JP5892357B2 - Fluoronaphthalene derivative and liquid crystal composition containing the same. - Google Patents

Description

  The present invention relates to a fluoronaphthalene derivative useful as an electro-optical liquid crystal display material, a liquid crystal composition containing the same, and a liquid crystal display element using the same.

Liquid crystal display elements are currently widely used because of their excellent features such as low power consumption and thin display.
There are TN (twisted nematic), STN (super twisted nematic), or active matrix (TFT: thin film transistor) based on TN, etc., which use liquid crystal composition with positive Δε. Is. However, one of the drawbacks of these display methods is the narrow viewing angle, and with the demand for larger liquid crystal panels, the improvement has been a major issue.

  As a solution to this, display methods such as a vertical alignment method and an IPS (in-plane switching) method have been put into practical use. The vertical alignment method is a method in which liquid crystal molecules are vertically aligned and multi-domained to improve the viewing angle, and a liquid crystal composition having a negative dielectric anisotropy value (Δε) is used. The IPS method is a method in which viewing angle is improved by switching liquid crystal molecules using a horizontal electric field in a horizontal direction with respect to a glass substrate, and a liquid crystal composition having a positive or negative Δε is used. As described above, the vertical alignment method and the IPS method, which are effective display methods for improving the viewing angle, require a liquid crystal composition having a negative Δε. Further, since such a liquid crystal display element is mainly used for moving image display, the response speed must be improved in order to improve display quality. In order to improve the response speed, it is necessary to increase the absolute value of Δε and decrease the viscosity of the liquid crystal composition. However, many compounds that increase the absolute value of Δε increase the viscosity of the composition, and various compounds have been developed.

  As another method for increasing the response speed, there is a method of reducing the cell thickness (d) of the liquid crystal display element. When the display quality is taken into consideration, the product of the refractive index anisotropy value (Δn) and the cell thickness is used. The proper value of retardation (d · Δn) should not be deviated. That is, it is necessary to reduce the cell thickness while keeping the product of the refractive index anisotropy value and the cell thickness constant, and in order to increase the refractive index anisotropy value of the liquid crystal composition, a liquid crystal material exhibiting a large Δn is required. There is a strong demand. However, compounds having the effect of increasing Δn also tend to increase the viscosity of the composition, and conventional compounds have not yet satisfied these required characteristics.

  Δε is a value defined as the difference between the dielectric constant (ε‖) in the molecular major axis direction and the dielectric constant (ε⊥) in the molecular minor axis direction (Δε = ε‖−ε⊥). Then, Δε is negative and its absolute value increases. In order to increase the value of the dielectric constant, it is effective to introduce an electron withdrawing group into the molecule. Therefore, in order to increase the value of ε⊥, an electron-withdrawing group may be introduced in the molecular minor axis direction. As a liquid crystal material used as a liquid crystal composition component having a negative Δε, a compound represented by the formula (A-1) having a 2,3-difluorophenylene group (Patent Document 1) and a formula (A-2) The compound represented (patent document 2) is mentioned.

  These compounds have a structure in which fluorine atoms, which are electron-withdrawing groups, are introduced with their directions aligned in the molecular minor axis direction. Although Δε of these compounds themselves is not described, it is unknown, but Δε of a liquid crystal composition to which these compounds are added shows a negative value. However, the absolute value was not large enough.

  Further, a fluorine atom is introduced into the molecule, and the formulas (A-3) and (A-4) having a 2,2 ', 3'-trifluorobiphenyl skeleton having three fluorine atoms in the molecule

Has been developed and reported as a compound having negative Δε having a large absolute value (Patent Document 3).

  However, these compounds have low compatibility with other liquid crystal compounds, and have problems such as precipitation from the liquid crystal composition when used as a liquid crystal composition. Moreover, since the viscosity is relatively high, there is a problem that the response speed is lowered.

  Further, in order to further increase the absolute value of Δε, a formula (A-5) in which the number of fluorine atoms in the molecule is four.

(Patent Document 3), however, there is no specific description about Δε and Δn, and the characteristics are unknown.

  As described above, it has been desired to develop a compound that reduces the viscosity of the liquid crystal composition and increases Δε and Δn.

JP-T-2-503441 JP-A-10-176167 WO 1999/21816

  The problem to be solved by the present invention is that a compound having a negative Δε has a large absolute value of Δε, a large Δn value, excellent compatibility with other liquid crystal materials, and high liquid crystallinity and reliability. An object of the present invention is to provide a compound that exhibits properties and reduce the viscosity of a liquid crystal composition, and to provide a practical liquid crystal composition and a liquid crystal display device using the compound.

  As a result of studying various fluoronaphthalene derivatives, nematic liquid crystal compositions using the same and liquid crystal display devices using the same, the present inventor has completed the present invention.

  The present invention relates to general formula (I)

Wherein R ¹ and R ² are each independently an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms, or 2 to 2 carbon atoms. 12 represents an alkenyloxy group, and one or more hydrogen atoms in each group may be each independently substituted with a fluorine atom, and one in each group or two or more not adjacent to each other Each of —CH ₂ — may be independently substituted with —O—, —CO—, —COO— or —OCO—,
A ¹ and A ² are each independently a trans-1,4-cyclohexylene group, a trans-1,3-dioxane-2,5-diyl group, a pyridine-2,5-diyl group, or a pyrimidine-2,5. -Represents a diyl group or a 1,4-phenylene group which may be unsubstituted or substituted with one or more hydrogen atoms by fluorine atoms,
X ¹ , X ² , X ³ , X ^4, X ⁵ , X ⁶ , X ⁷ and X ⁸ each independently represent a hydrogen atom or a fluorine atom, but X ¹ , X ² , X ³ , X ⁴ and At least 4 of X ⁵ represent fluorine atoms and X ⁶ , X ⁷ and X ⁸ represent hydrogen atoms, or at least 4 of X ¹ , X ² , X ⁶ , X ⁷ and X ⁸ are fluorine And X ³ , X ⁴ and X ⁵ represent a hydrogen atom,
Y ¹ , Y ² and Y ³ are each independently a single bond, —OCH ₂ —, —CH ₂ O—, —CF ₂ O—, —OCF ₂ —, —C ₂ H ₄ —, —COO—, -OCO -, - CH = CH - , - CF = CF -, - CF 2 CF 2 - or an -C≡C-,
p and q each independently represent 0 or 1, but when p represents 0, Y ¹ represents a single bond, and when q represents 0, Y ³ represents a single bond. ), A liquid crystal composition containing one or more fluoronaphthalene derivatives represented by general formula (I), and a liquid crystal display device using the same.

  The compound represented by the general formula (I) of the present invention has a very large absolute value with negative Δε. In addition, Δn has a very large value and low viscosity. For this reason, the liquid crystal composition containing the compound represented by the general formula (I) can respond at high speed. In addition, it is chemically stable to heat, light, water, etc., and is compatible with currently used liquid crystal compounds or liquid crystal compositions and has excellent liquid crystal properties, so that it can be driven at a low voltage. It was found that the liquid crystal display element of the vertical alignment method and the IPS method using the liquid crystal composition can be driven at a low voltage and has excellent display characteristics.

