phase transition temperature, for example, “C 50.0 N 100.0 I” means that the phase transition temperature (CN) from the crystal to the nematic phase is 50.0 ° C., and the phase from the nematic phase to the liquid The transition temperature (NI) is 100.0 ° C. The same applies to other notations.

Maximum temperature of nematic phase (T _NI ; ° C.): A sample (mixture of liquid crystal compound and mother liquid crystal) is placed on a hot plate (Mettler FP-52 type hot stage) of a melting point measuring apparatus equipped with a polarizing microscope. The polarizing microscope was observed while heating at a rate of ° C / min. The temperature at which a part of the sample changed from a nematic phase to an isotropic liquid was defined as the upper limit temperature of the nematic phase. Hereinafter, the upper limit temperature of the nematic phase may be simply abbreviated as “upper limit temperature”.

  Low temperature compatibility: A sample in which a mother liquid crystal and a liquid crystal compound were mixed so that the liquid crystal compound was in an amount of 20% by weight, 15% by weight, 10% by weight, 5% by weight, 3% by weight, and 1% by weight. Make and place sample in glass bottle. The glass bottle was stored in a freezer at −10 ° C. or −20 ° C. for a certain period, and then it was observed whether a crystal or smectic phase was precipitated.

  Viscosity (η; measured at 20 ° C .; mPa · s): A mixture of a liquid crystal compound and a mother liquid crystal was measured using an E-type rotational viscometer.

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

  Dielectric anisotropy (Δε; measured at 25 ° C.): Put a sample (mixture of liquid crystal compound and mother liquid crystal) into a liquid crystal cell with a gap (gap) between two glass substrates of about 9 μm and a twist angle of 80 degrees. It was. A voltage of 20 volts was applied to the cell, and the dielectric constant (ε‖) 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⊥.

[Example 1]
Synthesis of Compound (1-11) As one of the compounds (1), a compound represented by the formula (1-11) was synthesized.

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

(First stage)
Et ₂ O (50 ml) was cooled to −78 ° C. under a nitrogen atmosphere, t-butyllithium (1.7 mol / l) (13.325 ml) was added, and iodine (3.444 g) was added to Et ₂ O. What was melt | dissolved in (20 ml) was dripped at -70 degrees C or less. After 1 hour, 4-propylcyclohexanone (3.176 g) dissolved in Et ₂ O (10 ml) was added dropwise at −70 ° C. or lower. After 30 minutes, the mixture was returned to room temperature and stirred overnight, then quenched with saturated ammonium chloride and extracted three times with toluene (50 ml). The extract was washed with water in a conventional manner, dried over anhydrous magnesium sulfate, and concentrated. It was. The residue was passed through a silica gel column of heptane: ethyl acetate = 9: 1 to obtain an alcohol form (1-11a).
Subsequently, the alcohol (2.900 g) and p-toluenesulfonic acid monohydrate (130 mg) were dissolved in toluene (50 ml) and heated to reflux for 4 hours. The reaction mixture was cooled to room temperature, washed with saturated aqueous sodium hydrogen carbonate (20 ml) and water (20 ml), concentrated, and then purified by silica gel column chromatography and recrystallized from methanol to give a compound. (1-11b) (1.900 g) was isolated.
The physicochemical properties of the obtained compound (1-11b) are shown below.
¹ H-NMR (CDCl ₃ , ppm): δ 0.86 (3H, t, J = 7.4 Hz), 1.11-2.50 (24H, m), 5.36-5.37 (1H, m).
¹⁹ F-NMR (CDCl ₃ , ppm): δ-79.1 (3F, s).

(Second stage)
The dehydrated product (1-11b) (1.900 g) was dissolved in a mixed solvent (1: 1) of toluene-sol mix (50 ml), 5% Pd-C (190 mg) was added, and the mixture was stirred under a hydrogen atmosphere for 5 days. . The reaction solution was filtered to remove Pd—C, concentrated, purified by silica gel column chromatography, and recrystallized from methanol to isolate compound (1-11) 1.0 g).

The physicochemical properties of the obtained compound (1-11) are shown below.
¹ H-NMR (CDCl ₃ , ppm): δ 0.86 (3H, t, J = 7.4 Hz), 0.79-1.78 (14H, m), 1.38-1.41 (6H, m), 1.61-1.63 (6H, m ).
¹⁹ F-NMR (CDCl ₃ , ppm): δ-79.0 (3F, s).
MS: 302 (M ⁺ )

The phase transition temperature of the obtained compound (No. 1-11) was as follows.
Phase transition temperature: C 45.8 S _B 71.5 I.

