JP6048782B1 - Liquid crystal compound having an ethane bond - Google Patents

Abstract

A compound represented by the general formula (1) is provided, and a liquid crystal composition containing the compound and a liquid crystal display device using the liquid crystal composition are provided. By using the compound represented by the general formula (1) as a component of the liquid crystal composition, it exhibits high Tni, low viscosity (η), large Δn, and high miscibility in the liquid crystal composition, and is further chemically high. A liquid crystal composition having both stability can be obtained. For this reason, it is very useful as a component of a liquid crystal composition for a liquid crystal display element that requires a high-speed response.

Description

  The present invention relates to a compound having an ethane bond that is useful as an organic electronic material, medical pesticide, or a liquid crystal display element material, and a liquid crystal composition using the compound.

  Liquid crystal display elements are used in various measuring instruments, automobile panels, word processors, electronic notebooks, printers, computers, televisions, watches, advertisement display boards, etc., including watches and calculators. Typical liquid crystal display methods include TN (twisted nematic) type, STN (super twisted nematic) type, vertical alignment type using TFT (thin film transistor), and IPS (in-plane switching) type. There is a drive system such as. The liquid crystal compositions used in these liquid crystal display elements are stable against external factors such as moisture, air, heat, and light, and the liquid crystal phase (nematic phase, smectic phase) in the widest possible temperature range centering on room temperature. Phase, blue phase, etc.), low viscosity, and low driving voltage. Furthermore, the liquid crystal composition is selected from several to several tens of kinds of compounds in order to optimize the dielectric anisotropy (Δε) and the refractive index anisotropy (Δn) according to the individual display elements, It is configured.

When the liquid crystal composition is used as a display element or the like, it is required to exhibit a stable nematic phase in a wide temperature range. In order to maintain a nematic phase in a wide temperature range, it is required that individual components constituting the liquid crystal composition have high miscibility with other components and have a high clearing point (T _ni ). . However, compounds exhibiting high T _ni generally have high viscosity, and development of compounds having both high T _ni and low viscosity is required.

So far, the following compounds having four ring structures linked by a single bond have been reported, but there is a problem that the viscosity is relatively high although _Tni is high (Patent Document 1).

(In the formula, R and R ′ each independently represents an alkyl group having 1 to 9 carbon atoms.)

British Patent No. 2240778

The problem to be solved by the present invention is to provide a compound having a high T _ni , a low viscosity (η) and a high miscibility with other liquid crystal compounds, and a liquid crystal composition and a liquid crystal comprising the compound as a constituent member It is to provide a display element.

  In order to solve the above-mentioned problems, the present inventors have studied various compounds, and as a result, found that a specific compound having an ethane bond can effectively solve the problems, and have completed the present invention.

  The present invention provides a general formula (1)

(Wherein R ¹ and R ² each independently represents an alkyl group having 1 to 15 carbon atoms or an alkenyl group having 2 to 15 carbon atoms, and one —CH ₂ — present in these groups) Or two or more non-adjacent —CH ₂ — may be replaced by —C≡C—, —O—, —S—, —COO—, —OCO— or —CO—, The hydrogen atom present in may be replaced by a fluorine atom,
A ¹ and A ² are each independently (a) a 1,4-cyclohexylene group (one —CH ₂ — present in this group or two or more non-adjacent —CH ₂ — are — (It may be replaced by O- or -S-.)
(B) 1,4-phenylene group (one —CH═ present in this group or two or more non-adjacent —CH═ may be replaced by —N═ and present in this group) One hydrogen atom may be substituted with a fluorine atom.)
(C) a naphthalene-2,6-diyl group (one —CH═ present in this group or two or more non-adjacent —CH═ may be replaced by —N═, One hydrogen atom present in may be substituted with a fluorine atom.)
A group selected from the group consisting of:
X ¹ , X ² , X ³ and X ⁴ each independently represent a hydrogen atom or a fluorine atom, but X ¹ and X ² do not both represent a fluorine atom, and X ³ and X ⁴ both represent a fluorine atom. And at least one of X ^{2 and} X ⁴ represents a fluorine atom,
n ¹ represents 0, 1 or 2, n ² represents 1, 2 or 3, n ¹ + n ² represents 2 or 3, but when n ¹ is 2 and a plurality of A ¹ exist, A ^{1 1} may be the same or different, and when n ² is 2 or 3, and a plurality of A ² are present, A ² may be the same or different. )
A liquid crystal composition containing the compound and a liquid crystal display device using the liquid crystal composition are also provided.

The novel liquid crystal compound represented by the general formula (1) provided by the present invention can be easily produced industrially, and the obtained compound represented by the general formula (1) has a high T _ni. It exhibits a low viscosity and a high miscibility with a liquid crystal composition, and also has a high chemical stability.

  Therefore, a low-viscosity liquid crystal composition can be obtained by using the compound represented by the general formula (1) as a component of the liquid crystal composition. For this reason, it is very useful as a component of a liquid crystal composition for a liquid crystal display element that requires a high-speed response.

It is sectional drawing of the liquid crystal display element of this invention. A substrate having 100 to 105 is referred to as a “back plane”, and a substrate having 200 to 205 is referred to as a “front plane”. It is a figure of the exposure process using the pattern for columnar spacer preparation formed on a black matrix as a photomask pattern.

In general formula (1), R ¹ and R ² are preferably an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms in order to reduce the viscosity. Particularly preferred is an alkyl group of ˜5 or an alkenyl group of 2 to 5 carbon atoms. Moreover, it is preferable that it is linear. In order to increase miscibility with other liquid crystal components, it is preferable that R ¹ and R ² are different.

A ¹ and A ² are each independently a trans-1,4-cyclohexylene group, an unsubstituted 1,4-phenylene group, a 2-fluoro-1,4-phenylene group or 3 for decreasing the viscosity. It is preferably a -fluoro-1,4-phenylene group, more preferably a trans-1,4-cyclohexylene group. In order to improve miscibility with other liquid crystal components, it may be a trans-1,4-cyclohexylene group, a 2-fluoro-1,4-phenylene group or a 3-fluoro-1,4-phenylene group. preferable. In order to increase T _ni , an unsubstituted 1,4-phenylene group and an unsubstituted naphthalene-2,6-diyl group are preferable. In order to improve the long-term reliability when a liquid crystal display device is used, it is preferable not to contain a nitrogen atom. From the viewpoint of improving the viscosity, miscibility with other liquid crystal components, and T _ni in a well-balanced manner, at least one of A ^{1 and} A ² is a trans-1,4-cyclohexylene group, and A ¹ Alternatively, at least one of A ² is preferably an unsubstituted 1,4-phenylene group, a 2-fluoro-1,4-phenylene group, or a 3-fluoro-1,4-phenylene group. More specifically, when n ¹ + n ² represents ² , either A ¹ or A ² is a trans-1,4-cyclohexylene group and either A ¹ or A ² is absent. It is preferably a substituted 1,4-phenylene group, 2-fluoro-1,4-phenylene group or 3-fluoro-1,4-phenylene group, and A ¹ is a trans-1,4-cyclohexylene group And A ² is more preferably an unsubstituted 1,4-phenylene group, 2-fluoro-1,4-phenylene group or 3-fluoro-1,4-phenylene group. ^Further, when n 1 + ^{n 2} is 3, it is preferable that at least one or more of ^{A 1} or ^{A 2} is trans-1,4-cyclohexylene group, at least one of ^{A 1} or ^{A 2} is 2 -It is preferably a fluoro-1,4-phenylene group or a 3-fluoro-1,4-phenylene group.

When X ² and X ⁴ place importance on miscibility with other liquid crystal components, it is preferable that X ² represents a fluorine atom. X ¹ and X ³ are preferably both hydrogen atoms when importance is placed on the viscosity, and fluorine atoms are preferred when importance is placed on miscibility with other liquid crystal components. In addition, when the total number of fluorine atoms contained in the molecule is large, _Tni is excessively lowered and miscibility with other liquid crystal components is reduced. Therefore, the total number of fluorine atoms contained in the molecule is 1, 2. Or 3 is preferable, and 1 or 2 is more preferable. Specifically, X ¹ and X ³ are preferably hydrogen atoms, X ² and X ⁴ are preferably fluorine atoms, X ¹ , X ³ and X ⁴ are hydrogen atoms, and X ² is a fluorine atom. It is preferable that X ¹ , X ² and X ³ are hydrogen atoms, and X ⁴ is preferably a fluorine atom.

n ¹ is preferably 0 or 1 when emphasizing viscosity, and is preferably 1 or 2 when emphasizing T _ni . In order to increase the miscibility with other liquid crystal components, 0 or 1 is preferable.

n ² is preferably 1 when emphasizing viscosity, preferably 1 or 2 when emphasizing T _ni, and 1 for increasing miscibility with other liquid crystal components. Preferably there is.

n ¹ + n ² is preferably 2 when emphasizing viscosity, and preferably 3 when emphasizing T _ni , in order to increase the miscibility with other liquid crystal components. 2 is preferable. When n ¹ + n ² is 2, it is preferable that n ¹ is 1 and n ² is 1. If n ¹ + ^{n 2} is 3, is ^{n 1} is 1, it is preferable that ^{n 2} is 2, ^{n 1} is 0, it is preferred that ^{n 2} is 3.

  Note that the compound represented by the general formula (1) does not have a structure in which heteroatoms are directly bonded to each other.

  Specific examples of preferred compounds are shown below, but the present invention is not limited thereto.

  In general formula (1), each compound represented by the following general formula (1a)-general formula (1d) is preferable.

(Wherein R ¹ , R ² , X ¹ , X ² , X ³ and X ⁴ are each independently R ¹ , R ² , X ¹ , X ² , X ³ , X in the general formula (1)) ⁴ , A ^2a , A ^2b , A ^2c , A ^2d1 and A ^2d2 each independently represent the same meaning as A ² in the general formula (1), and n ^d1 and n ^d2 are each independently Represents 0 or 1, but n ^d1 + n ^d2 represents 1.)
As general formula (1a), the compound represented by the following general formula (1a-1)-general formula (1a-6) is preferable.