In the present invention, R ¹ and R ² in the general formula (I) are each independently a linear alkyl group having 1 to 7 carbon atoms, a linear alkenyl group having 2 to 7 carbon atoms, or carbon. A linear alkoxyl group having 1 to 7 atoms or a linear alkenyloxy group having 2 to 7 carbon atoms is preferred, a linear alkyl group having 1 to 7 carbon atoms, or 2 to 7 carbon atoms. A linear alkenyl group or a linear alkoxyl group having 1 to 7 carbon atoms is preferred. In order to lower the viscosity, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a vinyl group, 2- A propenyl group and a 3-butenyl group are more preferable, and a linear alkoxyl group having 1 to 7 carbon atoms is preferable for increasing the absolute value of dielectric anisotropy, and further a methoxy group, an ethoxy group, a propoxy group, Butoxy group and pentyloxy It is more preferable.

A ¹ and A ² are each independently preferably a trans-1,4-cyclohexylene group for improving the solubility, and a 1,4-phenylene group, 2-fluoro-1, for increasing Δn. A 4-phenylene group, a 3-fluoro-1,4-phenylene group, or a 2,3-difluoro-1,4-phenylene group is preferable. To increase the absolute value of Δε, a 2-fluoro-1,4-phenylene group 3-fluoro-1,4-phenylene group or 2,3-difluoro-1,4-phenylene group is preferable.

X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ and X ⁸ are X ¹ , X ² , X ³ , X ⁴ and X ⁵ are fluorine to increase the absolute value of Δε. X ⁶ , X ⁷ and X ⁸ represent a hydrogen atom, or X ¹ , X ² , X ⁶ , X ⁷ and X ⁸ represent a fluorine atom and X ³ , X ⁴ and X ⁵ represent a hydrogen atom It is preferable that it is a structure showing.

Y ¹ , Y ² and Y ³ are a single bond, —C ₂ H ₄ —, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —CF ₂ O to improve solubility. -, or -OCF ₂ -, more preferably a single bond to lower the _{viscosity, -CH 2 O -, - OCH} 2 -, - CF 2 O -, - OCF 2 - , more preferably a single bond is more preferable. In order to increase Δn, —CH═CH—, —CF═CF—, and —C≡C— are preferable. To increase Δε in absolute value, —OCH ₂ —, —CH ₂ O—, —CF ₂ O —, —OCF ₂ —, —COO— or —OCO— are preferred, and Y ¹ is particularly preferably —CH ₂ O—, —CF ₂ O—, —COO— or —OCO—, and Y ³ is particularly preferred— OCH ₂ —, —OCF ₂ — or —OCO— is preferable, and in order to increase reliability, a single bond, —C ₂ H ₄ —, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, -OCF ₂ - is preferable.
In order to improve the compatibility with other liquid crystals, p and q are preferably compounds in which p + q represents 0 or 1.

  Specifically, the compound represented by the general formula (I) is particularly preferably a compound represented by the following general formula (Ia-1) to general formula (Ic-9).

  The liquid crystal composition using one or two or more compounds represented by the general formula (I) is not particularly limited, but other liquid crystal compositions containing the compound represented by the general formula (I). As a component of general formula (II)

(In the formula, R ²¹ and R ²² each independently represents an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and one or more hydrogen atoms in each group are each independently represented. Optionally substituted with a fluorine atom, and one or two or more non-adjacent —CH ₂ — in each group are each independently —O—, —CO—, —COO— or -OCO- may be substituted,
M ²¹ , M ²² and M ²³ are each independently (a) a trans-1,4-cyclohexylene group (one or two or more non-adjacent —CH ₂ — present in this group is — O- or -S- may be substituted)
(B) 1,4-phenylene group (one or two or more non-adjacent —CH═ present in this group may be replaced by —N═), 2-fluoro-1,4- Phenylene group, 3-fluoro-1,4-phenylene group, 3,5-difluoro-1,4-phenylene group and (c) 1,4-cyclohexenylene group, 1,4-bicyclo (2.2.2) Octylene group, piperidine-2,5-diyl group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group and 1,2,3,4-tetrahydronaphthalene-2,6-diyl group Represents a group selected from the group consisting of
o represents 0, 1 or 2;
L ²¹ and L ²² are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O—. , —CH═CH—, —CH═N—N═CH— or —C≡C—, and when there are a plurality of L ^{22 s} , they may be the same or different, and a plurality of M ²³ are present. If so, they may be the same or different. )
It may contain the compound represented by these.

R ²¹ and R ²² in the general formula (II) are each independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms (one or not adjacent to these groups). Two or more —CH ₂ — are substituted with —O— or —S—, and one or more hydrogen atoms present in these groups are substituted with fluorine atoms or chlorine atoms And an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkenyloxy group having 3 to 6 carbon atoms is more preferable. And an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms is particularly preferable.

M ²¹ , M ²² and M ²³ are each independently a trans-1,4-cyclohexylene group (one CH ₂ group present in this group or _two non-adjacent CH ₂ groups are oxygen atoms) A substituted group), a 1,4-phenylene group (including one or more —CH═ present in the group substituted by —N═), 3-fluoro- 1,4-phenylene group, 3,5-difluoro-1,4-phenylene group, 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1,4- Diyl group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group is preferable, and trans-1,4-cyclohex A silylene group, a 1,4-phenylene group, or 4- bicyclo [2.2.2] octylene group are more preferable, trans-1,4-cyclohexylene group or 1,4-phenylene group is particularly preferred. o is preferably 0, 1 or 2, and more preferably 0 or 1. L ²¹ and L ²² are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O—. , —CH═CH—, —CH═N—N═CH— or —C≡C— are preferred, and a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ — or —CH. ₂ O-, more preferably a single bond, or a _-CH 2 CH ₂ - is more preferable. More specifically, the general formula (II) is preferably a compound represented by the following general formula (II-A) to general formula (II-P) as a specific structure.

(Wherein R ²³ and R ²⁴ are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or 3 to 3 carbon atoms. Represents 10 alkenyloxy groups.)
R ²³ and R ²⁴ are each independently preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, and preferably 1 to 5 carbon atoms. Are more preferably a linear alkyl group or a linear alkoxy group having 1 to 5 carbon atoms.

  Among the compounds represented by general formula (II-A) to general formula (II-P), general formula (II-A), general formula (II-B), general formula (II-C), and general formula (II) -E), general formula (II-H), general formula (II-I), general formula (II-I), or a compound represented by general formula (II-K) is preferred, and general formula (II-A) ), General formula (II-C), general formula (II-E), general formula (II-H) or general formula (II-I) is more preferred.

  In this invention, when it contains the compound represented by general formula (II), it is preferable to contain 1 type-10 types, It is especially preferable to contain 2 types-8 types, It represents with general formula (II) The lower limit of the content of the compound is preferably 5% by mass, more preferably 10% by mass, further preferably 20% by mass, particularly preferably 30% by mass, Is preferably 80% by mass, more preferably 70% by mass, and still more preferably 60% by mass.