[Example 2]
Synthesis of Compound (1-37) As one of the compounds (1), a compound represented by the formula (1-37) was synthesized.

Compound (1-37) was synthesized according to the following scheme.

(First stage)
Et ₂ O (50 ml) was cooled to −78 ° C. under a nitrogen atmosphere, t-butyllithium (1.7 mol / l) (4.640 ml) was added, and iodine (1.200 g) was added to Et ₂ O. What was melt | dissolved in (20 ml) was dripped at -70 degrees C or less. After 1 hour, a solution of 4-propylcyclohexylcyclohexanone (0.856 g) in Et ₂ O (10 ml) was added dropwise at −70 ° C. or lower. After 30 minutes, the mixture was returned to room temperature and stirred for 2 days, then quenched with saturated ammonium chloride and extracted three times with Et ₂ O (30 ml). The extract was washed with water in a conventional manner, dried over anhydrous magnesium sulfate, and concentrated. Went. The residue was passed through a silica gel column of heptane: ethyl acetate = 9: 1 to obtain an alcohol form (1-37a).
Subsequently, the alcohol (0.900 g) and p-toluenesulfonic acid monohydrate (90 mg) were dissolved in toluene (50 ml) and heated to reflux for 4 hours. The reaction solution is cooled to room temperature, washed with saturated aqueous sodium hydrogen carbonate (20 ml) and water (20 ml), concentrated, and then purified by silica gel column chromatography using heptane and recrystallized from methanol. The compound (1-37b) (0.690 g) was isolated by
The physicochemical properties of the obtained compound (1-37b) are shown below.
¹ H-NMR (CDCl ₃ , ppm): δ 0.80-2.10 (33H, m), 0.86 (3H, t, J = 7.4 Hz), 5.37 (1H, t,, J = 2.5 Hz).
¹⁹ F (CDCl ₃ , ppm): δ-79.1 (3F, s).

(Second stage)
The dehydrated form (1-37b) (0.690 g) was dissolved in a mixed solvent (1: 1) of toluene-sol mix (30 ml), 5% Pd-C (70 mg) was added, and the mixture was stirred under a hydrogen atmosphere for 3 days. . The reaction solution was filtered to remove Pd-C, concentrated, purified by silica gel column chromatography, and recrystallized from methanol and solmix to isolate compound (1-37) 1.0 g). did.

The physicochemical properties of the obtained compound (1-37) are shown below.
¹ H-NMR (CDCl ₃ , ppm): δ 0.79-1.74 (36H, m), 0.86 (3H, t, J = 7.4 Hz).
¹⁹ F (CDCl ₃ , ppm): δ-79.0 (3F, s).

[Example 3]
Based on [Example 1] and the synthesis method described above, compounds (1-10) to (1-104) which are the compound (1) of the present invention can be synthesized.

Next, typical composition examples of the present invention containing the compound (1) of the present invention are shown below. The physical property values were measured according to the methods described later.
[Example 4] (Composition Example 1)
A mother liquid crystal A having a nematic phase was prepared by mixing four compounds. 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 the mother liquid crystal A were as follows. Maximum temperature (NI) = 71.7 ° C .; viscosity (η ₂₀ ) = 27.0 mPa · s; optical anisotropy (Δn) = 0.137; dielectric anisotropy (Δε) = 11.0.
To the mother liquid crystal A, the compound (1-11) described in Example 1 was added to prepare (Composition Example 1). Specifically, the compound (1-11) was added so as to be 10% by weight with respect to the composition to prepare (Composition Example 1) of the present invention. As a result of measuring the physical property values of this (Composition Example 1), the maximum temperature (NI) = 11.7 ° C .; the optical anisotropy (Δn) = 0.0303; the dielectric anisotropy (Δε) = 7.6. Met.

[Example 5] (Composition Example 2)
A composition example 2 was prepared by adding the compound (1-37) described in Example 1 to the mother liquid crystal A. Specifically, Compound Example 1-3 of the present invention was prepared by adding the compound (1-37) so as to be 5% by weight based on the composition. As a result of measuring the physical property values of this (Composition Example 2), the maximum temperature (NI) = NI) = 157.7 ° C .; optical anisotropy (Δn) = 0.097; dielectric anisotropy (Δε) = 8.1.