(In the formula, R ¹ and R ² each independently represent the same meaning as R ¹ and R ² in the general formula (1).)
In particular, general formula (1a-2) is preferable.

  As the general formula (1b), compounds represented by the following general formula (1b-1) to general formula (1b-8) are preferable.

(In the formula, R ¹ and R ² each independently represent the same meaning as R ¹ and R ² in the general formula (1).)
In particular, general formulas (1b-1) and (1b-2) are preferable.

  As the general formula (1c), compounds represented by the following general formula (1c-1) to general formula (1c-7) are preferable.

(In the formula, R ¹ and R ² each independently represent the same meaning as R ¹ and R ² in the general formula (1).)
In particular, general formulas (1c-1), (1c-2) and (1c-7) are preferable.

  As the general formula (1d), compounds represented by the following general formula (1d-1) to general formula (1d-13) are preferable.

(In the formula, R ¹ and R ² each independently represent the same meaning as R ¹ and R ² in the general formula (1).)
Particularly, general formulas (1d-1), (1d-2), and (1d-13) are preferable.

  If the content of the compound represented by the general formula (1) is small in the liquid crystal composition of the present invention, the effect does not appear. Therefore, the lower limit value in the composition is 1% by mass (hereinafter,% in the composition is mass). %), Preferably 2% or more, more preferably 5% or more, and even more preferably 10% or more. Moreover, since it will cause problems, such as precipitation, if there is much content, as an upper limit, it is preferable to contain 70% or less, It is more preferable to contain 60% or less, It is further more preferable to contain 50% or less, 40 % Or less is particularly preferable. Although the compound represented by General formula (1) can also be used by 1 type, you may use 2 or more types of compounds simultaneously.

  In order to adjust the physical property value of the liquid crystal composition, a compound other than the compound represented by the general formula (1) may be used. In addition to a compound having a liquid crystal phase, a compound having no liquid crystal phase may be used as necessary. It can also be added.

  Thus, as a preferable representative example of the compound that can be used by mixing with the compound represented by the general formula (1), in the composition provided by the present invention, the general component (1) At least one compound represented by formula (1), but it is preferable to contain at least one of the following second to fourth components as other components.

  That is, the second component is a so-called p-type liquid crystal compound having a positive dielectric anisotropy, and examples thereof include compounds represented by the following general formulas (LC1) and (LC2).

(In the formula, R ^LC11 and R ^LC21 each independently represent an alkyl group having 1 to 15 carbon atoms, and one or two or more —CH ₂ — in the alkyl group is not directly adjacent to an oxygen atom. -O-, -CH = CH-, -CO-, -OCO-, -COO-, or -C≡C- and may be substituted with one or more hydrogen atoms in the alkyl group ^May be optionally substituted with a halogen atom, and A ^LC11 and A ^LC21 are each independently any one of the following structures:

(In the structure, one or more —CH ₂ — in the cyclohexylene group may be substituted with an oxygen atom, and one or more —CH— in the 1,4-phenylene group may be substituted. May be substituted with a nitrogen atom, and one or more hydrogen atoms in the structure may be substituted with a fluorine atom, a chlorine atom, —CF ₃ or —OCF ₃ ). ^{represents, X LC11, X LC12, X} LC21 ~X LC23 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a -CF ₃ or -OCF ^{_3, Y LC11} and ^{Y LC21} are each independently a hydrogen atom, Represents a fluorine atom, a chlorine atom, a cyano group, —CF ₃ , —OCH ₂ F, —OCHF ₂ or —OCF ₃ , and Z ^LC11 and Z ^LC21 each independently represent a single bond, —CH═CH—, ^—CF═ CF- _{-C≡C -, - CH 2 CH 2} -, - (CH 2) 4 -, - OCH 2 -, - CH 2 O -, - OCF 2 -, - CF 2 O -, - COO- or -OCO- ^{M LC11} and m ^LC21 each independently represents an integer of 1 to 4, and when there are a plurality of A ^LC11 , A ^LC21 , Z ^LC11 and Z ^LC21 , they may be the same or different. good. )
R ^LC11 and R ^LC21 are each independently preferably an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms, and an alkyl group having 1 to 5 carbon atoms. Group, an alkoxy group having 1 to 5 carbon atoms, and an alkenyl group having 2 to 5 carbon atoms are more preferable, and it is more preferably linear, and the alkenyl group most preferably represents the following structure.

(In the formula, it shall be bonded to the ring structure at the right end.)
A ^LC11 and A ^LC21 each independently preferably have the following structure.

Y ^LC11 and Y ^LC21 are each independently preferably a fluorine atom, a cyano group, —CF ₃ or —OCF ₃ , preferably a fluorine atom or —OCF ₃ , and particularly preferably a fluorine atom.

Z ^LC11 and Z ^LC21 are ^preferably a single bond, —CH ₂ CH ₂ —, ^{—COO—, —OCO—} , —OCH ₂ —, —CH ₂ O—, —OCF ₂ — or —CF ₂ O—. , —CH ₂ CH ₂ —, —OCH ₂ —, —OCF ₂ — or —CF ₂ O— are preferred, and a single bond, —OCH ₂ — or —CF ₂ O— is more preferred.

m ^LC11 and m ^LC21 are preferably 1, 2 or 3, preferably 1 or 2 when emphasizing storage stability at low temperature and response speed, and 2 or 3 for improving the upper limit of the nematic phase upper limit temperature. Is preferred.

  The general formula (LC1) is represented by the following general formula (LC1-a) to general formula (LC1-c).

^{(Wherein, R LC11, Y LC11, X} LC11 and ^{X LC12} each independently represent the same meaning as ^{R LC11,} Y ^{LC11, X} LC11 and ^{X LC12} in the general formula ^{(LC1), A LC1a1, A} LC1a2 and A ^LC1b1 represents a trans-1,4-cyclohexylene group, a tetrahydropyran-2,5-diyl group, or a 1,3-dioxane-2,5-diyl group, and ^XLC1b1 , ^XLC1b2 , ^{XLC1c1 to XLC1c4} Are each independently a hydrogen atom, a fluorine atom, a chlorine atom, —CF ₃ or —OCF ₃ ), and are preferably one or more compounds selected from the group consisting of compounds represented by:

R ^LC11 is preferably independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms, and an alkyl group having 1 to 5 carbon atoms, carbon An alkoxy group having 1 to 5 atoms and an alkenyl group having 2 to 5 carbon atoms are more preferable.

X ^{LC11 to} X ^LC1c4 are each independently preferably a hydrogen atom or a fluorine atom.

Y ^LC11 is preferably each independently a fluorine atom, —CF ₃ or —OCF ₃ .

  The general formula (LC1) is changed from the following general formula (LC1-d) to general formula (LC1-m).

^{(Wherein, R LC11, Y LC11, X} LC11 and ^{X LC12} each independently represent the same meaning as ^{R LC11,} Y ^{LC11, X} LC11 and ^{X LC12} in the general formula ^{(LC1), A LC1d1, A} LC1f1, A ^LC1g1 , ^ALC1j1 , ^ALC1k1 , ^ALC1k2 , ^{ALC1m1 to ALC1m3} are 1,4-phenylene group, trans-1,4-cyclohexylene group, tetrahydropyran-2,5-diyl group, 1,3- It represents dioxane-2,5-diyl ^{group, X LC1d1, X LC1d2, X} LC1f1, X LC1f2, X LC1g1, X LC1g2, X LC1h1, X LC1h2, X LC1i1, X LC1i2, X LC1j1 ~X LC1j4, X LC1k1, ^{X LC1k2,} X ^LC1m And ^{X LC1m2} are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a -CF ₃ or _{^{-OCF 3, Z LC1d1, Z LC1e1}} , Z LC1j1, Z LC1k1, Z LC1m1 each independently represent a single bond, - CH═CH—, —CF═CF—, —C≡C—, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O-, -COO- or -OCO-) is preferably selected from the group consisting of compounds represented by the following formula:

R ^LC11 is preferably independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms, and an alkyl group having 1 to 5 carbon atoms, carbon An alkoxy group having 1 to 5 atoms and an alkenyl group having 2 to 5 carbon atoms are more preferable.

X ^{LC11 to} X ^LC1m2 are preferably each independently a hydrogen atom or a fluorine atom.

Y ^LC11 is preferably each independently a fluorine atom, —CF ₃ or —OCF ₃ .

Z ^{LC1d1 to} Z ^LC1m1 are each independently preferably —CF ₂ O— or —OCH ₂ —.
The general formula (LC2) is represented by the following general formula (LC2-a) to general formula (LC2-g).

( ^Wherein R ^LC21 , Y ^LC21 , X ^{LC21 to} X ^LC23 each independently represent the same meaning as R ^LC21 , Y ^LC21 , X ^{LC21 to} X ^LC23 in the general formula (LC2), and X ^{LC2d1 to} X ^LC2d4 , ^{X LC2e1 ~X LC2e4, X LC2f1 ~X} LC2f4 and ^X LC2g1 ^{~X LC2g4} are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a -CF ₃ or _{^{-OCF 3, Z LC2a1, Z LC2b1}} , Z LC2c1, ^ZLC2d1 , ^ZLC2e1 , ^ZLC2f1 and ^ZLC2g1 are each independently a single bond, —CH═CH—, ^{—CF═CF—} , ^—C≡C— , —CH ₂ CH ₂ —, — (CH ₂ ) _{4. -, - OCH 2 -, -} CH 2 O -, - OCF 2 -, - CF 2 O -, - COO- also Is —OCO—.) It is preferably one or more compounds selected from the group consisting of compounds represented by:

R ^LC21 is preferably independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms, and an alkyl group having 1 to 5 carbon atoms, carbon An alkoxy group having 1 to 5 atoms and an alkenyl group having 2 to 5 carbon atoms are more preferable.

