JPH10237448A - Liquid crystalline compound with negative permittivity anisotropy, liquid crystal composition containing the same, and liquid crystal element prepared from the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a liq. crystalline compd. which has a negative permittivity anisotropy with a large absolute value and is satisfactory in characteristics such as low elasticity constant, compatibility, degree of freedom of refractory index anisotropy value, low viscosity, and chemical and physical stabilities by selecting a compd. having tetrahydropyran-2,5-diyl group and a substd. 1,4- phenylene ring in the backbone structure. SOLUTION: This compd. has a tetrahydropyran-2,5-diyl group and a ring represented by the formula (wherein W<1> and W<2> are each independently F or Cl), more specifically a 2,3-difluorobenzene-1,4-diyl, 2,3-dichlorobenzene-1,4-diyl, or 2-chloro-3-fluorobenzene-1,4-diyl group, in the backbone structure. A liq. crystal compsn. is prepd. by compounding 0.1-99.9wt.% at least one liq. crystalline compd. above-mentioned with at least one other component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention mainly relates to a liquid crystal display device, for example, a vertical alignment system, IPS = in-plane switching, TFT = thin film transistor, TN = twisted nematic, or STN = super twisted nematic, etc., and especially vertical alignment. TECHNICAL FIELD The present invention relates to a novel liquid crystal compound capable of exhibiting various physical properties suitable for a liquid crystal composition for a system and an IPS, a liquid crystal composition having suitable physical properties using the same, and a liquid crystal display device using the liquid crystal composition. In the present application, the term “liquid crystalline compound” is used as a general 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.

[0002]

BACKGROUND ART Conventionally, various liquid crystal display systems have been proposed. As an example of them, the following display method is mentioned (Latest technology of liquid crystal, edited by the Industrial Research Council (1983)). As a method of using a liquid crystal composition having a positive dielectric anisotropy value, T
There is a method such as AM = active matrix (TFT or MIM = metal / insulating film / metal etc.) based on N, STN or TN, and a liquid crystal composition having a negative dielectric anisotropy value is used. As a method, there are methods such as ECB = electric field control birefringence effect (HAN = hybrid molecular arrangement or DAP = vertical molecular arrangement), DS = dynamic scattering, GH = guest host, or PC = phase transition. Of these systems, the mainstream of those currently in practical use is a system using a liquid crystal composition having a positive dielectric anisotropy value. Compared to this, practical use of the method using a liquid crystal composition having a negative dielectric anisotropy value has been delayed. In connection with this,
The development of liquid crystal compositions with a negative dielectric anisotropy value and the compounds used for the same are not enough compared to the development of liquid crystal compositions with a positive dielectric anisotropy value and the compounds used for the same. is there.

Under these circumstances, recently, attempts to improve the narrow viewing angle, which is one of the drawbacks of the liquid crystal display, have been actively made. One of the methods is
IPS (R. Kiefer et al., JAPAN DISPLAY'92, 547 (19
92), M. Oh-e et al., ASIA DISPLAY '95, 577 (1995), JP-T-5-505247, JP-A-7-128647, etc.). One of the features of the IPS is that, in the conventional liquid crystal panel, electrodes are provided on upper and lower substrates, respectively, whereas in the liquid crystal panel of this system, interdigital electrodes are provided only on one substrate. It is. Another feature of this method is that the liquid crystal composition can be used regardless of the positive or negative value of the dielectric anisotropy value. As another example of an attempt to improve the narrow viewing angle, there is a method in which the vertical angle of liquid crystal molecules is used to improve the viewing angle (Japanese Patent Laid-Open No. 2-176625). One of the features of this method is that a liquid crystal composition having a negative dielectric anisotropy is used. From such a background, liquid crystal compounds and liquid crystal compositions having a negative dielectric anisotropy value have been strongly demanded.

In all display systems, the liquid crystal composition used has not only an appropriate dielectric anisotropy value but also other characteristics such as a refractive index anisotropy value (△ n) and an elastic constant ratio K. _It is necessary to adjust various physical property values such as ₃₃ / K ₁₁ (K ₃₃ : bend elastic constant, K ₁₁ : splay elastic constant) to an optimum value, and that the liquid crystal phase is in an appropriate temperature range In addition, low viscosity is required even at a low temperature. None of the conventionally known liquid crystalline compounds satisfy all of these conditions alone. Therefore, in order to obtain a composition that can be usually used as a liquid crystal phase, it is prepared by mixing a compound having several to twenty and several kinds of liquid crystal phases and, if necessary, a compound having no more than several kinds of liquid crystal phases. . Therefore, each liquid crystal compound is
Characteristics such as good compatibility with other liquid crystal compounds and good compatibility in a low temperature range are also required due to demand for use in a low temperature environment.

However, as described above, the conventional display system mainly uses a liquid crystal composition containing a liquid crystal compound having a positive dielectric anisotropy value. However, the development of the compound or composition was not sufficient. For this reason, the method of diversification in this way and the corresponding various characteristics have been insufficient. For example, even if the dielectric anisotropy value is negative, the absolute value is small, the driving voltage cannot be reduced due to the large elastic constant, the compatibility is poor, and the compound cannot be used in large quantities. It is difficult to freely set the value of the refractive index anisotropy, there is a problem that the viscosity is large, and the chemical and physical stability is poor.

An example of a liquid crystal compound having a negative dielectric anisotropy known before the present invention is a liquid crystal compound having a 2,3-difluorophenylene skeleton (JP-A-57-114532). ). However, the absolute value of the negative dielectric anisotropy value of these compounds is not always sufficiently large, and the elastic constant, compatibility, degree of freedom of the refractive index anisotropy value, low viscosity, Properties such as physical stability are not always satisfactory, and further improvement has been demanded. In addition, here, studies to improve the above-mentioned properties of the compound having a 2,3-difluorophenylene skeleton, for example, attempts to increase the absolute value of the negative dielectric anisotropy have not been sufficiently performed. Was. Especially,
In a compound having a 2,3-difluorophenylene skeleton,
For example, there has been no idea to introduce a tetrahydropyran-2,5-diyl skeleton. Thus, the compounds of the present invention are not readily conceivable from the prior art.

[0007]

An object of the present invention is to provide a vertical alignment system, IPS, ECB (HAN or DAP, etc.) as described in JP-A-2-176625,
Not only can it be used for various display methods using compounds or compositions having a negative dielectric anisotropy value such as S, GH or PC, but also TN, STN, or TN-based AM (TF
T or MIM), which solves the above-mentioned problem that can be used for adjusting various characteristics of a liquid crystal composition for various display systems using a compound or a composition having a positive dielectric anisotropy value. It is an object of the present invention to provide a novel liquid crystal compound, a liquid crystal composition containing the same, and a liquid crystal display device prepared using the liquid crystal composition.

[0008]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, the compounds according to claims 1 to 3 have not only a large absolute value but a negative dielectric anisotropy value. ,
A compound having an appropriate refractive index anisotropy value, a small elastic constant, good compatibility, low viscosity, high chemical and physical stability, and a compound according to claim 1 to claim 3. By using in a product, a liquid crystal composition having a small elastic constant, appropriate setting of dielectric anisotropy value and refractive index anisotropy value, low viscosity, and excellent chemical and physical stability, In particular, they have found that a liquid crystal composition having a large absolute value and a negative dielectric anisotropy value can be obtained, and that a liquid crystal display device can be obtained by using the composition, thereby completing the present invention.

That is, the present invention provides the following [1] to [1]
3]. [1] In a skeleton structure, a tetrahydropyran-2,5-diyl group and a compound represented by the general formula (1)

[0010]

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(Wherein, W ¹ and W ² each independently represent a fluorine atom or a chlorine atom, and each atom constituting the compound may be substituted with its isotope). Liquid crystal compound having a ring.