  Furthermore, general formula (IIIa), general formula (IIIb) and general formula (IIIc)

(Wherein R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ each independently represents an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, One or more hydrogen atoms in the group may be each independently substituted with a fluorine atom, and one or two or more non-adjacent —CH ₂ — in each group may be independently -O-, -CO-, -COO- or -OCO- may be substituted,
M ⁴¹ , M ⁴² , M ⁴³ , M ⁴⁴ , M ⁴⁵ , M ⁴⁶ , M ⁴⁷ , M ⁴⁸ , and M ⁴⁹ are each independently
(G) trans-1,4-cyclohexylene group (one or two or more non-adjacent —CH ₂ — present in this group may be replaced by —O— or —S—) ,
(H) a 1,4-phenylene group (one or two or more non-adjacent —CH═ present in this group may be replaced by —N═);
(I) 1,4-cyclohexenylene group, 1,4-bicyclo (2.2.2) octylene group, piperidine-2,5-diyl group, naphthalene-2,6-diyl group, 1,2,3 , 4-tetrahydronaphthalene-2,6-diyl group and decahydronaphthalene-2,6-diyl group are selected from the group consisting of the group (g), group (h) or group (i). Each hydrogen atom contained may be substituted with a cyano group, a fluorine atom, a trifluoromethyl group, a trifluoromethoxy group or a chlorine atom,
L ⁴¹ , L ⁴² , L ⁴³ , L ⁴⁴ , L ⁴⁵ , L ⁴⁶ , L ⁴⁷ , L ⁴⁸ , and L ⁴⁹ are each independently a single bond, —COO—, —OCO—, —CH ₂ CH ₂ —, _{- (CH 2) 4 -,} - OCH 2 -, - CH 2 O -, - OCF 2 -, - CF 2 O- or represents ^{-C≡C-, M 42, M 43,} M 45, M 46, When there are a plurality of M ⁴⁸ , M ⁴⁹ , L ⁴¹ , L ⁴³ , L ⁴⁴ , L ⁴⁶ , L ⁴⁷ and / or L ⁴⁹ , they may be the same or different,
X ⁴¹ and X ⁴² each independently represents a trifluoromethyl group, a trifluoromethoxy group or a fluorine atom, and X ⁴³ , X ⁴⁴ , X ⁴⁵ , X ⁴⁶ , X ⁴⁷ and X ⁴⁸ are each independently a hydrogen atom. , A trifluoromethyl group, a trifluoromethoxy group, or a fluorine atom, wherein any one of X ⁴¹ and X ⁴² represents a fluorine atom, and any one of X ⁴³ , X ⁴⁴ , and X ⁴⁵ represents a fluorine atom Any one of X ⁴⁶ , X ⁴⁷ and X ⁴⁸ represents a fluorine atom, but X ⁴⁶ and X ⁴⁷ do not represent a fluorine atom at the same time, and X ⁴⁶ and X ⁴⁸ represent fluorine at the same time. Never represent an atom,
G represents —CH ₂ — or —O—;
u, v, w, x, y, and z each independently represent 0, 1, or 2, but u + v, w + x, and y + z are 2 or less. ) May be used alone or in combination of two or more compounds selected from the group consisting of compounds represented by:

R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ in the compounds represented by the general formula (IIIa), the general formula (IIIb) and the general formula (IIIc) are each independently selected from 1 to 10 alkyl groups or alkenyl groups having 2 to 10 carbon atoms, linear alkyl groups having 1 to 15 carbon atoms, or alkenyl groups having 2 to 15 carbon atoms (one or Two or more non-adjacent —CH ₂ — are substituted by —O— or —S—, and one or two or more hydrogen atoms present in these groups are a fluorine atom or a chlorine atom. Are preferably substituted, and a linear alkyl group having 1 to 10 carbon atoms, a linear alkoxy group having 1 to 10 carbon atoms, or a straight chain having 2 to 10 carbon atoms. More preferably an alkenyl group having 1 to 8 carbon atoms Linear alkyl group or alkoxy group having 1 to 8 carbon atoms is particularly preferred. M ⁴¹ , M ⁴² , M ⁴³ , M ⁴⁴ , M ⁴⁵ , M ⁴⁶ , M ⁴⁷ , M ⁴⁸ and M ⁴⁹ are each independently a trans-1,4-cyclohexylene group (1 present in this group). Or two or more non-adjacent —CH ₂ — include those in which —O— or —S— is substituted.), 1,4-phenylene group (one — CH = or two or more non-adjacent —CH═ are substituted with —N═), 1,4-cyclohexenylene group, 1,4-bicyclo (2.2.2) octylene Group, piperidine-2,5-diyl group, naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group and decahydronaphthalene-2,6-diyl group Group (the hydrogen atom contained in each group is a cyano group, a fluorine atom, Including those substituted with a romethyl group, a trifluoromethoxy group, or a chlorine atom.), Trans-1,4-cyclohexylene group, 1,4-phenylene group, 3-fluoro-1,4-phenylene Group or 2,3-difluoro-1,4-phenylene group is more preferable, trans-1,4-cyclohexylene group or 1,4-phenylene group is more preferable, and trans-1,4-cyclohexylene group is more preferable. Particularly preferred. L ⁴¹ , L ⁴² , L ⁴³ , L ⁴⁴ , L ⁴⁵ , L ⁴⁶ , L ⁴⁷ , L ⁴⁸ and L ⁴⁹ are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, — _{OCO -, - COO -, -} OCH 2 -, - CH 2 O -, - OCF 2 -, - CF 2 O- or -C≡C-, more preferably a single ^{_{bond, -CH 2 CH 2 -, -}} OCH 2 -, or _-CH 2 O-are more preferred. X ⁴¹ , X ⁴² , X ⁴³ , X ⁴⁴ , X ⁴⁵ , X ⁴⁶ , and X ⁴⁷ each independently represent a hydrogen atom or a fluorine atom, G represents —CH ₂ — or —O—, u, v , W, x, y and z each independently represent 0, 1 or 2, but u + v, w + x and y + z are each represented by 2 or less.

  In the compound represented by the general formula (IIIa), specifically, the structure represented by the following general formula (IIIa-1) is preferably represented.

(Wherein R ⁴⁷ and R ⁴⁸ each independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, L ⁵⁰ , L ⁵¹ and L ⁵² are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O— or — C≡C—, M ⁵⁰ represents a 1,4-phenylene group or a trans-1,4-cyclohexylene group, and u ₁ and v ₁ each independently represent 0 or 1.)
More specifically, the following general formulas (IIIa-2a) to (IIIa-3i)

(Wherein R ⁴⁷ and R ⁴⁸ each independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms). In which R ⁴⁷ and R ⁴⁸ are each independently a linear alkyl group having 1 to 8 carbon atoms or a linear alkoxyl group having 1 to 8 carbon atoms.

  In the compound represented by the general formula (IIIb), specifically, a structure represented by the following general formula (IIIb-1) is preferably represented.

(Wherein R ⁴⁹ and R ⁵⁰ each independently represent an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, L ⁵² , L ⁵³ and L ⁵⁴ are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O— or — C≡C—, M ⁵¹ , M ⁵² and M ^{53 each} represent a 1,4-phenylene group or trans-1,4-cyclohexylene group, and w 1 and x 1 independently represent 0, 1 or 2. W1 + x1 represents 2 or less.)
More specifically, the following general formulas (IIIb-2a) to (IIIb-3f)

(Wherein R ⁴⁹ and R ⁵⁰ each independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms). In which R ⁴⁹ and R ⁵⁰ are each independently a linear alkyl group having 1 to 8 carbon atoms or a linear alkoxyl group having 1 to 8 carbon atoms.

  In the compound represented by the general formula (IIIc), specifically, it is preferable to represent a structure represented by the following general formula (IIIc-1a) and general formula (IIIc-1b).

Wherein R ⁵¹ and R ⁵² each independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, L ⁵⁶ , L ⁵⁷ and L ⁵⁸ are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O— or — C≡C—, M ⁵⁴ , M ⁵⁵ and M ^{56 each} represent a 1,4-phenylene group or a trans-1,4-cyclohexylene group, and y 1 and z 1 independently represent 0, 1 or 2. However, y1 + z1 represents 2 or less.)
More specifically, the following general formulas (IIIc-2a) to (IIIc-2g)

(Wherein, R ⁵¹ and R ⁵² each independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms). The structure is preferably represented, and R ⁵¹ and R ⁵² are each independently a linear alkyl group having 1 to 8 carbon atoms or a linear alkoxyl group having 1 to 8 carbon atoms.

