JPH08225786A - Liquid crystal composition and liquid crystal element containing the same - Google Patents

Abstract

PURPOSE: To obtain the subject composition, consisting essentially of two kinds of compounds having specific structures, capable of manifesting high-speed responsiveness, low temperature dependence of τ-V characteristics and a chiral smectic C phase and useful as an optical shutter, a display element, etc. CONSTITUTION: This composition consists essentially of a compound of formula I [R11 and R12 are each a 1-20C alkyl, an alkoxy, etc.; A11 to A13 are each formula II or III [(j) is 0-3], etc., with the proviso that (p+q) is 0 or 1 and A12 and A13 are each a monocyclic ring when A11 is a condensed ring and (p+q) is 1 or 2 when A11 is a monocyclic ring and A12 and A13 are each a monocyclic ring when (p+q) is 2; Z is H or F; (n) is 0-10; (r), (s), (t) and (u) are each 0 or 1, with the proviso that the compound is a trans-olefin when (u) is 1[ and (B) a compound of formula IV [R21 is a 3-20C (un)saturated alkyl or a 3-20C (un)saturated alkoxyalkyl; A21 to A23 are each A11 ; X2 is CH=CH, CH2 -CH2 , etc.; (n) is 1-10; (m), (p) and (q) are each 0 or 1, with the proviso that the relationship among (p), (q) and A21 to A23 is the same as that among (p), (q) and A11 to A13 ].

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel ferroelectric chiral smectic liquid crystal composition and a liquid crystal device using the same. More specifically, the present invention relates to a novel liquid crystal composition having an improved response speed, and a liquid crystal element that can be used for optical shutters and display elements using the same.

[0002]

2. Description of the Related Art With the progress of information society in recent years, various display devices have been used as one of man-machine interfaces.
Its importance is increasing. Among them, flat panel displays, especially liquid crystal displays (LCD),
It has features such as thinness, light weight, low voltage drive, and low power consumption, and has rapidly spread. Among liquid crystal elements represented by a liquid crystal display, a matrix type liquid crystal element having a large amount of information has two driving methods called an active matrix method and a simple matrix method.

In the active matrix system, a thin film transistor or diode such as polysilicon or amorphous silicon is mounted as a non-linear element for each pixel. However, the active matrix method has problems in terms of large area, low price, and high density due to complicated manufacturing process and poor yield. Considering price and productivity, the simple matrix method is preferable. It is influential.

As a simple matrix type liquid crystal element which has been put into practical use at present, a liquid crystal element using TN type / STN type liquid crystal is mainstream. But the optical response of these devices is
Based on the dielectric anisotropy of liquid crystal molecules generated when an electric field is applied, an average alignment of liquid crystal molecule axes in a specific direction is used. Therefore, the limit of optical response speed of these elements is
It is on the order of milliseconds, which is insufficient when considering the increase in the amount of information. In principle, if the number of scanning lines is increased in order to increase the amount of information, a decrease in contrast ratio and crosstalk cannot be avoided. This is an essential problem due to the fact that TN-type and STN-type liquid crystals do not exhibit a memory property (bistability). In order to improve this, various driving methods such as a dual frequency driving method, a voltage averaging method, and a multi-matrix method have been proposed, but this is not an essential solution to the problem but a large capacity,
Densification is not easy. Further, these liquid crystals have serious problems in view angle restriction and display quality.

With the goal of solving the essential problems of such liquid crystal elements, N. A. Clark and S.L. T. Lagerwall proposed a liquid crystal device utilizing a liquid crystal having bistability (US Patent No. 43679).
24, JP-A-56-107216, etc.).
Ferroelectric liquid crystals exhibiting a chiral smectic C phase are mainly used as liquid crystals exhibiting such bistability.

One of the characteristics of using the ferroelectric liquid crystal is that the ferroelectric liquid crystal exhibits bistability. Bistability means that when a ferroelectric liquid crystal is sandwiched between two glass substrates having transparent electrodes, it has two optically stable states depending on the direction of the applied electric field. The two optically stable states are properties that are maintained even when the applied electric field is removed. Due to such a property, it can be expected that the liquid crystal element using the ferroelectric liquid crystal does not have a decrease in contrast ratio or crosstalk even if the number of scanning lines is increased.

Another characteristic of the ferroelectric liquid crystal is high-speed response. That is, since the optical response of the ferroelectric liquid crystal utilizes the change in the alignment of the liquid crystal molecules caused by the direct interaction between the spontaneous polarization of the ferroelectric liquid crystal and the electric field, the TN-type / STN-type liquid crystal described above is used. It is about 1000 times faster than the optical response in the case.

That is, the ferroelectric liquid crystal element exhibits (1) two optically stable states, which are maintained as they are even after the electric field is removed (bistability), and (2) the two It has an essential feature of switching an optical stable state in microsecond order (fast response).
Further, the ferroelectric liquid crystal element is also characterized in that (3) the liquid crystal molecules respond in a plane parallel to the substrate and the cell thickness is thin so that the viewing angle dependence of the display is small (wide viewing angle). .
Therefore, the ferroelectric liquid crystal element does not require expensive non-linear elements as in the case of the active matrix system, and is expected as a high-quality large display capable of achieving a large display capacity and a high display quality by the simple matrix system.

Recently, an addressing method (inverse mode or τ-Vmin mode) of a matrix array type liquid crystal cell using a liquid crystal material in which the response time of the liquid crystal is adjusted to show a minimum value at a specific voltage has been proposed by Mashu Francis. Bourne (JP-A-3-20715). In such an addressing method, the fact that the response time of the liquid crystal exhibits the minimum value at a specific voltage is used to drive the liquid crystal element by using the positive slope portion in the voltage dependence of the response time. By using such a driving method, it is expected that flicker is reduced and good image quality is obtained.

A liquid crystal material suitable for such an inverse mode has a phase series necessary for obtaining a good alignment state, that is, a cholesteric phase, a smectic A phase, and a chiral smectic C phase when gradually cooled from an isotropic phase. In addition to the properties that have been conventionally required for ferroelectric liquid crystal materials that have a phase sequence that undergoes a transition and that exhibit low viscosity and high-speed response, the dielectric anisotropy has a negative value over a frequency range of at least 1 kHz to 40 kHz. It is to show.

Up to now, several liquid crystal materials for inverse mode have been reported in academic journals and conference presentations.
It has problems that must be solved. One of such problems is the development of a liquid crystal material which has a sufficiently wide temperature range showing a chiral smectic C phase and has a minimum response time in a specific electric field. For example, the compositions described on pages 249 and 251 of the proceedings of the 19th Liquid Crystal Symposium (1993) lecture are excellent as liquid crystal materials for the inverse mode, but the maximum temperature of the chiral smectic C phase is It is not satisfactory from a practical point of view. For this reason, enormous research has been conducted and reported so far on liquid crystal materials exhibiting ferroelectricity. There are some problems that need to be solved in order to put a ferroelectric liquid crystal device into practical use. In particular, a liquid crystal material that exhibits high-speed response and that has little temperature dependence of physical properties related to driving conditions is selected. Required to be provided.

[0012]

DISCLOSURE OF THE INVENTION The present invention exhibits a high-speed response and, in the case of an inverse mode liquid crystal material, τ-V
An object of the present invention is to provide a ferroelectric liquid crystal composition in which the min characteristic has small temperature dependence and a liquid crystal device using the composition.

[0013]

The present invention comprises the following inventions. [1] The following general formula (I)

[Chemical formula 22] (In the formula, R ₁₁ and R _{12 each} represent an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom, an alkoxy group or an alkoxyalkyl group, and an unsaturated bond is contained therein. May be A ₁₁ , A ₁₂ and A ₁₃
Each independently,

[Chemical formula 23] (In the formula, i represents an integer of 0 to 4, j and k represent integers of 0 to 3), and p and q are each independently selected. 0 or 1, and when A ₁₁ is a condensed ring, the sum of p and q is 0 or 1.
And A ₁₂ and A ₁₃ are monocycles, and when A ₁₁ is a monocycle, the sum of p and q is 1 or 2, and p and q
When the sum of the above is 2, both A ₁₂ and A ₁₃ are monocycles. * Represents an asymmetric carbon, Z represents a hydrogen atom or a fluorine atom, n is an integer of 0 to 10, and r, st and u are 0 or 1, respectively. However, when u = 1, it is a trans olefin. ) At least one compound represented by the formula

[Chemical formula 24] (In the formula, R ₂₁ represents a saturated or unsaturated alkyl group having 3 to 20 carbon atoms or a saturated or unsaturated alkoxyalkyl group having 3 to 20 carbon atoms. A ₂₁ , A ₂₂ , and A ₂₃
Respectively

[Chemical 25] And when A ₂₁ is a condensed ring, p + q is 0 or 1.
And A ₂₂ and A ₂₃ are monocycles. When A ₂₁ is a monocycle, p + q is 1 or 2. When p + q is 2, both A ₂₂ and A ₂₃ are monocycles. X ₂ is

[Chemical formula 26] Or

[Chemical 27] Or

[Chemical 28] , Z is a fluorine atom or a hydrogen atom, and n is 1
Is an integer of -10, m, p and q each represent 0 or 1, i represents an integer of 0 to 4, j and k each represent an integer of 0 to 3, and * represents an asymmetric carbon. Show. )
A ferroelectric chiral smectic liquid crystal composition comprising at least one compound represented by the formula (1) as an essential component.