[2] General formula (2)

[0013]

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(Wherein R¹And Y¹Are independently carbon numbers
1 to 20 alkyl groups, hydrogen atoms, halogen atoms, shea
, Cyanic acid, isocyano or isothiocyanic acid
Represents one or more non-adjacent ones in the above alkyl group
Is an oxygen atom, a sulfur atom, a nitrogen atom, -C≡
C- wherein at least one hydrogen atom has 1 to 10 carbon atoms
Silylene group or vinylene group which may be substituted with a group
May be substituted, and one of these alkyl groups
More than one hydrogen atom is replaced by a fluorine or chlorine atom
And these alkyl groups are optically active.
May be X¹, X^Two, X^ThreeAnd X^FourAre each independently connected
If-(CH_Two)_Two-, -CH = CH-, -C≡C-,-
COO-, -OCO-, -CH_TwoO-, -OCH_Two−, −
(CH _Two)_Four-,-(CH_Two)_ThreeO-, -O (CH_Two)_Three−,
-CH = CHCH_TwoCH_Two-, -CH_TwoCH = CHCH
_Two-, -CH_TwoCH_TwoCH = CH-, -CH = CHCH =
CH-, -CF_TwoO-, -OCF_Two-, -CH = CHCH
_TwoO-, -OCH_TwoCH = CH-, -CF = CF-, -C
H_TwoCF_Two-, -CF_TwoCH_Two−, − (CF_Two)_Two-,-(C
F_Two)_Four-,-(CH_Two)_TwoCOO-, -OCO (CH_Two)_Two
-, -CH = CHCOO-, -OCOCH = CH-,-
CH = CHC≡C- or -C≡CCH = CH-
And ring A¹, Ring A^Two, Ring A^Three, Ring A^FourAnd ring A^FiveAre independent
To give trans-cyclohexane-1,4-diyl,
Rohex-1-ene-1,4-diyl, 1,4-phenyl
Len, bicyclo [1.1.1] pentane-1,3-dii
, Tetrahydropyran-2,5-diyl or a general formula
(1)

[0015]

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(Wherein W ¹ and W ² each independently represent a fluorine atom or a chlorine atom), and these rings A ¹ , A ² , A ³ and A ⁴ and at least one of the ring a ⁵ are tetrahydropyran-2,5-diyl, and a ring at least one represented by the general formula (1), the carbon atoms constituting these rings nitrogen Atom, an oxygen atom or a sulfur atom, a hydrogen atom on the ring may be substituted with a halogen atom or a cyano group, a ¹ , a ² , a ³ , a ⁴ and a ⁵ are each It independently represents 0 or 1, but a ¹ + a ² + a ³ + a ⁴ + a ⁵ ≧ 1, and each atom constituting the compound may be substituted with its isotope. The liquid crystalline compound according to item [1], which is represented by the formula (1).

[3] When the ring represented by the general formula (1) is 2,
The liquid crystalline compound according to [1] or [2], which is 3-difluorobenzene-1,4-diyl.

[4] A liquid crystal composition comprising at least two components, comprising at least one liquid crystal compound according to any one of [1] to [3]. [5] As a first component, at least one compound according to any one of the items [1] to [3] is contained, and as a second component, the compounds represented by the general formulas (3), (4) and (5) A) a liquid crystal composition comprising at least one compound selected from the group consisting of:

[0019]

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(Wherein R ² represents an alkyl group having 1 to 10 carbon atoms, and one or more non-adjacent methylene groups in the alkyl group may be substituted with an oxygen atom or -CH ＝ CH-). And one or more hydrogen atoms in the alkyl group may be substituted with a fluorine atom, and Y ² represents a fluorine atom, a chlorine atom, —OCF ₃ , —OCF ₂ H, —C
_{F 3, -CF 2 H, -CFH} 2, -OCF 2 CF 2 H or -
Represents OCF ₂ CFHCF _3, L ¹ and L ² represents a hydrogen atom or a fluorine atom each independently, Z ¹ and Z ² are each independently _{- (CH 2) 2 -,} - (CH 2) 4 - , -COO-,-
CF ₂ O—, —OCF ₂ —, —CH ＝ CH— or a single bond, and ring Q ¹ is trans-cyclohexane-1,4-diyl, 1,3-dioxane-2,5-diyl, or a hydrogen atom Represents 1,4-phenylene which may be substituted by a fluorine atom, and ring Q ² is trans-cyclohexane-
1,4-diyl or 1,4-phenylene in which a hydrogen atom may be substituted with a fluorine atom, and atoms constituting these compounds may be substituted with an isotope thereof. )

[6] As the first component, [1] to [1]
[3] contains at least one kind of the compound according to any one of the above items, and contains, as a second component, at least one kind of a compound selected from the compound group consisting of the general formulas (6) and (7). A liquid crystal composition characterized by the following.

[0022]

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(Wherein R ³ and R ⁴ each independently represent an alkyl group having 1 to 10 carbon atoms, and one or more non-adjacent methylene groups in the alkyl group are an oxygen atom or —CH 又 は
May be substituted with CH-, one or more hydrogen atoms in the alkyl group may be substituted with a fluorine atom, and Y ³ represents a cyano group or -C 環 C-CN; Q ³ is trans-cyclohexane-1,4-diyl,
Represents 1,4-phenylene, 1,3-dioxane-2,5-diyl or pyrimidine-2,5-diyl, and ring Q ⁴ is trans-cyclohexane-1,4-diyl, pyrimidine-2,5-diyl, Or 1,4-phenylene in which a hydrogen atom may be substituted by a fluorine atom, and ring Q ⁵ is trans-cyclohexane-1,4-diyl or 1,4
Represents phenylene, and Z ³ represents — (CH ₂ ) ₂ —, —COO
Or represents a single bond, L ³ , L ⁴ and L ⁵ each independently represent a hydrogen atom or a fluorine atom, b, c and d each independently represent 0 or 1, and these compounds The constituent atoms may be substituted by their isotopes. )

[7] As the first component, [1] to
[3] It contains at least one kind of the compound according to any one of the items [3], and as the second component, the above-mentioned general formulas (3) and (4).
And at least one compound selected from the compound group consisting of (5) and at least one compound selected from the compound group consisting of general formulas (8), (9) and (10) as a third component. A liquid crystal composition characterized by containing various types.

[0025]

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(Wherein R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 10 carbon atoms, and one or more non-adjacent methylene groups in the alkyl group are an oxygen atom or —CHＣＨ
CH-, one or more hydrogen atoms in the alkyl group may be substituted with a fluorine atom, and ring Q ⁶ , ring Q ⁷ and ring Q ⁸ are each independently , Trans-cyclohexane-1,4-diyl, pyrimidine-
Represents 2,5-diyl or 1,4-phenylene in which a hydrogen atom may be substituted by a fluorine atom, and Z ⁴ and Z ⁵ each independently represent -C≡C-, -COO-,-( CH ₂ ) ₂
Represents-, -CH = CH- or a single bond, and atoms constituting these compounds may be substituted with an isotope thereof. )

[8] As the first component, [1] to
[3] The compound according to any one of the items [1] to [3], wherein at least one compound is contained as the second component.
A liquid crystal composition comprising at least one compound selected from the group consisting of compounds (2) and (13).

[0028]

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(In the formula, R ⁷ and R ⁸ each independently represent an alkyl group having 1 to 10 carbon atoms, and one or more non-adjacent methylene groups in the alkyl group are an oxygen atom or —CH ＝
CH-, one or more hydrogen atoms in the alkyl group may be substituted with a fluorine atom, and ring Q ⁹ and ring Q ¹⁰ are each independently trans-
Represents cyclohexane-1,4-diyl or 1,4-phenylene, it represents an L ⁶ and L ⁷ each independently represent a hydrogen atom or a fluorine atom not represent simultaneously hydrogen atoms, Z ⁶
And Z ⁷ are each independently — (CH ₂ ) ₂ —, —COO—
Or a single bond, and the atoms constituting these compounds may be substituted with isotopes thereof. )

[0030]

[9] As the first component, the first [1] to
[3] The compound according to any one of the items [1] to [3], wherein at least one compound according to any one of [3] to [9] is contained as a second component.
And at least one compound selected from the compound group consisting of (10) and at least a compound selected from the compound group consisting of the general formulas (11), (12) and (13) as the third component. A liquid crystal composition comprising one type. [10] The first component contains at least one kind of the compound according to any one of the items [1] to [3], and the second component consists of the general formulas (6) and (7). Containing at least one compound selected from the group of compounds,
As the third component, the above general formulas (8), (9) and (1)
A liquid crystal composition comprising at least one compound selected from the group consisting of 0).

[11] As the first component, [1] to [1]
[3] It contains at least one kind of the compound according to any one of the items [3], and as the second component, the above-mentioned general formulas (3) and (4).
And at least one compound selected from the compound group consisting of (5) and at least one compound selected from the compound group consisting of the general formulas (6) and (7) as the third component. A liquid crystal composition comprising, as a fourth component, at least one compound selected from the compound group consisting of the general formulas (8), (9) and (10). [12] A liquid crystal composition, which further comprises one or more optically active compounds in addition to the liquid crystal composition according to any one of the items [4] to [11]. [13] A liquid crystal display device comprising the liquid crystal composition according to any one of [4] to [12].

Item [8] and Item

The invention of the item [9] relates to an N-type (negative Δε) liquid crystal composition. The N-type liquid crystal composition can be driven by various display methods such as a vertical alignment method described in JP-A-2-176625 and IPS. In addition, [5], [6],
The inventions of the items [7], [10] and [11] relate to a P-type (positive Δε) liquid crystal composition.
An N-type compound can also be used as a component of the liquid crystal composition. This not only allows the dielectric anisotropy value to be freely set according to the intended use of the liquid crystal composition, but also
Other characteristics, such as control of the refractive index anisotropy value and elastic constant of the liquid crystal composition, are also possible.

In the skeleton structure, tetrahydropyran-2,
Preferred embodiments of the compound of the present invention having a 5-diyl group and a ring represented by the general formula (1) are shown below.