  When the present invention contains a compound selected from the group consisting of compounds represented by the general formula (IIIa), general formula (IIIb) and general formula (IIIc), it is preferable to contain 2 to 10 types. ~ 8 types are particularly preferred, the lower limit of the content is preferably 5% by mass, more preferably 10% by mass, more preferably 20% by mass, and the upper limit is 80% by mass. %, Preferably 70% by mass, preferably 60% by mass, and preferably 50% by mass.

  In the liquid crystal composition of the present invention, Δn is preferably in the range of 0.08 to 0.25.

  The liquid crystal composition of the present invention has a wide liquid crystal phase temperature range (the absolute value of the difference between the liquid crystal phase lower limit temperature and the liquid crystal phase upper limit temperature), but the liquid crystal phase temperature range is preferably 100 ° C. or higher, preferably 120 ° C. or higher. Is more preferable. The upper limit temperature of the liquid crystal phase is preferably 70 ° C. or higher, and more preferably 80 ° C. or higher. Furthermore, the lower limit temperature of the liquid crystal phase is preferably −20 ° C. or lower, and more preferably −30 ° C. or lower.

  The liquid crystal composition of the present invention may contain a normal nematic liquid crystal, a smectic liquid crystal, a cholesteric liquid crystal and the like in addition to the above compounds. Furthermore, an optically active compound, a stabilizer, a monomer, an antistatic agent and the like can be added as required.

  The liquid crystal composition of the present invention is used for the liquid crystal display element of the present invention that controls the amount of transmitted light by utilizing its birefringence. As the liquid crystal display element of the present invention, TN-LCD (nematic liquid crystal display element), STN-LCD (super twisted nematic liquid crystal display element), OCB-LCD, TFT-LCD (thin film transistor liquid crystal display element), VA-LCD (vertical) Oriented liquid crystal display elements) and IPS-LCDs (in-plane switching liquid crystal display elements) are preferred, but TFT-LCD, VA-LCD and IPS-LCD are particularly preferred. The liquid crystal display element of the present invention may be a PSA (Polymer Sustained Alignment) type liquid crystal display element.

  The two substrates of the liquid crystal cell used in the liquid crystal display element of the present invention can be made of a transparent material having flexibility such as glass or plastic, and one of them can be an opaque material such as silicon. A transparent substrate having a transparent electrode layer can be obtained, for example, by sputtering indium tin oxide (ITO) on a transparent substrate such as a glass plate.

  The color filter can be prepared by, for example, a pigment dispersion method, a printing method, an electrodeposition method, or a dyeing method. A method for producing a color filter by a pigment dispersion method will be described as an example. A curable coloring composition for a color filter is applied on the transparent substrate, subjected to patterning treatment, and cured by heating or light irradiation. By performing this process for each of the three colors red, green, and blue, a pixel portion for a color filter can be created. In addition, a pixel electrode provided with an active element such as a TFT, a thin film diode, or a metal insulator metal specific resistance element may be provided on the substrate.

  The said board | substrate is made to oppose so that a transparent electrode layer may become an inner side. In that case, you may adjust the space | interval of a board | substrate through a spacer. At this time, it is preferable to adjust so that the thickness of the light control layer obtained may be set to 1-100 micrometers. More preferably, the thickness is 1.5 to 10 μm. When a polarizing plate is used, it is preferable to adjust the product of the refractive index anisotropy Δn of the liquid crystal and the cell thickness d so that the contrast is maximized. In addition, when there are two polarizing plates, the polarizing axis of each polarizing plate can be adjusted so that the viewing angle and contrast are good. Furthermore, a retardation film for widening the viewing angle can also be used. Examples of the spacer include glass particles, plastic particles, alumina particles, and a photoresist material. Thereafter, a sealant such as an epoxy thermosetting composition is screen-printed on the substrates with a liquid crystal inlet provided, the substrates are bonded together, and heated to thermally cure the sealant.

  As a method for sandwiching the liquid crystal composition between the two substrates, a normal vacuum injection method, an ODF method, or the like can be used.

  In the present invention, production examples of the compound represented by the general formula (I) are given below. Of course, the gist and scope of the present invention are not limited by these production examples.

  (Production method 1) Alcohol (IX)

(Wherein X ¹ , X ² , Y ¹ , A ¹ and R ¹ represent the same meaning as X ¹ , X ² , Y ¹ , A ¹ and R ¹ in general formula (I), and p is 0 or 1 In the presence of a base such as pyridine, triethylamine, 4- (N, N-dimethylamino) pyridine, diazabicyclooctane, benzenesulfonyl chloride, p-toluenesulfonyl chloride, methanesulfonyl chloride, or trifluoromethanesulfonyl chloride. Or hydrobromic acid or hydroiodic acid in sulfuric acid, or thionyl chloride or thionyl bromide, or phosphorous trichloride, phosphorous pentachloride or phosphorous tribromide Or by reacting carbon tetrachloride or carbon tetrabromide in the presence of triphenylphosphine.

(Wherein X ¹ , X ² , Y ¹ , A ¹ and R ¹ represent the same meaning as X ¹ , X ² , Y ¹ , A ¹ and R ¹ in general formula (I), and p is 0 or 1 W represents a leaving group such as chlorine, bromine, iodine, benzenesulfonyl group, p-toluenesulfonyl group, methanesulfonyl group or trifluoromethanesulfonyl group. The compound represented by the general formula (X) and the general formula (XI)

(Wherein X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , Y ³ , A ² and R ² are X ³ , X ⁴ , X ⁵ , X ⁶ , X in the general formula (I) ⁷ , X ⁸ , Y ³ , A ² and R ² have the same meaning, and q represents 0 or 1.) The phenol represented by metal sodium, metal potassium, metal cesium, or a carbonate thereof, hydroxide By reacting in the presence of a product, hydride, etc., general formula (I-1)

(In the formula, A ¹ , A ² , R ¹ , R ² , X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , Y ¹ and Y ³ are represented by the general formula (I ) Represents the same meaning as A ¹ , A ² , R ¹ , R ² , X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , Y ¹ and Y ³ And q represents 0 or 1.) can be obtained.

  (Manufacturing method 2) General formula (IX)

(Wherein X ¹ , X ² , Y ¹ , A ¹ and R ¹ represent the same meaning as X ¹ , X ² , Y ¹ , A ¹ and R ¹ in general formula (I), and p is 0 or 1 And a compound represented by the general formula (XI)

(Wherein X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , Y ³ , A ² and R ² are X ³ , X ⁴ , X ⁵ , X ⁶ , X in the general formula (I) ⁷ , X ⁸ , Y ³ , A ² and R ² have the same meaning, q represents 0 or 1.) by reacting in the presence of azodicarboxylic acid ester and triphenylphosphine, Formula (I-1)

(In the formula, A ¹ , A ² , R ¹ , R ² , X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , Y ¹ and Y ³ are represented by the general formula (I ) Represents the same meaning as A ¹ , A ² , R ¹ , R ² , X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , Y ¹ and Y ³ And q represents 0 or 1.) can be obtained.