[2] At least one compound represented by general formula (I) described in item [1] and at least one compound represented by general formula (II) described in item [1], The following general formula (V)

[Chemical 29] (In the formula, R ₅₁ represents an alkyl group or an alkoxyl group having 2 to 20 carbon atoms, and X ₅ represents —COO— or —CH ₂ O.
-(However, the binding site does not matter) is shown, and 1 and m are 1 or 2, respectively. n is an integer of 0-5. Z represents a hydrogen atom or a fluorine atom. A compound represented by (* indicates an asymmetric carbon) or the general formula (VI)

Embedded image (In the formula, R ₆₁ represents an alkyl group having 1 to 20 carbon atoms,
X ₆ represents —COO— or —CH ₂ O— (however, the binding site does not matter), Y ₆ represents —O— or —COO— (however, the binding site does not matter), and A ₆ is

[Chemical 31] Is shown, n is an integer of 0-5, and m is 0 or 1. Z represents a hydrogen atom or a fluorine atom. * Indicates a compound having an asymmetric carbon) or a compound represented by the general formula (VII)

Embedded image (In the formula, R ₇₁ represents a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, a saturated or unsaturated alkoxyalkyl group having 2 to 20 carbon atoms, and l, m, p and q are 0 or 1 And n represents an integer of 0 to 8. Y ₇ is

[Chemical 33] Or

Embedded image Or

Embedded image Represents either A ₇₁ , A ₇₂ and A ₇₃ are respectively

Embedded image (Wherein i represents an integer of 0 to 4 and j and k represent integers of 0 to 3), and A ₇₁ is a condensed ring. In this case, the sum of p and q is 0 or 1, and A ₇₂ and A ₇₃ are monocycles.
_{When 71} is a monocycle, the sum of p and q is 1 or 2, and when the sum of p and q is 2, both A ₇₂ and A ₇₃ are monocycles. * Indicates a compound having an asymmetric carbon), or a compound represented by the general formula (VIII)

Embedded image (In the formula, R ₈₁ and R ₈₂ represent an alkyl group having 1 to 18 carbon atoms, X ₈ represents a single bond or —O—, and m represents 0 or 1
And ring A represents a phenylene group or cyclohexylene group which may be fluorine-substituted, and ring B represents a phenylene group which may be fluorine-substituted. n is an integer of 0-5. The * mark indicates an asymmetric carbon. However, among them, compounds represented by the general formulas (V) to (VII) are excluded), and at least one compound selected from the compounds represented by the formulas (V) to (VII) is contained. Stuff.

[3] The following general formula (III)

[Chemical 38] (In the formula, A ₃₁ and A ₃₂ are

[Chemical Formula 39] Which is a condensed ring or a monocyclic ring represented by
m and n are each independently 0 or 1, the sum of m and n is 1 when A ₃₁ or A ₃₂ is a condensed ring, and the sum of m and n when A ₃₁ or A ₃₂ is a monocycle. Is 1 or 2. R
₃₁ and R ₃₂ represent an alkyl group alkoxy group having 3 to 15 carbon atoms or an alkoxyalkyl group which may be substituted with a halogen atom. ) At least one compound represented by the following general formula (IV)

[Chemical 40] (In the formula, c and d are each independently 1 or 2, the sum of c and d is 3, e is an integer of 0 to 10, and f is 0.
Or 1, g and h are each independently 0 or 1, X ₄ is —COO— or —OCO—,
At least one hydrogen atom of the benzene ring is substituted with a fluorine atom, R ₄₁ is an alkyl group having 5 to 15 carbon atoms,
R ₄₂ represents an alkoxy group or an alkoxyalkyl group.
Is 1 to 10 carbon atoms which may be substituted with a halogen atom.
Represents an alkyl group or an alkoxy group of or an alkoxyalkyl group having 2 to 10 carbon atoms which may be substituted with a halogen atom, and the continuous methylene chain of R ₄₁ and R ₄₂ is substituted with a double bond or a triple bond. Well, *
Represents an asymmetric carbon, and Z represents a hydrogen atom or a fluorine atom. ) A ferroelectric chiral smectic liquid crystal composition containing at least one compound represented by the formula (1) and at least one compound represented by the general formula (II) according to item [1] as an essential component. . [4] At least one kind of compounds represented by the general formula (I) described in the item [1], wherein u = 1 and at least one compound represented by the general formula (II) described in the item [1]. A ferroelectric chiral smectic liquid crystal composition containing one kind and at least one kind of the compound represented by the general formula (IV) described in the item [3] as an essential component.

[5] As the compound represented by the general formula (I), any one of A ₁₁ , A ₁₂ and A ₁₃ is

Embedded image Is a trans-olefin compound (R ₁₁ , R ₁₂ , n,
p, q, r, s, and t have the same meanings as described above), and the ferroelectric chiral smectic liquid crystal composition according to item [1], [2], or [4].

[6] As the compound represented by the general formula (I), any one of A ₁₁ , A ₁₂ and A ₁₃ is

Embedded image And a trans-olefin compound in which r, s, and t are 0 (R ₁₁ , R ₁₂ , n, p, q, r, s, and t have the same meaning as described above). 1],
The ferroelectric chiral smectic liquid crystal composition according to [2] or [4].

[7] A compound represented by the general formula (I):
Composition ratio of the compound represented by the general formula (II) (on a molar basis)
However, (I) :( II) = (98-50) :( 2-50)
The ferroelectric chiral smectic liquid crystal composition according to item [1], wherein [8] The composition ratio (molar basis) of the compound represented by the general formula (III), the compound represented by the general formula (IV), and the compound represented by the general formula (II) is (III): (I
V) :( II) = (10-90) :( 87-7) :( 3
To 50), The ferroelectric chiral smectic liquid crystal composition according to item [3].

[9] a compound represented by the general formula (I),
The composition ratio (molar basis) of the compound represented by the general formula (IV) and the compound represented by the general formula (II) is (I) :( I
V) :( II) = (87-7) :( 3-50) :( 10
To 90), the ferroelectric chiral smectic liquid crystal composition according to item [4], [5] or [6].

[10] Terms [1], [3], [4],
The ferroelectric chiral smectic liquid crystal composition described in [5] or [6] and the general formulas (V) and (V described in [2].
A ferroelectric chiral smectic liquid crystal composition comprising at least one compound selected from I), (VII) and (VIII).

[11] A ferroelectric chiral smectic liquid crystal composition according to item [10], which has the above general formulas (V) and (V
A ferroelectric chiral smectic liquid crystal composition, wherein the ratio (molar basis) of the compounds represented by I), (VII) and (VIII) is 1 to 20%.

[12] Item [1], [2], [3],
[4], [5], [6], [7], [8], [9],
A liquid crystal element comprising the ferroelectric chiral smectic liquid crystal composition according to [10] or [11] sandwiched between a pair of electrode substrates.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION Specific examples of the compound represented by the general formula (I) include those shown below. Hereinafter, in the compounds of (I-1) to (I-30) [Chemical Formula 50 to Chemical Formula 52], R ₁₁ and R ₁₂ are each an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom, an alkoxy group. It represents either a group or an alkoxyalkyl group, and may contain an unsaturated bond in these groups. In the compounds (I-1a) to (I-9as) [Chemical Formula 53 to Chemical Formula 110], all double bonds in the formula are trans bonds. G is

[0024]

[Chemical 43] Or

[Chemical 44] Is. Also, E is

Embedded image Or

[0025]

Embedded image Or

[Chemical 47] Or

Embedded image Or

[Chemical 49] Or a hydrogen atom. Z in the formula is a hydrogen atom or a fluorine atom. In the formula, n is an integer of 0 to 10 and i and k are each independently an integer of 1 to 20.