[Example 6] (Composition Examples 3 to 16)
Further, as a representative composition of the present invention containing the compound (1), for (Composition Example 3) to (Composition 16), the compound as a component of the composition, its amount (% by weight), and physical properties showed that.
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. If there is no end group symbol, it means that the end group is hydrogen.

Moreover, the physical property value of each composition example was measured and shown. Specifically, the upper limit temperature of a nematic phase (NI; ° C.), the lower limit temperature of a nematic phase _{(T C;} ℃), compatibility of compounds, the viscosity (eta; measured at 20 ℃; mPa · s), optically anisotropic (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 according to the method described in the 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 was stored in a freezer at 0 ° C., −10 ° C., −20 ° C., −30 ° C., and −40 ° C. Observed. For example, the sample remained in the -20 ° C. in a nematic phase, when the change in the -30 ° C. crystals (or a smectic phase), described as ≦ -20 ° C. The T _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 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 device in which the distance (gap) between two glass substrates is about 9 μm and processed in 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 3)
3-HBi-CF3 20%

2-BEB (F) -C 5%
3-BEB (F) -C 4%
4-BEB (F) -C 12%
1V2-BEB (F, F) -C 13%
3-HB-O2 5%
3-HH-4 3%
3-HHB-F 3%
3-HHB-1 4%
3-HHB-O1 4%
3-HBEB-F 3%
3-HHEB-F 4%
5-HHEB-F 4%
3-H2BTB-2 4%
3-H2BTB-3 4%
3-H2BTB-4 4%
3-HB (F) TB-2 4%
NI = 71.6 ° C .; Δn = 0.127; Δε = 27.0; Vth = 1.11V.

(Composition Example 4)
3-HHBi-CF3 8%

2-HB-C 5%
3-HB-C 12%
3-HB-O2 7%
2-BTB-1 3%
3-HHB-F 4%
3-HHB-1 8%
3-HHB-O1 5%
3-HHB-3 14%
3-HHEB-F 4%
5-HHEB-F 4%
2-HHB (F) -F 7%
3-HHB (F) -F 7%
5-HHB (F) -F 7%
3-HHB (F, F) -F 5%

(Composition Example 5)
3-HHVBi-CF3 8%

3-BEB (F) -C 8%
3-HB-C 8%
V-HB-C 8%
1V-HB-C 8%
3-HB-O2 3%
3-HH-2V 6%
3-HH-2V1 7%
V2-HHB-1 15%
3-HHB-1 5%
3-HHEB-F 7%
3-H2BTB-2 6%
3-H2BTB-3 6%
3-H2BTB-4 5%

(Composition Example 6)
3-HBi-CF3 10%
3-HHBi-CF3 5%

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

(Composition Example 7)
3-HHBi-CF3 5%
3-HHVBi-CF3 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 8)
3-HBi-CF3 10%

5-HB-CL 16%
3-HH-4 8%
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 8%
5-HHB (F) -F 8%
7-HHB (F) -F 7%
5-HBB (F) -F 3%
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 = 107.3 ° C .; Δn = 0.087; Δε = 4.2; Vth = 2.07V.
When 0.25 part of optically active compound (Op-05) was added to 100 parts of the composition, the pitch was 61.0 μm.

(Composition Example 9)
3-HBi-CF3 7%
3-HHVBi-CF3 7%

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 17%
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 10)
3-HBi-CF3 5%
3-HHBi-CF3 5%
3-HHVBi-CF3 5%

5-HB-F 8%
6-HB-F 8%
7-HB-F 7%
2-HHB-OCF3 7%
3-HHB-OCF3 7%
4-HHB-OCF3 7%
5-HHB-OCF3 5%
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 11)
3-HHBi-CF3 10%

5-HB-CL 11%
3-HH-4 8%
3-HHB-1 5%
3-HHB (F, F) -F 8%
3-HBB (F, F) -F 20%
5-HBB (F, F) -F 5%
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 6%