In the ring represented by the general formula (1), W ¹
And W ² each independently represent a fluorine atom or a chlorine atom. Specific examples of the ring represented by formula (1) include the following. 2,3-difluorobenzene-1,4-diyl, 2,3-dichlorobenzene-1,
4-diyl and 2-chloro-3-fluorobenzene-
1,4-diyl.

Preferred embodiments of the compound of the present invention represented by the general formula (2) are shown below. R ¹ and Y ¹ of the compound represented by the general formula (2) are each independently an alkyl group having 1 to 20 carbon atoms, a hydrogen atom, a halogen atom, a cyano group, a cyanic acid group, an isocyano group or an isothiocyanic acid group. In the above alkyl group, one or more non-adjacent methylene groups are an oxygen atom, a sulfur atom, a nitrogen atom, -C≡C-, and one or more hydrogen atoms are substituted with an alkyl group having 1 to 10 carbon atoms. May be substituted with a silylene group which may be substituted, or a vinylene group, and one or more hydrogen atoms in these alkyl groups may be substituted with a fluorine atom or a chlorine atom,
These alkyl groups may be optically active.

As the alkyl group represented by R ¹ and Y ¹ in the general formula (2), specifically, a saturated alkyl group consisting only of carbon atoms and hydrogen atoms, a haloalkyl group,
Alkoxy, haloalkoxy, alkenyl, haloalkenyl, alkenyloxy, haloalkenyloxy, alkynyl, haloalkynyl, alkynyloxy, haloalkynyloxy, alkoxyalkyl, haloalkoxyalkyl, alkoxyalkoxy Group, haloalkoxyalkoxy group, alkanoyl group,
Examples include a haloalkanoyl group, an alkanoyloxy group, a haloalkanoyloxy group, an alkoxycarbonyl group, and a haloalkoxycarbonyl group.

More specifically, examples of R ¹ and Y ¹ include the following groups or atoms. -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, -C 10 H 21, -CF
_{H 2, -CF 2 H, -CF} 3, -CH 2 CH 2 F, -CH 2 C
_{HF 2, -CH 2 CF 3,} -CF 2 CH 3, -CF 2 CF
_{2 H, -CFHCF 3, -CF 2} CF 3, - (CH 2) 2 CH
₂ F,-(CH ₂ ) ₂ CHF ₂ ,-(CH ₂ ) ₂ CF ₃ , -C
_{H 2 CF 2 CH 3, -CH} 2 CF 2 CF 3, -CF 2 C 2 H 5,
_{-C 3 F 7, -CF 2 CFHCF} 3, - (CH 2) 3 CH
_{2 F, - (CH 2)} 4 CH 2 F, - (CH 2) 5 CH 2 F, -
_{CF 2 C 3 H 7, -CH} 2 CF 2 C 2 H 5, - (CH 2) 2 CF 2
_{CH 3, -CF 2 C 4 H} 9, -CH 2 CF 2 CH 3, - (C
_{H 2) 2 CF 2 C 2} H 5, - (CH 2) 3 CF 2 CH 3,

-OCH ₃ , -OC ₂ H ₅ , -OC ₃ H ₇ ,-
_{OC 4 H 9, -OC 5 H} 11, -OC 6 H 1 3, -OC 7 H 15,
_{-OC 8 H 17, -OC 9 H} 19, -OC 10 H 21, -OCFH
_{2, -OCF 2 H, -OCF 3} , -OCH 2 CH 2 F, -O
_{CH 2 CHF 2, -OCH 2 CF} 3, -OCF 2 CH 3, -O
_{CF 2 CF 2 H, -OCFHCF 3} , -OCF 2 CF 3, -
O (CH ₂ ) ₂ CH ₂ F, —O (CH ₂ ) ₂ CHF ₂ , —O
(CH ₂ ) ₂ CF ₃ , —OCH ₂ CF ₂ CH ₃ , —OCH ₂ C
_{F 2 CF 3, -OCF 2 C} 2 H 5, -OC 3 F 7, -OCF 2 C
FHCF ₃ , —O (CH ₂ ) ₃ CH ₂ F, —O (CH ₂ ) ₄ C
_{H 2 F, -O (CH 2} ) 5 CH 2 F, -OCF 2 C 3 H 7, -
OCH ₂ CF ₂ C ₂ H ₅ , —O (CH ₂ ) ₂ CF ₂ CH ₃ , —O
_{CF 2 C 4 H 9, -OCH} 2 CF 2 CH 3, -O (CH 2) 2 C
_{F 2 C 2 H 5, -O} (CH 2) 3 CF 2 CH 3,

-CH = CH ₂ , -CH = CHCH ₃ , -C
_{H = CHC 2 H 5, -CH} = CHC 3 H 7, -CH = CHC
_{4 H 9, -CH 2 CH =} CHCH 3, -CH 2 CH = CHC 2
_{H 5, -CH 2 CH = CHC} 3 H 7, -CH 2 CH = CHC 4
_{H 9, - (CH 2)} 2 CH = CHCH 3, - (CH 2) 2 CH
_{= CHC 2 H 5, - (} CH 2) 2 CH = CHC 3 H 7, - (C
_{H 2) 2 CH = CHC 4} H 9, -CH 2 CH = CH 2, - (C
_{H 2) 2 CH = CH 2} , - (CH 2) 3 CH = CH 2, - (C
_{H 2) 4 CH = CH 2} , - (CH 2) 5 CH = CH 2, -CH
ＣＨCHCH ＝ CH ₂ , —CH ＝ CHCH ₂ CH ＝ CH ₂ ,
_{-CH = CH (CH 2) 2} CH = CH 2, -CH = CH
_{(CH 2) 3 CH = CH} 2, -CH 2 CH = CH (CH 2) 2
_{CH = CH 2, - (CH} 2) 2 CH = CH (CH 2) 2 CH
= CH ₂ ,

-CF = CF ₂ , -CH = CF ₂ , -CH =
_{CHF, -CH 2 CF = CF 2} , -CH 2 CH = CFH,
_{- (CH 2) 2 CH =} CF 2, - (CH 2) 2 CH = CH
_{F, - (CH 2) 3} CH = CF 2, - (CH 2) 3 CH = C
_{HF, - (CH 2) 4} CH = CF 2, - (CH 2) 4 CH =
_{CHF, - (CH 2) 5} CH = CF 2, - (CH 2) 5 CH
_{= CHF, -CH = CHCH 2 CH} 2 F, -CH = CHC
_{H 2 CH 2 Cl, -CH =} CHCH 2 CHF 2, -CH = C
_{HCH 2 CF 3, -CH = CH} (CH 2) 2 CH 2 F, -C
_{H = CH (CH 2) 2} CHF 2, -CH = CH (CH 2) 2
_{CF 3, -CH = CH (CH} 2) 3 CH 2 F, -CH = CH
(CH ₂ ) ₃ CHF ₂ , —CH ＝ CH (CH ₂ ) ₃ CF ₃ ,
_{CH = CH (CH 2) 4} CH 2 F, -CH = CH (CH 2)
₄ CHF ₂ , —CH ＝ CH (CH ₂ ) ₄ CF ₃ , —CH ₂ CH
_{= CH (CH 2) 2 CH} 2 F, -CH 2 CH = CHCH 2 C
_{H 2 F, - (CH 2} ) 2 CH = CH (CH 2) 2 CH 2 F, -
_{(CH 2) 2 CH = CHCH} 2 CH 2 F, -CH = CHCH
_{2 CH = CF 2, -CH =} CH (CH 2) 2 CH = CF 2,
_{-CH = CH (CH 2) 2} CF = CF 2, -CH = CH
(CH ₂ ) ₃ CHFCH ₃ ,

--OCH ₂ CH = CHCH ₃ , --OCH ₂ C
_{H = CHC 2 H 5, -OCH} 2 CH = CHC 3 H 7, -OC
_{H 2 CH = CHC 4 H 9} , -O (CH 2) 2 CH = CHC
_{H 3, -O (CH 2)} 2 CH = CHC 2 H 5, -O (CH 2)
₂ CH = CHC ₃ H ₇ , —O (CH ₂ ) ₂ CH = CHC
_{4 H 9, -OCH 2 CH =} CH 2, -O (CH 2) 2 CH = C
_{H 2, -O (CH 2)} 3 CH = CH 2, -O (CH 2) 4 CH
ＣＨCH ₂ , —O (CH ₂ ) ₅ CH ＝ CH ₂ , —OCH ₂ CH
ＣＨCH (CH ₂ ) ₂ CH 2CH ₂ , —O (CH ₂ ) ₂ CH =
CH (CH ₂ ) ₂ CH = CH ₂ ,