[0026]

Embedded image

[0027]

[Chemical 51]

[0028]

Embedded image

[0029]

Embedded image

[0030]

[Chemical 54]

[0031]

[Chemical 55]

[0032]

[Chemical 56]

[0033]

[Chemical 57]

[0034]

Embedded image

[0035]

Embedded image

[0036]

Embedded image

[0037]

[Chemical formula 61]

[0038]

Embedded image

[0039]

[Chemical formula 63]

[0040]

[Chemical 64]

[0041]

Embedded image

[0042]

[Chemical formula 66]

[0043]

Embedded image

[0044]

[Chemical 68]

[0045]

[Chemical 69]

[0046]

Embedded image

[0047]

Embedded image

[0048]

Embedded image

[0049]

Embedded image

[0050]

[Chemical 74]

[0051]

[Chemical 75]

[0052]

[Chemical 76]

[0053]

Embedded image

[0054]

Embedded image

[0055]

Embedded image

[0056]

Embedded image

[0057]

[Chemical 81]

[0058]

[Chemical formula 82]

[0059]

[Chemical 83]

[0060]

[Chemical 84]

[0061]

Embedded image

[0062]

[Chemical 86]

[0063]

[Chemical 87]

[0064]

Embedded image

[0065]

[Chemical 89]

[0066]

[Chemical 90]

[0067]

Embedded image

[0068]

Embedded image

[0069]

Embedded image

[0070]

Embedded image

[0071]

Embedded image

[0072]

[Chemical 96]

[0073]

Embedded image

[0074]

Embedded image

[0075]

Embedded image

[0076]

[Chemical 100]

[0077]

[Chemical 101]

[0078]

Embedded image

[0079]

Embedded image

[0080]

[Chemical 104]

[0081]

Embedded image

[0082]

[Chemical formula 106]

[0083]

[Chemical formula 107]

[0084]

[Chemical 108]

[0085]

[Chemical 109]

[0086]

[Chemical 110]

Specific examples of the compound represented by the general formula (II) include those shown below. 4 "-alkyl-4- (6-fluoro-1-heptinyl) -p-
Terphenyl, 4 ″ -alkyloxy-4- (6-fluoro-1-heptinyl) -p-terphenyl, 6-alkyl-2- {4- (6-fluoro-1-heptinyl)-
Phenyl} naphthalene, 6-alkyloxy-2- {4
-(6-fluoro-1-heptinyl) -phenyl} naphthalene, 6- (4-alkylphenyl) -2- (6-fluoro-1-heptynyl) naphthalene,

6- (4-alkyloxyphenyl) -2
-(6-Fluoro-1-heptinyl) naphthalene, 5-
Alkyl- {4- (6-fluoro-1-heptinyl)-
Phenyl} pyridine, 5-alkyloxy- {4- (6
-Fluoro-1-heptinyl) -phenyl} pyridine,
2- (4-alkylphenyl) -5- (6-fluoro-
1-heptynyl) pyridine, 2- (4-alkyloxyphenyl) -5- (6-fluoro-1-heptinyl) pyridine, 2-alkyl-5- {4- (6-fluoro-1)
-Heptinyl) -phenyl} pyridine, 2-alkyloxy-5- {4- (6-fluoro-1-heptynyl)-
Phenyl} pyridine, 5- (4-alkylphenyl)-
2- (6-Fluoro-1-heptinyl) pyridine, 5-
(4-Alkyloxyphenyl) -2- (6-fluoro-1-heptynyl) pyridine, 5-alkyl-2-
{4 '-(6-Fluoro-1-heptinyl) -4-biphenylyl} pyridine, 5-alkyloxy-2-
{4 ′-(6-Fluoro-1-heptinyl) -4-biphenylyl} pyridine, 2- (4′-alkyl-4-biphenylyl) -5- (6-fluoro-1-heptynyl) pyridine, 2- (4 '-Alkyloxy-4-biphenylyl) -5- (6-fluoro-1-heptynyl) pyridine, 5- (4-alkylphenyl) -2- {4- (6-
Fluoro-1-heptynyl) phenyl} pyridine, 5-
(4-Alkyloxyphenyl) -2- {4- (6-fluoro-1-heptinyl) phenyl} pyridine, 2-
(4-Alkylphenyl) -5- {4- (6-fluoro-1-heptinyl) phenyl} pyridine, 2- (4-alkyloxyphenyl) -5- {4- (6-fluoro-
1-heptynyl) phenyl} pyridine, 5-alkyl-
{4- (6-Fluoro-1-heptinyl) -phenyl}
Pyrimidine,

5-alkyloxy- {4- (6-fluoro-1-heptinyl) -phenyl} pyrimidine, 2-
(4-Alkylphenyl) -5- (6-fluoro-1-)
Heptinyl) pyrimidine, 2- (4-alkyloxyphenyl) -5- (6-fluoro-1-heptynyl) pyrimidine, 2-alkyl-5- {4- (6-fluoro-1)
-Heptinyl) -phenyl} pyrimidine, 2-alkyloxy-5- {4- (6-fluoro-1-heptynyl)
-Phenyl} pyrimidine, 5- (4-alkylphenyl) -2- (6-fluoro-1-heptinyl) pyrimidine, 5- (4-alkyloxyphenyl) -2- (6-
Fluoro-1-heptinyl) pyrimidine, 5-alkyl-2- {4 '-(6-fluoro-1-heptinyl)-
4-biphenylyl} pyrimidine, 5-alkyloxy-
2- {4 '-(6-fluoro-1-heptynyl) -4-
Biphenylyl} pyrimidine, 2- (4'-alkyl-4
-Biphenylyl) -5- (6-fluoro-1-heptynyl) pyrimidine, 2- (4'-alkyloxy-4-biphenylyl) -5- (6-fluoro-1-heptynyl)
Pyrimidine, 5- (4-alkylphenyl) -2- {4
-(6-Fluoro-1-heptinyl) phenyl} pyrimidine,

5- (4-alkyloxyphenyl) -2
-{4- (6-Fluoro-1-heptynyl) phenyl}
Pyrimidine, 2- (4-alkylphenyl) -5- {4
-(6-Fluoro-1-heptinyl) phenyl} pyrimidine, 2- (4-alkyloxyphenyl) -5- {4
-(6-Fluoro-1-heptynyl) phenyl} pyrimidine, 5-alkyl- {4- (6-fluoro-1-heptinyl) -phenyl} pyrazine, 5-alkyloxy-
{4- (6-Fluoro-1-heptinyl) -phenyl}
Pyrazine, 2- (4-alkylphenyl) -5- (6-
Fluoro-1-heptynyl) pyrazine, 2- (4-alkyloxyphenyl) -5- (6-fluoro-1-heptynyl) pyrazine, 5-alkyl-2- {4 '-(6-
Fluoro-1-heptynyl) -4-biphenylyl} pyrazine, 5-alkyloxy-2- {4 '-(6-fluoro-1-heptynyl) -4-biphenylyl} pyrazine, 2- (4'-alkyl-4- Biphenylyl) -5-
(6-Fluoro-1-heptinyl) pyrazine, 2-
(4'-alkyloxy-4-biphenylyl) -5-
(6-Fluoro-1-heptinyl) pyrazine, 5- (4
-Alkylphenyl) -2- {4- (6-fluoro-1)
-Heptinyl) phenyl} pyrazine, 5- (4-alkyloxyphenyl) -2- {4- (6-fluoro-1-)
Heptynyl) phenyl} pyrazine, 6- (4-alkylphenyl) -3- {4- (6-fluoro-1-heptynyl) phenyl} pyridazine,

6- (4-alkyloxyphenyl) -3
-{4- (6-Fluoro-1-heptynyl) phenyl}
Pyridazine, 2- (6-alkyl-naphthalen-2-yl) -5- (6-fluoro-1-heptinyl) pyrimidine, 2- (6-alkyloxy-naphthalen-2-yl) -5- (6-fluoro -1-Heptinyl) pyrimidine, 5- (6-alkyl-naphthalen-2-yl) -2
-(6-Fluoro-1-heptinyl) pyrimidine, 5-
(6-alkyloxy-naphthalen-2-yl) -2-
(6-Fluoro-1-heptinyl) pyrimidine, 2-alkyl-5- {6- (6-fluoro-1-heptinyl)
-Naphthalen-2-yl) pyrimidine, 2-alkyloxy-5- {6- (6-fluoro-1-heptinyl)-
Naphthalen-2-yl) pyrimidine, 5-alkyl-2
-{6- (6-Fluoro-1-heptinyl) -naphthalen-1-yl} pyrimidine, 5-alkyloxy-2--
{6- (6-Fluoro-1-heptinyl) -naphthalen-1-yl} pyrimidine, 7-alkyl-3- {4-
(6-Fluoro-1-heptinyl) -phenyl} isoquinoline, 7-alkyloxy-3- {4- (6-fluoro-1-heptinyl) -phenyl} isoquinoline, 3-
(4-Alkyl-phenyl) -7- (6-fluoro-1)
-Heptinyl) isoquinoline, 3- (4-alkyloxy-phenyl) -7- (6-fluoro-1-heptynyl) isoquinoline, 6-alkyl-2- {4- (6-fluoro-1-heptinyl) phenyl} quinoline ,

6-alkyloxy-2- {4- (6-fluoro-1-heptinyl) phenyl} quinoline, 2-
(4-Alkyl-phenyl) -6- (6-fluoro-1)
-Heptinyl) quinoline, 2- (4-alkyloxy-)
Phenyl) -6- (6-fluoro-1-heptinyl) quinoline, 3-alkyl-7- {4- (6-fluoro-1)
-Heptinyl) phenyl} quinoxaline, 3-alkyloxy-7- {4- (6-fluoro-1-heptynyl)
Phenyl} quinoxaline, 2-alkyloxy-6-
{4- (6-fluoro-1-heptynyl) phenyl}
Quinazoline, 4 "-alkyl-4- (6-fluoro-1)
-Heptyl) -p-terphenyl, 4 "-alkyloxy-4- (6-fluoro-1-heptyl) -p-terphenyl, 6-alkyl-2- {4- (6-fluoro-1)
-Heptyl) -phenyl} naphthalene, 6-alkyloxy-2- {4- (6-fluoro-1-heptyl) -phenyl} naphthalene, 6- (4-alkylphenyl)-
2- (6-Fluoro-1-heptyl) naphthalene, 6-
(4-Alkyloxyphenyl) -2- (6-fluoro-1-heptyl) naphthalene, 5-alkyl- {4-
(6-Fluoro-1-heptyl) -phenyl} pyridine, 5-alkyloxy- {4- (6-fluoro-1-)
Heptyl) -phenyl} pyridine, 2- (4-alkylphenyl) -5- (6-fluoro-1-heptyl) pyridine,