X ^{LC21 to} X ^LC2g4 are each independently preferably a hydrogen atom or a fluorine atom,
Y ^LC21 is preferably each independently a fluorine atom, —CF ₃ or —OCF ₃ .

Z ^{LC2a1 to} Z ^LC2g4 are each independently preferably —CF ₂ O— or —OCH ₂ —.

  The third component is a so-called n-type liquid crystal compound having a negative dielectric anisotropy, and examples thereof include compounds represented by the following general formulas (LC3) to (LC5).

^(Wherein represents ^{R LC31, R LC32, R LC41} , R LC42, alkyl groups ^{R LC51} and ^{R LC52} is 1-15 carbon atoms independently, one in the alkyl group or two or more —CH ₂ — may be substituted with —O—, —CH═CH—, —CO—, —OCO—, —COO— or —C≡C— so that the oxygen atom is not directly adjacent. one or more hydrogen atoms in the group may be optionally substituted by a halogen ^{atom, a LC31, a LC32, a} LC41, a LC42, a LC51 and ^{a LC52} each independently any of the following Structure

(In the structure, one or more —CH ₂ — in the cyclohexylene group may be substituted with an oxygen atom, and one or more —CH— in the 1,4-phenylene group is Any one of which may be substituted with a nitrogen atom, and one or more hydrogen atoms in the structure may be substituted with a fluorine atom, a chlorine atom, —CF ₃ or —OCF ₃ ). indicates ^{whether, Z LC31, Z LC32, Z} LC41, Z LC42, Z LC51 and ^{Z LC51} each independently represent a single bond, -CH = CH -, - C≡C -, - CH 2 CH 2 -, - ( CH ₂ ) ₄ —, —COO—, —OCH ₂ —, —CH ₂ O—, —OCF ₂ — or —CF ₂ O—, Z ⁵ represents —CH ₂ — or an oxygen atom, and X ^LC41 represents ^Represents a hydrogen atom or a fluorine atom, m ^LC31 , m ^{L C32, m LC41, m LC42,} m LC51 and ^{m LC52} represent each independently ^{0~3, m LC31 + m LC32,} m LC41 + m LC42 and ^m LC51 ^{+ m LC52} is 1, 2 or ^{3, A LC31} ~ When a plurality of A ^LC52 and Z ^{LC31 to} Z ^LC52 are present, they may be the same or different. )
R ^{LC31 to} R ^LC52 are each independently preferably an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms. Most preferably,

(In the formula, it shall be bonded to the ring structure at the right end.)
A ^{LC31 to} A ^LC52 each independently preferably have the following structure:

Z ^{LC31 to} Z ^LC51 are each independently a single bond, —CH ₂ O—, —COO—, ^—OCO— , —CH ₂ CH ₂ —, —CF ₂ O—, —OCF ₂ — or —OCH ₂ —. preferable.

  General formula (LC3) is represented by the following general formula (LC3-a) and general formula (LC3-b).

(Wherein R ^LC31 , R ^LC32 , A ^LC31 and Z ^LC31 each independently represent the same meaning as R ^LC31 , R ^LC32 , A ^LC31 and Z ^LC31 in the general formula (LC3), and X ^{LC3b1 to} X ^LC3b6 are Represents a hydrogen atom or a fluorine atom, and at least one of X ^LC3b1 and X ^LC3b2 or X ^LC3b3 and X ^LC3b4 represents a fluorine atom, m ^LC3a1 is 1, 2 or 3, and m ^LC3b1 is 0 or In the case where a plurality of A ^LC31 and Z ^LC31 are present, they may be the same or different, but are represented by the general formula (LC3-b) in the general formula (LC3-a). Or a compound selected from the group of compounds represented by the formula: Rukoto is preferable.
R ^LC31 and R ^LC32 are each independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 2 to 7 carbon atoms. Is preferably represented.
A ^LC31 preferably represents a 1,4-phenylene group, a trans-1,4-cyclohexylene group, a tetrahydropyran-2,5-diyl group, or a 1,3-dioxane-2,5-diyl group. , 4-phenylene group and trans-1,4-cyclohexylene group are more preferable.
Z ^LC31 is a single _{bond, -CH 2 O -, - COO} -, - OCO -, - CH 2 CH 2 - is preferred to represent, and more preferably a single bond.
The general formula (LC3-a) preferably represents the following general formula (LC3-a1) to general formula (LC3-a4).

(In the formula, R ^LC31 and R ^LC32 each independently represent the same meaning as R ^LC31 and R ^LC32 in General Formula (LC3).)
R ^LC31 and R ^LC32 are each independently preferably an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms, and R ^LC31 has 1 carbon atom. It is more preferable that R 7 represents an alkyl group having ^˜7 , and R ^LC32 represents an alkoxy group having 1 to 7 carbon atoms.

  As general formula (LC3-b), it is preferable to represent the following general formula (LC3-b1) to general formula (LC3-b12), and general formula (LC3-b1), general formula (LC3-b6), and general formula (LC3-b8) and general formula (LC3-b11) are more preferable, general formula (LC3-b1) and general formula (LC3-b6) are more preferable, and general formula (LC3-b1) is represented. Most preferably it represents.

(In the formula, R ^LC31 and R ^LC32 each independently represent the same meaning as R ^LC31 and R ^LC32 in General Formula (LC3).)
R ^LC31 and R ^LC32 are each independently preferably an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms, and R ^LC31 has 2 carbon atoms. Or an alkyl group having 3 carbon atoms, and more preferably R ^LC32 represents an alkyl group having 2 carbon atoms.

  The general formula (LC4) is from the following general formula (LC4-a) to the general formula (LC4-c), and the general formula (LC5) is from the following general formula (LC5-a) to the general formula (LC5-c).

^{(Wherein, R LC41,} R ^LC42 and ^{X LC41} each independently represent the same meaning as ^{R LC41, R LC42} and ^{X LC41} in the general formula ^{(LC4), R LC51} and ^{R LC52} is the general independently It represents the same meaning as ^{R LC51} and ^{R LC52} in formula ^{(LC5), Z LC4a1, Z} LC4b1, Z LC4c1, Z LC5a1, Z LC5b1 and ^{Z LC5c1} each independently represent a single bond, -CH = CH -, - C≡ C—, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —COO—, —OCH ₂ —, —CH ₂ O—, —OCF ₂ — or —CF ₂ O—. More preferably, it is one or more compounds selected from the group consisting of the following compounds.

^{R LC41,} R LC42, R ^LC51 and ^{R LC52} each independently represents an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, the number alkenyl group or a carbon atom of 2 to 7 carbon atoms 2 It preferably represents -7 alkenyloxy groups.

Z ^{LC4a1 to} Z ^LC5c1 each independently preferably represents a single bond, —CH ₂ O—, ^{—COO—, —OCO—} , —CH ₂ CH ₂ —, and more preferably represents a single bond.

  The fourth component is a so-called nonpolar liquid crystal compound having a dielectric anisotropy of about 0, and examples thereof include a compound represented by the following general formula (LC6).

( ^Wherein , R ^LC61 and R ^LC62 each independently represent an alkyl group having 1 to 15 carbon atoms, and one or two or more —CH ₂ — in the alkyl group is not directly adjacent to an oxygen atom. -O-, -CH = CH-, -CO-, -OCO-, -COO-, or -C≡C- and may be substituted with one or more hydrogen atoms in the alkyl group ^May be optionally halogen-substituted, and A ^{LC61 to} A ^LC63 are each independently

(In the structure, one or more —CH ₂ CH ₂ — in the cyclohexylene group may be substituted with —CH═CH—, —CF ₂ O—, —OCF ₂ —. ^-One or two or more CH groups in the phenylene group may be substituted with a nitrogen atom), and Z ^LC61 and Z ^LC62 each independently represent a single bond, —CH═CH—, —C≡C—, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —COO—, —OCH ₂ —, —CH ₂ O—, —OCF ₂ — or —CF ₂ O— ⁱⁱⁱ¹ represents 0-3. However, the compound represented by General Formula (LC1) to General Formula (LC6) and General Formula (1) are excluded. )
R ^LC61 and R ^LC62 are each independently preferably an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms. Most preferably,

(In the formula, it shall be bonded to the ring structure at the right end.)
A ^{LC61 to} A ^LC63 each independently preferably have the following structure:

Z ^LC61 and Z ^LC62 are each independently ^preferably a single bond, —CH ₂ CH ₂ —, ^—COO— , —OCH ₂ —, —CH ₂ O—, —OCF ₂ — or —CF ₂ O—.

  The general formula (LC6) is changed from the general formula (LC6-a) to the general formula (LC6-m).

(In the formula, R ^LC61 and R ^LC62 are each independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or 2 to 7 carbon atoms. It is more preferable that it is 1 type, or 2 or more types of compounds chosen from the group which consists of a compound represented by this.

In the present invention, the compound represented by the general formula (1) can be produced as follows. Of course, the spirit and scope of the present invention are not limited by these production examples.
(Production method 1)
General formula (2)

(Wherein, ^{A 2} and ^{R 2} are as defined ^{A 2} and ^{R 2} in the general formula (1), ^{n 3} represents 0 or 1, respectively ^{X 5} and ^{X 6} are independently hydrogen or fluorine And a compound represented by the general formula (3):

(Wherein, ^{X 3} and ^{X 4} have the same meanings as ^{X 3} and ^{X 4} in the general formula (1), respectively, ^{Y 1} and ^{Y 2} independently chlorine atom, bromine atom, iodine atom, trifluoromethanesulfonyloxy A compound represented by formula (4) is reacted in the presence of a transition metal catalyst, a copper catalyst, and a base in an organic solvent, to give a general formula (4)

^{(Wherein, A 2, R 2, X} 3 and ^{X 4} are as defined ^{A 2,} R ^{2, X 3} and ^{X 4} in the general formula ^{(1), n 3, X} 5 and ^{X 6} are the general formula (2) represents the same meaning as ⁿ 3, ^{X 5} and ^{X 6} in, ^{Y 1} is the formula represents the same meaning as ^{Y 1} in (3).) in the compound represented by the obtained it is possible.