-OCH ₂ CF = CF ₂ , -OCH ₂ CH =
_{CF 2, -OCH 2 CF = CHF} , -O (CH 2) 2 CH =
_{CF 2, -O (CH 2)} 2 CH = CHF, -O (CH 2) 3
CH = CF ₂ , —O (CH ₂ ) ₃ CH = CHF, —O (C
_{H 2) 4 CH = CF 2} , -O (CH 2) 4 CH = CHF, -
_{O (CH 2) 5 CH =} CF 2, -O (CH 2) 5 CH = CH
_{F, -OCH 2 CH = CHCH 2} CH 2 F, -O (CH 2)
_{2 CH = CH (CH 2)} 2 CH 2 F, -O (CH 2) 2 CH =
CHCH ₂ CH ₂ F,

-C≡CH, -C≡CCH ₃ , -C≡CC _{2
H 5, -C≡CC 3 H 7,} -C≡CC 4 H 9, -CH 2 C≡C
_{H, -CH 2 C≡CCH 3, -CH} 2 C≡CC 2 H 5, -C
_{H 2 C≡CC 3 H 7, -CH} 2 C≡CC 4 H 9, - (CH 2) 2
C≡CH, — (CH ₂ ) ₂ C≡CCH ₃ , — (CH ₂ ) ₂ C
_{≡CC 2 H 5, - (CH} 2) 2 C≡CC 3 H 7, - (CH 2) 2
C≡CC ₄ H ₉ , — (CH ₂ ) ₃ C≡CH, — (CH ₂ ) ₃ C
{CCH ₃ ,-(CH ₂ ) ₃ C} CC ₂ H ₅ ,-(CH ₂ ) _{3
C≡CC 3 H 7, - (CH} 2) 3 C≡CC 4 H 9, -C≡CC
_{F 3, -C≡CC 2 F 5,} -C≡CC 3 F 7, -CH 2 C≡C
CF ₃ , — (CH ₂ ) ₂ C≡CCF ₃ ,

[0044] -OCH ₂ C≡CH, -OCH ₂ C≡CCH
₃ , —OCH ₂ C≡CC ₂ H ₅ , —OCH ₂ C≡CC ₃ H ₇ ,
—OCH ₂ C≡CC ₄ H ₉ , —O (CH ₂ ) ₂ C≡CH,
O (CH ₂ ) ₂ C≡CCH ₃ , —O (CH ₂ ) ₂ C≡CC ₂ H
_{5, -O (CH 2) 2} C≡CC 3 H 7, -O (CH 2) 2 C≡
CC ₄ H ₉ , —O (CH ₂ ) ₃ C≡CH, —O (CH ₂ ) ₃ C
{CCH ₃ , —O (CH ₂ ) ₃ C} CC ₂ H ₅ , —O (C
_{H 2) 3 C≡CC 3 H 7} , -O (CH 2) 3 C≡CC 4 H 9,

—OCH ₂ C≡CCF ₃ , —O (CH ₂ ) ₂ C
≡CCF ₃ , —CH ₂ OCH ₃ , —CH ₂ OC ₂ H ₅ , —CH
_{2 OC 3 H 7, -CH 2} OC 4 H 9, -CH 2 OC 5 H 11, -
_{(CH 2) 2 OCH 3,} - (CH 2) 2 OC 2 H 5, - (C
_{H 2) 2 OC 3 H 7} , - (CH 2) 2 OC 4 H 9, - (CH 2) 2
_{OC 5 H 11, - (CH} 2) 3 OCH 3, - (CH 2) 3 OC 2
_{H 5, - (CH 2)} 3 OC 3 H 7, - (CH 2) 3 OC 4 H 9,
— (CH ₂ ) ₃ OC ₅ H ₁₁ , — (CH ₂ ) ₄ OCH ₃ ,

--CF ₂ OCH ₃ , --CF ₂ OC ₂ H ₅ , --C
_{F 2 OC 3 H 7, -CF} 2 OC 4 H 9, -CF 2 OC 5 H 11, -
_{CH 2 OCF 3, -CH 2 OC} 2 F 5, -OCH 2 OCH 3,
_{-OCH 2 OC 2 H 5, -OCH} 2 OC 3 H 7, -OCH 2 O
_{C 4 H 9, -OCH 2 OC} 5 H 11, -O (CH 2) 2 OC
_{H 3, -O (CH 2)} 2 OC 2 H 5, -O (CH 2) 2 OC 3 H
_{7, -O (CH 2) 2} OC 4 H 9, -O (CH 2) 2 OC
_{5 H 11, -O (CH 2} ) 3 OCH 3, -O (CH 2) 3 OC 2
_{H 5, -O (CH 2)} 3 OC 3 H 7, -O (CH 2) 3 OC 4 H
_{9, -O (CH 2) 3} OC 5 H 11, -O (CH 2) 4 OC
H ₃ ,

--OCH ₂ OCF ₃ , --OCH ₂ OC ₂ F ₅ ,
_{-COCF 3, -COCHF 2, -COC 2} F 5, -CO
_{C 3 F 7, -COCH 2 CF} 3, -OCOCH 3, -OCO
_{C 2 H 5, -OCOC 3 H} 7, -OCOC 5 H 11, -OCO
_{C 7 H 15, -OCOCF 3,} -OCOCHF 2, -OCO
_{C 2 F 5, -OCOC 3 F} 7, -OCOCH 2 CF 3, -CO
_{OCH 3, -COOC 2 H 5,} -COOC 3 H 7, -COO
_{C 4 H 9, -COOC 5 H} 11, -COOCH (CH 3) C 6
_{H 13, -COOCH 2 F, -COOCH} 2 CF 3, -CO
_{O (CH 2) 2 CF 3} , -COO (CH 2) 3 CF 3, -CO
O (CH ₂ ) ₄ CH ₂ F,

A hydrogen atom, a halogen atom, a cyano group, a cyanate group, an isocyano group, and an isothiocyanate group.

Chemical formula of the compound represented by the general formula (2)
When particular attention is paid to physical stability, R ¹ and Y ¹ are a saturated alkyl group, a haloalkyl group, an alkoxy group, a haloalkoxy group, an alkoxyalkyl group, a haloalkoxyalkyl group consisting only of a carbon atom and a hydrogen atom, Alkoxyalkoxy group, haloalkoxyalkoxy group, alkanoyl group, haloalkanoyl group, alkanoyloxy group, haloalkanoyloxy group, alkoxycarbonyl group, haloalkoxycarbonyl group, hydrogen atom, halogen atom, cyano group, cyano group, or isocyano group It is preferred that

When it is desired to increase the absolute value of the negative dielectric anisotropy value of the compound represented by the general formula (2), R ¹ and Y ¹ are the same as those of the saturated alkyl composed of only carbon atoms and hydrogen atoms. Group, alkoxy group, alkenyl group, alkenyloxy group, alkynyl group, alkynyloxy group, alkoxyalkyl group, alkoxyalkoxy group, alkanoyl group, alkanoyloxy group, alkoxycarbonyl group,
Alternatively, a substituent having low polarity such as a hydrogen atom is preferable.

X ^{1 of} the compound represented by the general formula (2),
X ² , X ³ and X ⁴ are a single bond, — (CH ₂ ) ₂ —, —CH
= CH-, -C≡C-, -COO-, -OCO-, -C
_{H 2 O -, - OCH 2} -, - (CH 2) 4 -, - (CH 2) 3
_{O -, - O (CH 2} ) 3 -, - CH = CHCH 2 CH 2 -,
_{-CH 2 CH = CHCH 2 -,} - CH 2 CH 2 CH = CH
-, - CH = CHCH = CH -, - CF 2 O -, - OC
F ₂ —, —CH ＝ CHCH ₂ O—, —OCH ₂ CH ＝ CH
-, - CF = CF -, - CH 2 CF 2 -, - CF 2 CH
_{2 -, - (CF 2)} 2 -, - (CF 2) 4 -, - (CH 2) 2
_{COO -, - OCO (CH 2} ) 2 -, - CH = CHCOO
—, —OCOCH ＝ CH—, —CH ＝ CHC≡C—, or —C≡CCH ＝ CH—.

The chemical reaction of the compound represented by the general formula (2)
When paying particular attention to physical stability, X ¹ , X ² , X ³ and X ⁴ are each a single bond, — (CH ₂ ) ₂ —, —COO—, or —OC.
_{O -, - CH 2 O -} , - OCH 2 -, - (CH 2) 4 -, -
_{(CH 2) 3 O -,} - O (CH 2) 3 -, - CF 2 O -, -
_{OCF 2 -, - CH 2 CF} 2 -, - CF 2 CH 2 -, - (C
_{F 2) 2 -, - (} CF 2) 4 -, - (CH 2) 2 COO-, or -OCO (CH _{2) 2} - or the like is preferably.

The ring A ^{1 of the} compound represented by the general formula (2)
At least one of ring A ² , ring A ³ , ring A ⁴ and ring A ⁵ is tetrahydropyran-2,5-diyl and at least 1
Is a ring represented by the general formula (1). Specific examples of the ring represented by the general formula (1) include the following rings. 2,3-difluorobenzene-1,4-diyl,
2,3-dichlorobenzene-1,4-diyl, and 2-
Chloro-3-fluorobenzene-1,4-diyl.