2- (4-alkyloxyphenyl) -5
-(6-Fluoro-1-heptyl) pyridine, 2-alkyl-5- {4- (6-fluoro-1-heptyl) -phenyl} pyridine, 2-alkyloxy-5- {4-
(6-Fluoro-1-heptyl) -phenyl} pyridine, 5- (4-alkylphenyl) -2- (6-fluoro-1-heptyl) pyridine, 5- (4-alkyloxyphenyl) -2- (6 -Fluoro-1-heptyl) pyridine, 5-alkyl-2- {4 '-(6-fluoro-
1-heptyl) -4-biphenylyl} pyridine, 5-
Alkyloxy-2- {4 '-(6-fluoro-1-heptyl) -4-biphenylyl} pyridine, 2- (4'-
Alkyl-4-biphenylyl-5- (6-fluoro-
1-heptyl) pyridine, 2- (4'-alkyloxy-4-biphenylyl) -5- (6-fluoro-1-heptyl) pyridine, 5- (4-alkylphenyl) -2-
{4- (6-Fluoro-1-heptyl) phenyl} pyridine, 5- (4-alkyloxyphenyl) -2- {4
-(6-Fluoro-1-heptyl) phenyl} pyridine, 2- (4-alkylphenyl) -5- {4- (6-
Fluoro-1-heptyl) phenyl} pyridine, 2-
(4-alkyloxyphenyl) -5- {4- (6-fluoro-1-heptyl) phenyl} pyridine, 5-alkyl- {4- (6-fluoro-1-heptyl) -phenyl} pyrimidine,

5-alkyloxy- {4- (6-fluoro-1-heptyl) -phenyl} pyrimidine, 2- (4
-Alkylphenyl) -5- (6-fluoro-1-heptyl) pyrimidine, 2- (4-alkyloxyphenyl) -5- (6-fluoro-1-heptyl) pyrimidine, 2-alkyl-5- {4- (6-Fluoro-1-heptyl) -phenyl} pyrimidine, 2-alkyloxy-5- {4- (6-fluoro-1-heptyl) -phenyl} pyrimidine, 5- (4-alkylphenyl) -2-
(6-Fluoro-1-heptyl) pyrimidine, 5- (4
-Alkyloxyphenyl) -2- (6-fluoro-1)
-Heptyl) pyrimidine, 5-alkyl-2- {4'-
(6-Fluoro-1-heptyl) -4-biphenylyl} pyrimidine, 5-alkyloxy-2- {4'-
(6-Fluoro-1-heptyl) -4-biphenylyl}
Pyrimidine, 2- (4'-alkyl-4-biphenylyl) -5- (6-fluoro-1-heptyl) pyrimidine, 2- (4'-alkyloxy-4-biphenylyl)
-5- (6-Fluoro-1-heptyl) pyrimidine, 5
-(4-Alkylphenyl) -2- {4- (6-fluoro-1-heptyl) phenyl} pyrimidine, 5- (4-
Alkyloxyphenyl) -2- {4- (6-fluoro-1-heptyl) phenyl} pyrimidine, 2- (4-alkylphenyl) -5- {4- (6-fluoro-1-heptyl) phenyl} pyrimidine,

2- (4-alkyloxyphenyl) -5
-{4- (6-Fluoro-1-heptyl) phenyl} pyrimidine, 5-alkyl- {4- (6-fluoro-1-)
Heptyl) -phenyl} pyrazine, 5-alkyloxy- {4- (6-fluoro-1-heptyl) -phenyl}
Pyrazine, 2- (4-alkylphenyl) -5- (6-
Fluoro-1-heptyl) pyrazine, 2- (4-alkyloxyphenyl) -5- (6-fluoro-1-heptyl) pyrazine, 5-alkyl-2- {4 '-(6-fluoro-1-heptyl) —4-Biphenylyl} pyrazine, 5-alkyloxy-2- {4 ′-(6-fluoro-1-heptyl) -4-biphenylyl} pyrazine, 2-
(4'-Alkyl-4-biphenylyl) -5- (6-fluoro-1-heptyl) pyrazine, 2- (4'-alkyloxy-4-biphenylyl) -5- (6-fluoro-
1-heptyl) pyrazine, 5- (4-alkylphenyl) -2- {4- (6-fluoro-1-heptyl) phenyl} pyrazine, 5- (4-alkyloxyphenyl)
-2- {4- (6-Fluoro-1-heptyl) phenyl} pyrazine, 6- (4-alkylphenyl) -3-
{4- (6-Fluoro-1-heptyl) phenyl} pyridazine, 6- (4-alkyloxyphenyl) -3-
{4- (6-Fluoro-1-heptyl) phenyl} pyridazine, 2- (6-alkyl-naphthalen-2-yl)
-5- (6-Fluoro-1-heptyl) pyrimidine, 2
-(6-Alkyloxy-naphthalen-2-yl) -5
-(6-Fluoro-1-heptyl) pyrimidine,

5- (6-Alkyl-naphthalen-2-yl) -2- (6-fluoro-1-heptyl) pyrimidine, 5- (6-alkyloxy-naphthalen-2-yl) -2- (6- Fluoro-1-heptyl) pyrimidine, 2-alkyl-5- {6- (6-fluoro-1-heptyl) -naphthalen-2-yl) pyrimidine, 2-alkyloxy-5- {6- (6-fluoro- 1-heptyl) -naphthalen-2-yl) pyrimidine, 5-alkyl-2- {6- (6-fluoro-1-heptyl) -naphthalen-1-yl} pyrimidine, 5-alkyloxy-
2- {6- (6-fluoro-1-heptyl) -naphthalen-1-yl} pyrimidine, 7-alkyl-3- {4-
(6-Fluoro-1-heptyl) -phenyl} isoquinoline, 7-alkyloxy-3- {4- (6-fluoro-1-heptyl) -phenyl} isoquinoline, 3- (4
-Alkyl-phenyl) -7- (6-fluoro-1-heptyl) isoquinoline, 3- (4-alkyloxy-phenyl) -7- (6-fluoro-1-heptyl) isoquinoline, 6-alkyl-2- { 4- (6-Fluoro-1
-Heptyl) phenyl} quinoline, 6-alkyloxy-2- {4- (6-fluoro-1-heptyl) phenyl} quinoline, 2- (4-alkyl-phenyl) -6-
(6-Fluoro-1-heptyl) quinoline, 2- (4-
Alkyloxy-phenyl) -6- (6-fluoro-1)
-Heptyl) quinoline, 3-alkyl-7- {4- (6
-Fluoro-1-heptyl) phenyl} quinoxaline,

3-alkyloxy-7- {4- (6-fluoro-1-heptyl) phenyl} quinoxaline, 2-
Alkyloxy-6- {4- (6-fluoro-1-heptyl) phenyl} quinazoline, 4 ″ -alkyl-4-
(6-Fluoro-1-heptenyl) -p-terphenyl, 4 ″ -alkyloxy-4- (6-fluoro-1-
Heptenyl) -p-terphenyl, 6-alkyl-2-
{4- (6-Fluoro-1-heptenyl) -phenyl}
Naphthalene, 6-alkyloxy-2- {4- (6-fluoro-1-heptenyl) -phenyl} naphthalene, 6
-(4-Alkylphenyl) -2- (6-fluoro-1)
-Heptenyl) naphthalene, 6- (4-alkyloxyphenyl) -2- (6-fluoro-1-heptenyl) naphthalene, 5-alkyl- {4- (6-fluoro-1--
Heptenyl) -phenyl} pyridine, 5-alkyloxy- {4- (6-fluoro-1-heptenyl) -phenyl} pyridine, 2- (4-alkylphenyl) -5-
(6-Fluoro-1-heptenyl) pyridine, 2- (4
-Alkyloxyphenyl) -5- (6-fluoro-1)
-Heptenyl) pyridine, 2-alkyl-5- {4-
(6-fluoro-1-heptenyl) -phenyl} pyridine,