  (Manufacturing method 3) General formula (XII)

(Wherein X ¹ , X ² , Y ¹ , A ¹ and R ¹ represent the same meaning as X ¹ , X ² , Y ¹ , A ¹ and R ¹ in general formula (I), and p is 0 or 1 Z represents a leaving group such as chlorine, bromine and iodine.) A phenol represented by the general formula (XI) is reacted in the presence of a base, and the general formula (I- 2)

(In the formula, A ¹ , A ² , R ¹ , R ² , X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , Y ¹ and Y ³ are represented by the general formula (I And A ¹ , A ² , R ¹ , R ² , X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , Y ^1, and Y ³ in this formula). To obtain an ester represented by: This is treated with Lawesson's reagent, and further fluorinated with a fluorinating agent such as hydrogen fluoride-pyridine in the presence of an oxidizing agent such as N-bromosuccinimide, and then represented by the general formula (I-3)

(In the formula, A ¹ , A ² , R ¹ , R ² , X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , Y ¹ and Y ³ are represented by the general formula (I And A ¹ , A ² , R ¹ , R ² , X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , Y ^1, and Y ³ in this formula). Can be obtained.

  (Manufacturing method 4) General formula (XIII)

(Wherein R ¹ represents the same meaning as R ¹ in formula (I)) and cyclohexanone represented by formula (XIV)

(In the formula, A ² , R ² , X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , Y ² and Y ³ are A ² , R in the general formula (I) ² , X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , Y ^2, and Y ³ . General formula (I-4) by acid catalyst dehydration and hydrogenation

(Wherein R ¹ , A ² , R ² , X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , Y ² and Y ³ are R in the general formula (I) ¹ , A ² , R ² , X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , Y ² and Y ³ . Can be obtained.

  (Manufacturing method 5) General formula (XV)

(Wherein X ¹ , X ² , Y ¹ , A ¹ and R ¹ represent the same meaning as X ¹ , X ² , Y ¹ , A ¹ and R ¹ in general formula (I), and p is 0 or 1 The aldehyde represented by formula (XVI)

(In the formula, A ² , R ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ and Y ³ are A ² , R ² , X ³ , X ⁴ , X in the general formula (I) ⁵ , X ⁶ , X ⁷ , X ⁸ and Y ³ have the same meaning.) After acting the Grineer reagent represented by the formula (I-5), dehydration with an acid catalyst and hydrogenation are performed.

(In the formula, A ¹ , A ² , R ¹ , R ² , X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , Y ¹ and Y ³ are represented by the general formula (I ) Represents the same meaning as A ¹ , A ² , R ¹ , R ² , X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , Y ¹ and Y ³ Represents 0 or 1.) can be obtained.

  (Manufacturing method 6) General formula (XVII)

(Wherein X ¹ , X ² , Y ¹ , A ¹ and R ¹ represent the same meaning as X ¹ , X ² , Y ¹ , A ¹ and R ¹ in general formula (I), and p is 0 or 1 W represents a leaving group such as chlorine, bromine, iodine, benzenesulfonyl group, p-toluenesulfonyl group, methanesulfonyl group or trifluoromethanesulfonyl group) and a general formula (XVIII)

(Wherein X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , Y ³ , A ² and R ² are X ³ , X ⁴ , X ⁵ , X ⁶ , X in the general formula (I) ⁷ , X ⁸ , Y ³ , A ² and R ^2, and q represents 0 or 1.) A boronic acid derivative represented by tetrakistriphenylphosphine palladium (0), palladium acetate (II ), Palladium such as bis (triphenylphosphino) palladium (II), or a nickel-based transition metal catalyst in the presence of a basic reaction to perform a general reaction (I-6)

(In the formula, A ¹ , A ² , R ¹ , R ² , X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , Y ¹ and Y ³ are represented by the general formula (I ) Represents the same meaning as A ¹ , A ² , R ¹ , R ² , X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , Y ¹ and Y ³ Represents 0 or 1.) can be obtained.

  EXAMPLES Hereinafter, although an Example is given and this invention is further explained in full detail, this invention is not limited to these Examples. The structure of the compound was confirmed by nuclear magnetic resonance spectrum (NMR), mass spectrum (MS) and the like. Further, “%” in the compositions of the following examples and comparative examples means “mass%”.

The following abbreviations are used in compound descriptions.
Me: methyl group
Et: ethyl group
Pr: Propyl group
Bu: Butyl group
Pen: pentyl group
THF: Tetrahydrofuran (Example 1) Preparation of 6-butoxy-2- (4-propyloxy-2,3-difluorophenyl) -3,4,5-trifluoronaphthalene (IA)

  47.0 g of 6-butoxy-3,4,5-trifluoro-2-naphthol was dissolved in 150 mL of dichloromethane and then cooled to 5 ° C., and 32 mL of trifluoromethanesulfonic anhydride and 17.5 mL of pyridine were added dropwise at 20 ° C. or lower. . The reaction solution was stirred at 10 ° C. for 1 hour, and then 200 mL of water was added. The aqueous layer was extracted with dichloromethane, and the collected organic layer was washed with 3M hydrochloric acid, water and saturated brine in that order, and dried over anhydrous magnesium sulfate. The solvent was distilled off to obtain trifluoromethanesulfonic acid = 6-butoxy-3,4,5-trifluoro-2-naphthyl as a pale yellow solid (76 g).

  30.5 g of diisopropylamine was dissolved in 240 mL of THF. This solution was cooled to −10 ° C., 170 mL of n-butyllithium (1.6 mol / L hexane solution) was added dropwise while maintaining the temperature at −3 ° C. or lower, and the mixture was stirred for 30 minutes. To this reaction solution, a solution prepared by dissolving 35 g of 2,3-difluoropropyloxybenzene and 56.5 g of triisopropyl borate in 100 mL of THF was added dropwise while maintaining the temperature at −4 ° C. or lower and stirred at −10 ° C. for 1 hour. The reaction solution was heated to 0 ° C., and 500 mL of 10% hydrochloric acid was added dropwise. After separating the organic layer, the organic phase was further washed with saturated brine. The resulting organic phase was dehydrated by adding anhydrous sodium sulfate, and the solid content was collected by filtration. The solvent was distilled off from the resulting solution under reduced pressure, and 2,3-difluoro-4-propyloxyphenylboric acid was pale yellow. As a solid (48 g).

Next, together with the obtained trifluoromethanesulfonic acid = 6-butoxy-3,4,5-trifluoro-2-naphthyl 20.0 g and 2,3-difluoro-4-propyloxyphenyl boric acid 10.5 g, triphenylphosphine 0.53 g, 10.4 g of potassium carbonate, and 37 mL of water were dissolved in 60 mL of THF. To the resulting solution was added 217 mg of palladium (II) acetate, and the mixture was further heated to reflux for 5 hours and then cooled to room temperature. 50 mL of 10% hydrochloric acid and 60 mL of toluene were added to separate the organic phase. The aqueous layer was further extracted twice with toluene, and the obtained organic layers were combined and washed with water and saturated brine in this order. After dehydrating the organic phase with anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the resulting solid was dissolved in toluene and purified using column chromatography (alumina / silica gel, toluene), and the solvent was distilled off under reduced pressure. And 6-butoxy-2- (4-propyloxy-2,3-difluorophenyl) -3,4,5-trifluoronaphthalene (IA) as white crystals by further recrystallization (acetone / methanol). (13.23 g).
Phase transition temperature (℃) Cry 107 Iso
¹ H-NMR (400MHz, CDCl ₃ ) δ: 1.01 (t, J = 7.2Hz, 3H), 1.09 (t, J = 7.2Hz, 3H), 1.52-1.59 (m, 2H), 1.81-1.92 (m , 4H), 4.07 (t, J = 6.4Hz, 2H), 4.22 (t, J = 6.4Hz, 2H), 6.82-6.86 (m, 1H), 7.1-7.54 (m, 2H), 7.56 (m, 2H),
EI-MS: 424 [M ⁺ ]
Example 2 Production of 6-butoxy-2- (4- (trans-4-propylcyclohexylmethyloxy) -2,3-difluorophenyl) -3,4,5-trifluoronaphthalene (IB)