Preferred rings other than those described above include bicyclo [1.1.1] pentane-1,3-diyl, trans-cyclohexane-1,4-diyl, and cyclohexa-
1-ene-1,4-diyl and 1,4-phenylene, and a carbon atom constituting these rings is a nitrogen atom,
An oxygen atom or a sulfur atom may be substituted, and a hydrogen atom on the ring may be substituted with a halogen atom or a cyano group.

Specifically, 1-cyano-trans-cyclohexane-1,4-diyl, 2,2-difluoro-trans-cyclohexane-1,4-diyl, 2-fluorocyclohex-1-ene-1, 4-diyl, and 2,
2-dichlorobicyclo [1.1.1] pentane-1,3
-Diyl. Further, as the ring in which a hydrogen atom on the ring may be substituted with a fluorine atom, a chlorine atom or a cyano group, the following rings may be mentioned. Bicyclo [1.
1.1] pentane-1,3-diyl, trans-cyclohexane-1,4-diyl, cyclohex-1-ene-
1,4-diyl, 1,4-phenylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl,
Pyridine-2,5-diyl, pyrazine-2,5-diyl, pyridazine-3,6-diyl, 1,3-dithiane-
2,5-diyl, 1,3-oxathiane-2,5-diyl, and bicyclo [2.2.2] octane-1,4-diyl).

Chemical formula of the compound represented by the general formula (2)
When particular attention is paid to physical stability, ring A ¹ , ring A ² , ring A
^3, the preferred ring to the ring A ⁴ and ring A ⁵ are, is ring (such as 2,3-difluoro-1,4-diyl) represented tetrahydropyran-2,5-diyl and the general formula (1) However, other than the above, preferred rings for ring A ¹ , ring A ² , ring A ³ , ring A ⁴ and ring A ⁵ include the following rings. 1-cyano-trans-cyclohexane-1,4
-Diyl, 2,2-difluoro-trans-cyclohexane-1,4-diyl, 2-fluorocyclohexa-1
-Ene-1,4-diyl and 2,2-dichlorobicyclo [1.1.1] pentane-1,3-diyl. Examples of the ring in which a hydrogen atom on the ring may be substituted with a fluorine atom, a chlorine atom or a cyano group include bicyclo [1.1.1] pentane-1,3-diyl, trans-cyclohexane-1,
4-diyl, cyclohex-1-ene-1,4-diyl, 1,4-phenylene, 1,3-dioxane-2,5
-Diyl, pyrimidine-2,5-diyl, pyridine-
2,5-diyl, pyridazine-3,6-diyl, 1,3
-Dithiane-2,5-diyl, 2,3-difluorobenzene-1,4-diyl, and 1,3-oxathiane-
2,5-diyl.

When it is desired to increase the absolute value of the negative dielectric anisotropy value of the compound represented by the general formula (2), the ring A ¹ ,
Preferred rings for ring A ² , ring A ³ , ring A ⁴ and ring A ⁵ are tetrahydropyran-2,5-diyl and a ring represented by the general formula (1) (for example, 2,3-difluorobenzene-1, 4-
Diyl), but other than that, ring A ¹ , ring A ² ,
Preferred rings for the ring A ³ , the ring A ⁴ and the ring A ⁵ include the following rings. 1-cyano-trans-cyclohexane-1,4-diyl, 2,2-difluoro-trans-
Cyclohexane-1,4-diyl, 2-fluorocyclohex-1-ene-1,4-diyl, and 2,2-dichlorobicyclo [1.1.1] pentane-1,3-diyl. Examples of the ring in which a hydrogen atom on the ring may be substituted with a fluorine atom, a chlorine atom or a cyano group include trans-cyclohexane-1,4-diyl, cyclohex-1-ene-
1,4-diyl, and pyridazine-3,6-diyl.

The compounds of the present invention described in claims 1 to 3 have a negative value of a large dielectric constant anisotropy. For this reason,
By mainly using the compound of the present invention, a liquid crystal composition having a negative dielectric anisotropy value can be adjusted. This liquid crystal composition is particularly suitable for a device using a liquid crystal composition having a negative dielectric anisotropy value, such as a vertical alignment method described in JP-A-2-176625 or IPS. It is useful for making. In addition, by mixing and using the compound of the present invention with another liquid crystal compound or composition, an appropriate setting of the dielectric anisotropy value can be performed. Can be spread. The compounds of the present invention according to claims 1 to 3 have a small elastic constant and the temperature dependence of the constant is small. Therefore, a novel liquid crystal composition having a low driving voltage can be prepared by using the compound of the present invention.

The compounds of the present invention described in claims 1 to 3 have good compatibility with other liquid crystal compounds. For this reason, when the compound of the present invention is compounded in a liquid crystal composition, problems such as precipitation of the compound hardly occur. Further, the compound of the present invention can be incorporated in a large amount into the liquid crystal composition, and as a result, the excellent properties of the compound of the present invention can be strongly reflected in the liquid crystal composition.

The compound of the present invention according to claims 1 to 3,
By appropriately designing the structure, a desired value of the refractive index anisotropy value can be obtained. That is, when a particularly high refractive index anisotropy value is required, a ring having many sites having a resonance structure such as an aromatic ring may be selected. When a low refractive index anisotropy value is required, trans-cyclohexane-
What is necessary is just to select the ring which has many sites which do not have a resonance structure, such as a 1, 4- diyl ring. More specifically, the compound of the present invention represented by the general formula (2) is represented by R ¹ , Y ¹ , X ¹ ,
X ² , X ³ , X ⁴ , ring A ¹ , ring A ² , ring A ³ , ring A ⁴ , ring A ⁵ ,
By appropriately selecting a ¹ , a ² , a ³ , a ⁴ and a ⁵ , it is possible to obtain a desired value of the refractive index anisotropy value. More specifically, the refractive index anisotropy value can be adjusted by appropriately selecting the ring A ¹ , the ring A ² , the ring A ³ , the ring A ⁴ and the ring A ⁵ . That is, when a particularly high refractive index anisotropy value is required, a ring having many sites having a resonance structure such as an aromatic ring may be selected. When a low refractive index anisotropy value is required, a ring having many sites having no resonance structure, such as a trans-cyclohexane-1,4-diyl ring, may be selected. By freely selecting the refractive index anisotropy value, the degree of freedom in designing the liquid crystal panel is increased.

Each of the compounds of the present invention according to claims 1 to 3 has a low viscosity and can be used in a large amount in a liquid crystal composition.
It does not significantly increase the viscosity of the entire liquid crystal composition.
Further, the temperature dependence of the viscosity, particularly at low temperatures, is extremely small. By using the liquid crystal compound having the excellent viscosity, a liquid crystal composition having a high-speed response can be adjusted. The compounds of the present invention described in claims 1 to 3 are chemically and physically stable, and the liquid crystal composition using the compounds has high specific resistance and high voltage holding ratio. It has high stability against external factors such as ultraviolet rays and heating, and has sufficient chemical and physical stability as a component of a practical liquid crystal composition.

The phase transition temperature of the compounds of the present invention described in claims 1 to 3 can be adjusted by appropriately selecting the number of rings. That is, a compound having four or more rings is required when a particularly high clearing point is required, a three-ring compound is required when a moderate clearing point is required, and a two-ring compound is required when a particularly low clearing point is required. You just have to select More specifically, the compound of the present invention represented by the general formula (2) includes a ¹ ,
By appropriately selecting a ² , a ³ , a ⁴ and a ⁵ , the phase transition temperature can be adjusted. That is, in the case of a particularly high require clearing point ^{a 1 + a 2 + a 3} + a 4 + a 5 to ≧ 4 a is 4 or more rings compounds, when requiring a moderate clearing point a ¹ + a ² + a ³ + A ⁴ + a ⁵ = 3 tricyclic compound, especially when a low clearing point is required, a ¹ + a ² + a ³
A bicyclic compound in which + a ⁴ + a ⁵ = 2 may be selected.

As described above, the compounds of the present invention described in claims 1 to 3 have various physical properties suitable as electro-optical display materials. By using the compound of the present invention, a novel liquid crystal composition having good characteristics can be prepared. In addition, a liquid crystal compound having desired characteristics, a liquid crystal composition and a liquid crystal display device using the same can be obtained by appropriately designing the structure according to the application. For example, although the compound of the present invention is characterized by exhibiting a large negative dielectric anisotropy value, it can be used not only for a liquid crystal composition having a negative dielectric anisotropy value but also for a positive liquid crystal composition. It can be added to a composition having a dielectric anisotropy value to adjust the dielectric anisotropy value and other properties. More specifically, the compound of the present invention or a liquid crystal composition using the same may be prepared in various display systems using a compound or a composition having a negative dielectric anisotropy value (for example, described in JP-A-2-176625). IPS, ECB (HAN or DAP)
), DS, GH or PC, etc.
It can be used for a vertical alignment method as described in JP-A-76625 and IPS. However, not only can these methods be used, but also various display methods (for example, TN, STN,
Or TN-based AM (TFT or MIM)
It can also be used to improve or adjust various properties (for example, dielectric anisotropy value, elastic constant, refractive index anisotropy value, viscosity, or chemical and physical stability) of a liquid crystal composition for use. .