  The organic solvent to be used may be any as long as the reaction can proceed suitably, but an ether solvent such as diethyl ether, diisopropyl ether or tetrahydrofuran, or N, N-dimethylformamide, N, N-dimethylacetamide or Amide solvents such as N-methylpyrrolidinone are preferred, and tetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide or N-methylpyrrolidinone is particularly preferred. Moreover, you may mix several solvent as needed.

  The reaction temperature may be any as long as the reaction can proceed suitably, but is preferably a temperature from room temperature to the reflux of the organic solvent, more preferably a temperature from 40 ° C. to the reflux of the organic solvent, 60 ° C. To the temperature at which the solvent is refluxed is particularly preferred.

  The copper catalyst to be used may be any as long as the reaction can proceed suitably, but copper (I) chloride, copper (I) bromide or copper (I) iodide is preferred, and copper iodide (I More preferably,

Any transition metal catalyst may be used as long as it allows the reaction to proceed suitably. Tetrakis (triphenylphosphine) palladium (0), palladium (II) acetate, bis (triphenylphosphine) palladium dichloride Palladium such as (II), [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride or bis [di-tert-butyl (4-dimethylaminophenyl) phosphine] palladium (II) dichloride A transition metal catalyst or a nickel-based transition metal catalyst is preferred. Tetrakis (triphenylphosphine) palladium (0), palladium (II) acetate, bis [di-tert-butyl (4-dimethylaminophenyl) phosphine] palladium ( II) or dichloride [1,1′-bis (diphenylphosphine) ) Ferrocene] palladium (II) is more preferable. Moreover, in order to accelerate | stimulate progress of reaction, you may add a phosphine-type ligand as needed.
Any base can be used as long as it allows the reaction to proceed appropriately. Aqueous ammonia, amine reagents such as triethylamine or diisopropylamine, pyridine reagents such as pyridine or 2,6-dimethylpyridine, carbonic acid Carbonates such as potassium, potassium hydrogen carbonate, sodium carbonate or cesium carbonate are preferred, and triethylamine diisopropylamine is more preferred.

In order to efficiently obtain the target compound represented by the general formula (4), it is preferable that Y ¹ and Y ² in the general formula (3) are different.

  Subsequently, the compound represented by the general formula (4) is converted into the general formula (5).

^{(Wherein, A 1, X 1, X} 2, n 1 and ^{R 1} are as defined ^{A 1, X 1, X 2} , n 1 and ^{R 1} in the general formula (1), ^{R 3} and ^{R 4} Each independently represents a linear or branched alkyl group having 1 to 5 carbon atoms.) The compound represented by the above is reacted in an organic solvent in the presence of a transition metal catalyst and a base. The general formula (6)

^{(Wherein, R 1, R 2, A} 1, A 2, X 1, R 1 X 2 and ^{n 1} in the general formula ^{(1), R 2, A} 1, A 2, X 1, X 2 and n represents the same meaning as ^{1, X 5,} X ⁶ and ^{n 3} the general formula (2) in the ^X 5, ^{X 6} and represent the same meaning as ^{n 3.)} in the compound represented by the obtained it is possible.

  Any organic solvent may be used as long as it allows the reaction to proceed suitably, but ether solvents such as diethyl ether, diisopropyl ether, 1,4-dioxane or tetrahydrofuran, hexane, heptane, toluene or xylene, etc. Preferred are hydrocarbon solvents, amide solvents such as N-methylpyrrolidinone such as N, N-dimethylformamide and N, N-dimethylacetamide, and alcohol solvents such as methanol, ethanol, propanol and isopropyl alcohol. -Dioxane, tetrahydrofuran, methanol and ethanol are more preferred.

The reaction temperature may be any temperature as long as the reaction proceeds suitably, but is preferably a temperature from room temperature to reflux of the organic solvent, more preferably from 40 ° C. to reflux of the organic solvent, 60 ° C. To the temperature until the organic solvent is refluxed is particularly preferred.
Any transition metal catalyst may be used as long as it allows the reaction to proceed suitably. Tetrakis (triphenylphosphine) palladium (0), palladium (II) acetate, bis (triphenylphosphine) palladium dichloride Palladium such as (II), [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride or bis [di-tert-butyl (4-dimethylaminophenyl) phosphine] palladium (II) dichloride A transition metal catalyst or a nickel-based transition metal catalyst is preferred. Tetrakis (triphenylphosphine) palladium (0), palladium (II) acetate, bis [di-tert-butyl (4-dimethylaminophenyl) phosphine] palladium ( II) or dichloride [1,1′-bis (diphenylphosphine) ) Ferrocene] palladium (II) is more preferable. Moreover, in order to accelerate | stimulate progress of reaction, you may add a phosphine-type ligand as needed.
Any base can be used as long as it allows the reaction to proceed appropriately. Alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, potassium hydrogen carbonate, Carbonates such as cesium carbonate are preferable, and potassium carbonate or cesium carbonate is more preferable. Moreover, it is also preferable to use as aqueous solution as needed.
Subsequently, the compound represented by the general formula (6) is reacted with hydrogen gas in an organic solvent in the presence of a metal catalyst, whereby A ² bonded to the ethane linking group is a 1,4-phenylene group, 2-fluoro- A compound represented by the general formula (1) representing a 1,4-phenylene group or a 3-fluoro-1,4-phenylene group can be obtained.

  The organic solvent to be used may be any as long as it allows the reaction to proceed suitably, but ether solvents such as diisopropyl ether, diethyl ether, 1,4-dioxane or tetrahydrofuran, hexane, heptane, toluene or xylene, etc. Hydrocarbon solvents, alcohol solvents such as methanol, ethanol, propanol, isopropyl alcohol or butanol, and ester solvents such as ethyl acetate or butyl acetate are preferred, and tetrahydrofuran, hexane, heptane, toluene, ethanol or ethyl acetate are preferred. Moreover, it is also preferable to add acids, such as hydrochloric acid, acetic acid, or a sulfuric acid, as needed.

  The reaction temperature may be any temperature as long as the reaction proceeds suitably, but is preferably 0 ° C. to 80 ° C., more preferably room temperature to 60 ° C.

  Any metal catalyst may be used as long as the reaction proceeds suitably, but palladium carbon, ruthenium carbon, platinum black or platinum oxide is preferable, and palladium carbon is more preferable.

The hydrogen pressure at the time of reaction may be any as long as it allows the reaction to proceed suitably, but is preferably from atmospheric pressure to 0.5 MPa, and more preferably from 0.2 MPa to 0.5 MPa.
(Manufacturing method 2)
General formula (7)

(Wherein X ³ and X ⁴ represent the same meaning as X ³ and X ⁴ in formula (1), and Y ³ and Y ⁴ each independently represent a chlorine atom, a bromine atom, or an iodine atom). By reacting the represented compound with triphenylphosphine in an organic solvent or in a solvent-free condition, the general formula (8)

(Wherein, ^{X 3} and ^{X 4} have the same meanings as ^{X 3} and ^{X 4} in the general formula (1), ^{Y 3} and ^{Y 4} have the same meanings as ^{Y 3} and ^{Y 4} in the general formula (7). ) Can be obtained.

  In the case of using an organic solvent, any organic solvent may be used as long as the reaction proceeds suitably, but a saturated hydrocarbon solvent such as hexane, heptane, cyclohexane or methylcyclohexane, aromatic such as toluene, xylene or mesitylene. Preferred solvents are ether solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran or 1,4-dioxane, and amide solvents such as N-methylpyrrolidinone such as N, N-dimethylformamide and N, N-dimethylacetamide. Hydrocarbon solvents or aromatic solvents are more preferable, and toluene and xylene are particularly preferable.

  The reaction temperature may be any temperature as long as the reaction proceeds suitably, but the temperature from room temperature to the reflux of the organic solvent is preferred, and the temperature from 50 ° C. to the reflux of the organic solvent is more preferred. A temperature from 90 ° C. to the reflux of the organic solvent is particularly preferred.

  Subsequently, after the compound represented by the general formula (8) is reacted with a base in an organic solvent to prepare a phosphorus ylide reagent, the general formula (9)

^(Wherein, A 2, ^{n 2} and ^{R 2,} the general formula represents the same meaning as ^A 2, ^{n 2} and ^{R 2} in (1).) In represented by it is reacted with a compound with the general formula (10 )

^{(Wherein, X 3, X 4, A} 2, n 2 and ^{R 2} represents ^{X 3, X 4, A 2} , same meaning as ^{n 2} and ^{R 2} in the general formula (1), ^{Y 3} has the general formula (It represents the same meaning as Y ³ in (7))).

  Any organic solvent may be used as long as it allows the reaction to proceed suitably, but ether solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran or 1,4-dioxane, hexane, heptane, cyclohexane, methylcyclohexane. Hydrocarbon solvents such as toluene and xylene are preferred, and tetrahydrofuran is preferred. Moreover, it is also preferable to mix and use a some solvent as needed.

  The reaction temperature may be any temperature as long as the reaction proceeds suitably, but is preferably -60 ° C to 20 ° C, and more preferably -40 ° C to 0 ° C.

Any base can be used as long as the reaction proceeds suitably, but alkoxide reagents such as sodium methoxide, sodium ethoxide or potassium tertiary butoxide, butyl lithium, secondary butyl lithium or tertiary butyl. Alkyllithium reagents such as lithium and sodium hydride are preferred, and potassium tertiary butoxide, sodium hydride and butyllithium are more preferred.