  4-Bromo-2,3-difluoro-1- (trans-4-propylcyclohexylmethyloxy) benzene (15 g) was dissolved in THF (75 mL), cooled to -50 ° C, and n-butyllithium (1.6 mol / L hexane solution). ) 31 mL was added dropwise while maintaining at -50 ° C or lower, and the mixture was stirred at -50 ° C for 30 minutes. To this reaction solution, a solution prepared by dissolving 5.6 g of trimethyl borate in 15 mL of THF was added dropwise while maintaining the temperature at -50 ° C. or lower, and then stirred at -50 ° C. for 30 minutes. The reaction solution was warmed to 0 ° C., 18 mL of 6M hydrochloric acid was added to stop the reaction, and the mixture was stirred at room temperature for 1 hour. The organic layer was separated and further extracted with toluene from the aqueous layer. The collected organic layer was washed with water and saturated brine in that order, and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain 2,3-difluoro-4- (trans-4-propylcyclohexylmethyloxy) phenylboric acid as a pale yellow solid (14.5 g).

Next, 15.5 g of trifluoromethanesulfonic acid = 6-butoxy-3,4,5-trifluoro-2-naphthyl obtained in Example 1 and 2,3-difluoro-4- (trans-4-propylcyclohexyl) Along with 12.7 g of methyloxyphenyl boric acid, 0.40 g of triphenylphosphine, 8.0 g of potassium carbonate, and 29 mL of water were dissolved in 60 mL of THF, and 170 mg of palladium (II) acetate was added to this solution. The reaction solution was heated to reflux for 8 hours and then cooled to room temperature. After adding 50 mL of 10% hydrochloric acid and 60 mL of toluene to separate the organic phase, the aqueous layer was further extracted twice with toluene, and the collected organic layer was washed with water and saturated brine in this order. After dehydrating the organic phase with anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the resulting solid was dissolved in toluene and purified using column chromatography (alumina / silica gel, toluene), and the solvent was distilled off under reduced pressure. And recrystallized (acetone / methanol) to give 6-butoxy-2- (4- (trans-4-propylcyclohexylmethyloxy) -2,3-difluorophenyl) -3,4,5-trimethyl as white crystals. Fluoronaphthalene (IB) was obtained (13.04 g).
Phase transition temperature (℃) Cry 114 N 167 Iso
¹ H-NMR (400MHz, CDCl ₃ ) δ: 0.97-1.35 (m, 15H), 1.52-1.59 (m, 2H), 1.80-1.86 (m, 5H), 1.92-1.95 (m, 2H), 3.89 ( d, J = 6.4Hz, 2H), 4.22 (t, J = 6.4Hz, 2H), 6.81-6.84 (m, 1H), 7.16-7.31 (m, 2H), 7.52-7.56 (m, 2H),
EI-MS: 520 [M ⁺ ]
Example 3 2- (2,3-difluoro-4- (2- (trans-4-propylcyclohexyl) ethyl) phenyldifluoromethyloxy) -6-propyloxy-3,4,5-trifluoronaphthalene ( I-C)

  To a solution of magnesium suspended in THF, a THF solution of 4-bromomethyl-2,3-difluoro-1- (2- (trans-4-propylcyclohexyl) ethyl) benzene was added dropwise with stirring, followed by further stirring. A Grignard reagent was prepared. Carbon disulfide was added dropwise to this solution. After further stirring, the reaction was stopped by adding dilute hydrochloric acid, extracted with toluene, and dried over anhydrous magnesium sulfate. The solvent was distilled off to obtain 2,3-difluoro-4- (2- (trans-4-propylcyclohexyl) ethyl) thiocarboxybenzene.

  A tetrahydrofuran solution of 3-difluoro-4- (2- (trans-4-propylcyclohexyl) ethyl) thiocarboxybenzene was added dropwise to a THF suspension of sodium hydride, and the mixture was further stirred. A solution of 6-propyloxy-3,4,5-trifluoro-2-naphthol in tetrahydrofuran was added dropwise to the reaction solution, and the mixture was further stirred. To this reaction solution was added dropwise a THF solution of iodine, and the mixture was further stirred, then returned to room temperature and stirred overnight at the same temperature. The reaction solution was poured into dilute hydrochloric acid, extracted with toluene, and dried over anhydrous magnesium sulfate. After magnesium sulfate was filtered off, the filtrate was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 6-propyloxy-3,4,5-trifluoro-2-naphthyl = 2,3-difluoro-4- ( 2- (Trans-4-propylcyclohexyl) ethyl) thiobenzoate was obtained.

A dichloromethane suspension of N-bromosuccinimide was cooled to −78 ° C., and hydrogen fluoride-pyridine was added dropwise and stirred. To this reaction solution, the above 6-propyloxy-3,4,5-trifluoro-2-naphthyl = 2,3-difluoro-4- (2- (trans-4-propylcyclohexyl) ethyl) thiobenzoate in dichloromethane solution Was added dropwise and stirred further. The reaction solution was poured into a saturated aqueous sodium carbonate solution to terminate the reaction, and the dichloromethane phase was separated, washed successively with an aqueous sodium hydrogensulfite solution and water, and dried over anhydrous magnesium sulfate. After magnesium sulfate was filtered off, the solvent was distilled off, the residue was purified by silica gel column chromatography, the solvent was distilled off and 2- (2,3-difluoro-4- (2- (trans-4-propylcyclohexyl) ) Ethyl) phenyl) difluoromethyloxy-6-propyloxy-3,4,5-trifluoronaphthalene (IC) was obtained.
EI-MS: 570 [M ⁺ ]
Example 4 Production of 2- (2- (2,3-difluoro-4-pentyloxyphenyl) ethenyl) -6-propoxy-3,4,5-trifluoronaphthalene (ID)

Under a nitrogen atmosphere, the grineer reagent prepared from 2-bromo-6-propoxy-3,4,5-trifluoronaphthalene was added dropwise to a THF solution of 2,3-difluoro-4-pentyloxyphenylacetaldehyde with stirring. After completion of the reaction, the mixture was extracted with toluene, washed with water and saturated brine, and dried over anhydrous magnesium sulfate. After magnesium sulfate was filtered off, the solvent was distilled off and the residue was purified by silica gel column chromatography. The alcohol obtained after distilling off the solvent was dissolved in toluene, p-toluenesulfonic acid was added, and the mixture was heated to reflux until no distillation of water occurred. The extract was washed with water and saturated brine, and then dried over anhydrous magnesium sulfate. After magnesium sulfate was filtered off, the solvent was distilled off, the residue was purified by silica gel column chromatography, and 2- (2- (2,3-difluoro-4-pentyloxyphenyl) ethenyl) -6-propoxy-3, 4,5-trifluoronaphthalene (ID) was obtained.
EI-MS: 464 [M ⁺ ]
Example 5 Production of 2- (2- (2,3-difluoro-4-pentyloxyphenyl) ethyl) -6-propoxy-3,4,5-trifluoronaphthalene (IE)

(ID) obtained in Example 4 was dissolved in ethyl acetate, Pd / C was added, and the mixture was stirred under hydrogen pressure. After filtering off Pd / C, the solvent was distilled off, and the residue was purified by silica gel column chromatography to obtain 2- (2- (2,3-difluoro-4-pentyloxyphenyl) ethyl) -6-propoxy-3. , 4,5-trifluoronaphthalene (IE) was obtained.
EI-MS: 466 [M ⁺ ]
(Example 6) Preparation of liquid crystal composition (1)
Host liquid crystal composition (HA) comprising the following composition

Was prepared. Here, the physical properties of (HA) were as follows.