2-alkyloxy-5- {4- (6-fluoro-1-heptenyl) -phenyl} pyridine, 5-
(4-Alkylphenyl) -2- (6-fluoro-1-)
Heptenyl) pyridine, 5- (4-alkyloxyphenyl) -2- (6-fluoro-1-heptenyl) pyridine, 5-alkyl-2- {4 '-(6-fluoro-1-
Heptenyl) -4-biphenylyl} pyridine, 5-alkyloxy-2- {4 '-(6-fluoro-1-heptenyl) -4-biphenylyl} pyridine, 2- (4'-alkyl-4-biphenylyl) -5 -(6-Fluoro-1
-Heptenyl) pyridine, 2- (4'-alkyloxy-4-biphenylyl) -5- (6-fluoro-1-heptenyl) pyridine, 5- (4-alkylphenyl) -2
-{4- (6-Fluoro-1-heptenyl) phenyl}
Pyridine, 5- (4-alkyloxyphenyl) -2-
{4- (6-Fluoro-1-heptenyl) phenyl} pyridine, 2- (4-alkylphenyl) -5- {4-
(6-Fluoro-1-heptenyl) phenyl} pyridine, 2- (4-alkyloxyphenyl) -5- {4-
(6-Fluoro-1-heptenyl) phenyl} pyridine, 5-alkyl- {4- (6-fluoro-1-heptenyl) -phenyl} pyrimidine, 5-alkyloxy-
{4- (6-Fluoro-1-heptenyl) -phenyl}
Pyrimidine, 2- (4-alkylphenyl) -5- (6
-Fluoro-1-heptenyl) pyrimidine,

2- (4-alkyloxyphenyl) -5
-(6-Fluoro-1-heptenyl) pyrimidine, 2-
Alkyl-5- {4- (6-fluoro-1-heptenyl) -phenyl} pyrimidine, 2-alkyloxy-5
-{4- (6-Fluoro-1-heptenyl) -phenyl} pyrimidine, 5- (4-alkylphenyl) -2-
(6-Fluoro-1-heptenyl) pyrimidine, 5-
(4-Alkyloxyphenyl) -2- (6-fluoro-1-heptenyl) pyrimidine, 5-alkyl-2-
{4 '-(6-Fluoro-1-heptenyl) -4-biphenylyl} pyrimidine, 5-alkyloxy-2-
{4 '-(6-Fluoro-1-heptenyl) -4-biphenylyl} pyrimidine, 2- (4'-alkyl-4-biphenylyl) -5- (6-fluoro-1-heptenyl)
Pyrimidine, 2- (4'-alkyloxy-4-biphenylyl) -5- (6-fluoro-1-heptenyl) pyrimidine, 5- (4-alkylphenyl) -2- {4-
(6-Fluoro-1-heptenyl) phenyl} pyrimidine, 5- (4-alkyloxyphenyl) -2- {4-
(6-Fluoro-1-heptenyl) phenyl} pyrimidine, 2- (4-alkylphenyl) -5- {4- (6-
Fluoro-1-heptenyl) phenyl} pyrimidine, 2
-(4-alkyloxyphenyl) -5- {4- (6-
Fluoro-1-heptenyl) phenyl} pyrimidine, 5
-Alkyl- {4- (6-fluoro-1-heptenyl)
-Phenyl} pyrazine,

5-alkyloxy- {4- (6-fluoro-1-heptenyl) -phenyl} pyrazine, 2- (4
-Alkylphenyl) -5- (6-fluoro-1-heptenyl) pyrazine, 2- (4-alkyloxyphenyl) -5- (6-fluoro-1-heptenyl) pyrazine, 5-alkyl-2- {4 ' -(6-Fluoro-1
-Heptenyl) -4-biphenylyl} pyrazine, 5-alkyloxy-2- {4 '-(6-fluoro-1-heptenyl) -4-biphenylyl} pyrazine, 2- (4'-
Alkyl-4-biphenylyl-5- (6-fluoro-
1-heptenyl) pyrazine, 2- (4'-alkyloxy-4-biphenylyl) -5- (6-fluoro-1-heptenyl) pyrazine, 5- (4-alkylphenyl)-
2- {4- (6-fluoro-1-heptenyl) phenyl} pyrazine, 5- (4-alkyloxyphenyl)-
2- {4- (6-fluoro-1-heptenyl) phenyl} pyrazine, 6- (4-alkylphenyl) -3-
{4- (6-Fluoro-1-heptenyl) phenyl} pyridazine, 6- (4-alkyloxyphenyl) -3-
{4- (6-Fluoro-1-heptenyl) phenyl} pyridazine, 2- (6-alkyl-naphthalen-2-yl) -5- (6-fluoro-1-heptenyl) pyrimidine, 2- (6-alkyloxy -Naphthalen-2-yl) -5- (6-fluoro-1-heptenyl) pyrimidine, 5- (6-alkyl-naphthalen-2-yl) -2
-(6-Fluoro-1-heptenyl) pyrimidine,

5- (6-alkyloxy-naphthalene-
2-yl) -2- (6-fluoro-1-heptenyl) pyrimidine, 2-alkyl-5- {6- (6-fluoro-
1-heptenyl) -naphthalen-2-yl) pyrimidine, 2-alkyloxy-5- {6- (6-fluoro-
1-heptenyl) -naphthalen-2-yl) pyrimidine, 5-alkyl-2- {6- (6-fluoro-1-heptenyl) -naphthalen-1-yl} pyrimidine, 5-
Alkyloxy-2- {6- (6-fluoro-1-heptenyl) -naphthalen-1-yl} pyrimidine, 7-alkyl-3- {4- (6-fluoro-1-heptenyl)
-Phenyl} isoquinoline, 7-alkyloxy-3-
{4- (6-Fluoro-1-heptenyl) -phenyl}
Isoquinoline, 3- (4-alkyl-phenyl) -7-
(6-Fluoro-1-heptenyl) isoquinoline, 3-
(4-Alkyloxy-phenyl) -7- (6-fluoro-1-heptenyl) isoquinoline, 6-alkyl-2
-{4- (6-Fluoro-1-heptenyl) phenyl}
Quinoline, 6-alkyloxy-2- {4- (6-fluoro-1-heptenyl) phenyl} quinoline, 2- (4
-Alkyl-phenyl) -6- (6-fluoro-1-heptenyl) quinoline, 2- (4-alkyloxy-phenyl) -6- (6-fluoro-1-heptenyl) quinoline, 3-alkyl-7- { 4- (6-Fluoro-1-heptenyl) phenyl} quinoxaline, 3-alkyloxy-7- {4- (6-fluoro-1-heptenyl) phenyl} quinoxaline, 2-alkyloxy-6- {4-
(6-fluoro-1-heptenyl) phenyl} quinazoline,

And the above-mentioned substituted (6-fluoro-1-heptinyl), (6-fluoro-1-heptyl), (6-
A fluoro-1-heptenyl) group is 4-fluoro-1-pentynyl, 5-fluoro-1-hexynyl,
7-Fluoro-1-octynyl, 8-Fluoro-1-nonyl, 9-Fluoro-1-decyl, 10-Fluoro-1-undecyl, 11-Fluoro-1-dodecyl, 12-Fluoro-1-tridecyl, 13- Fluoro-1-tetradecyl group, 4-fluoro-1-pentyl, 5-fluoro-1-hexyl, 7-fluoro-1-
Octyl, 8-fluoro-1-nonyl, 9-fluoro-
1-decyl, 10-fluoro-1-undecyl, 11-
Fluoro-1-dodecyl, 12-fluoro-1-tridecyl, 13-fluoro-1-tetradecyl group, 4-fluoro-1-pentenyl, 5-fluoro-1-hexenyl, 7-fluoro-1-octenyl, 8-fluoro -1
-Noneyl, 9-fluoro-1-decyl, 10-fluoro-1-undecyl, 11-fluoro-1-dodecyl, 12-fluoro-1-tridecyl, or 13-fluoro-1-tetradecyl group The compound and the phenyl group in the above compound may be substituted with 1 to 3 fluorine atoms.

Further, it is a compound in which the alkyl group and the alkyloxy group of the above compounds are replaced by an alkenyl group and an alkenyloxy group, respectively. Here, alkyl and alkenyl represent an alkyl group having 3 to 20 carbon atoms or an alkoxyalkyl group having 3 to 20 carbon atoms.

The compound represented by the general formula (II) is
It can be synthesized as follows. That is, an alcohol derivative represented by the following general formula (IX)

[Chemical 111] (In the formula, R ₂₁ , A ₂₁ , A ₂₂ , A ₂₃ , X ₂ , Z, m, n,
p and q have the same meanings as shown in the general formula (II). ) Is fluorinated with a fluorinating agent (eg hydrogen fluoride). The alcohol derivative (IX) used as a raw material can be produced, for example, by the following method.

[0105]

[Chemical 112]

Specific examples of the compound represented by the general formula (III) include those shown below. Less than,
In the compounds [Chemical formula 113 to chemical formula 115] represented by (III-1) to (III-28), R ₃₁ and R ₃₂ each have 3 to 15 carbon atoms which may be substituted with a halogen atom.
Is an alkyl group, an alkoxy group or an alkoxyalkyl group.

[0107]

[Chemical 113]

[0108]

[Chemical 114]

[0109]

[Chemical 115]

Specific examples of the compound represented by the general formula (IV) include those shown below. Less than,
In the compounds represented by (IV-1) to (IV-51) [Chemical Formula 116 to Chemical Formula 119], R ₄₁ is an alkyl group having 5 to 15 carbon atoms, an alkoxy group or an alkoxyalkyl group, and R
₄₂ has 1 to 1 carbon atoms which may be substituted with a halogen atom.
0 alkyl group or alkoxy group, or 2 carbon atoms
An alkoxyalkyl group of 10 to R ₄₁ and R ₄₂
The continuous methylene chain of may be substituted with a double bond or a triple bond, r is an integer of 0 to 10, and * represents an asymmetric carbon.