  Subsequently, by reacting the compound represented by the general formula (10) and the compound represented by the general formula (5) in an organic solvent in the presence of a transition metal catalyst and a base, the general formula (11)

(In the formula, X ¹ , X ² , X ³ , X ⁴ , A ¹ , A ² , n ¹ , n ² , R ¹ and R ² are X ¹ , X ² , X ³ , X in the general formula (1). ⁴ , A ¹ , A ² , n ¹ , n ² , R ¹ and R ² represent the same meaning).

  Any organic solvent may be used as long as it allows the reaction to proceed suitably, but ether solvents such as diethyl ether, diisopropyl ether, 1,4-dioxane or tetrahydrofuran, hexane, heptane, toluene or xylene, etc. Preferred are hydrocarbon solvents, amide solvents such as N-methylpyrrolidinone such as N, N-dimethylformamide and N, N-dimethylacetamide, and alcohol solvents such as methanol, ethanol, propanol and isopropyl alcohol. -Dioxane, tetrahydrofuran, methanol and ethanol are more preferred.

The reaction temperature may be any temperature as long as the reaction proceeds suitably, but is preferably a temperature from room temperature to reflux of the organic solvent, more preferably from 40 ° C. to reflux of the organic solvent, 60 ° C. To the temperature until the organic solvent is refluxed is particularly preferred.
Any transition metal catalyst may be used as long as it allows the reaction to proceed suitably. Tetrakis (triphenylphosphine) palladium (0), palladium (II) acetate, bis (triphenylphosphine) palladium dichloride Palladium such as (II), [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride or bis [di-tert-butyl (4-dimethylaminophenyl) phosphine] palladium (II) dichloride A transition metal catalyst or a nickel-based transition metal catalyst is preferred. Tetrakis (triphenylphosphine) palladium (0), palladium (II) acetate, bis [di-tert-butyl (4-dimethylaminophenyl) phosphine] palladium ( II) or dichloride [1,1′-bis (diphenylphosphine) ) Ferrocene] palladium (II) is more preferable. Moreover, in order to accelerate | stimulate progress of reaction, you may add a phosphine-type ligand as needed.
Any base can be used as long as it allows the reaction to proceed appropriately. Alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, potassium hydrogen carbonate, Carbonates such as cesium carbonate are preferable, and potassium carbonate or cesium carbonate is more preferable. Moreover, it is also preferable to use as aqueous solution as needed.
Subsequently, the compound represented by the general formula (1) can be obtained by reacting the compound represented by the general formula (11) with hydrogen gas in the presence of a metal catalyst in an organic solvent.

  Any organic solvent may be used as long as it allows the reaction to proceed suitably, but ether solvents such as diisopropyl ether, diethyl ether, 1,4-dioxane or tetrahydrofuran, hexane, heptane, toluene or xylene, etc. Hydrocarbon solvents, alcohol solvents such as methanol, ethanol, propanol, isopropyl alcohol or butanol, and ester solvents such as ethyl acetate or butyl acetate are preferred, and tetrahydrofuran, hexane, heptane, toluene, ethanol or ethyl acetate are preferred. Moreover, it is also preferable to add acids, such as hydrochloric acid, acetic acid, or a sulfuric acid, as needed.

  The reaction temperature may be any temperature as long as the reaction proceeds suitably, but is preferably 0 ° C. to 80 ° C., more preferably room temperature to 60 ° C.

  Any metal catalyst may be used as long as the reaction proceeds suitably, but palladium carbon, ruthenium carbon, platinum black or platinum oxide is preferable, and palladium carbon is more preferable.

  The hydrogen pressure at the time of reaction may be any as long as it allows the reaction to proceed suitably, but is preferably from atmospheric pressure to 0.5 MPa, and more preferably from 0.2 MPa to 0.5 MPa.

  The liquid crystal display device using the liquid crystal composition containing the compound of the present invention is useful for achieving both high-speed response and suppression of display failure, and is particularly useful for a liquid crystal display device for active matrix driving. The present invention can be applied to liquid crystal display elements in various modes such as a mode, a PSVA mode, a PSA mode, an IPS mode, an FFS mode, or an ECB mode.

  Hereinafter, preferred embodiments of a liquid crystal display device according to the present invention will be described in detail with reference to the drawings.

  FIG. 1 is a cross-sectional view showing a liquid crystal display element including two substrates facing each other, a sealing material provided between the substrates, and liquid crystal sealed in a sealing region surrounded by the sealing material. It is.

Specifically, the TFT layer 102 and the pixel electrode 103 are provided on the substrate a100, the backplane on which the passivation film 104 and the alignment film a105 are provided, and the black matrix 202, the color filter 203, A planarizing film (overcoat layer) 201 and a transparent electrode 204 are provided, an alignment film b205 is provided thereon, a front plane facing the back plane, a sealing material 301 provided between the substrates, and the seal A specific mode of a liquid crystal display element including a liquid crystal layer 303 sealed in a sealing region surrounded by a material and provided with a protrusion 304 on a substrate surface in contact with the sealing material 301 is shown.
The substrate a or the substrate b is not particularly limited as long as it is substantially transparent, and glass, ceramics, plastics, or the like can be used. Examples of plastic substrates include cellulose derivatives such as cellulose, triacetyl cellulose, diacetyl cellulose, polycycloolefin derivatives, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polypropylene, and polyethylene. Polyolefin, polycarbonate, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyamide, polyimide, polyimide amide, polystyrene, polyacrylate, polymethyl methacrylate, polyether sulfone, polyarylate, and glass fiber-epoxy resin Inorganic-organic composite materials such as glass fiber and acrylic resin can be used.

  When a plastic substrate is used, it is preferable to provide a barrier film. The function of the barrier film is to reduce the moisture permeability of the plastic substrate and to improve the reliability of the electrical characteristics of the liquid crystal display element. The barrier film is not particularly limited as long as it has high transparency and low water vapor permeability. Generally, vapor deposition, sputtering, chemical vapor deposition method (CVD method) using an inorganic material such as silicon oxide is used. ) Is used.

  In the present invention, the same material or different materials may be used as the substrate a or the substrate b, and there is no particular limitation. Use of a glass substrate is preferable because a liquid crystal display element having excellent heat resistance and dimensional stability can be produced. In addition, a plastic substrate is preferable because it is suitable for a manufacturing method using a roll-to-roll method and is suitable for weight reduction or flexibility. For the purpose of imparting flatness and heat resistance, good results can be obtained by combining a plastic substrate and a glass substrate.

  In the backplane, a TFT layer 102 and a pixel electrode 103 are provided on a substrate a100. These are manufactured by a normal array process. A backplane is obtained by providing a passivation film 104 and an alignment film a105 thereon.

  A passivation film 104 (also referred to as an inorganic protective film) is a film for protecting the TFT layer. Usually, a nitride film (SiNx), an oxide film (SiOx), or the like is formed by a chemical vapor deposition (CVD) technique or the like.

  The alignment film a105 is a film having a function of aligning liquid crystals, and a polymer material such as polyimide is usually used in many cases. As the coating solution, an alignment agent solution composed of a polymer material and a solvent is used. Since the alignment film may hinder the adhesive force with the sealing material, a pattern is applied in the sealing region. For the application, a printing method such as a flexographic printing method or a droplet discharge method such as an ink jet is used. The applied alignment agent solution is crosslinked and cured by baking after the solvent is evaporated by temporary drying. Thereafter, an alignment process is performed to provide an alignment function.

  The alignment treatment is usually performed by a rubbing method. The polymer film formed as described above is rubbed in one direction using a rubbing cloth made of fibers such as rayon, thereby producing liquid crystal alignment ability.

  Moreover, the photo-alignment method may be used. The photo-alignment method is a method of generating alignment ability by irradiating polarized light on an alignment film containing an organic material having photosensitivity, and does not cause the generation of scratches or dust on the substrate due to the rubbing method. Examples of the organic material in the photo-alignment method include a material containing a dichroic dye. Dichroic dyes include molecular orientation induction or isomerization reaction (eg, azobenzene group), dimerization reaction (eg, cinnamoyl group), photocrosslinking reaction (eg, benzophenone group) due to Weigert effect resulting from photodichroism. Alternatively, those having a group (hereinafter abbreviated as a photo-alignment group) that causes a photoreaction that causes liquid crystal alignment ability, such as a photolysis reaction (eg, polyimide group), can be used. After the solvent is evaporated by temporary drying, the applied alignment agent solution is irradiated with light having an arbitrary deflection (polarized light), whereby an alignment film having alignment ability in an arbitrary direction can be obtained.

  One front plane is provided with a black matrix 202, a color filter 203, a planarization film 201, a transparent electrode 204, and an alignment film b205 on a substrate b200.

  The black matrix 202 is produced by, for example, a pigment dispersion method. Specifically, a color resin solution in which a black colorant is uniformly dispersed for forming a black matrix is applied on a substrate b200 provided with a barrier film 201, thereby forming a colored layer. Subsequently, the colored layer is baked and cured. A photoresist is applied on this and prebaked. After exposing the photoresist through a mask pattern, development is performed to pattern the colored layer. Thereafter, the photoresist layer is peeled off and the colored layer is baked to complete the black matrix 202.

  Alternatively, a photoresist type pigment dispersion may be used. In this case, a photoresist-type pigment dispersion is applied, pre-baked, exposed through a mask pattern, and then developed to pattern the colored layer. Thereafter, the photoresist layer is peeled off and the colored layer is baked to complete the black matrix 202.

  The color filter 203 is created by a pigment dispersion method, an electrodeposition method, a printing method, a dyeing method, or the like. Taking the pigment dispersion method as an example, a color resin solution in which a pigment (for example, red) is uniformly dispersed is applied onto the substrate b200, and after baking and curing, a photoresist is applied thereon and prebaked. After the photoresist is exposed through a mask pattern, development is performed and patterning is performed. Thereafter, the photoresist layer is peeled off and baked again to complete the (red) color filter 203. There is no particular limitation on the color order to be created. Similarly, a green color filter 203 and a blue color filter 203 are formed.