Nematic phase upper limit temperature (T _NI ): 103.2 ℃
Dielectric anisotropy (Δε): 0.03
Refractive index anisotropy (Δn): 0.099
Viscosity (η20): 16.1 mPa / sec
A liquid crystal composition (MA) comprising 95% of the host liquid crystal composition (HA) and 5% of the compound represented by the formula (IA) obtained in Example 1 was prepared. The physical properties of this composition were as follows.

Nematic phase upper limit temperature (T _NI ): 100.6 ° C
Dielectric anisotropy (Δε): −0.46
Refractive index anisotropy (Δn): 0.105
Viscosity (η20): 17.0 mPa / sec
In the liquid crystal composition (MA) containing the compound represented by the formula (IA) of the present invention, Δε is greatly reduced to a negative value as compared with the host liquid crystal composition (HA). It was. From this, it was found that the compound represented by the formula (IA) of the present invention had a negative Δε and an extremely large absolute value (Δε: −9.77 (extrapolated value)). In addition, since Δn was larger than that of the host liquid crystal composition (HA), it was found that the compound represented by the formula (IA) of the present invention had a large Δn (Δn: 0). .218 (extrapolated value)).

The liquid crystal composition (MA) was allowed to stand at −20 ° C. for 1 week, and showed a nematic phase. Therefore, the compound represented by the formula (IA) of the present invention is superior to other liquid crystal materials. It was found to have compatibility. It was found that the nematic phase upper limit temperature (T _NI ) was as high as 100.6 ° C.

  Furthermore, when the voltage holding ratio of the liquid crystal composition (MA) was measured at 80 ° C., the voltage holding ratio of the host liquid crystal composition (HA) was as high as 98% or more. From this, it was found that the compound (IA) of the present invention can be sufficiently used as a liquid crystal material from the viewpoint of reliability.

(Example 7) Preparation of liquid crystal composition (2)
A liquid crystal composition (MB) comprising 95% of the host liquid crystal composition (HA) prepared in Example 6 and 5% of the compound represented by the formula (IB) obtained in Example 2 was prepared. did. The physical properties of this composition were as follows.

Nematic phase upper limit temperature (T _NI ): 105.4 ℃
Dielectric anisotropy (Δε): -0.41
Refractive index anisotropy (Δn): 0.104
Viscosity (η20): 17.1 mPa / sec
In the liquid crystal composition (MB) containing the compound represented by the formula (IB) of the present invention, Δε is greatly reduced and becomes a negative value as compared with the host liquid crystal composition (HA). It was. From this, it was found that the compound represented by the formula (IB) of the present invention had a negative Δε and an extremely large absolute value (Δε: −8.77 (extrapolated value)). In addition, since Δn was larger than that of the host liquid crystal composition (HA), the compound represented by the formula (IB) of the present invention was found to have a large Δn (Δn: 0). 198 (extrapolated value)).

Further, although (MB) was allowed to stand at −20 ° C. for 1 week, it showed a nematic phase, and no precipitation of crystals was observed. From this, it was found that the compound represented by the formula (IB) of the present invention has excellent compatibility with other liquid crystal materials. The nematic phase upper limit temperature (T _NI ) was 105.4 ° C, indicating high liquid crystallinity.

Furthermore, when the voltage holding ratio of (MB) was measured at 80 ° C., it showed a high value of 98% or more with respect to the voltage holding ratio of the host liquid crystal composition (HA). From this, it was found that the compound (IB) of the present invention can be sufficiently used as a liquid crystal display material from the viewpoint of reliability.
(Example 8) Preparation of liquid crystal composition (3)
Host liquid crystal composition (H-B) having the following composition

Was prepared. Here, the physical properties of (H-B) were as follows.

Nematic phase upper limit temperature (T _NI ): 80 ℃
Dielectric anisotropy (Δε): -3.5
Refractive index anisotropy (Δn): 0.087
A liquid crystal composition (M-C) comprising 90% of the host liquid crystal composition (H-B) and 10% of the compound represented by the formula (IA) obtained in Example 1 was prepared. The physical properties of this composition were as follows.

Nematic phase upper limit temperature (T _NI ): 76.7 ℃
Dielectric anisotropy (Δε): -4.1
Refractive index anisotropy (Δn): 0.099
In the liquid crystal composition (MC) containing the compound represented by the formula (IA) of the present invention, Δε is greatly reduced to a negative value as compared with the host liquid crystal composition (H-B). It was. From this, it was found that the compound represented by the formula (IA) of the present invention has a negative Δε and an extremely large absolute value. Moreover, since Δn was larger than that of the host liquid crystal composition (H-B), it was found that the compound represented by the formula (IA) of the present invention had a large Δn.

The liquid crystal composition (MC) was allowed to stand at −20 ° C. for 1 week, but showed a nematic phase. From this, it was found that the compound represented by the formula (IA) of the present invention has excellent compatibility with other liquid crystal materials. The nematic phase upper limit temperature (T _NI ) was 76.7 ° C, indicating high liquid crystallinity.

Furthermore, when the voltage holding ratio of the liquid crystal composition (MC) was measured at 80 ° C., it showed a high value of 98% or more with respect to the voltage holding ratio of the host liquid crystal composition (H-B). From this, it was found that the compound (IA) of the present invention can be sufficiently used as a liquid crystal material from the viewpoint of reliability.
(Example 9) Preparation of liquid crystal composition (4)
Host liquid crystal composition (HC) comprising the following composition

Was prepared. Here, the physical properties of (HC) were as follows.

Nematic phase upper limit temperature (T _NI ): 85 ℃
Dielectric anisotropy (Δε): -3.4
Refractive index anisotropy (Δn): 0.094
A liquid crystal composition (MD) comprising 90% of the host liquid crystal composition (HC) and 10% of the compound represented by the formula (IA) obtained in Example 1 was prepared. The physical properties of this composition were as follows.

Nematic phase upper limit temperature (T _NI ): 81.6 ℃
Dielectric anisotropy (Δε): -4.0
Refractive index anisotropy (Δn): 0.103
In the liquid crystal composition (MD) containing the compound represented by the formula (IA) of the present invention, Δε is greatly reduced to a negative value as compared with the host liquid crystal composition (HC). It was. From this, it was found that the compound represented by the formula (IA) of the present invention has a negative Δε and an extremely large absolute value. Moreover, since Δn is larger than that of the host liquid crystal composition (HC), it can be seen that the compound represented by the formula (IA) of the present invention has a large Δn.

The liquid crystal composition (MD) was allowed to stand at −20 ° C. for 1 week, but showed a nematic phase. From this, it was found that the compound represented by the formula (IA) of the present invention has excellent compatibility with other liquid crystal materials. The nematic phase upper limit temperature (T _NI ) was 81.6 ° C, indicating high liquid crystallinity.