[0111]

[Chemical formula 116]

[0112]

[Chemical 117]

[0113]

[Chemical 118]

[0114]

[Chemical formula 119]

Specific examples of the compound represented by the general formula (V) include those shown below. Below, (V
-1) to (V-24)
In formula 121], R ₅₁ represents an alkyl group having 2 to 20 carbon atoms. n is an integer of 1 to 5.

[0116]

[Chemical 120]

[0117]

[Chemical 121]

Specific examples of the compound represented by the general formula (VI) include those shown below. Less than,
In the compounds (formula 122 to formula 123) represented by (VI-1) to (VI-24), R ₆₁ represents an alkyl group having 1 to 20 carbon atoms. n is an integer of 1 to 5.

[0119]

[Chemical formula 122]

[0120]

[Chemical 123]

Specific examples of the compound represented by the general formula (VII) include those shown below. Less than,
In the compounds of the formulas (VII-1) to (VII-150) [Chemical formulas 124 to 135], R ₇₁ has 1 to 10 carbon atoms
20 alkyl groups are shown. n is an integer of 0-8.

[0122]

[Chemical formula 124]

[0123]

Embedded image

[0124]

[Chemical formula 126]

[0125]

Embedded image

[0126]

[Chemical 128]

[0127]

[Chemical formula 129]

[0128]

Embedded image

[0129]

[Chemical 131]

[0130]

[Chemical 132]

[0131]

Embedded image

[0132]

Embedded image

[0133]

[Chemical 135]

Specific examples of the compound represented by the general formula (VIII) include those shown below. The following chemical formula 136 [(VIII-1) to (VIII-1
6)], R ₈₁ and R ₈₂ each represent an alkyl group having 1 to 18 carbon atoms. n is an integer of 0-5.

[0135]

[Chemical 136]

The above-mentioned optically active compounds are, for example, JP-A-1-104026, JP-A-2-275864 and JP-A-3.
It can be synthesized by the method described in JP-A-264566. The liquid crystal composition of the present invention may be mixed with one or more other optically active compounds in an appropriate ratio for the purpose of adjusting the spontaneous polarization value in the ferroelectric liquid crystal phase and adjusting the helical pitch in the cholesteric phase. it can. The optically active compound does not necessarily have to exhibit a liquid crystal phase itself. Further, one or more other non-chiral compounds may be mixed in an appropriate ratio for the purpose of expanding and maintaining the liquid crystal temperature range.

The optically active compound and the non-chiral compound used in the present invention are not particularly limited, but the compounds as described below can be used as specific examples. Hereinafter, in the compounds [Chemical Formula 137 to Chemical Formula 138] represented by (X-1) to (X-19), R ₁₀ may be substituted with an alkyl group having 5 to 15 carbon atoms and R ₁₁ may be substituted with a halogen atom. It represents an alkyl group or alkoxy group having 1 to 10 carbon atoms, or an alkoxyalkyl group having 2 to 10 carbon atoms which may be substituted with a halogen atom, m represents an integer of 0 to 10, Z represents a hydrogen atom or fluorine. Represents an atom, and * represents an asymmetric carbon.

[0138]

[Chemical 137]

[0139]

[Chemical 138]

Specific examples of other liquid crystal compounds used in the present invention are shown, but the present invention is not limited to these examples.

The liquid crystal element according to the present invention can be used as various types of liquid crystal elements and display devices. Although the structure of the liquid crystal element is not particularly limited, FIG. 1 shows a schematic view of an example of the ferroelectric liquid crystal element. In FIG. 1, 1
Is a polarizing plate, 2 is a glass substrate, 3 is a transparent electrode, 4 is an insulating alignment control film, 5 is a ferroelectric liquid crystal, and 6 is a spacer.

As an example of the liquid crystal element having the structure as shown in FIG. 1, there is a surface-stabilized ferroelectric liquid crystal display device. In this display device, a ferroelectric liquid crystal is horizontally aligned in a cell in which an interval between two glass substrates 2 is extremely thin. The thickness of the ferroelectric liquid crystal layer 5 is determined only by the distance between the two glass substrates 2 and the thickness of the transparent electrode 3 and the insulating alignment film 4 placed on the glass substrates 2 in the direction of the ferroelectric liquid crystal layer 5. Usually 0.5 to 20
μm, preferably 1 to 5 μm.

The transparent electrode 3 is coated on the glass substrate 2 on the liquid crystal layer side, and is usually made of ITO (Indium-Tin Oxide),
In ₂ O _3, SnO ₂ and the like are used. An insulating alignment film is provided on the liquid crystal layer side 5 of the transparent electrode 3.
At this time, if the alignment film has a sufficient insulating property by itself, only the alignment film is necessary, but if necessary, an alignment film and an insulating film may be provided under the alignment film, and both of them may have an insulating alignment property. It may be used as a film.

As the alignment film, known ones such as organic substances, inorganic substances, low molecular weight compounds and high molecular substances can be used.
As the polymer substance, for example, polyimide, polyamide, polyamideimide, polyvinyl alcohol, polystyrene, polyester, polyesterimide and various photoresists can be used as necessary.

When these polymer substances are used as the alignment film, the surface of the alignment film is rubbed in one direction with gauze or acetate flock cloth, if necessary.
By performing a so-called rubbing treatment, the alignment of liquid crystal molecules can be further promoted.

As the insulating film, for example, titanium oxide,
Aluminum oxide, zirconium oxide, silicon oxide, silicon nitride, or the like can be used.

As a method of forming these alignment films and insulating films, an optimum method can be used depending on the materials used, if necessary. For example, in the case of a polymeric substance, the polymeric substance or a precursor thereof can be dissolved in a solvent capable of dissolving these substances and then applied by a method such as a screen printing method, a spinner coating method, or a dipping method. In the case of an inorganic substance, a dipping method, a vapor deposition method, an oblique vapor deposition method or the like can be used.

The thickness of these insulating alignment films is not particularly limited, but is 10Å to 20 μm, preferably 20Å to 1000Å. The two glass substrates 3 on which the insulating alignment film 4 and the transparent electrode 3 are installed are held at a predetermined interval via a spacer 6. As the spacer, beads, fibers or film-like insulating material made of silica, alumina or polymer and having a predetermined diameter or thickness can be used. After sandwiching these spacers 6 between two glass substrates 2 and sealing the periphery with, for example, an epoxy adhesive or the like, a ferroelectric liquid crystal can be enclosed.

Usually, one or two polarizing plates 1 are installed outside the two glass substrates. In the guest-host method in which a dichroic dye is added, one polarizing plate is used, and in the birefringence method, two polarizing plates are used. FIG.
Shows a case where two polarizing plates are used. At this time, the two polarizing plates are in a state where their polarization axes are orthogonal to each other, that is, in a crossed Nicol state. Appropriate lead wires are connected to the transparent electrode 3 and are connected to an external drive circuit.

[0150]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. Example 1 Smectic liquid crystal composition A was prepared by mixing the compounds represented by the general formula (I) shown in Table 1 in the proportions (mol%, the same hereinafter) shown in Table 1.

[0151]

[Table 1] Ferroelectric smectic liquid crystal composition 1 was prepared by mixing the composition with the optically active compound (2-1) represented by the general formula (II) at a ratio shown in Table 2.

[0152]

[Table 2] For comparison, the liquid crystal composition A was mixed with the compound (9) at a ratio shown in Table 3 to prepare a ferroelectric smectic liquid crystal composition 1R.

[0153]

[Table 3] These compositions were coated with a transparent electrode and a polyimide alignment film on a glass substrate, and were sandwiched between two glass substrates with a spacer so as to have a gap of 2 μm. A liquid crystal element was prepared by installing two polarizing plates with the polarization plane rotated by 90 °. At this time, the polarization axis on the light incident side was set so as to match the rubbing direction of the polyimide alignment film. Next, the response time was measured using these liquid crystal elements. Response time is 10V /
The full width at half maximum of the polarization reversal current flowing when a μm rectangular wave was applied was defined. The measured response time is shown in Table 4.

[0154]

[Table 4] When the magnitude of spontaneous polarization of the liquid crystal compositions 1 and 1R at 25 ° C. was measured by the triangular wave method, both compositions were ² nC / cm ² . Although the magnitude of spontaneous polarization is the same, the liquid crystal composition 1 according to the present invention is superior in that the response time is shorter.

Next, the electric field dependence of the response time (τ-V characteristic) was measured using the above ferroelectric liquid crystal element, and the performance as an inverse mode liquid crystal material was evaluated. Here, the response time is the minimum pulse width with which a good switching state can be obtained when a monopolar pulse is applied.

The τ-V characteristic was evaluated as follows. That is, the liquid crystal element has a duty ratio of 1: as shown in FIG.
400 monopolar pulses were applied and switched, and the change in the amount of transmitted light at that time was detected by a photomultiplier tube, converted into current-voltage, and input to an oscilloscope for observation.

The minimum pulse width with which a good switching can be obtained in a certain electric field, that is, the memory property can be maintained is defined as the minimum pulse width with respect to the applied electric field. Here, the memory property cannot be maintained means that the contrast ratio between the two stable states decreases. In this way, the τ-V characteristic was obtained by plotting against the minimum pulse width applied electric field. The minimum value of the applied electric field in the τ-V characteristic is Vmin
(The applied voltage is divided by the cell gap.), And the pulse width at that time was defined as τmin.

25 of Liquid Crystal Composition 1 and Liquid Crystal Composition 1R
FIG. 3 shows a comparison of τ-V characteristics at ° C. As is clear from FIG. 3, the liquid crystal composition 1 according to the present invention has Vmi
n and τmin are small and excellent. In order to compare the temperature dependence of the τ-V characteristic, the τ-V characteristic at 40 ° C was measured, and Vmin at 40 ° C to V at 25 ° C was measured.
The values minus min were compared. The evaluation results are shown in Table 5.

[0159]

[Table 5] As is clear from Table 5, the liquid crystal composition 1 according to the present invention
Is superior in that the temperature dependence of Vmin is smaller.

Example 2 Ferroelectric smectic liquid crystal composition B was prepared by mixing the compounds represented by formulas (I) and (VII) in the proportions shown in Table 6.
Was prepared.

[0161]

[Table 6] A liquid crystal element similar to that described in Example 1 was produced using this liquid crystal composition B, and the response time was measured by the same method as in Example 1. In addition, the liquid crystal composition 2 was prepared by mixing the liquid crystal composition B with the compound (2-1) represented by the general formula (II) at a ratio shown in Table 7.

[0162]

[Table 7] Using this liquid crystal composition 2, a liquid crystal element similar to the liquid crystal composition B was prepared and the response time was measured. The measurement results are shown in Table 8.

[0163]

[Table 8] As is clear from the measured response times shown in Table 8, the liquid crystal composition 2 according to the present invention has a shorter response time and is superior.

Example 3 Smectic liquid crystal composition C was prepared by mixing the compounds represented by the general formulas (II), (III) and (IV) in the proportions shown in Table 9.

[0165]

[Table 9] Ferroelectric smectic liquid crystal composition 3 was prepared by mixing liquid crystal composition C with optically active compound (2-1) represented by general formula (II) at a ratio shown in Table 10.

[0166]

[Table 10] For comparison, the liquid crystal composition C was mixed with the compound (4-1) represented by the general formula (IV) at a ratio shown in Table 11 to prepare a ferroelectric smectic liquid crystal composition 3R.

[0167]

[Table 11] A liquid crystal element similar to that described in Example 1 was produced using these liquid crystal compositions, and the response time was measured by the same method as in Example 1. The measurement results are shown in Table 12.

[0168]

[Table 12] When the magnitudes of the spontaneous polarizations of the liquid crystal compositions 3 and 3R at 25 ° C. were measured by the triangular wave method, both compositions were 3 nC / cm ² . Although the magnitude of spontaneous polarization is the same, the liquid crystal composition 3 according to the present invention is superior in that the response time is shorter.

Next, using the above ferroelectric liquid crystal element, the electric field dependence of the response time (τ-V characteristic) was measured in the same manner as in Example 1. Liquid crystal composition 3 and liquid crystal composition 3R 2
The τ-V characteristics at 5 ° C. are compared and shown in FIG. As is clear from FIG. 4, the liquid crystal composition 3 according to the present invention has a smaller Vmin and τmin and is superior. In order to compare the temperature dependence of τ-V characteristics, τ-V at 40 ° C
The characteristics were measured and the values obtained by subtracting Vmin at 25 ° C from Vmin at 40 ° C were compared. The evaluation results are shown in Table 13.

[0170]

[Table 13] As is clear from Table 13, the liquid crystal composition 3 according to the present invention has a smaller temperature dependency of Vmin and is superior.

Example 4 The compounds represented by the general formulas (I), (IV) and (VI) were mixed in the proportions shown in Table 14 to prepare a ferroelectric chiral smectic liquid crystal composition D.

[0172]

[Table 14] A liquid crystal element similar to that described in Example 1 was produced using this liquid crystal composition D, and the response time was measured by the same method as in Example 1. Further, the liquid crystal composition 4 was prepared by mixing the liquid crystal composition D with the compound (2-2) represented by the general formula (II) in the following ratio.
Was prepared.

[0173]

[Table 15] Using this liquid crystal composition 4, a liquid crystal element similar to the liquid crystal composition D was prepared and the response time was measured. Table 16 shows the measurement results.
Shown in

[0174]

[Table 16] As is clear from the measured response times shown in Table 16, the liquid crystal composition 4 according to the present invention has a shorter response time and is superior.

Example 5 A liquid crystal composition 5 was prepared by mixing the liquid crystal composition D described in Example 4 with the compound (2-3) represented by the general formula (II) in the following ratio.

[0176]

[Table 17] Using this liquid crystal composition 5, a ferroelectric liquid crystal device was produced in the same manner as in Example 1, and the response time was measured. Table 18 shows the measurement results.

[0177]

[Table 18] As is clear from the measured response times shown in Table 18, the liquid crystal composition 5 according to the present invention has a shorter response time and is superior.

Example 6 The liquid crystal composition D described in Example 4 was mixed with the compound (2-4) represented by the general formula (II) in the following proportions to give a liquid crystal composition 6 as shown in Table 19. Prepared.

[0179]

[Table 19] Using this liquid crystal composition 6, a ferroelectric liquid crystal device was produced in the same manner as in Example 1 and the response time was measured. Table 20 shows the measurement results.

[0180]

[Table 20] As is clear from the measured response times shown in Table 20, the liquid crystal composition 6 according to the present invention has a shorter response time and is superior. Next, the τ-V characteristic of the liquid crystal composition 6 was measured by the same method as in Example 1. The τ-V characteristics of liquid crystal composition D and liquid crystal composition 6 at 25 ° C. are compared and shown in FIG. 5. As is clear from FIG. 5, the compound (2-4) represented by the general formula (II) can achieve a high-speed response without significantly increasing Vmin.

In order to compare the temperature dependence of the τ-V characteristic, the τ-V characteristic at 40 ° C. was measured and the value obtained by subtracting Vmin at 25 ° C. from Vmin at 40 ° C. was compared. The evaluation results are shown in Table 21.

[0182]

[Table 21] As is clear from Table 21, the temperature dependence of Vmin can be reduced by mixing the compound (2-4) represented by the general formula (II).

Example 7 The liquid crystal composition D described in Example 4 was mixed with the compound (2-1) represented by the general formula (II) in the following ratio to give a liquid crystal composition 7 as shown in Table 22. Prepared.

[0184]

[Table 22] Using this liquid crystal composition 7, a ferroelectric liquid crystal device was produced in the same manner as in Example 1 and the response time was measured. The measurement results are shown in Table 23.

[0185]

[Table 23] As is clear from the measured response times shown in Table 23, the liquid crystal composition 7 according to the present invention has a shorter response time and is superior. Next, the τ-V characteristic of the liquid crystal composition 7 was measured by the same method as in Example 1. The τ-V characteristics of liquid crystal composition D and liquid crystal composition 7 at 25 ° C. are compared and shown in FIG. 6. As is clear from FIG. 6, the compound (2-1) represented by the general formula (II) can achieve a high-speed response without significantly increasing Vmin.

In order to compare the temperature dependence of the τ-V characteristic, the τ-V characteristic at 40 ° C. was measured, and the value obtained by subtracting Vmin at 25 ° C. from Vmin at 40 ° C. was compared. The evaluation results are shown in Table 24.

[0187]

[Table 24] As is clear from Table 24, by mixing the compound (2-1) represented by the general formula (II), the temperature dependence of Vmin can be reduced.

[0188]

The liquid crystal composition exhibiting the chiral smectic C phase of the present invention is a conventional ferroelectric chiral smectic C phase.
Compared with liquid crystal compounds and compositions exhibiting a phase, it exhibits high-speed response, has small temperature dependence of τ-V characteristics, and can be used for liquid crystal elements such as optical shutters and display elements.

[Brief description of drawings]

FIG. 1 is a schematic view showing an example of a display device using a ferroelectric liquid crystal.

FIG. 2 shows a waveform applied to a liquid crystal cell.

FIG. 3 shows a τ-V characteristic of the first embodiment.

FIG. 4 shows τ-V characteristics of Example 3.

5 shows a τ-V characteristic of Example 6. FIG.

FIG. 6 shows a τ-V characteristic of Example 7.