  The transparent electrode 204 is provided on the color filter 203 (an overcoat layer (201) may be provided on the color filter 203 for planarization as necessary). The transparent electrode 204 preferably has a high transmittance, and preferably has a low electrical resistance. The transparent electrode 204 is formed by sputtering an oxide film such as ITO.

  In addition, a passivation film may be provided on the transparent electrode 204 for the purpose of protecting the transparent electrode 204.

  The alignment film b205 is the same as the alignment film a105 described above.

  Although specific embodiments of the backplane and the front plane used in the present invention have been described above, the present invention is not limited to the specific embodiments, and changes in the embodiments according to the desired liquid crystal display element are possible. Is free.

  The shape of the columnar spacer is not particularly limited, and the horizontal cross section can be various shapes such as a circle and a polygon such as a quadrangle. A polygonal shape is particularly preferable. The protrusion shape is preferably a truncated cone or a truncated pyramid.

  The material of the columnar spacer is not particularly limited as long as it is a sealing material, an organic solvent used for the sealing material, or a material that does not dissolve in liquid crystal, but it may be a synthetic resin (curable resin) in terms of processing and weight reduction. preferable. On the other hand, the protrusion can be provided on the surface of the first substrate in contact with the sealing material by a photolithography method or a droplet discharge method. For these reasons, it is preferable to use a photocurable resin suitable for a photolithography method or a droplet discharge method.

  As an example, a case where the front columnar spacer is obtained by photolithography will be described.

  On the transparent electrode 204 of the front plane, a resin solution for forming columnar spacers (not containing a colorant) is applied. Subsequently, the resin layer is baked and cured. A photoresist is applied on this and prebaked. After exposing the photoresist through a mask pattern, development is performed to pattern the resin layer. Thereafter, the photoresist layer is peeled off, and the resin layer is baked to complete the columnar spacer.

  The formation position of the columnar spacer can be determined at a desired position by a mask pattern. Therefore, both the inside of the sealing region of the liquid crystal display element and the outside of the sealing region (sealing material application portion) can be created at the same time. The columnar spacer is preferably formed so as to be positioned on the black matrix so that the quality of the sealing region does not deteriorate. A columnar spacer manufactured by a photolithography method in this way is sometimes called a column spacer or a photospacer.

  As the material of the spacer, a negative water-soluble resin such as PVA-stilbazo photosensitive resin, a mixture of a polyfunctional acrylic monomer, an acrylic acid copolymer, a triazole initiator, or the like is used. Alternatively, there is a method using a color resin in which a colorant is dispersed in a polyimide resin. In the present invention, there is no particular limitation, and a spacer can be obtained from a known material in accordance with the compatibility with the liquid crystal or the sealing material to be used.

  Thus, after providing a columnar spacer on the surface to be a sealing region on the front plane, a seal material (301 in FIG. 1) is applied to the surface of the back plane that contacts the seal material.

  The material of the sealing material is not particularly limited, and a curable resin composition obtained by adding a polymerization initiator to an epoxy or acrylic photocurable, thermosetting, or photothermal combination curable resin is used. In order to control moisture permeability, elastic modulus, viscosity, etc., fillers made of inorganic or organic substances may be added. The shape of these fillers is not particularly limited, and includes a spherical shape, a fiber shape, and an amorphous shape. Furthermore, in order to control the cell gap satisfactorily, a spherical or fibrous gap material having a monodisperse diameter is mixed, or in order to further strengthen the adhesive force with the substrate, a fibrous substance that is easily entangled with the protrusion on the substrate You may mix. The diameter of the fibrous material used at this time is desirably about 1/5 to 1/10 or less of the cell gap, and the length of the fibrous material is desirably shorter than the seal coating width.

  The material of the fibrous substance is not particularly limited as long as a predetermined shape can be obtained, and synthetic fibers such as cellulose, polyamide and polyester, and inorganic materials such as glass and carbon can be appropriately selected.

  As a method for applying the sealing material, there are a printing method and a dispensing method, but a dispensing method with a small amount of the sealing material used is desirable. The application position of the sealing material is usually on the black matrix so as not to adversely affect the sealing area. In order to form a liquid crystal dropping region in the next step (so that the liquid crystal does not leak), the sealing material application shape is a closed loop shape.

  Liquid crystal is dropped onto the closed loop shape (sealing region) of the front plane to which the sealing material is applied. Usually a dispenser is used. Since the amount of liquid crystal to be dropped coincides with the volume of the liquid crystal cell, the amount is basically the same as the volume obtained by multiplying the height of the column spacer and the seal application area. However, in order to optimize liquid crystal leakage and display characteristics in the cell bonding process, the amount of liquid crystal to be dropped may be adjusted as appropriate, or the liquid crystal dropping position may be dispersed.

  Next, a back plane is bonded to the front plane on which the sealing material is applied and liquid crystal is dropped. Specifically, the front plane and the back plane are adsorbed on a stage having a mechanism for adsorbing a substrate such as an electrostatic chuck, and the alignment film b on the front plane and the alignment film a on the back plane face each other. It is arranged at a position (distance) where the sealing material does not contact the other substrate. In this state, the system is depressurized. After decompression is completed, the positions of both substrates are adjusted while confirming the bonding position between the front plane and the back plane (alignment operation). When the adjustment of the bonding position is completed, the substrate is brought close to a position where the sealing material on the front plane and the back plane are in contact with each other. In this state, the system is filled with an inert gas, and the pressure is gradually returned to normal pressure while releasing the reduced pressure. At this time, the front plane and the back plane are bonded together by atmospheric pressure, and a cell gap is formed at the height of the columnar spacer. In this state, the sealing material is irradiated with ultraviolet rays to cure the sealing material, thereby forming a liquid crystal cell. Thereafter, a heating step is added in some cases to promote curing of the sealing material. A heating process is often added to enhance the adhesive strength of the sealing material and improve the reliability of electrical characteristics.

  EXAMPLES Hereinafter, although an Example is given and this invention is further explained in full detail, this invention is not limited to these Examples. Further, “%” in the compositions of the following examples and comparative examples means “mass%”. The specific resistance value of the liquid crystal composition was obtained by putting the liquid crystal composition in a measurement cell and measuring the resistance value when a voltage (DC) of 1 V was applied at 25 ° C. The phase transition temperature was measured using a polarizing microscope equipped with a temperature control stage and a differential scanning calorimeter (DSC).

T _n−i represents a transition temperature between a nematic phase and an isotropic phase.

  The following abbreviations are used in compound descriptions.

DMF: N, N-dimethylformamide THF: tetrahydrofuran Te: methyl group, Et: ethyl group, Pr: n-propyl group, Bu: n-butyl group (Example 1) 4- (trans-4-ethylcyclohexyl)- Production of 2-fluoro-4 ′-[2- (4-propylphenyl) -1-ethyl] biphenyl (a compound in which R ^{1 in the} general formula (1a-2) represents an ethyl group and R ² represents a propyl group)

(1-1) Under a dry nitrogen atmosphere, 4-iodobromobenzene (101.0 g), copper (I) iodide (2.72 g), tetrakis (triphenylphosphine) palladium (0) (8.25 g), DMF (400 mL) and triethylamine (200 mL) were mixed and heated to 75 ° C. While heating, a solution of 4-propylphenylacetylene (51.5 g) dissolved in DMF (200 mL) was added dropwise, followed by further stirring for 3 hours. After cooling the reaction solution to room temperature, water (400 mL) and toluene (400 mL) were added to separate the layers. The organic layer was washed twice with saturated brine (400 mL), dried over anhydrous sodium sulfate. Sodium sulfate was filtered, concentrated under reduced pressure, and purified by silica gel column chromatography. Furthermore, 4-bromo-4′-propyltolane (94.6 g) was obtained by recrystallization from a mixed solvent of acetone and methanol.
(1-2) 4-Bromo-4′-propyltolane (20.0 g), tetrakis (triphenylphosphine) palladium (0) (0.77 g) obtained in step (1-1) under a dry nitrogen atmosphere , THF (60 mL) and 2 mol / L potassium carbonate aqueous solution (65 mL) were mixed and heated to 60 ° C. Under heating, 4- (trans-4-ethylcyclohexyl) -2-fluorophenylboric acid (18.4 g) dissolved in THF (55 mL) was added dropwise, and the mixture was further stirred for 2 hours. The reaction mixture was ice-cooled, and water (200 mL) was added to precipitate the target compound. The target compound is filtered, purified by silica gel column chromatography, and recrystallized from a mixed solvent of toluene and acetone to give 4- [4- (trans-4-ethylcyclohexyl) -2-fluorophenyl] -4. '-Propyltolane (26.1 g) was obtained.
(1-3) 4- [4- (trans-4-ethylcyclohexyl) -2-fluorophenyl] -4′-propyltran (26.1 g), 5 wt% palladium carbon obtained in step (1-2) (Water-containing product) (1.3 g) and THF (260 mL) were charged into an autoclave reactor and stirred at room temperature for 2 hours in a hydrogen atmosphere (0.5 MPa). The reaction solution was filtered to remove the palladium catalyst, and then concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography, and then recrystallized from a mixed solvent of methanol and acetone to give 4- (trans-4-propylcyclohexyl) -2-fluoro-4 ′-[2- ( 2-1.1 g of 4-propylphenyl) -1-ethyl] biphenyl (a compound in which R ^{1 in the} general formula (1a-2) represents an ethyl group and R ² represents a propyl group) was obtained.
Phase transition temperature (° C.): Cr 68.6 N 190.5 Iso
MS m / z: 428 [M ⁺ ]
¹ HNMR (CDCl ₃ , TMS internal standard) δ (ppm) = 7.47 (2H, dd, J ₁ = 1.40 Hz, J ₂ = 8.02 Hz), 7.35 (1H, t, J = 8. 12 Hz), 7.27 (2H, d, J = 8.16 Hz), 7.13 (4H, d, J = 5.24 Hz), 7.06-6.98 (2H, m), 2.93 ( 4H, s), 2.57 (2H, t, J = 7.52 Hz), 2.50 (1H, tt, J ₁ = 3.24 Hz, J ₂ = 12.0 Hz), 1.92 (4H, t , J = 12.1 Hz), 1.62 (2H, sex, J = 7.44 Hz), 1.51-1.40 (2H, m), 1.31-1.18 (3H, m), 1 .10-1.00 (2H, m), 0.94 (3H, t, J = 7.3 Hz), 0.92 (3H, t, J = 7.44 Hz)
Example 2 4- (trans-4-propylcyclohexyl) -2-fluoro-4 ′-[2- (4-ethylphenyl) -1-ethyl] biphenyl (R ^{1 in the} general formula (1a-2) is Propyl group, compound in which R ² represents an ethyl group)