Furthermore, when the voltage holding ratio of the liquid crystal composition (MD) was measured at 80 ° C., it showed a high value of 98% or more with respect to the voltage holding ratio of the host liquid crystal composition (HC). From this, it was found that the compound (IA) of the present invention can be sufficiently used as a liquid crystal material from the viewpoint of reliability.
(Example 10) Preparation of liquid crystal composition (5)
Host liquid crystal composition (HD) comprising the following composition

Was prepared. Here, the physical properties of (HD) were as follows.

Nematic phase upper limit temperature (T _NI ): 72 ° C
Dielectric anisotropy (Δε): -3.3
Refractive index anisotropy (Δn): 0.086
A liquid crystal composition (ME) comprising 90% of the host liquid crystal composition (HD) and 10% of the compound represented by the formula (IA) obtained in Example 1 was prepared. The physical properties of this composition were as follows.

Nematic phase upper limit temperature (T _NI ): 69.9 ℃
Dielectric anisotropy (Δε): -3.9
Refractive index anisotropy (Δn): 0.096
In the liquid crystal composition (ME) containing the compound represented by the formula (IA) of the present invention, Δε is greatly reduced and becomes a negative value as compared with the host liquid crystal composition (HD). It was. From this, it was found that the compound represented by the formula (IA) of the present invention has a negative Δε and an extremely large absolute value. Moreover, since Δn was larger than that of the host liquid crystal composition (HD), it was found that the compound represented by the formula (IA) of the present invention had a large Δn.

The liquid crystal composition (ME) was allowed to stand at −20 ° C. for 1 week, but showed a nematic phase. From this, it was found that the compound represented by the formula (IA) of the present invention has excellent compatibility with other liquid crystal materials. It was found that the nematic phase upper limit temperature (T _NI ) was as high as 69.9 ° C.

  Further, when the voltage holding ratio of the liquid crystal composition (ME) was measured at 80 ° C., the voltage holding ratio of the host liquid crystal composition (HD) was as high as 98% or more. From this, it was found that the compound (IA) of the present invention can be sufficiently used as a liquid crystal material from the viewpoint of reliability.

(Comparative Example 1)
Formula (A-3) and Formula (A-4)

The Δε and Δn of the liquid crystal compound represented by the formula (IA) of the present invention obtained in Example 1 were compared by extrapolation values.

  From the description in Patent Document 3, Δε in formula (A-3) was −7.37, and Δn was 0.155. Moreover, (DELTA) epsilon of Formula (A-4) was -6.84, and (DELTA) n was 0.176.

  On the other hand, since Δε of the liquid crystal compound represented by the formula (IA) of the present invention obtained in Example 1 is −9.77 as shown in Example 6, The absolute value of Δε of the liquid crystal compound was found to be 1.33 times larger than that of conventionally known compounds.

  Moreover, since Δn of the liquid crystal compound represented by the formula (IA) of the present invention obtained in Example 1 is 0.218 as shown in Example 6, Δε of the liquid crystal compound of the present invention is The absolute value of was found to be 1.24 times larger than that of conventionally known compounds.

(Comparative Example 2)
Formula (A-5)

The Δε and Δn of the liquid crystal compound represented by the formula (IA) of the present invention obtained in Example 1 were compared by extrapolation values.

  A liquid crystal composition comprising 95% of the host liquid crystal composition (HA) prepared in Example 6 and 5% of the compound represented by the formula (A-5), wherein a compound represented by the formula (A-5) was produced. A product (MF) was prepared. The physical properties of this composition are as follows.

Nematic phase upper limit temperature (T _NI ): 103.0 ℃
Dielectric anisotropy (Δε): -0.31
Refractive index anisotropy (Δn): 0.102
Viscosity (η20): 17.6 mPa / sec
From the above results, it can be seen that Δε of the compound represented by the formula (A-5) is −6.8 and Δn is 0.158. On the other hand, since the value of Δε of the liquid crystal compound represented by the formula (IA) of the present invention is −9.8 and the value of Δn is 0.218, The absolute value of Δε was 1.44 times larger than that of the compound represented by the formula (A-5), and Δn was 1.38 times larger.

  Furthermore, it can be seen that the liquid crystal composition (MF) has a higher viscosity than the liquid crystal composition (MA) described in Example 6 and the liquid crystal composition (MB) described in Example 7. From this, it was found that Δε and Δn can be improved without increasing the viscosity when the compound of the present application is added to the liquid crystal composition.

  Comparing the results of Comparative Example 1 and Comparative Example 2, the value of Δε (−6.8) of the compound represented by the above formula (A-5) is the same as the formula (A-3) and It is a value comparable to the value of Δε of the compound represented by (A-4). For this reason, it was found that even when three or more fluorine atoms were introduced into the biphenyl compound, the absolute value of negative Δε did not increase any more. On the other hand, in the naphthalene compound like the present compound, it was found that the absolute value of Δε can be further increased by introducing a fluorine atom. Since the naphthalene skeleton can introduce three or more fluorine atoms on the same ring, it is considered that the absolute value of Δε can be increased. Thus, it turned out that this-application compound is a very useful compound.

Claims (5)

Formula (I)

(In the formula, R ¹ and R ² are each independently methyl, ethyl, propyl, butyl, pentyl, vinyl, 2-propenyl, 3-butenyl, methoxy, ethoxy, propoxy Represents a group, butoxy group or pentyloxy group, one or more hydrogen atoms in each group may be independently substituted with fluorine atoms, and one or not in each group is not adjacent to each other Two or more —CH ₂ — may be independently substituted with —O—, —CO—, —COO— or —OCO—,
A ¹ and A ² are each independently a trans-1,4-cyclohexylene group , or a 1,4-phenylene group that is unsubstituted or one or more hydrogen atoms may be substituted with fluorine atoms. Represent,
X ¹ , X ² , X ³ , X ^4, X ⁵ , X ⁶ , X ⁷ and X ⁸ each independently represent a hydrogen atom or a fluorine atom, but X ¹ , X ² , X ³ , X ⁴ and X ⁵ represents a fluorine atom and ^X 6, ^{X 7} and ^{X 8} is either a hydrogen atom, or ^{X 1,} X ^2, X 6, ^{X 7} and ^{X 8} represents a fluorine atom and ^X 3, ^{X 4} and X ⁵ represents a hydrogen atom,
Y ¹ , Y ² and Y ³ are each independently a single bond, —OCH ₂ —, —CH ₂ O—, —CF ₂ O—, —OCF ₂ —, —C ₂ H ₄ —, —COO—, -OCO -, - CH = CH - , - CF = CF -, - CF 2 CF 2 - or an -C≡C-,
p and q each independently represent 0 or 1, p + q represents 0 or 1, Y ¹ represents a single bond when p represents 0, and Y ³ when q represents 0. Represents a single bond. ) A fluoronaphthalene derivative represented by: In the general formula (I), Y ¹ , Y ² and Y ³ represent a single bond, —C ₂ H ₄ —, —OCH ₂ —, —CH ₂ O—, —CF ₂ O— or —OCF ₂ —. The fluoronaphthalene derivative according to claim 1 . The fluoronaphthalene derivative according to claim 1 or 2 , wherein Y ² represents a single bond. Claim 1-3 compound represented by the formula (I) 1 kind or nematic liquid crystal composition characterized by containing two or more according. A liquid crystal display device using the liquid crystal composition according to claim 4 .