(Composition Example 12)
3-HHVBi-CF3 15%

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

(Composition Example 13)
3-HBi-CF3 5%
3-HHBi-CF3 5%

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

(Composition Example 14)
3-HHBi-CF3 4%
3-HHVBi-CF3 6%

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-HGB (F, F) -F 5%
5-HGB (F, F) -F 6%
2-H2GB (F, F) -F 4%
3-H2GB (F, F) -F 5%
5-GHB (F, F) -F 7%

(Composition Example 15)
3-HBi-CF3 5%
3-HHBi-CF3 5%
3-HHVBi-CF3 5%

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 15%
3-BB (F, F) XB (F, F) -F 20%
1O1-HBBH-5 7%
2-HHBB (F, F) -F 3%
3-HHBB (F, F) -F 3%
3-HH2BB (F, F) -F 4%

(Composition Example 16)
3-HBi-CF3 8%
3-HHBi-CF3 6%

5-HB-CL 7%
3-HB-O2 10%
3-PyB (F) -F 7%
5-PyB (F) -F 7%
3-HBB (F, F) -F 7%
3-PyBB-F 10%
4-PyBB-F 10%
5-PyBB-F 10%
5-HBB (F) B-2 9%
5-HBB (F) B-3 9%

The present invention provides a liquid crystal compound having a novel bicyclooctane having excellent compatibility with other liquid crystal materials and having a small Δn value.
In addition, the present invention provides a new liquid crystal composition having the above characteristics having desired physical properties by appropriately selecting a ring, a substituent, a bonding group and the like constituting the compound from the liquid crystal compound as a component. Furthermore, a liquid crystal display element constituted by using this liquid crystal composition is provided.

Claims (18)

The compound represented by Formula (1).

Wherein R is alkyl having 1 to 10 carbons, and any —CH ₂ — in the alkyl may be replaced by —O—, —S—, —CO— or —CH═CH—;
Ring A ¹ , Ring A ² and Ring A ³ are independently 1) or 2):
1) 1,4-cyclohexylene or 1,4-cyclohexenylene, and these one —CH ₂ — or two or more non-adjacent —CH ₂ — may be replaced by —O—. Often;
2) 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, or decahydronaphthalene-2,6-diyl, one of these 1,4-phenylene or Two -CH = may be replaced by -N =;
Any hydrogen in the group described in 1) or 2) is replaced with halogen, —C≡N, —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₃ , —OCHF _2, or —OCH ₂ F. May be;
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 —, _{-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 -, - CF = CF-, or -C≡C-;
Y is perfluoroalkyl having 1 to 10 carbon atoms;
m and n are independently 0 or 1. R is alkyl having 1 to 10 carbons, alkenyl having 2 to 11 carbons or alkoxy having 1 to 9 carbons;
Ring A ¹ , Ring A ² and Ring A ³ are independently the following 1) or 2):
1) 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, or 1,3-dioxane-2,5-diyl;
2) 1,4-phenylene, naphthalene-2,6-diyl, pyridine-2,5-diyl, or pyrimidine-2,5-diyl;
Any hydrogen in the group described in 2) may be replaced by fluorine;
Z ¹ , Z ² and Z ³ are independently a single bond, — (CH ₂ ) ₂ —, —CH ₂ O—, —CH═CH—, — (CH ₂ ) ₄ —, —CH ₂ CH ₂ CH ₂ O—, —CH═CHCH ₂ CH ₂ —, or —COO—,
The compound of claim 1. R is alkyl having 1 to 10 carbons, alkenyl having 2 to 11 carbons or alkoxy having 1 to 5 carbons;
Ring A ¹ , Ring A ² and Ring A ³ are independently 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, pyridine-2,5-diyl, 3-fluoropyridine-2,5-diyl, or pyrimidine-2,5-diyl;
Z ¹ , Z ² and Z ³ are each independently a single bond, — (CH ₂ ) ₂ —, —CH ₂ O—, —CH═CH—, — (CH ₂ ) ₄ —, or —COO—. ,
The compound of claim 1. R is alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons or alkoxy having 1 to 5 carbons;
Ring A ¹ , Ring A ² and Ring A ³ are independently 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 independently a single bond, — (CH ₂ ) ₂ —, —CH ₂ O—, or —CH═CH—.
The compound of claim 1. A compound represented by any one of formulas (1-1) to (1-6).