By producing in the same manner as described in Example 1, 4- (trans-4-propylcyclohexyl) -2-fluoro-4 ′-[2- (4-ethylphenyl) -1-ethyl] biphenyl ( In the general formula (1a-2), 9.2 g of a compound in which R ¹ represents a propyl group and R ² represents an ethyl group was obtained.
Phase transition temperature (° C.): Cr 75.6 N 211.6 Iso
MS m / z: 428 [M ⁺ ]
¹ HNMR (CDCl ₃ , TMS internal standard) δ (ppm) = 7.47 (2H, dd, J ₁ = 1.42 Hz, J ₂ = 8.02 Hz), 7.35 (1H, t, J = 8. 12 Hz), 7.28 (2H, d, J = 8.16 Hz), 7.15 (4H, s), 7.06 to 6.98 (2H, m), 2.94 (4H, s), 2 .64 (2H, t, J = 7.49 Hz), 2.50 (1H, tt, J ₁ = 3.24 Hz, J ₂ = 12.0 Hz), 1.90 (4H, t, J = 12.1 Hz) ), 1.51-1.29 (5H, m), 1.24 (3H, t, J = 7.54 Hz), 1.18-1.19 (2H, m), 1.10-1.01. (2H, m), 0.91 (3H, t, J = 7.44 Hz)
Example 3 4- (trans-4-propylcyclohexyl) -2-fluoro-4 ′-[2- (4-propylphenyl) -1-ethyl] biphenyl (R ^{1 in the} general formula (1a-2) and Compound in which R ² represents a propyl group

By producing in the same manner as described in Example 1, 4- (trans-4-propylcyclohexyl) -2-fluoro-4 ′-[2- (4-propylphenyl) -1-ethyl] biphenyl ( 9.2 g of a compound in which R ¹ and R ^{2 in the} general formula (1a-2) both represent a propyl group was obtained.
Phase transition temperature (° C.): Cr 90.4 N 213.1 Iso
MS m / z: 428 [M ⁺ ]
¹ HNMR (CDCl ₃ , TMS internal standard) δ (ppm) = 7.47 (2H, d, J = 18.00 Hz), 7.36 (1H, t, J = 8.08 Hz), 7.27 (2H , D, J = 8.04 Hz), 7.13 (4H, d, J = 5.40 Hz), 7.06-6.98 (2H, m), 2.93 (4H, s), 2.56 (2H, t, J = 7.56 Hz), 2.50 (1H, tt, J ₁ = 3.29 Hz, J ₂ = 12.0 Hz), 1.90 (4H, t, J = 15.0 Hz) 1 .63 (2H, sex, J = 7.64 Hz), 1.51-1.41 (2H, m), 1.38-1.89 (5H, m), 1.10-1.00 (2H, m), 0.95 (3H, t, J = 7.32 Hz), 0.90 (3H, t, J = 7.24 Hz)
¹ HNMR (CDCl ₃ , TMS internal standard)
Example 4 4- (Ethylphenyl) -2-fluoro-4 ′-[2- (4-propylphenyl) -1-ethyl] biphenyl (R ^{1 in the} general formula (1b-2) is an ethyl group, R Compound in which ² represents a propyl group)

4- (Ethylphenyl) -2-fluoro-4 ′-[2- (4-propylphenyl) -1-ethyl] biphenyl (general formula (1b) was prepared in the same manner as described in Example 1. -2) 23.6 g of a compound in which R ¹ represents an ethyl group and R ² represents a propyl group.
Phase transition temperature (° C.): Cr 111.0 SmA 130.9 N 219.7 Iso
^{MS m / z: 422 [M} +]
¹ HNMR (CDCl ₃ , TMS internal standard) δ (ppm) = 7.54 (4H, t, J = 8.12 Hz), 7.50-7.37 (3H, m), 7.31 (4H, d , J = 7.96 Hz), 7.14 (4H, d, J = 5.96 Hz), 2.95 (4H, s), 2.71 (2H, t, J = 7.56 Hz), 2.57 (2H, t, J = 7.60 Hz), 1.64 (2H, sex, J = 7.52 Hz), 1.29 (3H, t, J = 7.56 Hz), 0.95 (3H, t, J = 7.24Hz)
Example 5 4- (trans-4-propylcyclohexyl) -2-fluoro-4 ′-[2- (4- (trans-4-ethylcyclohexyl) phenyl) -1-ethyl] biphenyl (general formula (1d -2) Compound in which R ¹ represents a propyl group and R ² represents an ethyl group)

4- (trans-4-propylcyclohexyl) -2-fluoro-4 ′-[2- (4- (trans-4-ethylcyclohexyl) phenyl) can be produced in the same manner as described in Example 1. 3.4 g of -1-ethyl] biphenyl (a compound in which R ^{1 in the} general formula (1d-2) represents a propyl group and R ² represents an ethyl group) was obtained.
MS m / z: 510 [M ⁺ ]
¹ HNMR (CDCl ₃ , TMS internal standard) δ (ppm) = 7.47 (2H, dd, J ₁ = 1.41 Hz, J ₂ = 8.01 Hz), 7.33 (1H, t, J = 8. 11 Hz), 7.28 (2H, d, J = 8.16 Hz), 7.15 (4H, s), 7.06 to 6.98 (2H, m), 2.94 (4H, s), 2 .55-1.53 (1H, m), 2.50 (1H, tt, J ₁ = 3.24 Hz, J ₂ = 12.0 Hz), 1.90 (4H, t, J = 12.1 Hz), 1.55-1.23 (9H, m), 1.20-1.01 (11H, m), 0.97 (3H, t, J = 7.53 Hz), 0.90 (3H, t, J = 7.45Hz)
Comparative Example 1 Synthesis of 4 ″-(4-trans-butylcyclohexyl) -2′fluoro-4-propyl-1,1 ′: 4 ′, 1 ″ -terphenyl

In the same manner as described in GB 2240778, 4 ″-(4-trans-butylcyclohexyl) -2′fluoro-4-propyl-1,1 ′: 4 ′, 1 ″ -tel Phenyl was synthesized.
Phase transition temperature (° C.): Cr 154 SmA 234 N 302 Iso
MS m / z: 428 [M ⁺ ]
¹ HNMR (CDCl ₃ , TMS internal standard) δ (ppm) = 7.55 (2H, d, J = 8.16 Hz), 7.52 (2H, d, J = 6.80 Hz), 7.48 (1H , D, J = 8.08 Hz), 8.04 (1H, dd, J ₁ = 1.68 Hz, J ₂ = 8.04 Hz), 7.37 (1H, dd, J ₁ = 1.44 Hz, J ₂ = 12.1 Hz), 7.31 (2H, d, J = 8.12 Hz), 7.28 (2H, d, J = 8.20 Hz), 2.64 (2H, d, J = 7.44 Hz) , 2.52 (1H, tt, J ₁ = 3.28 Hz, J ₂ = 12.1 Hz), 1.91 (4H, t, J = 9.88 Hz), 1.69 (2H, sex, J = 7 .64 Hz), 1.51-1.45 (2H, m), 1.32-1.23 (8H, m), 1.11-1.02 (2 , M), 0.99 (3H, t, J = 7.28Hz), 0.91 (3H, t, J = 6.96Hz)
Comparative Example 2 Synthesis of 4- (ethylphenyl) -3-fluoro-4 ′-[2- (4-propylphenyl) -1-ethyl] biphenyl

4- (Ethylphenyl) -3-fluoro-4 ′-[2- (4-propylphenyl) -1-ethyl] biphenyl was synthesized in the same manner as described in British Patent No. 2240778.
^{MS m / z: 422 [M} +]
¹ HNMR (CDCl ₃ , TMS internal standard) δ (ppm) = 7.56 (4H, t, J = 8.10 Hz), 7.48-7.40 (3H, m), 7.31 (4H, d , J = 7.95 Hz), 7.14 (4H, d, J = 5.99 Hz), 2.93 (4H, s), 2.70 (2H, t, J = 7.49 Hz), 2.57 (2H, t, J = 7.60 Hz), 1.62 (2H, sex, J = 7.55 Hz), 1.29 (3H, t, J = 7.58 Hz), 0.95 (3H, t, J = 7.21Hz)
Example 6 Preparation of Liquid Crystal Composition-1
Host liquid crystal composition (H) having the following composition

Was prepared.
80% of the base liquid crystal (H) and 4- (trans-4-ethylcyclohexyl) -2-fluoro-4 ′-[2- (4-propylphenyl) -1-ethyl] biphenyl obtained in Example 1 (A compound in which R ^{1 in the} general formula (1a-2) represents an ethyl group and R ² represents a propyl group) A liquid crystal composition (MA) comprising 20% was prepared. The _{values of} extrapolation T _n−i , extrapolation Δε, extrapolation Δn, and extrapolation η ₂₀ of this composition are as follows.