Hereinafter, the liquid crystal composition of the present invention will be described. The liquid crystal composition according to the present invention comprises at least one of the compounds according to any one of claims 1 to 3 in an amount of from 0.1 to 99.9.
It is preferable that the content is contained in a ratio of% by weight in order to exhibit excellent characteristics. More specifically, the liquid crystal composition provided by the present invention comprises, in addition to a first component containing at least one compound according to any one of claims 1 to 3, a general formula ( It is completed by mixing the compounds selected from the compound group represented by 3) to (13) at an appropriate ratio. The compounds represented by the general formulas (3) to (5) used in the liquid crystal composition of the present invention preferably include the following compounds. (R ² and Y ² represent the same meaning as described above.)

[0065]

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[0066]

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[0067]

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The compounds represented by the general formulas (3) to (5) are compounds having a positive dielectric anisotropy value, have excellent thermal stability and chemical stability, and have a high voltage holding ratio. T, which requires high reliability such as high resistance or large specific resistance
When a liquid crystal composition for FT is prepared, it is a particularly preferable compound. When adjusting the liquid crystal composition for TFT,
The compound represented by the general formulas (3) to (5) can be used in an amount of 0.1 to 99.9% by weight, preferably 10 to 97% by weight, based on the total weight of the liquid crystal composition. %, More preferably 40 to 95% by weight. Further, the compounds represented by the general formulas (8) to (10) may be further contained for the purpose of adjusting the viscosity. When preparing a liquid crystal composition for STN or TN, the compounds represented by the general formulas (3) to (5) can be used. In that case, the use amount of 50% by weight or less is preferable.

The compounds represented by formulas (6) and (7) used in the liquid crystal composition of the present invention preferably include the following compounds. (R ³ , Y ³ and R ⁴
Represents the same meaning as described above. )

[0070]

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[0071]

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The compounds represented by the general formulas (6) and (7) have a positive and large dielectric anisotropy value, and are used particularly for the purpose of reducing the threshold voltage of the liquid crystal composition. Also,
It is also used for the purpose of expanding the nematic range such as adjusting the refractive index anisotropy value and increasing the clearing point. Further, it is also used for the purpose of improving the steepness of the VT curve of the liquid crystal composition for STN or TN.

The compounds represented by the general formulas (6) and (7) are preferred especially when preparing liquid crystal compositions for STN and TN. When the amount of the compound represented by the general formulas (6) and (7) is increased, the threshold voltage of the liquid crystal composition decreases and the viscosity increases. Therefore,
As long as the viscosity of the liquid crystal composition satisfies the required characteristics, it is advantageous to use a large amount of the liquid crystal composition because low-voltage driving can be performed. The amount of the compound represented by the general formulas (6) to (7) is 0.1 to 9 when adjusting the liquid crystal composition for STN or TN.
Although it can be used in the range of 9.9% by weight,
It is 97% by weight, more preferably 40 to 95% by weight.

The compounds represented by formulas (8) to (10) used in the liquid crystal composition of the present invention preferably include the following compounds. (R ⁵ and R ⁶ represent the same meaning as described above.)

[0075]

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The compounds represented by the general formulas (8) to (10) have a small absolute value of dielectric anisotropy and are almost neutral. The compound represented by the general formula (8) is mainly used for adjusting the viscosity or adjusting the value of the refractive index anisotropy. Further, the compounds represented by the general formulas (9) and (10) are used for the purpose of expanding the nematic range such as increasing the clearing point or adjusting the refractive index anisotropy value. General formula (8)
When the amount of the compound represented by (10) is increased, the threshold voltage of the liquid crystal composition increases, and the viscosity decreases. Therefore, as long as the required value of the threshold voltage of the liquid crystal composition is satisfied, it can be used in a large amount. The amounts of the compounds represented by the general formulas (8) to (10)
When preparing a liquid crystal composition for use, the content is preferably 40% by weight, more preferably 35% by weight or less. Also, S
When preparing TN or a liquid crystal composition for TN, the content is preferably 70% by weight or less, more preferably 60% by weight or less.

The compounds represented by formulas (11) to (13) used in the liquid crystal composition of the present invention preferably include the following compounds. (R ⁷ and R ⁸ represent the same meaning as described above.)

[0078]

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The compounds represented by the general formulas (11) to (13) are compounds having a negative value of dielectric anisotropy, like the compounds according to the first to third aspects of the present invention. As a base compound of the liquid crystal composition of the present invention or for controlling the dielectric anisotropy of a P-type liquid crystal composition. For other uses,
The compound represented by the general formula (11) is a bicyclic compound,
It is mainly used for adjusting the threshold voltage, adjusting the viscosity or adjusting the refractive index anisotropy value. The compound represented by the general formula (12) is used for the purpose of widening the nematic range such as increasing the clearing point or adjusting the refractive index anisotropy value. The compound represented by the general formula (13) is used for the purpose of increasing the nematic range, reducing the threshold voltage, and increasing the refractive index anisotropy value.

The compounds represented by the general formulas (11) to (13) are mainly used for N-type liquid crystal compositions. Increasing the amount thereof decreases the threshold voltage of the liquid crystal composition, Becomes larger. Therefore, it is desirable to use a small amount as long as the required value of the threshold voltage of the liquid crystal composition is satisfied. However, the absolute value of the negative dielectric anisotropy is 5
If the amount is less than 40% by weight, low-voltage driving may not be performed. General formulas (11) to (1)
The amount of the compound represented by 3) is preferably 40% by weight or more, more preferably 50 to 95% by weight, when a liquid crystal composition for an N-type TFT is prepared. In order to control the elastic constant and control the voltage-transmittance curve (VT curve) of the liquid crystal composition, the general formula (11) is used.
The compound represented by (13) may be mixed with the P-type composition. In this case, the amount of the compounds represented by the general formulas (11) to (13) is preferably 30% by weight or less.

The liquid crystal composition of the present invention contains OCB
(Optically Compensated Bi
Except for a special case such as a liquid crystal composition for reference, usually, a helical structure of the liquid crystal composition is induced to adjust a required twist angle, and reverse twist (reverse twist) is performed.
For the purpose of preventing ist), an optically active compound is added. In the present invention, any of the known optically active compounds used for such a purpose can be used. Preferred examples of the compound include the following optically active compounds.

[0082]

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In the liquid crystal composition 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 for a liquid crystal composition for TFT and TN. In the case of a liquid crystal composition for STN, it is preferable to adjust the composition to a range of 6 to 20 μm. In addition, bistable TN (Bis
In the case of table TN), the thickness is preferably adjusted to a range of 1.5 to 4 μm. Further, 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 comprises a merocyanine compound,
A dichroic dye such as a styryl-based, azo-based, azomethine-based, azoxy-based, quinophthalone-based, anthraquinone-based, or tetrazine-based dye can be added to be used as a liquid crystal composition for GH. Alternatively, NCAP prepared by microencapsulating nematic liquid crystal, or polymer network liquid crystal display device (PN
Polymer-dispersed liquid crystal display device (P
It can also be used as a liquid crystal composition for DLCD). In addition, it can be used as a liquid crystal composition for DS.

The liquid crystal composition of the present invention is prepared by a conventional method. Generally, a method of dissolving various components at a high temperature is used.

The compounds of the present invention described in claims 1 to 3 can be easily produced by known organic synthetic chemistry techniques. One example of the production method is shown in Reaction Formula 1.

[0087]

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The above synthesis route will be described below. The compound represented by the formula 1 is derived from a compound represented by the formula 2 by adding 3-chloropropionic chloride by a Friedel-Crafts reaction in the presence of anhydrous aluminum chloride. The compound represented by Formula 3 is reacted with ethyl chlorocarbonate in the presence of LDA (lithium diisopropylamide) to be derived into a compound represented by Formula 4 .