In the formula, R is alkyl having 1 to 10 carbons or alkenyl having 2 to 5 carbons;

Is 1,4-phenylene, or 1,4-phenylene in which one to two hydrogens are replaced by fluorine;
Z ³ is a single bond;
Y is -CF _3. The compound represented by any one of Formula (1-7)-Formula (1-9).

In the formula, R is alkyl having 1 to 5 carbon atoms.   A liquid crystal composition comprising two or more components, comprising 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) as one component.

In the formula, R ³ is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in alkyl and alkenyl, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be —O—. May be replaced by;
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 ;
Ring A ¹ , Ring A ² and Ring A ³ are independently 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, 1-pyran-2,5. -Diyl or 1,4-phenylene in which any hydrogen may be replaced by fluorine;
Z ¹ and Z ² are independently — (CH ₂ ) ₂ —, — (CH ₂ ) ₄ —, —COO—, —CF ₂ O—, —OCF ₂ —, —CH═CH—, —C≡. C—, —CH ₂ O—, or a single bond;
L ¹ and L ² are independently hydrogen or fluorine. The liquid crystal composition according to claim 7, further comprising at least one compound selected from the group of compounds represented by formula (5).

In the formula, R ⁴ is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in alkyl and alkenyl, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be —O—. May be replaced by;
X ² is —C≡N or —C≡C—C≡N;
Ring B ¹ , Ring B ² and Ring B ³ are independently 1,4-cyclohexylene, 1,4-phenylene, 1,3-dioxane-2,5- in which any hydrogen may be replaced by fluorine Diyl, 1-pyran-2,5-diyl, or pyrimidine-2,5-diyl;
Z ³ is — (CH ₂ ) ₂ —, —COO—, —CF ₂ O—, —OCF ₂ —, —C≡C—, —CH ₂ O—, or a single bond;
L ³ and L ⁴ are independently hydrogen or fluorine;
q is independently 0, 1 or 2, and r is independently 0 or 1. 8. The composition according to claim 7, comprising at least one compound selected from the group of compounds represented by formulas (6), (7), (8), (9) and (10) as one component. Liquid crystal composition.

In the formula, R ⁵ and R ⁶ are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, any hydrogen may be replaced by fluorine, and any — CH ₂ — may be replaced by —O—;
Ring C ¹ , Ring C ² , Ring C ³ and Ring C ⁴ are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4- Phenylene, 6-pyran-2,5-diyl or decahydro-2,6-naphthalene;
Z ⁴ , Z ⁵ , Z ⁶ and Z ⁷ are independently — (CH ₂ ) ₂ —, —COO—, —CH ₂ O—, —OCF ₂ —, —OCF ₂ (CH ₂ ) ₂ —, or A bond;
L ⁵ and L ⁶ are independently fluorine or chlorine;
j, k, l, m and n are each independently 0 or 1, and k + l + m + n is 1 or 2. The liquid crystal composition according to claim 7, comprising at least one compound selected from the group of compounds represented by formulas (11), (12) and (13) as one component.

In the formula, R ⁷ and R ⁸ are each independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in this alkyl and alkenyl, any hydrogen may be replaced by fluorine, and any — CH ₂ — may be replaced by —O—;
Ring D ¹ , Ring D ² and Ring D ³ are independently 1,4-cyclohexylene, pyrimidine-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro- 1,4-phenylene or 2,5-difluoro 1,4-phenylene;
Z ⁸ and Z ⁹ are independently —C≡C—, —COO—, — (CH ₂ ) ₂ —, —CH═CH—, or a single bond.   The liquid crystal composition according to claim 8, further comprising at least one compound selected from the group of compounds represented by formula (5) according to claim 9.   The liquid crystal composition according to claim 8, further comprising at least one compound selected from the group of compounds represented by formulas (11), (12) and (13) according to claim 11.   The liquid crystal composition according to claim 9, further comprising at least one compound selected from the group of compounds represented by formulas (11), (12) and (13) according to claim 11.   The liquid crystal composition according to claim 10, further comprising at least one compound selected from the group of compounds represented by formulas (11), (12) and (13) according to claim 11.   The liquid crystal composition according to claim 7, further comprising at least one optically active compound.   The liquid crystal composition according to any one of claims 7 to 16, comprising at least one antioxidant and / or ultraviolet absorber.   The liquid crystal display element containing the liquid-crystal composition of any one of Claims 7-17.