Extrapolation T _n-i : 183.9 ° C
Extrapolation Δε: 0.25
Extrapolation Δn: 0.1886
Extrapolation η ₂₀ : 46.5 mPa · s
In addition, the prepared liquid crystal composition (MA) maintained a uniform nematic liquid crystal state at room temperature for one month or longer.

Furthermore, the liquid crystal display device produced using the liquid crystal composition (MA) exhibited excellent display characteristics, maintained stable display characteristics over a long period, and exhibited high reliability.
(Example 7) Preparation of liquid crystal composition-2
The base liquid crystal (H) 80% and 4- (trans-4-propylcyclohexyl) -2-fluoro-4 ′-[2- (4-ethylphenyl) -1-ethyl] biphenyl obtained in Example 2 ( A liquid crystal composition (MB) comprising 20% of a compound of the general formula (1a-2) in which R ¹ represents a propyl group and R ² represents an ethyl group was prepared. The _{values of} extrapolation T _n−i , extrapolation Δε, extrapolation Δn, and extrapolation η ₂₀ of this composition are as follows.

Extrapolation T _n−i : 201.4 ° C.
Extrapolation Δε: 0.15
Extrapolation Δn: 0.1921
Extrapolation η ₂₀ : 33.5 mPa · s
Further, the prepared liquid crystal composition (MB) maintained a uniform nematic liquid crystal state for one month or more at room temperature.

Furthermore, the liquid crystal display device produced using the liquid crystal composition (MB) exhibited excellent display characteristics, maintained stable display characteristics over a long period of time, and exhibited high reliability.
(Example 8) Preparation of liquid crystal composition-3
80% of the base liquid crystal (H) and 4- (trans-4-propylcyclohexyl) -2-fluoro-4 ′-[2- (4-propylphenyl) -1-ethyl] biphenyl obtained in Example 3 ( A liquid crystal composition (MC) comprising 20% of a compound in which R ¹ and R ^{2 in the} general formula (1a-2) both represent a propyl group was prepared. The _{values of} extrapolation T _n−i , extrapolation Δε, extrapolation Δn, and extrapolation η ₂₀ of this composition are as follows.

Extrapolation T _n−i : 203.3 ° C.
Extrapolation Δε: 0.20
Extrapolation Δn: 0.1900
Extrapolation η ₂₀ : 36.6 mPa · s
The prepared liquid crystal composition (MC) maintained a uniform nematic liquid crystal state for one month or more at room temperature.

Furthermore, the liquid crystal display device produced using the liquid crystal composition (MC) exhibited excellent display characteristics, maintained stable display characteristics over a long period of time, and exhibited high reliability.
Example 9 Preparation of Liquid Crystal Composition-4
The base liquid crystal (H) 85% and 4- (ethylphenyl) -2-fluoro-4 ′-[2- (4-propylphenyl) -1-ethyl] biphenyl (general formula (1b) obtained in Example 4) -2) A liquid crystal composition (MD) comprising 15% of a compound in which R ¹ represents an ethyl group and R ² represents a propyl group was prepared. The _{values of} extrapolation T _n−i , extrapolation Δε, extrapolation Δn, and extrapolation η ₂₀ of this composition are as follows.

Extrapolation T _n-i : 196.8 ° C
Extrapolation Δε: −0.39
Extrapolation Δn: 0.2884
Extrapolation η ₂₀ : 40.3 mPa · s
Moreover, the prepared liquid crystal composition (MD) maintained a uniform nematic liquid crystal state for one month or more at room temperature.

Furthermore, a liquid crystal display device manufactured using the liquid crystal composition (MD) exhibited excellent display characteristics, maintained stable display characteristics over a long period, and exhibited high reliability.
Example 10 Preparation of Liquid Crystal Composition-5
90% of base liquid crystal (H) and 4- (trans-4-propylcyclohexyl) -2-fluoro-4 ′-[2- (4- (trans-4-ethylcyclohexyl) phenyl) obtained in Example 5 A liquid crystal composition (ME) comprising 10% of -1-ethyl] biphenyl (a compound in which R ^{1 in the} general formula (1d-2) represents a propyl group and R ² represents an ethyl group) was prepared. The _{values of} extrapolation T _n−i , extrapolation Δε, extrapolation Δn, and extrapolation η ₂₀ of this composition are as follows.

Extrapolation T _n-i : 284.6 ° C
Extrapolation Δε: 0.11
Extrapolation Δn: 0.1512
Extrapolation η ₂₀ : 80.6 mPa · s
Further, the prepared liquid crystal composition (ME) maintained a uniform nematic liquid crystal state at room temperature for one month or longer.

Furthermore, the liquid crystal display device produced using the liquid crystal composition (ME) exhibited excellent display characteristics, maintained stable display characteristics over a long period, and exhibited high reliability.
Comparative Example 3 Preparation of Liquid Crystal Composition-6
80% of base liquid crystal (H) and 4 ″-(4-trans-butylcyclohexyl) -2′fluoro-4-propyl-1,1 ′ obtained in Comparative Example 1: 4 ′, 1 ″ -tel A liquid crystal composition (MF) composed of 20% phenyl was prepared. The _{values of} extrapolation T _n−i , extrapolation Δε, extrapolation Δn, and extrapolation η ₂₀ of this composition are as follows.

Extrapolation T _n−i : 239.7 ° C.
Extrapolation Δε: 0.26
Extrapolation Δn: 0.2471
Extrapolation η ₂₀ : 55.5 mPa · s
In addition, it was confirmed that the prepared liquid crystal composition (MF) was solid on the next day of measurement.

When the extrapolation T _{n-i of} the present compound obtained in Example 7 and extrapolation η ₂₀ are compared, the present compound obtained in Example 7 has a slightly lower T _n-i than the compound of Comparative Example 3. Although shown, it has been found that η ₂₀ can be greatly reduced. In addition, since the compound of the present application maintained a stable nematic liquid crystal state, it was found that the compound of the present application was excellent in miscibility with other liquid crystal compositions.
Comparative Example 4 Preparation of Liquid Crystal Composition-7
Liquid crystal composed of 90% of the base liquid crystal (H) and 10% of 4- (ethylphenyl) -3-fluoro-4 '-[2- (4-propylphenyl) -1-ethyl] biphenyl obtained in Comparative Example 2 A composition (MG) was prepared. The _{values of} extrapolation T _n−i , extrapolation Δε, extrapolation Δn, and extrapolation η ₂₀ of this composition are as follows.

Extrapolation T _n-i : 189.1 ° C
Extrapolation Δε: −0.55
Extrapolation Δn: 0.2893
Extrapolation η ₂₀ : 49.4 mPa · s
The prepared liquid crystal composition (MG) maintained a uniform nematic liquid crystal state at room temperature for one month or longer.

Comparing the extrapolation T _n-i and extrapolation η ₂₀ of the compound of the present invention obtained in Example 9, the compound of the present application obtained in Example 9 is almost the same as the compound of Comparative Example 4 in terms of T _{n−. Although i} is shown, it has been found that η ₂₀ can be reduced. From this, the effect that the fluorine substitution position of this-application compound reduces a viscosity compared with the fluorine substitution position of a comparative example compound was recognized.

Claims (7)

General formula (1)

(Wherein R ¹ and R ² each independently represents an alkyl group having 1 to 15 carbon atoms or an alkenyl group having 2 to 15 carbon atoms, and one —CH ₂ — present in these groups) Or two or more non-adjacent —CH ₂ — may be replaced by —C≡C—, —O—, —S—, —COO—, —OCO— or —CO—, The hydrogen atom present in may be replaced by a fluorine atom,
A ¹ and A ² are each independently (a) a 1,4-cyclohexylene group (one —CH ₂ — present in this group or two or more non-adjacent —CH ₂ — are — (It may be replaced by O- or -S-.)
(B) 1,4-phenylene group (one —CH═ present in this group or two or more non-adjacent —CH═ may be replaced by —N═ and present in this group) One hydrogen atom may be substituted with a fluorine atom.)
(C) a naphthalene-2,6-diyl group (one —CH═ present in this group or two or more non-adjacent —CH═ may be replaced by —N═, One hydrogen atom present in may be substituted with a fluorine atom.)
A group selected from the group consisting of:
X ¹ , X ² , X ³ and X ⁴ each independently represent a hydrogen atom or a fluorine atom, but X ¹ and X ² do not both represent a fluorine atom, and X ³ and X ⁴ both represent a fluorine atom. And at least one of X ^{2 and} X ⁴ represents a fluorine atom,
n ¹ represents 0, 1 or 2, n ² represents 1, 2 or 3, n ¹ + n ² represents 2 or 3, but when n ¹ is 2 and a plurality of A ¹ exist, A ^{1 1} may be the same or different, and when n ² is 2 or 3, and a plurality of A ² are present, A ² may be the same or different. )
Represented by
The total number of fluorine atoms in the general formula (1) is 1 or 2 der Ru compound. In the general formula (1), A ¹ and A ² are

The compound according to claim 1, which represents a group selected from: The compound according to claim 1 or ² , wherein, in the general formula (1), R ¹ and R ² represent an unsubstituted alkyl group having 1 to 6 carbon atoms or an unsubstituted alkenyl group having 2 to 6 carbon atoms. . In the general formula (1) compound of any one of claims 1 to 3 ^{in which n 1} and ^{n 2} is 1. In the general formula (1), at least one of A ¹ or A ² is (a) a 1,4-cyclohexylene group (one —CH ₂ — present in the group or two or more non-adjacent ones). —CH ₂ — may be replaced by —O— or —S—.
The compound according to any one of claims 1 to 4 , which represents A composition comprising one or more compounds according to any one of claims 1 to 5 . A liquid crystal display device using the composition according to claim 6 .

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