[Explanation of symbols]

 1. Polarizer 2. Glass substrate 3. Transparent electrode 4. Insulating orientation control film 5. Ferroelectric liquid crystal layer 6. spacer

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location C09K 19/44 C09K 19/44 19/46 19/46 G02F 1/13 500 G02F 1/13 500 / / C07M 7:00 (72) Inventor Yukari Fujimoto 2-10-1, Tsukahara, Takatsuki-shi, Osaka Sumitomo Chemical Co., Ltd. (72) Inventor Tsutomu Matsumoto 2-10-1, Tsukahara, Takatsuki-shi, Osaka Sumitomo Chemical Gaku Kogyo Co., Ltd. (72) Inventor Masayoshi Minai 2-10-1, Tsukahara, Takatsuki City, Osaka Sumitomo Chemical Gaku Kogyo Co., Ltd.

Claims (12)

[Claims] 1. A compound represented by the following general formula (I): (In the formula, R ₁₁ and R _{12 each} represent an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom, an alkoxy group or an alkoxyalkyl group, and an unsaturated bond is contained therein. May be A ₁₁ , A ₁₂ and A ₁₃
Are independent of each other. (In the formula, i represents an integer of 0 to 4, j and k represent integers of 0 to 3), and p and q are each independently selected. 0 or 1, and when A ₁₁ is a condensed ring, the sum of p and q is 0 or 1.
And A ₁₂ and A ₁₃ are monocycles, when A ₁₁ is a monocycle, the sum of p and q is 1 or 2, and when the sum of p and q is 2, A ₁₂ and A _{All 13} are monocyclic.
* Represents an asymmetric carbon, Z represents a hydrogen atom or a fluorine atom, n is an integer of 0 to 10, and r, s, t and u.
Are 0 or 1, respectively. However, when u = 1, it is a trans olefin. ), And at least one compound represented by the general formula (II): (Wherein, R ₂₁ is, .A ₂₁ showing the alkoxyalkyl group, saturated or unsaturated alkyl group or a C3-20 saturated or unsaturated 3 to 20 carbon atoms, A _22, A
₂₃ are respectively When A ₂₁ is a condensed ring, the sum of p and q is 0 or 1, and A ₂₂ and A ₂₃ are monocycles. When A ₂₁ is a monocycle, the sum of p and q is 1 or 2, and when the sum of p and q is 2, both A ₂₂ and A ₂₃ are monocycles. X ₂
Is Or Or [Chemical 7] , Z is a fluorine atom or a hydrogen atom, and n is 1
Is an integer of -10, m, p and q each represent 0 or 1, i represents an integer of 0 to 4, j and k each represent an integer of 0 to 3, and * represents an asymmetric carbon. Show. )
A ferroelectric chiral smectic liquid crystal composition comprising at least one compound represented by the formula (1) as an essential component. 2. At least one compound represented by the general formula (I) according to claim 1 and the general formula (I) according to claim 1.
At least one compound represented by formula (I) and the following general formula (V): (In the formula, R ₅₁ is an alkyl group or an alkoxyl group having 2 to 20 carbon atoms, and X ₅ is —COO— or —CH ₂ O.
-(However, the binding site does not matter), and l and m are 1 or 2, respectively. n is an integer of 0-5. Z represents a hydrogen atom or a fluorine atom. The symbol * indicates an asymmetric carbon) or a compound represented by the general formula (VI): (In the formula, R ₆₁ represents an alkyl group having 1 to 20 carbon atoms,
X ₆ represents —COO— or —CH ₂ O— (however, the binding site does not matter), Y ₆ represents —O— or —COO— (however, the binding site does not matter), and A ₆ is Chemical 10] Is shown, n is an integer of 0-5, and m is 0 or 1. Z represents a hydrogen atom or a fluorine atom. The symbol * indicates an asymmetric carbon) or a compound represented by the general formula (VII): (In the formula, R ₇₁ represents a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, a saturated or unsaturated alkoxyalkyl group having 2 to 20 carbon atoms, and l, m, p and q are 0 or 1 In the formula, n represents an integer of 0 to 8. Y ₇ is Or [Chemical 13] Or Represents either A ₇₁ , A ₇₂ , and A ₇₃ are respectively (Wherein i represents an integer of 0 to 4 and j and k represent integers of 0 to 3), and A ₇₁ is a condensed ring. Then the sum of p and q is 0
Or 1 and A ₇₂ and A ₇₃ are monocycles, when A ₇₁ is a monocycle, the sum of p and q is 1 or 2, and when the sum of p and q is 2, A ₇₂ , A ₇₃ are both monocyclic.
* Indicates that the compound is an asymmetric carbon),
Or general formula (VIII) (In the formula, R ₈₁ and R ₈₂ represent an alkyl group having 1 to 18 carbon atoms, X ₈ represents a single bond or —O—, and m represents 0 or 1
And ring A represents a phenylene group or cyclohexylene group which may be fluorine-substituted, and ring B represents a phenylene group which may be fluorine-substituted. n is an integer of 0-5. The * mark indicates an asymmetric carbon. Provided that at least one compound selected from the compounds represented by the general formulas (V) to (VII) is excluded.
A ferroelectric chiral smectic liquid crystal composition containing at least one kind. 3. The following general formula (III): Where A ₃₁ and A ₃₂ are Selected from a condensed ring or a monocycle represented by,
m and n are each independently 0 or 1, when A ₃₁ or A ₃₂ is a condensed ring, the sum of m and n is 1, and when A ₃₁ or A ₃₂ is a monocycle, the sum of m and n. Is 1 or 2.
R ₃₁ and R ₃₂ represent an alkyl group, an alkoxy group or an alkoxyalkyl group having 3 to 15 carbon atoms which may be substituted with a halogen atom. ) And at least one compound represented by the following general formula (IV) (In the formula, c and d are each independently 1 or 2, the sum of c and d is 3, e is an integer of 0 to 10, and f is 0.
Or 1, g and h are each independently 0 or 1, X ₄ is —COO— or —OCO—,
At least one hydrogen atom of the benzene ring is substituted with a fluorine atom, R ₄₁ is an alkyl group having 5 to 15 carbon atoms,
R ₄₂ represents an alkoxy group or an alkoxyalkyl group.
Is 1 to 10 carbon atoms which may be substituted with a halogen atom.
Represents an alkyl group or an alkoxy group of or an alkoxyalkyl group having 2 to 10 carbon atoms which may be substituted with a halogen atom, and the continuous methylene chain of R ₄₁ and R ₄₂ is substituted with a double bond or a triple bond. Well, *
Represents an asymmetric carbon, and Z represents a hydrogen atom or a fluorine atom. ) A ferroelectric chiral smectic liquid crystal composition comprising at least one compound represented by the formula (1) and at least one compound represented by the general formula (II) according to claim 1 as an essential component. 4. A compound represented by the general formula (I) according to claim 1, wherein at least one kind of compounds having u = 1, and a compound represented by the general formula (II) according to claim 1. At least one and the general formula (IV) according to claim 3.
A ferroelectric chiral smectic liquid crystal composition comprising at least one compound represented by the formula (1) as an essential component. 5. A compound represented by the general formula (I) is A
Any one of ₁₁ , A ₁₂ and A ₁₃ is Is a trans-olefin compound (R ₁₁ , R ₁₂ , n,
p, q, r, s, and t have the same meanings as described above), and the ferroelectric chiral smectic liquid crystal composition according to claim 1, 2 or 4. 6. A compound represented by the general formula (I) is A
Any one of ₁₁ , A ₁₂ and A ₁₃ is a chemical formula 21 And a trans-olefin compound in which r, s, and t are 0 (R ₁₁ , R ₁₂ , n, p, q, r, s, and t have the same meanings as described above). One, two
Alternatively, the ferroelectric chiral smectic liquid crystal composition described in 4 above. 7. The composition ratio (molar basis) of the compound represented by the general formula (I) and the compound represented by the general formula (II) is
The ferroelectric chiral smectic liquid crystal composition according to claim 1, wherein (I) :( II) = (98 to 50) :( 2 to 50). 8. The composition ratio (molar basis) of the compound represented by the general formula (III), the compound represented by the general formula (IV) and the compound represented by the general formula (II) is (III ):
(IV) :( II) = (10-90) :( 87-7):
The ferroelectric chiral smectic liquid crystal composition according to claim 3, which is (3 to 50). 9. A composition ratio (molar basis) of the compound represented by the general formula (I), the compound represented by the general formula (IV) and the compound represented by the general formula (II) is (I ): (IV):
(II) = (87-7) :( 3-50) :( 10-9
0) The ferroelectric chiral smectic liquid crystal composition according to claim 4, 5, or 6. 10. A ferroelectric chiral smectic liquid crystal composition according to claim 1, 3, 4, 5 or 6, and the general formula (V), general formula (VI) or general formula (VII) according to claim 2.
And a ferroelectric chiral smectic liquid crystal composition containing at least one compound selected from the general formula (VIII). 11. The ferroelectric chiral smectic liquid crystal composition according to claim 10, wherein the general formulas (V), (VI),
A ferroelectric chiral smectic liquid crystal composition, wherein the ratio (molar basis) of the compounds represented by (VII) and (VIII) is 1 to 20%. 12. A method according to claim 1, 2, 3, 4, 5, 6, 7,
A liquid crystal device comprising a ferroelectric chiral smectic liquid crystal composition described in 8, 9, 10 or 11 sandwiched between a pair of electrode substrates.