The compound represented by the formula ( 4 ) is reacted with NaOEt (sodium ethoxide) and then reacted with the compound represented by the formula ( 2 ) to obtain a compound represented by the formula ( 5) .
Subsequently, the compound is derived into a compound represented by the formula 6 by hydrolysis with NaOH, further reduced to LAH (lithium aluminum hydride) to a compound represented by the formula 7 , and finally dehydrated by an acid catalyst to obtain the compound represented by the formula 8 To the target compound represented by

[0090]

EXAMPLES The production method and use examples of the compound of the present invention will be described in more detail with reference to the following examples. The present invention is not limited by the embodiments. In the description of the examples, N is the specified concentration (gram equivalent / l), M
Represents a molar concentration (mol / l), and Δε of the liquid crystalline compound
(Dielectric anisotropy value) is an extrapolated value (2) from a composition comprising the following base liquid crystal A (85 wt%) and the compound (15 wt%).
Δn (measured at 5 ° C.)
Is the following mother liquid crystal B85wt% and the compound 15wt%
And the measured value (measured at 25 ° C.) of the composition consisting of: Composition of mother liquid crystal A

[0091]

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Five types of ester compounds represented by the above general formula and having different alkyl groups (R ⁹ , R ¹⁰ ) at both terminals are represented by the following formula:
The following mixture was mixed to obtain mother liquid crystal A. Δε = -1.5

Composition of Mother Liquid Crystal B

[0094]

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Mother liquid crystals B were obtained by mixing four kinds of compounds represented by the above general formulas and having different terminal alkyl groups (R ¹¹ and R ¹² ) at the following ratios. Δn = 0.137

Example 1 Synthesis of 2- (4-n-propylphenyl) -5- (2,3-difluoro-4-n-propyloxyphenyl) tetrahydropyran ( 8 ) First Step 1-n-propyl- 4- (1-oxo-3-chloro-n
Synthesis of -propyl) benzene ( 2 ) Propylbenzene ( 1 ) (120.2g, 1.00mo
1), 3-chloropropionic acid chloride (139.7)
g, 1.10 mol), anhydrous aluminum chloride (14
6.7 g, 1.10 mol) and methylene chloride (120
0 ml) was reacted under a nitrogen atmosphere at room temperature for 12 hours. After completion of the reaction, 1N diluted hydrochloric acid (1500 m
l), the reaction solution was introduced thereinto, and then toluene (2000 m
Extracted in l). The obtained organic layer was washed with water (1500 ml).
And dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography (elution solvent: hexane / toluene = 1/1).
And purified by 1-n-propyl-4- (1-oxo-3).
-Chloro-n-propyl) benzene ( 2 ) (84.28)
g, 0.400 mol; yield 40%). MS / 2
11 (M ⁺ ).

Second Stage Synthesis of diethyl 2- (2,3-difluoro-4-n-propyloxyphenyl) malonate ( 4 ) Ethyl 2,3-difluoro-4-propyloxyphenylacetate ( 3 ) (258. 3 g, 1.00 mol) and diethyl ether (800 ml) were added to a mixture of lithium diisopropylamide (107.1 g, 1.0 ml) at -78 ° C.
(0 mol) in tetrahydrofuran (500 ml) was added dropwise over 30 minutes and reacted at the same temperature for 1 hour. While maintaining the same temperature, ethyl chlorocarbonate (108.5) was added to the reaction mixture.
g, 1.00 mol) of diethyl ether (300 m
l) The solution was dropped in 30 minutes, and then the temperature was gradually raised to 0 ° C.
For 12 hours. After completion of the reaction, water (1
000 ml) and then hexane (1000 ml)
Extracted. After the obtained organic layer was washed with water (800 ml), it was dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (elution solvent: hexane) to give 2- (2,3
Thus, diethyl (difluoro-4-propyloxyphenyl) malonate ( 4 ) (218.2 g, 0.661 mol; yield 66%) was obtained. MS / 330 (M ^<+> ).

Third stage 2-ethoxycarbonyl-2- (2,3-difluoro-
4-n-propyloxyphenyl) -5-oxo-5-
Synthesis of ethyl (4-n-propylphenyl) valerate ( 5 ) Diethyl 2- (2,3-difluoro-4-propyloxyphenyl) malonate ( 4 ) (13) obtained in the second step
2.0 g, 0.400 mol) of diethyl ether (5
00 ml) solution at −10 ° C. with NaOEt (40.83).
g, 0.600 mol) of diethyl ether (300 m
l) The solution was added dropwise over 30 minutes and reacted for 2 hours. Thereafter, at the same temperature, 1-n-propyl-4 obtained in the first stage
A solution of-(1-oxo-3-chloro-n-propyl) benzene ( 2 ) (84.20 g, 0.400 mol) in diethyl ether (200 ml) was added dropwise over 30 minutes, and the mixture was reacted at room temperature for 8 hours. . After completion of the reaction, water (400
ml) and then extracted with toluene (400 ml). The obtained organic layer was dried with anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography (elution solvent: hexane / ethyl acetate =
5/1) to give 2-ethoxycarbonyl-2-
(2,3-difluoro-4-n-propyloxyphenyl) -5-oxo-5- (4-n-propylphenyl)
Ethyl valerate ( 5 ) (86.38 g, 0.171 mol)
1; yield 43%). MS / 505 (M ^<+> ).

Fourth Step Synthesis of 2- (2,3-difluoro-4-n-propyloxyphenyl) -5-oxo-5- (4-n-propylphenyl) valeric acid ( 6 ) Obtained in the third step 2-ethoxycarbonyl-2- (2,
3-difluoro-4-n-propyloxyphenyl)-
Ethyl 5-oxo-5- (4-n-propylphenyl) valerate ( 5 ) (85.72 g, 0.170 mol) was added with sodium hydroxide (8.00 g, 0.200 mo) under ice-cooling.
l) water / ethanol (1/1) mixed solvent solution (200
ml). After heating the reaction solution to reflux for 1 hour,
After cooling to room temperature, the pH was adjusted to about 2 by adding 1N-HCl, and the mixture was again heated to reflux. After completion of the reaction, the reaction solution was concentrated under reduced pressure, and extracted with diethyl ether (600 ml). The obtained organic phase was dried with anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was recrystallized (solvent:
Acetic acid) to give 2- (2,3-difluoro-4-n
-Propyloxyphenyl) -5-oxo-5- (4-
n-propylphenyl) valeric acid ( 6 ) (38.02 g,
0.0940 mol; yield 55%). MS / 40
4 (M ⁺ ).

Fifth Step Synthesis of 1- (4-n-propylphenyl) -4- (2,3-difluoro-4-n-propyloxyphenyl) pentane-1,5-diol ( 7 ) The obtained 2- (2,3-difluoro-4-n-
Propyloxyphenyl) -5-oxo-5- (4-n
-Propylphenyl) valeric acid ( 6 ) (37.98 g,
A solution of 0.0939 mol) in ethanol (200 ml) was cooled and LAH (3.57 g, 0.094
0 mol) was added. The temperature of the reaction solution was gradually raised to room temperature,
The reaction was carried out at the same temperature for 8 hours. After completion of the reaction, water (100 ml) was added under ice-cooling, and 1N diluted hydrochloric acid (50 ml) was added.
l) was added. After completion of the reaction, the reaction solution was concentrated under reduced pressure,
Extracted with ethyl acetate (400 ml). The obtained organic phase was dried with anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (elution solvent: toluene) to give 1- (4-n-propylphenyl) -4- (2,3-difluoro-4-n
-Propyloxyphenyl) pentane-1,5-diol ( 7 ) (28.64 g, 0.0730 mol; yield 7)
8%). MS / 392 (M ^<+> ).

Sixth Step Synthesis of 2- (4-n-propylphenyl) -5- (2,3-difluoro-4-n-propyloxyphenyl) tetrahydropyran ( 8 ) (4-n-propylphenyl)-
4- (2,3-difluoro-4-n-propyloxyphenyl) pentane-1,5-diol ( 7 ) (28.5)
A mixture of 5 g (0.0727 mol), p-toluenesulfonic acid monohydrate (0.691 g, 0.0036 mol) and toluene (100 ml) was heated and refluxed for 5 hours while distilling off water. After the completion of the reaction, the resultant was cooled to room temperature and washed twice with water (100 ml). The obtained organic phase was dried with anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (elution solvent: hexane) and then recrystallized (hexane) to give 2- (4-n-propylphenyl) -5-
(2,3-difluoro-4-n-propyloxyphenyl) tetrahydropyran ( 8 ) (9.34 g, 0.02
49 mol; yield 34%). MS / 374
(M ⁺ ), Δε = −4.4, Δn = 0.138.

According to the method of Example 1, the following compounds can be synthesized.

[0103]

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[0104]

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[0105]

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[0106]

As described above, according to the present invention, a negative dielectric anisotropy value having a large absolute value, a low viscosity, a controlled optical anisotropy value, a high specific resistance value and a high It is possible to provide a liquid crystal compound which has a voltage holding ratio and is stable against heat or ultraviolet irradiation, a liquid crystal composition containing the same, and a liquid crystal display device manufactured using the liquid crystal composition. Was.

Claims (13)

[Claims] 1. The method according to claim 1, wherein tetrahydropyran-
2,5-diyl group and general formula (1) (Wherein W ¹ and W ² each independently represent a fluorine atom or a chlorine atom, and each atom constituting the compound may be substituted with its isotope.) Liquid crystal compound. 2. A compound of the general formula (2)(Where R¹And Y¹Each independently represents an atom having 1 to 20 carbon atoms.
Alkyl group, hydrogen atom, halogen atom, cyano group, cyanide
Represents an acid group, an isocyano group or an isothiocyanate group,
One or more non-adjacent methylene groups in said alkyl group
Is an oxygen atom, a sulfur atom, a nitrogen atom, -C≡C-, one or more
The above hydrogen atom is substituted by an alkyl group having 1 to 10 carbon atoms
Optionally substituted with a silylene group or a vinylene group
And one or more hydrogen atoms in these alkyl groups
Atoms may be substituted by fluorine or chlorine atoms
And these alkyl groups may be optically active,
X¹, X^Two, X^ThreeAnd X^FourAre each independently a single bond,-(CH
_Two)_Two-, -CH = CH-, -C≡C-, -COO-,-
OCO-, -CH_TwoO-, -OCH_Two-,-(CH _Two)
_Four-,-(CH_Two)_ThreeO-, -O (CH_Two)_Three-, -CH =
CHCH_TwoCH_Two-, -CH_TwoCH = CHCH_Two-, -CH
_TwoCH_TwoCH = CH-, -CH = CHCH = CH-, -C
F_TwoO-, -OCF_Two-, -CH = CHCH_TwoO-, -O
CH_TwoCH = CH-, -CF = CF-, -CH_TwoCF
_Two-, -CF_TwoCH_Two−, − (CF_Two)_Two−, − (CF_Two)_Four
-,-(CH_Two)_TwoCOO-, -OCO (CH_Two)_Two−, −
CH = CHCOO-, -OCOCH = CH-, -CH =
CHC≡C— or —C≡CCH ＝ CH—, and a ring A
¹, Ring A^Two, Ring A^Three, Ring A^FourAnd ring A^FiveAre independent tigers
-Cyclohexane-1,4-diyl, cyclohexa
-1-ene-1,4-diyl, 1,4-phenylene, bi
Cyclo [1.1.1] pentane-1,3-diyl, tet
Lahydropyran-2,5-diyl or general formula (1)(Where W¹And W^TwoAre each independently a fluorine atom or chlorine
Represents an atom. ), The ring A¹,
Ring A^Two, Ring A^Three, Ring A^FourAnd ring A^FiveAt least one of the
Trahydropyran-2,5-diyl and less
And one is a ring represented by the general formula (1).
The carbon atoms that make up the ring can be nitrogen, oxygen, or sulfur
A hydrogen atom on the ring may be halogen
May be substituted with an atom or a cyano group;¹, A^Two,
a^Three, A^FourAnd a^FiveEach independently represents 0 or 1, but a¹
+ A^Two+ A^Three+ A^Four+ A^Five≧ 1 and the compound is
Each constituent atom may be substituted with its isotope
No. The liquid crystalline compound according to claim 1, which is represented by the formula: 3. The liquid crystal compound according to claim 1, wherein the ring represented by the general formula (1) is 2,3-difluorobenzene-1,4-diyl. 4. A liquid crystal composition comprising at least two components, comprising at least one liquid crystal compound according to claim 1. Description: 5. A compound comprising at least one compound according to claim 1 as a first component, and a compound represented by general formulas (3), (4) and (5) as a second component. A liquid crystal composition comprising at least one compound selected from the group consisting of: Embedded image (Wherein, R ² represents an alkyl group having 1 to 10 carbon atoms, and one or more non-adjacent methylene groups in the alkyl group may be substituted with an oxygen atom or —CH ＝ CH—,
One or more hydrogen atoms in the alkyl group may be substituted with a fluorine atom, and Y ² is a fluorine atom, a chlorine atom, —OCF ₃ , —OCF ₂ H, —CF ₃ , —CF ₂ H ,
-CFH _2, -OCF ₂ CF ₂ H or -OCF ₂ CFHCF
₃ represents, L ¹ and L ² represents a hydrogen atom or a fluorine atom each independently, Z ¹ and Z ² are each independently - (CH _{2) 2
-, - (CH 2) 4} -, - COO -, - CF 2 O -, - O
CF ₂ —, —CH ＝ CH— or a single bond, and ring Q ¹ is trans-cyclohexane-1,4-diyl, 1,3-dioxane-2,5-diyl, or a hydrogen atom is substituted by a fluorine atom. And ring Q ² is trans-cyclohexane-1,4-diyl or 1,4 optionally substituted with a hydrogen atom by a fluorine atom.
Represents phenylene, and each atom constituting these compounds may be substituted with its isotope. ) 6. A compound comprising at least one compound according to any one of claims 1 to 3 as a first component, and a compound represented by general formulas (6) and (7) as a second component. A liquid crystal composition comprising at least one selected compound. Embedded image (Wherein, R ³ and R ⁴ each independently represent an alkyl group having 1 to 10 carbon atoms, and one or more non-adjacent methylene groups in the alkyl group are substituted with an oxygen atom or —CH ＝ CH—. may be, also, one or more hydrogen atoms in the alkyl group may be substituted with a fluorine atom, Y ³
Represents a cyano group or —C≡C—CN, and ring Q ³ represents trans-cyclohexane-1,4-diyl, 1,4-phenylene, 1,3-dioxane-2,5-diyl or pyrimidine-2,5. A ring Q ⁴ represents trans-cyclohexane-1,4-diyl, pyrimidine-2,5-diyl, or 1,4-phenylene in which a hydrogen atom may be substituted by a fluorine atom; ⁵ represents trans-cyclohexane-1,4-diyl or 1,4-phenylene, Z ³ represents — (CH ₂ ) ₂ —, —COO— or a single bond, and L ³ , L ⁴ and L ⁵ each represent Each independently represents a hydrogen atom or a fluorine atom, and b, c and d each independently represent 0 or 1
And the atoms constituting these compounds may be substituted with their isotopes. ) 7. A compound comprising at least one compound according to any one of claims 1 to 3 as a first component, and the compounds represented by the general formulas (3), (4) and (5) as a second component. And at least one compound selected from the group consisting of compounds represented by general formulas (8), (9) and (1).
A liquid crystal composition comprising at least one compound selected from the group consisting of 0). Embedded image (Wherein, R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 10 carbon atoms, and one or more non-adjacent methylene groups in the alkyl group are substituted with an oxygen atom or —CH ＝ CH—. And at least one hydrogen atom in the alkyl group may be substituted with a fluorine atom.
^6, ring Q ⁷ and ring Q ⁸ are each independently trans - cyclohexane-1,4-diyl, pyrimidine-2,5-diyl, or a hydrogen atom may be substituted with a fluorine atom 1,4 Represents phenylene, and Z ⁴ and Z ⁵ are each independently —C≡C—, —COO—, — (CH ₂ ) ₂ —, —CH
ＣＨCH— or a single bond, and the atoms constituting these compounds may be substituted with their isotopes. ) 8. A compound containing at least one compound according to claim 1 as a first component, and a compound represented by general formulas (11), (12) and (13) as a second component. A liquid crystal composition comprising at least one compound selected from the group consisting of: Embedded image (Wherein, R ⁷ and R ⁸ each independently represent an alkyl group having 1 to 10 carbon atoms, and one or more non-adjacent methylene groups in the alkyl group are substituted with an oxygen atom or —CH ＝ CH—. And at least one hydrogen atom in the alkyl group may be substituted with a fluorine atom.
⁹ and ring Q ¹⁰ are each independently trans - represents a cyclohexane-1,4-diyl or 1,4-phenylene, L
⁶ and L ⁷ each independently represent a hydrogen atom or a fluorine atom but do not represent a hydrogen atom at the same time, and Z ⁶ and Z ⁷ each independently represent-(CH ₂ ) _2- , -COO- or The atoms representing a bond and constituting these compounds may be substituted with their isotopes. ) 9. As a first component, at least one compound according to any one of claims 1 to 3 is contained, and as a second component, the compounds represented by formulas (8), (9) and (10) are used. And at least one compound selected from the group consisting of the compounds represented by formulas (11) and (1).
A liquid crystal composition comprising at least one compound selected from the group consisting of compounds (2) and (13). 10. A compound group comprising at least one compound according to any one of claims 1 to 3 as a first component, and a compound group consisting of the general formulas (6) and (7) as a second component. Containing at least one compound selected from
As the third component, the above general formulas (8), (9) and (1)
A liquid crystal composition comprising at least one compound selected from the group consisting of 0). 11. A compound containing at least one compound according to any one of claims 1 to 3 as a first component, and a compound represented by the above general formula (3), (4) or (5) as a second component. And at least one compound selected from the group consisting of the compounds represented by formulas (6) and (7)
At least one compound selected from the group consisting of
Contains, as the fourth component, the general formula (8),
A liquid crystal composition comprising at least one compound selected from the group consisting of compounds (9) and (10). 12. A liquid crystal composition comprising at least one optically active compound in addition to the liquid crystal composition according to claim 4. Description: 13. A liquid crystal display device comprising the liquid crystal composition according to claim 4. Description: