JPH07309799A - 2-fluorocyclopentanone compound, 1,4-dioxa-6-fluorospiro(4,4)nonane compound, liquid crystal composition containing the compounds, liquid crystal element using the composition, displaying method using the composition or element and display device - Google Patents

Abstract

PURPOSE:To provide a new spiro compound exhibiting high response speed in a liquid crystal mixture system, effective for reducing the temperature dependence of the response and increasing the contrast and giving a ferroelectric liquid crystal element having excellent characteristics. CONSTITUTION:This spiro compound is expressed by formula R-A-Y-X [R is H, CN, etc.; A is A1, A1-Z1-A2 (A1 and A2 each is 1,4-phenylene, pyrimidine-2,5- diyl, etc.; Z1 is single bond, COO, etc.), etc.; Y is OCO or OCH2; X is 2- fluorocyclopentanon-2-yl], e.g. 5-decyl-2-[4-{6-(1,4-dioxa-6-fluorospiro[4,4]nonyl) methoxy}phenyl]pyrimidine. The compound can be produced e.g. by reacting a compound of formula X-COOH with a compound of formula R-A-OH in the presence of 1,3-dicyclohexylcarbodiimide.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel 2-fluorocyclopentanone compound, a 1,4-dioxa-6-fluorospiro [4,4] nonane compound, a liquid crystal composition containing the same and a use thereof. More specifically, the present invention relates to a liquid crystal element and a display device, and more specifically, a novel liquid crystal composition having improved response characteristics against an electric field, a liquid crystal display element using the same, a liquid crystal element used in a liquid crystal-optical shutter, and the liquid crystal element. The present invention relates to a display device used for display.

[0002]

2. Description of the Related Art Conventionally, liquid crystals have been applied as electro-optical elements in various fields. Most of the liquid crystal elements currently in practical use are, for example, M. Sch.
adt) and W. Helfri
ch) "Applied Physics Letters"
("Applied Physics Letter
s ") Vol. 18, No. 4 (1971.2.15)
P. 127-128 "Voltage Depend"
ent Optical Activity of a
Twisted Nematic Liquid Cr
TN (Twisted Nem)
atic) type liquid crystal is used.

These are based on the dielectric alignment effect of liquid crystals, and utilize the effect that the average molecular axis direction is directed in a specific direction by an applied electric field due to the dielectric anisotropy of liquid crystal molecules. The optical response speed limit of these devices is said to be milliseconds, which is too slow for many applications.

On the other hand, in the application to a large flat display, the simple matrix drive is the most effective in consideration of price, productivity and the like. The simple matrix method employs an electrode configuration in which a scan electrode group and a signal electrode group are arranged in a matrix, and in order to drive the scan electrode group, an address signal is sequentially and selectively selected and applied to the scan electrode group. Employs a time-division drive system in which a predetermined information signal is synchronized with an address signal and selectively applied in parallel.

However, when the above-mentioned TN type liquid crystal is adopted for the element of such a driving system, the scan electrode is selected and the signal electrode is not selected, or the scan electrode is not selected and the signal electrode is selected. An electric field is applied to a finite amount (so-called "half selection point").

If the difference between the voltage applied to the selection point and the voltage applied to the half selection point is sufficiently large and the voltage threshold value required to align the liquid crystal molecules perpendicularly to the electric field is set to an intermediate voltage value, The display element works normally,
When the number of scanning lines (N) is increased, the time (duty ratio) during which an effective electric field is applied to one selected point while scanning the entire screen (one frame) is reduced by 1 / N. Resulting in.

For this reason, the voltage difference as the effective value applied to the selected point and the non-selected point in the case of repeating scanning is
As the number of scanning lines increases, the number becomes smaller, and as a result, deterioration of image contrast and crosstalk are inevitable drawbacks.

Such a phenomenon is caused by a liquid crystal having no bistability (a stable state in which liquid crystal molecules are aligned horizontally with respect to an electrode surface, and a vertical state only while an electric field is effectively applied). This is an essentially unavoidable problem that occurs when driving (that is, repeatedly scanning) using the temporal accumulation effect.

In order to improve this point, the voltage averaging method, 2
The frequency drive method and the multi-matrix method have already been proposed, but none of them is sufficient, and the increase in the screen size and the density of the display element are stopped because the number of scanning lines cannot be increased sufficiently. This is the current situation.

In order to improve the drawbacks of the conventional liquid crystal device, the use of a liquid crystal device having bistability is explained by Clark and Lagerwell.
11) (Japanese Patent Laid-Open No. 56-10721).
6 gazette, US Pat. No. 4,367,924, etc.). Ferroelectric liquid crystals having a chiral smectic C phase (SmC ^* phase) or H phase (SmH ^* phase) are generally used as the bistable liquid crystal.

This ferroelectric liquid crystal has a bistable state consisting of a first optical stable state and a second optical stable state with respect to an electric field, and therefore the optical modulation used in the above-mentioned TN type liquid crystal. Unlike the element, for example, the liquid crystal is oriented in the first optically stable state with respect to one electric field vector, and the liquid crystal is oriented in the second optically stable state with respect to the other electric field vector. Further, this type of liquid crystal has a property (bistability) of taking one of the two stable states described above in response to an applied electric field and maintaining that state when no electric field is applied.

In addition to the above-mentioned characteristic of having bistability, the ferroelectric liquid crystal has an excellent characteristic of high-speed response. This is because the spontaneous polarization of the ferroelectric liquid crystal and the applied electric field act directly to induce the transition of the alignment state.
It is 3 to 4 orders faster than the response speed due to the effect of the dielectric anisotropy and the electric field.

As described above, the ferroelectric liquid crystal potentially has extremely excellent characteristics, and by utilizing such characteristics, many of the problems of the conventional TN type element described above are solved. A fairly substantial improvement is obtained. In particular, it is expected to be applied to high-speed optical optical shutters, high-density, large-screen displays. For this reason, there has been extensive research on ferroelectric liquid crystal materials, but the ferroelectric liquid crystal materials that have been developed to date are sufficient for use in liquid crystal devices, including low-temperature operating characteristics, high-speed response, and contrast. It is hard to say that it has such characteristics.

Between the response time r, the magnitude Ps of spontaneous polarization and the viscosity η, the following equation [1]

[0015]

[Equation 1] (However, E is the applied electric field.)

Therefore, in order to increase the response speed, there are methods of (a) increasing the magnitude Ps of spontaneous polarization (b) decreasing the viscosity η (c) increasing the applied electric field E.

However, the applied electric field has an upper limit because it is driven by an IC or the like, and it is desirable that the applied electric field be as low as possible. Therefore, it is actually necessary to reduce the viscosity η or increase the value of the spontaneous polarization magnitude Ps.

Generally, in a ferroelectric chiral smectic liquid crystal compound having a large spontaneous polarization, the internal electric field of the cell caused by the spontaneous polarization is also large, and there is a tendency that there are many restrictions on the device structure capable of assuming a bistable state. Further, even if the spontaneous polarization is unnecessarily increased, the viscosity tends to increase accordingly, and as a result, the response speed may not be so fast.

When the operating temperature range of the actual display is, for example, about 5 to 40 ° C., the response speed generally changes about 20 times, which exceeds the limit of adjustment by the drive voltage and frequency. The current situation.

In general, in the case of a liquid crystal element utilizing the birefringence of liquid crystal, the transmittance under the crossed Nicols is expressed by the following formula [2].

[0021]

[Equation 2] In the formula [2], I ₀ is the incident light intensity, I is the transmitted light intensity, θ
_a is the apparent tilt angle defined below, Δn is the refractive index anisotropy, d is the thickness of the liquid crystal layer, and λ is the wavelength of incident light.

The tilt angle θ _a in the above-mentioned non-helical structure
Will appear as the angle in the average molecular axis direction of the twisted liquid crystal molecules in the first and second alignment states.
According to the equation [2], the apparent tilt angle θ _a is 22.5.
The maximum transmittance is obtained at an angle of °, and the tilt angle θ _a in the non-helical structure that realizes the bistability needs to be as close as possible to 22.5 °.

However, when it is applied to the ferroelectric liquid crystal having a non-helical structure exhibiting the bistability announced by Clark and Lagerwall, it has the following problems and causes a decrease in contrast. Has become.

First, the apparent tilt angle θ _a in the ferroelectric liquid crystal having a non-helical structure obtained by orienting with a conventional rubbing-treated polyimide film (the angle formed by the molecular axes of two stable states is 1 / 2) is the tilt angle in the ferroelectric liquid crystal (angle θ that is 1/2 the apex angle of the triangular pyramid shown in FIG. 4 described later)
Since it is smaller than that, the transmittance is low.

Secondly, even if the contrast is high in the static state in which no electric field is applied, when driving display is performed by applying a voltage, liquid crystal molecules fluctuate due to a slight electric field during the non-selection period in matrix driving, so that black is produced. It becomes pale.

As described above, in order to put the ferroelectric liquid crystal device into practical use, a liquid crystal composition having a chiral smectic phase having a high-speed response, a small temperature dependence of the response speed, and a high contrast. Is required.

Further, the spontaneous polarization of the liquid crystal composition, the chiral smectic C pitch, the cholesteric pitch, and the temperature at which the liquid crystal phase is taken for uniform switching of the display, good viewing angle characteristics, low temperature storage stability, and reduction of load on the driving IC. It is necessary to optimize the range, optical anisotropy, tilt angle, dielectric anisotropy and the like.

[0028]

DISCLOSURE OF THE INVENTION An object of the present invention is to make the above-mentioned ferroelectric liquid crystal device practical, to have a high response speed in a liquid crystal mixture system, and to reduce its temperature dependence. Novel compound effective for increasing contrast, liquid crystal composition containing the same, particularly liquid crystal composition showing ferroelectric chiral smectic phase, liquid crystal device using the liquid crystal composition, and display method using the same And to provide a display device.

[0029]

The present invention is a 2-fluorocyclopentanone compound represented by the following general formula (I):

[0030]

Embedded image R-A-Y-X (I)

(Wherein R is a hydrogen atom, halogen, CN
Alternatively, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms is shown. However, in the alkyl group,
CH ₂ — is —O—, —S under the condition that hetero atoms are not adjacent to each other.
-, -CO-, -CH = CH-, -C≡C-, -C ^(*)
It may be replaced by H (CN)-, and the hydrogen atom in the alkyl group may be replaced by a fluorine atom.

A is -A _1- , -A ₁ -Z ₁ -A _2- ,
-A ₁ -Z ₁ -A ₂ -Z ₂ -A _3- , A ₁ , A
₂ , A ₃ are independently unsubstituted or F, Cl, B
1 or 2 selected from r, CH ₃ , CF ₃ or CN
1,4-phenylene having 1 substituent, pyrimidine-
2,5-diyl, pyridine-2,5-diyl, pyrazine-2,5-diyl, pyridazine-3,6-diyl, 1,
4-cyclohexylene, 1,3-dioxane-2,5-
Diyl, 1,3-dithian-2,5-diyl, furan-
2,5-diyl, thiadiazole-2,5-diyl, thiophene-2,5-diyl, thiazole-2,5-diyl, benzothiazole-2,6-diyl, benzothiazole-2,5-diyl, benzoxazole -2,5-
Diyl, benzoxazole-2,6-diyl, indan-2,5-diyl, 2-alkylindan-2,5-
Diyl (the alkyl group is a linear or branched alkyl group having 1 to 18 carbon atoms), indanone-2,6-diyl, 2-alkylindanone-2,6-diyl (wherein the alkyl group is a carbon atom) Number 1-18 is a linear or branched alkyl group), coumarane-2,5-diyl, 2-alkylcoumaran-2,5-diyl (the alkyl group is a straight chain having 1 to 18 carbon atoms). A branched or branched alkyl group),
2,6-naphthylene, quinoxaline-2,6-diyl,
It is selected from quinoline-2,6-diyl, benzofuran-2,5-diyl and benzofuran-2,6-diyl. Z ₁ and Z ₂ are each independently a single bond, —COO—,
_{-OCO -, - CH 2 O -} , - OCH 2 -, - CH 2 C
H ₂ —, —CH═CH—, —C≡C—. Y
Is -OCO -, - OCH ₂ - indicates, X is shows a 2-fluoro cyclopentanone-2-yl. And a 1,4-dioxa-6-fluorospiro [4,4] nonane compound represented by the following general formula (II):

[0033]

R-A-Y-X '(II) (In the formula, R represents a hydrogen atom, halogen, CN, or a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms. shown, however, -CH ₂ in the alkyl group -. is -O under the condition that heteroatoms are not adjacent -, - S -, - CO
-, -CH = CH-, -C≡C-, -C ^(*) H (CN)
It may be replaced with-and a hydrogen atom in the alkyl group may be replaced with a fluorine atom.

A is -A _1- , -A ₁ -Z ₁ -A _2- ,
-A ₁ -Z ₁ -A ₂ -Z ₂ -A _3- , A ₁ , A
₂ , A ₃ are independently unsubstituted or F, Cl, B
1 or 2 selected from r, CH ₃ , CF ₃ or CN
1,4-phenylene having 1 substituent, pyrimidine-
2,5-diyl, pyridine-2,5-diyl, pyrazine-2,5-diyl, pyridazine-3,6-diyl, 1,
4-cyclohexylene, 1,3-dioxane-2,5-
Diyl, 1,3-dithian-2,5-diyl, furan-
2,5-diyl, thiadiazole-2,5-diyl, thiophene-2,5-diyl, thiazole-2,5-diyl, benzothiazole-2,6-diyl, benzothiazole-2,5-diyl, benzoxazole -2,5-
Diyl, benzoxazole-2,6-diyl, indan-2,5-diyl, 2-alkylindan-2,5-
Diyl (the alkyl group is a linear or branched alkyl group having 1 to 18 carbon atoms), indanone-2,6-diyl, 2-alkylindanone-2,6-diyl (wherein the alkyl group is a carbon atom) Number 1-18 is a linear or branched alkyl group), coumarane-2,5-diyl, 2-alkylcoumaran-2,5-diyl (the alkyl group is a straight chain having 1 to 18 carbon atoms). A branched or branched alkyl group),
2,6-naphthylene, quinoxaline-2,6-diyl,
It is selected from quinoline-2,6-diyl, benzofuran-2,5-diyl and benzofuran-2,6-diyl. Z ₁ and Z ₂ are each independently a single bond, —COO—,
_{-OCO -, - CH 2 O -} , - OCH 2 -, - CH 2 C
H ₂ —, —CH═CH—, —C≡C—. Y
Is -OCO -, - OCH ₂ - indicates, X 'represents a 1,4-dioxa-6-fluoro-spiro [4,4] nonane-6-yl. )

A liquid crystal composition containing at least one of these compounds, a liquid crystal element in which the liquid crystal composition is disposed between a pair of electrode substrates, and a display method and a display device using the same are provided. is there.

Whether or not the compound represented by the general formula (I) or (II) is a liquid crystal itself is not particularly limited, and it shows liquid crystallinity as a composition mixed with other components. Among such compounds, the following compounds (Ia) to (Ic) are preferable compounds in view of the temperature range of the liquid crystal phase and the responsiveness, viscosity, orientation when the liquid crystal composition is used as the composition.
(IIa)-(IIc) are mentioned.

(Ia), (IIa) In the general formula (I) or (II), A represents -A _1- , A ₁ is unsubstituted or F, Cl, Br, CH ₃ , CF ₃ or CN.
1,4-phenylene having 1 or 2 substituents selected from 1,4-cyclohexylene, 2,6-naphthylene, quinoxaline-2,6-diyl, quinoline-2,
A compound selected from 6-diyl.

[0038] (Ib), (IIb) in the general formula (I) or (II), A is -A ₁ -Z ₁ -A ₂ - indicates, A _1, at least one of A ₂ is unsubstituted or F ,
1 selected from Cl, Br, CH ₃ , CF ₃ or CN
1,4-phenylene having 1 or 2 substituents, pyrimidine-2,5-diyl, pyridine-2,5-diyl,
A compound selected from 1,4-cyclohexylene.

(Ic), (IIc) In the general formula (I) or (II), A is -A ₁ -Z ₁ -A ₂ -Z _2-.
A ₃ −, at least one of A ₁ , A ₂ and A ₃ is unsubstituted or F, Cl, Br, CH ₃ , CF ₃ or C
1,4-having 1 or 2 substituents selected from N
Phenylene, the rest being pyrimidine-2,5-diyl, pyridine-2,5-diyl, 1,4-cyclohexylene, thiadiazole-2,5-diyl, thiazole-
A compound selected from 2,5-diyl, thiophene-2,5-diyl, indane-2,5-diyl and coumarane-2,5-diyl.

More preferred compounds (Iba)
(Icb) and (IIba) to (IIcb). (Iba), (IIba) General formula (I) or (I
In I), A ₁ represents -A ₁ -Z ₁ -A _2- ,
₁ and A ₂ are both unsubstituted or F, Cl, Br, C
1,4-phenylene having 1 or 2 substituents selected from H ₃ , CF ₃ or CN, Z ₁ is a single bond, —CH ₂ O—, —OCH ₂ —, —CH ₂ CH. _2- ,
A compound wherein -C≡C-.

(Ibb), (IIbb) General formula (I)
Or in (II), A represents -A ₁ -Z ₁ -A _2- , A ₁ is unsubstituted or F, Cl, Br, CH ₃ ,
1,4-phenylene having 1 or 2 substituents selected from CF ₃ or CN, A ₂ is pyrimidine-
2,5-diyl, pyridine-2,5-diyl, pyrazine-2,5-diyl, pyridazine-3,6-diyl, 1,
4-cyclohexylene, thiadiazole-2,5-diyl, thiophene-2,5-diyl, thiazole-2,5
-Diyl, benzothiazole-2,6-diyl, benzoxazole-2,5-diyl, indane-2,5-diyl, coumarane-2,5-diyl, 2,6-naphthylene, quinoxaline-2,6-diyl Quinoline-2,6
A compound selected from diyl, wherein Z ₁ is a single bond.

(Ibc), (IIbc) General formula (I)
Alternatively, in (II), A represents -A ₁ -Z ₁ -A _2- , A ₁ is pyridine-2,5-diyl, A ₂ is 1,4-cyclohexylene, indane-2,5-. A compound selected from diyl, coumarane-2,5-diyl and 2,6-naphthylene, wherein Z ₁ is a single bond.

(Ibd), (IIbd) General formula (I)
Alternatively, in (II), A represents -A ₁ -Z ₁ -A _2- , A ₁ is pyrimidine-2,5-diyl, and A ₃
Is a compound selected from 1,4-cyclohexylene, indane-2,5-diyl, coumarane-2,5-diyl and 2,6-naphthylene, and Z ₁ is a single bond.

(Ica), (IIca) General formula (I)
Or in (II), A is -A ₁ -Z ₁ -A ₂ -Z
_2- A _3- , wherein A ₁ , A ₂ and A _{3 each} are unsubstituted or have 1 or 2 substituents selected from F, Cl, Br, CH ₃ , CF ₃ or CN 1, is 4-phenylene, one of Z _1, Z ₂ is a single bond and the other is a single _{bond, -CH 2 O -, - OCH} 2 -, - CH 2 CH
_A compound which is either _2- or -C≡C-.

(Icb), (IIcb) General formula (I)
Or in (II), A is -A ₁ -Z ₁ -A ₂ -Z
_2- A ₃ —, _{two of} A ₁ , A ₂ and A ₃ are unsubstituted or have 1 or 2 substituents selected from F, Cl, Br, CH ₃ , CF ₃ or CN. 1,4-phenylene having the other one, pyrimidine-2,5-diyl, pyridine-2,5-diyl, 1,4-cyclohexylene, thiadiazole-2,5-diyl, thiazole-
A compound selected from 2,5-diyl, thiophene-2,5-diyl, indane-2,5-diyl and coumarane-2,5-diyl, wherein Z ₁ and Z ₂ are single bonds.

When 1,4-phenylene having 1 or 2 substituents is present in the compound represented by the above general formula (I) or (II), preferred substituents are F, Cl,
Br and CF ₃ , and more preferably F.

R of the compound represented by the general formula (I) or (II) is preferably the following (i) to (xvi).
Chosen from.

[0048]

[Chemical 9]

(Where a is an integer from 1 to 16, d, g,
i is an integer of 0 to 7, b, c, h, j, and k are 1 to 10
, F, w are 0 or 1, and m, n, q, r, s, and t are 0 to 10 integers. However, b + d ≦ 16, e + f + g ≦ 1
6, the condition of h + i ≦ 16 is satisfied. E is CH ₃ or C
Shows the F _3. Y ₁ is a single bond, —O—, —COO—, —O.
CO- indicates, Y ₂ is _{-COO -, - CH 2 O -} , - C
_{H 2 CH 2 O -, -} CH 2 CH 2 CH 2 O -, - CH 2 CH 2
-Indicates. Y ₃ is a single bond, —COO—, —CH ₂ O—,
-OCO -, - OCH ₂ - shows a. It may be optically active. )

More preferably, in the general formula (I) or (II), R is the following (xvii), and A
Represents -A ₁ -Z ₁ -A _2- , and A ₁ is pyrimidine-
2,5-diyl, A ₂ is 1,4-phenylene, Z
₁ is a compound that is a single bond.

[0051]

Embedded image (xvii) n—C _a H _{2a + 1} —Y ₄ — (wherein a represents an integer of 1 to 17 and Y ₄ represents a single bond or —O—).

The present inventors have made general formula (I) or (I
As a result of detailed examination of the compound represented by I), a liquid crystal composition containing the novel compound of the present invention, particularly a ferroelectric chiral smectic liquid crystal composition, and a liquid crystal device using the same have excellent alignment property and high speed. It has been found that various characteristics such as responsiveness, temperature dependence of response speed, and high contrast have been improved, and good display characteristics can be obtained.

Further, a compound having a large spontaneous polarization can be obtained by making X and X ′ an optically active substance, and a liquid crystal composition containing the compound and a liquid crystal device using the same have a further high speed response. It has been found that it exhibits excellent properties.

Further, the compound represented by the general formula (I) or (I
The compound I) has good compatibility with other compounds and is a chiral smectic C pitch, a cholesteric pitch as a liquid crystal mixture, a temperature range for taking a liquid crystal phase, viscosity, optical anisotropy, tilt angle, and dielectric anisotropy. It can also be used for adjustment such as.

Next, an example of a synthetic method applicable to any of the compounds represented by the general formula (I) or (II) will be shown.

[0056]

[Chemical 11]

(However, R, A, X, and X'are as defined above. DCC is 1,3-dicyclohexylcarbodiimide, and Ts is an abbreviation for p-toluenesulfonyl group.)

The optically active 1,4-dioxa-6-fluorospiro [4, which is one of the starting materials for the compounds of the present invention,
4] Nonane-6-carboxylic acid is a racemic 1,4-dioxa-6-fluorospiro [4,4] nonanecarboxylic acid which is reacted with an optically active amine to form a diastereomeric salt, which has a solubility difference in a solvent. It is possible to obtain by dissolving the sparingly soluble salt by filtration followed by hydrolysis. In addition, this optically active 1,4-dioxa-6
By reducing fluoro-spiro [4,4] nonane-6-carboxylic acid, an optically active 1,4-dioxa-6
It is also possible to obtain -fluorospiro [4,4] nonane-6-methanol.

It is also possible to obtain the 2-fluoropentanone compound by removing the acetal of the compound having a 1,4-dioxa-6-fluorospiro [4,4] nonyl group.

Next, the general formula (I) or (II)

[0061]

Embedded image The specific structural formulas of the compounds represented by R—A—Y—X (I) R—A—Y—X ′ (II) are shown below, and the abbreviations used in the present invention are as follows. The group of is shown.

[0062]

[Chemical 13]

[0063]

[Chemical 14]

[0064]

[Chemical 15]

[0065]

[Chemical 16]

[0066]

[Chemical 17]

[0067]

[Chemical 18]

[0068]

[Chemical 19]

[0069]

[Chemical 20]

[0070]

[Chemical 21]

[0071]

[Chemical formula 22]

[0072]

[Chemical formula 23]

[0073]

[Chemical formula 24]

[0074]

[Chemical 25]

[0075]

[Chemical formula 26]

The liquid crystal composition of the present invention can be obtained by mixing at least one compound represented by the general formula (I) or (II) with one or more other liquid crystal compounds in an appropriate ratio. . The number of other liquid crystal compounds used in combination is 1 to 50, preferably 1 to 30, and more preferably 3 to
The range is 30.

The liquid crystal composition according to the present invention is preferably a ferroelectric liquid crystal composition, particularly a ferroelectric chiral smectic liquid crystal composition.

Other liquid crystal compounds used in the present invention are disclosed in JP-A-4-272989 (23) to (39).
Compounds (III) to (XII), preferred compounds (IIIa) to (XIId), and more preferred compounds (IIIaa) to (XIIdb) described on the page are mentioned. In addition, compounds (III) to (VI), preferred compounds (I
IIa) to (VIf), more preferred compounds (IIIa
a) to (VIfa), at least one of R ′ ₁ and R ′ ₂ is also a compound (VII), (VIII), a preferred compound (VIIa) to (VIIIb), a more preferred compound (VIIIba), (VIIIbb). At least one of R ′ ₃ and R ′ ₄ , and compounds (IX) to (XII), and preferred compounds (IXa) to
(XIId), more preferred compounds (IXba), (X
In _{IIdb) R '5, R'} 6 of at least one of _{- (CH 2) E C G} F 2G + 1 (E: 0~10, G:
A compound of 1 to 15 integer) can be used as well. Furthermore, liquid crystal compounds represented by the following general formulas (XIII) to (XVIII) can also be used.

[0079]

[Chemical 27]

[0080] wherein R _'7, R' ₈ represents a linear or branched alkyl group having 1 to 18 hydrogen atoms or carbon atoms, bonded directly and X ^{_'6, X'} ₉ in the alkyl group -CH ₂
-One excluding groups, or two or more -CH that are not adjacent
₂ -group is -O-, -CO-, -OCO-, -COO
-, - CH (CN) - , - C (CN) (CH 3) -,
May be replaced with.

Further, R ′ ₇ and R ′ ₈ are preferably i) below.
~ Viii).

I) a straight-chain alkyl group having 1 to 15 carbon atoms

[0083]

[Chemical 28] p: 0-5, q: 2-11 integer optically active

[0084]

[Chemical 29] r: 0 to 6, s: 0 or 1, t: 1 to 14 integer optically active

[0085]

[Chemical 30] w: 1 to 15 integer Optically active

[0086]

[Chemical 31] A: 0 to 2, B: 1 to 15 integer Optically active

[0087]

[Chemical 32] C: 0 to 2, D: 1 to 15 integer Optically active

Vii)-(CH ₂ ) _E C _G F _{2G + 1} E: 0-10, G: 1-15 integer

[0089] viii) -H N, Q, R , T: 0 or _{1 Y '7, Y' 8} , Y '9:
H or _{F A '4: Ph, Np} X' 6, X '9: a single bond, -COO -, - OCO -, - O- X' 7, X '8: single bond, -COO -, - OCO- , -C
_{H 2 O -, - OCH 2} -

As a preferred compound of (XIII), (X
IIIa).

[0091]

Embedded image R ′ ₇ —X ^′ ₆ — [Py2]-[Ph] -OC
O- [Tn] -R ' ₈ (XIIIa)

Preferred compounds of (XVI) are (XV
Ia) and (XVIb).

[0093]

Embedded image _{R '7 - [Tz1] -} [Ph] -X' 9 -R '8 (XVIa) R' 7 - [PhY '7] - [Tz1] - [PhY' 8] -X '9 - R _'8 (XVIb)

Preferred compounds of (XVII) are (X
VIIa) and (XVIIb).

[0095]

Embedded image _{R '7 - [Boa2] -} [Ph] -O-R' 8 (XVIIa) R '7 - [Boa2] - [Np] -O-R' 8 (XVIIb)

Preferred compounds of (XVIII) include (XVIIIa) to (XVIIIc).

[0097]

Embedded image _{R '7 - [Btb2] -} [Ph] -R' 8 (XVIIIa) R '7 - [Btb2] - [Ph] -O-R' 8 (XVIIIb) R '7 - [Btb2] - [Np] -OR ' ₈ (XVIIIc)

Preferred compounds of (XVIa) and (XVIb) include (XVIaa) to (XVIbc).

[0099]

Embedded image _{R '7 - [Tz1] -} [Ph] -O-R' 8 (XVIaa) R '7 - [Ph] - [Tz1] - [Ph] -R' 8 (XVIba) R '7 - [Ph] - [Tz1] - [Ph] -O-R '8 (XVIbb) R' 7 - [Ph] - [Tz1] - [Ph] -OCO-R '8 (XVIbc)

Ph, Py2, Tn, Tz1, Cy, Bo
The abbreviations a2 and Btb2 are in accordance with the above definitions, and other abbreviations are the following groups.

[0101]

[Chemical 38]

When the compound of the general formula (I) or (II) of the present invention is mixed with one or more kinds of the above-mentioned liquid crystalline compounds or the liquid crystal composition, the liquid crystal composition obtained by mixing is added. The proportion of the compound of the present invention occupying is preferably in the range of 1% by weight to 80% by weight depending on the combination of the compounds used. In order to put a ferroelectric liquid crystal device into practical use, it is indispensable to satisfy many conditions such as liquid crystallinity in a wide temperature range, high speed response, high contrast and uniform switching. However, it is difficult to satisfy all of them with a single compound, and it is common to prepare a liquid crystal composition using various compounds that are excellent in each aspect. In this respect, the proportion of the compound of the present invention in the liquid crystal composition is preferably 1% by weight to 60% by weight, and further considering that the characteristics of the other liquid crystal compounds constituting the composition are taken into consideration, 1% by weight to 40% by weight. It is particularly desirable to set it as%. If it is less than 1% by weight, the effect of the compound of the present invention is too small, and the characteristics may not be utilized.

Further, the compound represented by the general formula (I) or (I
When two or more compounds of I) are used, the proportion of the mixture of two or more compounds of the present invention in the liquid crystal composition obtained by mixing is from 1% by weight to 80% by weight, and as described above, various types can be used. From the viewpoint of producing a liquid crystal composition composed of a compound, it is preferably 1% by weight to 60% by weight, and further considering the characteristics of other liquid crystal compounds constituting the composition, 1% by weight to 4% by weight.
It is particularly desirable that the content be 0% by weight.

Further, the ferroelectric liquid crystal layer in the ferroelectric liquid crystal device of the present invention is prepared by applying the liquid crystal composition containing the compound of the present invention prepared as described above in vacuum to an isotropic liquid temperature. It is preferably obtained by heating, enclosing in an element cell, gradually cooling to form a liquid crystal layer, and returning to normal pressure.

FIG. 1 is a schematic cross-sectional view showing an example of a liquid crystal element having a ferroelectric liquid crystal layer of the present invention for explaining the structure of the ferroelectric liquid crystal element.

Referring to FIG. 1, in the liquid crystal element, a liquid crystal layer 1 exhibiting a chiral smectic phase is arranged between a pair of glass substrates 2 provided with a transparent electrode 3 and an insulating alignment control layer 4, respectively, and the layer is formed. The thickness is set by a spacer 5, and a voltage is applied between a pair of transparent electrodes 3 via a lead wire 6 so that a voltage can be applied from a power supply 7. Also, a pair of substrates 2
Are sandwiched between a pair of crossed Nicol polarizing plates 8, and a light source 9 is arranged outside one of them.

The two glass substrates 2 were each coated with In ₂
A transparent electrode 3 made of a thin film of O ₃ , SnO ₂ or ITO (Indium Tin Oxide) is covered. An insulating alignment control layer 4 for arranging the liquid crystal in the rubbing direction is formed by rubbing a polymer thin film such as polyimide with gauze or acetate flocking cloth or the like.

As the insulating material, for example, silicon nitride, silicon nitride containing hydrogen, silicon carbide, silicon carbide containing hydrogen, silicon oxide,
Boron nitride, hydrogen-containing boron nitride, cerium oxide, aluminum oxide, zirconium oxide, titanium oxide or an inorganic material insulating layer such as magnesium fluoride is formed, on which polyvinyl alcohol, polyimide, polyamide Orient organic insulating materials such as imides, polyester imides, polyparaxylene, polyesters, polycarbonates, polyvinyl acetals, polyvinyl chlorides, polyvinyl acetates, polyamides, polystyrenes, cellulose resins, melamine resins, urea resins, acrylic resins and photoresist resins As the control layer, the insulating orientation control layer 4 may be formed of two layers, or may be an inorganic material insulating orientation control layer or an organic material insulating orientation control layer single layer.

If this insulating orientation control layer is an inorganic type, it can be formed by a vapor deposition method or the like, and if it is an organic type, a solution in which an organic insulating substance is dissolved or its precursor solution (0.1 to 20 in a solvent) is used.
% By weight, preferably 0.2 to 10% by weight) and applied by a spinner coating method, a dip coating method, a screen printing method, a spray coating method, a roll coating method, etc. under predetermined curing conditions (for example, under heating). ) And can be formed by curing.

The layer thickness of the insulating orientation control layer 4 is usually 10Å to
1 μm, preferably 10 Å to 3000 Å, more preferably 10 Å to 1000 Å are suitable.

The two glass substrates 2 are held by the spacer 5 at arbitrary intervals. For example, there is a method in which silica beads and alumina beads having a predetermined diameter are sandwiched between two glass substrates as spacers, and the periphery is sealed with a sealing material, for example, an epoxy adhesive material. Other,
A polymer film or glass fiber may be used as the spacer. Ferroelectric liquid crystal (the liquid crystal composition of the present invention) is enclosed between the two glass substrates.

The ferroelectric liquid crystal layer 1 in which the ferroelectric liquid crystal is enclosed is generally 0.5 to 20 μm, preferably 1 to 5 μm.
m.

The transparent electrode 3 is connected to an external power source 7 by a lead wire. A polarizing plate 8 is attached to the outside of the glass substrate 2. The example of FIG. 1 is a transmissive type, and includes a light source 9.

FIG. 2 is a schematic drawing of an example of a cell for explaining the operation of the ferroelectric liquid crystal element. 21a and 2
1b is In ₂ O ₃ , SnO ₂ or ITO (indium tin oxide; Indium).
A substrate (glass plate) covered with a transparent electrode composed of a thin film such as Tin Oxide), in which liquid crystal of SmC ^* phase or SmH ^* phase in which the liquid crystal molecular layer 22 is oriented perpendicular to the glass surface is enclosed. ing. A thick line 23 represents a liquid crystal molecule, and this liquid crystal molecule 23
Is the dipole moment (P⊥) in the direction orthogonal to the molecule
Has 24. When a voltage of a certain threshold value or more is applied between the electrodes on the substrates 21a and 21b, the helical structure of the liquid crystal molecules 23 is unraveled, and the dipole moment (P⊥) 24 is entirely oriented in the electric field direction. Can be changed. The liquid crystal molecule 23 has an elongated shape and exhibits refractive index anisotropy in the major axis direction and the minor axis direction thereof,
Therefore, it is easily understood that, for example, by disposing crossed Nicols polarizers above and below a glass surface, a liquid crystal optical modulation element whose optical characteristics change depending on the polarity of voltage application is obtained.

The liquid crystal cell preferably used in the optical modulator of the present invention has a sufficiently thin thickness (for example, 1
0 μ or less). As the liquid crystal layer becomes thinner in this way, as shown in FIG. 3, the helical structure of the liquid crystal molecules is unwound even when no electric field is applied, and the dipole moment Pa or Pb thereof is directed upward (34a) or downward (34b). Take either state. When an electric field Ea or Eb having a polarity equal to or greater than a certain threshold is applied to such a cell by the voltage applying means 31a and 31b, the dipole moment corresponds to the electric field vector of the electric field Ea or Eb. The liquid crystal molecules are turned to the upward stable state 34a or the downward stable direction 34b, and accordingly, the liquid crystal molecules move to the first stable state 3
3a or the second stable state 33b.

As described above, there are two advantages of using such a ferroelectric liquid crystal element as an optical modulation element. The first is that the response speed is extremely fast, and the second is that the alignment of the liquid crystal molecules has bistability. The second point will be further explained with reference to FIG. 3, for example.
When a is applied, the liquid crystal molecules are aligned in the first stable state 33a, but this state is stable even when the electric field is cut off. When a reverse electric field Eb is applied, the liquid crystal molecules are oriented in the second stable state 33b to change the orientation of the molecules, but they remain in this state even when the electric field is cut off. Further, as long as the applied electric field Ea or Eb does not exceed a certain threshold value, the previous alignment state is still maintained.

FIG. 5 shows an example of the drive waveform used in the present invention. In FIG. 5A, S _S is a selected scan waveform applied to the selected scan line, S _N is a non-selected scan waveform not selected, and I _S is selection information applied to the selected data line. waveform (black), I _N represents the non-selection information signal applied to the data line which is not selected (white). In the figure the _{(I S -S S) (I} N -S S) is the voltage waveforms applied to pixels on a selected scanning line, the voltage _{(I S} -S S) is applied pixel black take the display state, the pixel voltage (I N _{-S S)} is applied takes the display state of white.

FIG. 5B shows the drive waveform shown in FIG.
7 is a time series waveform when the display shown in FIG. 6 is performed. Figure 5
In the driving example shown in FIG. 3, the minimum application time Δt of the single polarity voltage applied to the pixel on the selected scan line is the writing phase t ₂
And the time of 1 line clear t ₁ phase is 2
It is set to Δt.

The values of the parameters V _S , V _I and Δt of the drive waveform shown in FIG. 5 are determined by the switching characteristics of the liquid crystal material used. Here, the bias ratio V _I / (V _I + V _S ) = 1/3 is fixed.

Although it is possible to increase the width of the appropriate driving voltage by increasing the bias ratio, increasing the bias ratio means increasing the amplitude of the information signal, and the flicker in image quality increases. However, the contrast is lowered, which is not preferable. In our study, the bias ratio is 1/3 ~
About 1/4 was practical.

A liquid crystal display device using the liquid crystal device of the present invention in a display panel section and taking a communication synchronizing means by a data format of image information having scanning line address information and a SYNC signal shown in FIGS. 7 and 8. To realize.

In the figure, the symbols are as follows. 101 ferroelectric liquid crystal display device 102 graphics controller 103 display panel 104 scanning line driving circuit 105 information line driving circuit 106 decoder 107 scanning signal generating circuit 108 shift register 109 line memory 110 information signal generating circuit 111 driving control circuit 112 GCPU 113 host CPU 114 VRAM

The image information is generated by the graphics controller 102 on the main body side and transferred to the display panel 103 according to the signal transfer means shown in FIGS. 7 and 8. The graphics controller 102 is a CP
U (central processing unit, hereinafter abbreviated as GCPU 112) and VRAM (memory for storing image information) 114 are used as cores for managing image information and communication between the host CPU 113 and the liquid crystal display device 101, and controlling the present invention. The method is mainly implemented on the graphics controller 102. A light source is arranged on the back surface of the display panel.

[0124]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 5-decyl-2- [4- {6- (1,4-dioxa-6
-Preparation of fluorospiro [4,4] nonyl) methoxy} phenyl] pyrimidine. (Exemplified Compound No. 159)

<Step 1> p-toluenesulfonic acid 6-
Production of (1,4-dioxa-6-fluorospiro [4,4] nonane) methyl In a 30 ml reaction vessel racemic 1,4-dioxa-6.
1.0 g of -fluorospiro [4,4] nonane-6-methanol and 3 ml of dry pyridine were charged, and 2.2 g of p-toluenesulfonic acid chloride was added dropwise at 5 ° C or lower over 30 minutes. After stirring for 30 minutes, the mixture was further stirred at room temperature for 2 hours. The obtained reaction product was poured into water and the organic layer was extracted with ethyl acetate. This was dried over anhydrous magnesium sulfate and the solvent was distilled off to obtain the desired product. Yield 1.9g.

<Step 2> 5-decyl-2- [4- {6
-(1,4-Dioxa-6-fluorospiro [4,4]
Production of nonyl) methoxy} phenyl] pyrimidine 1.2 g of 5-decyl-2- (4-hydroxyphenyl) pyrimidine and 15 ml of dimethylformamide were placed in a 30 ml reaction vessel, cooled in an ice bath, and 60% sodium hydride 0 0.17 g was added over 15 minutes. After further stirring at room temperature for 1 hour, 1.3 g of 6- (1,4-dioxa-6-fluorospiro [4,4] nonane) methyl p-toluenesulfonate obtained in step 1 was added, and the mixture was heated at 100 ° C. It was stirred for 72 hours. After the reaction was completed, the product was poured into water,
The organic layer was extracted with ethyl acetate. This was dried over anhydrous magnesium sulfate, the solvent was evaporated, and the residue was purified by silica gel column chromatography to obtain the desired product. Yield 1.0
g.

Example 2 Preparation of 5-decyl-2- [4- {2- (2-fluoro-1-pentanone) methoxy} phenyl] pyrimidine (Exemplified Compound No. 87) In Example 1 in a 50 ml reaction vessel. 5-decyl produced
0.3 g of 2- [4- {6- (1,4-dioxa-6-fluorospiro [4,4] nonyl) methoxy} phenyl] pyrimidine, 0.2 g of triphenylcarbenium tetrafluoroborate, and 30 ml of methylene chloride were added. Then, the mixture was stirred under an argon atmosphere at room temperature for 147 hours. Then, 15 ml of a saturated aqueous sodium hydrogencarbonate solution was added and the mixture was stirred for 30 minutes, and then the organic layer was extracted with methylene chloride. This was washed with water, dried over anhydrous sodium sulfate, evaporated to remove the solvent, and purified by silica gel column chromatography. Yield 40
mg. Melting point 57 [deg.] C.

Example 3 Production of Optically Active 5-decyl-2- [4- {6- (1,4-dioxa-6-fluorospiro [4,4] nonyl) methoxy} phenyl] pyrimidine (Exemplified Compound No. 1
17)

<Step 1> Production of optically active 6- (1,4-dioxa-6-fluorospiro [4,4] nonane) methyl p-toluenesulfonate (+)-1,4-in a 30 ml reaction vessel. Dioxa-6-
Fluorospiro [4,4] nonane-6-methanol ([α] _D ²⁰ + 21 ° (cl, methanol)) 2.
Charge 0 g and 6 ml of dry pyridine and p-chloride at 5 ° C or below.
-Toluenesulfonic acid 4.3 g was added dropwise over 30 minutes. After stirring for 30 minutes, the mixture was further stirred at room temperature for 2 hours. The obtained reaction product was poured into water and the organic layer was extracted with ethyl acetate. This was dried over anhydrous magnesium sulfate and the solvent was distilled off to obtain the desired product. Yield 4.1g.

<Step 2> Optically active 5-decyl-2-
Preparation of [4- {6- (1,4-dioxa-6-fluorospiro [4,4] nonyl) methoxy} phenyl] pyrimidine 5-decyl-2- (4-hydroxyphenyl) pyrimidine 2 in a 100 ml reaction vessel. 0.4 g and 30 ml of dimethylformamide were added, the mixture was cooled in an ice bath, and 0.35 g of 60% sodium hydride was added over 15 minutes. After further stirring at room temperature for 1 hour, 2,6 g of 6- (1,4-dioxa-6-fluorospiro [4,4] nonane) methyl optically active p-toluenesulfonate obtained in Step 1 was added, and
The mixture was stirred at 0 ° C for 72 hours. After completion of the reaction, the product was poured into water and the organic layer was extracted with ethyl acetate. This was dried over anhydrous magnesium sulfate, the solvent was distilled off, and the residue was purified by silica gel column chromatography to obtain the desired product. Yield 2.3g. Melting point: 62 ° C.

Example 4 Production of Optically Active 5-decyl-2- [4- {2- (2-fluoro-1-pentanone) methoxy} phenyl} pyrimidine (Exemplified Compound No. 2) Example in a 100 ml reaction vessel Optically active 5-decyl-2- [4- {6- (1,4-dioxa-6 prepared in
0.6 g of -fluorospiro [4,4] nonyl) methoxy} phenyl] pyrimidine, 0.7 g of triphenylcarbenium tetrafluoroborate, and 50 ml of methylene chloride were added, and the mixture was stirred under an argon atmosphere at room temperature for 150 hours.
Then, 25 ml of a saturated sodium hydrogencarbonate aqueous solution was added and the mixture was stirred for 30 minutes, and then the organic layer was extracted with methylene chloride. The obtained organic layer was washed with water, dried over anhydrous sodium sulfate, the solvent was distilled off, and the residue was purified by silica gel column chromatography. Yield 98 mg. Melting point 48 [deg.] C.

Example 5 Production of Optically Active 5-Dodecyl-2- [4- {6- (1,4-dioxa-6-fluorospiro [4,4] nonyl) carbonyloxy} phenyl] pyrimidine (Exemplified Compound No. .153)

In a 20 ml reaction vessel, 5-dodecyl-2
0.34 g of-(4-hydroxyphenyl) pyrimidine,
(+)-1,4-Dioxa-6-fluorospiro [4,
4] Nonane-6-carboxylic acid ([α] _D ²⁰ -25 °
(Cl, methanol)) 0.19 g, 1,3-dicyclohexylcarbodiimide 0.21 g, 4-pyrrolidinopyridine 0.01 g, and methylene chloride 3 ml were added, and the mixture was stirred at room temperature for 2 hours and a half. After completion of the reaction, insoluble materials were removed by filtration, the solvent was distilled off, and the residue was purified by silica gel column chromatography. Further, recrystallization was carried out with a mixed solvent of toluene / methanol to obtain 0.3 g of the desired product. Melting point:
51 ° C.

Example 6 Liquid Crystal Composition A was prepared by mixing the following compounds in the following parts by weight.

[0136]

[Chemical Formula 39]

Further, with respect to this liquid crystal composition A, the following exemplified compounds were mixed in the respective parts by weight shown below to prepare a liquid crystal composition B.

[0138]

[Chemical 40]

Prepare two 0.7 mm thick glass plates,
An ITO film was formed on each glass plate to form a voltage application electrode, and SiO ₂ was further vapor-deposited on this to form an insulating layer. A silane coupling agent [KBM-602 manufactured by Shin-Etsu Chemical Co., Ltd.] 0.2% isopropyl alcohol solution was spun on a glass plate at a rotation speed of 2000 r. p. m spinner applied for 15 seconds and surface-treated. After this, 120 ℃
It was heat-dried for 20 minutes.

Further, a polyimide resin precursor [Toray Industries, Inc. SP-
510] Rotate the 1.5% dimethylacetamide solution at a rotation speed of 2
000r. p. m spinner for 15 seconds. After the film formation, the film was heat-condensed and baked at 300 ° C. for 60 minutes.
At this time, the film thickness of the coating film was about 250Å.

The film after firing was rubbed with an acetate flocked cloth, washed with an isopropyl alcohol solution, sprayed with silica beads having an average particle diameter of 2 μm on one glass plate, and then rubbed. The axes were made parallel to each other, and glass plates were laminated using an adhesive sealant [Rixon Bond (Chisso Corporation)] and dried by heating at 100 ° C. for 60 minutes to prepare a cell.

The liquid crystal composition B mixed in Example 5 was injected into this cell in an isotropic liquid state and gradually cooled from the isotropic phase to 25 ° C. at 20 ° C./h to obtain a ferroelectric liquid crystal element. Created. When the cell thickness of this cell was measured with a Berek phase plate, it was about 2 μm.

Using this ferroelectric liquid crystal element, the optical response (transmission light amount change 0 to 90%) under orthogonal Nicols is detected by applying a voltage of peak-to-peak voltage Vpp = 20V, and the response speed ( Hereinafter, the optical response speed) was measured. The measurement results are shown below.

[0144]

[Table 1] 10 ° C 25 ° C 40 ° C Response speed 398 μsec 212 μsec 118 μsec

Comparative Example 1 A ferroelectric liquid crystal device was prepared in the same manner as in Example 6 except that the liquid crystal composition A mixed in Example 6 was injected into the cell, and the optical response speed was measured. The measurement results are shown below.

[0146]

[Table 2] 10 ° C 25 ° C 40 ° C Response speed 668 μsec 340 μsec 182 μsec

Example 7 A liquid crystal composition C was prepared by mixing the exemplified compounds shown below instead of the exemplified compound used in Example 6 in the respective parts by weight shown below.

[0148]

[Chemical 41]

A ferroelectric liquid crystal device was prepared in the same manner as in Example 6 except that the liquid crystal composition C was injected into the cell.
The optical response speed was measured. The measurement results are shown below.

[0150]

[Table 3] 10 ° C 25 ° C 40 ° C Response speed 416 μsec 220 μsec 118 μsec

Example 8 The following compounds were mixed in the following parts by weight to prepare a liquid crystal composition D.

[0152]

[Chemical 42]

Further, with respect to this liquid crystal composition D, the following exemplary compounds were mixed in the respective parts by weight shown below to prepare a liquid crystal composition E.

[0154]

[Chemical 43]

A ferroelectric liquid crystal device was prepared in the same manner as in Example 6 except that the liquid crystal composition E was injected into the cell.
The optical response speed was measured and the switching state was observed.
The uniform alignment in this liquid crystal element was good, and a monodomain state was obtained. The measurement results are shown below.

[0156]

[Table 4] 10 ° C 25 ° C 40 ° C Response speed 408 μsec 206 μsec 110 μsec

Comparative Example 2 A ferroelectric liquid crystal device was prepared in the same manner as in Example 6 except that the liquid crystal composition D mixed in Example 8 was injected into the cell, and the optical response speed was measured. The measurement results are shown below.

[0158]

[Table 5] 10 ° C 25 ° C 40 ° C Response speed 653 μsec 317 μsec 159 μsec

Example 9 Liquid crystal composition F was prepared by mixing the following compounds in the weight parts shown below instead of the exemplified compounds mixed in Example 8.

[0160]

[Chemical 44]

A ferroelectric liquid crystal device was prepared in the same manner as in Example 6 except that the liquid crystal composition F was injected into the cell.
The optical response speed was measured and the switching state was observed.
The uniform alignment in this liquid crystal element was good, and a monodomain state was obtained. The measurement results are shown below.

[0162]

[Table 6] 10 ° C 25 ° C 40 ° C Response speed 414 μsec 210 μsec 112 μsec

Example 10 Liquid Crystal Composition G was prepared by mixing the following compounds in the following parts by weight.

[0164]

[Chemical formula 45]

Further, with respect to this liquid crystal composition G, the following exemplary compounds were mixed in the respective parts by weight shown below to prepare a liquid crystal composition H.

[0166]

[Chemical formula 46]

A ferroelectric liquid crystal device was prepared in the same manner as in Example 6 except that the liquid crystal composition H was injected into the cell.
The optical response speed was measured and the switching state was observed.
The uniform alignment in this liquid crystal element was good, and a monodomain state was obtained. The measurement results are shown below.

[0168]

[Table 7] 10 ° C 25 ° C 40 ° C Response speed 726 μsec 354 μsec 190 μsec

Comparative Example 3 A ferroelectric liquid crystal device was prepared in the same manner as in Example 6 except that the liquid crystal composition G mixed in Example 10 was injected into the cell, and the optical response speed was measured. The results are shown below.

[0170]

[Table 8] 10 ° C 25 ° C 40 ° C Response speed 784 μsec 373 μsec 197 μsec

Example 11 Liquid crystal composition J was prepared by mixing the following compounds instead of the exemplified compounds mixed in Example 10 in the following parts by weight.
It was created.

[0172]

[Chemical 47]

A ferroelectric liquid crystal device was prepared in the same manner as in Example 6 except that the liquid crystal composition J was injected into the cell.
The optical response speed was measured and the switching state was observed.
The uniform alignment in this liquid crystal element was good, and a monodomain state was obtained. The measurement results are shown below.

[0174]

[Table 9] 10 ° C 25 ° C 40 ° C Response speed 734 μsec 356 μsec 190 μsec

As is clear from Examples 6 to 11, the ferroelectric liquid crystal devices containing the liquid crystal compositions B, C, E, F, H and J according to the present invention have improved operating characteristics at low temperatures, and The temperature dependence of the response speed is also reduced. In particular, the liquid crystal compositions B, C, E and F using the optically active substance of the present invention are also excellent in high speed response.

Example 12 Except that the polyimide resin precursor 1.5% dimethylacetamide solution used in Example 6 was replaced with a 2% aqueous solution of polyvinyl alcohol resin [PUA-117 manufactured by Kuraray Co., Ltd.]. Create a ferroelectric liquid crystal element by the method of
The optical response speed was measured in the same manner as in Example 6. The measurement results are shown below.

[0177]

[Table 10] 10 ° C 25 ° C 40 ° C Response speed 392 μsec 206 μsec 114 μsec

Example 13 A ferroelectric liquid crystal element was prepared and carried out in the same manner as in Example 6 except that the alignment control layer was prepared only with a polyimide resin without using SiO ₂ used in Example 6. The optical response speed was measured in the same manner as in Example 6. The measurement results are shown below.

[0179]

[Table 11] 10 ° C 25 ° C 40 ° C Response speed 380 μsec 200 μsec 110 μsec

As is apparent from Examples 12 and 13, even when the element structure was changed, the element containing the ferroelectric liquid crystal composition according to the present invention had much improved low temperature operating characteristics as in Example 6. Moreover, the temperature dependence of the response speed is reduced.

Example 14 The following compounds were mixed in the following parts by weight to prepare a liquid crystal composition K.

[0182]

[Chemical 48]

Further, with respect to this liquid crystal composition K, the following exemplary compounds were mixed in the respective parts by weight shown below to prepare a liquid crystal composition M.

[0184]

[Chemical 49]

Next, the optical response was observed using a cell prepared by the following procedure from these liquid crystal compositions. Two 0.7 mm-thick glass plates were prepared, an ITO film was formed on each glass plate, a voltage application electrode was prepared, and SiO ₂ was further vapor-deposited on this to form an insulating layer. Silane coupling agent on glass plate [KBM manufactured by Shin-Etsu Chemical Co., Ltd.
-602] A 0.2% isopropyl alcohol solution was rotated at a rotation speed of 2000 r.p. p. m spinner for 15 seconds,
A surface treatment was applied. After that, heat drying treatment was performed at 120 ° C. for 20 minutes.

Further, a polyimide resin precursor [Toray Industries, Inc. SP-
510] Rotate the 1.0% dimethylacetamide solution at a rotation speed of 3
000r. p. m spinner for 15 seconds. After the film formation, the film was heat-condensed and baked at 300 ° C. for 60 minutes.
The film thickness of the coating film at this time was about 120Å.

[0187] The fired coating was rubbed with an acetate flocked cloth, washed with an isopropyl alcohol solution, and silica beads having an average particle size of 1.5 µm were sprinkled on one glass plate. The rubbing axes were made parallel to each other, the glass plates were laminated using an adhesive sealant [Rixon Bond (Chisso Corporation)], and heated and dried at 100 ° C. for 60 minutes to prepare a cell.

The cell thickness of this cell was measured by a Berek phase plate and found to be about 1.5 μm. The liquid crystal composition M was injected into this cell in an isotropic liquid state, and the
A ferroelectric liquid crystal element was prepared by gradually cooling to 25 ° C at a rate of ° C / h.

When the ferroelectric liquid crystal element was used to measure the contrast at the time of driving at 30 ° C. with the driving waveform (1/3 bias ratio) shown in FIG. 5, the result was 14.8.

Comparative Example 4 A ferroelectric liquid crystal device was prepared in the same manner as in Example 14 except that the liquid crystal composition K mixed in Example 14 was injected into the cell, and the same driving waveform was used at 30 ° C. The contrast at the time of driving was measured. As a result, the contrast was 8.1.

Example 15 A liquid crystal composition N was prepared by mixing the exemplified compounds shown below instead of the exemplified compound used in Example 14 in the respective parts by weight shown below.

[0192]

[Chemical 50]

A ferroelectric liquid crystal device was prepared in the same manner as in Example 14 except that this liquid crystal composition N was injected into the cell, and the same driving waveform as in Example 14 was used to drive at 30 ° C. Was measured. As a result, the contrast was 15.3.

Example 16 A liquid crystal composition P was prepared by mixing the following exemplary compounds in the following parts by weight instead of the exemplary compound used in Example 14.

[0195]

[Chemical 51]

A ferroelectric liquid crystal device was prepared in the same manner as in Example 14 except that this liquid crystal composition P was injected into the cell, and the same driving waveform was used to obtain the contrast at the time of driving. It was measured. As a result, the contrast was 18.4.

As is clear from Examples 14 to 16, the ferroelectric liquid crystal device containing the liquid crystal compositions M, N and P according to the present invention has a high contrast during driving.

Example 17 The procedure of Example 14 was repeated except that a 2% aqueous solution of polyvinyl alcohol resin [PUA-117 manufactured by Kuraray Co., Ltd.] was used in place of the 1.0% dimethylacetamide solution of the polyimide resin precursor used in Example 14. A ferroelectric liquid crystal device was produced by the same method as in Example 14, and the contrast at the time of driving at 30 ° C. was measured by the same method as in Example 14. As a result, the contrast was 16.2.

Example 18 Except that the SiO ₂ used in Example 14 was not used and the alignment control layer was formed only with a polyimide resin, Example 1 was carried out at all.
A ferroelectric liquid crystal device was prepared in the same manner as in Example 4, and Example 1
As a result of measuring the contrast at the time of driving at 30 ° C. in the same manner as in 4, the contrast was 14.9.

Example 19 A polyamic acid (LQ1802, manufactured by Hitachi Chemical Co., Ltd.) 1% NMP solution was used in place of the polyimide resin precursor 1.0% dimethylacetamide solution used in Example 14.
A ferroelectric liquid crystal element was prepared in the same manner as in Example 14 except that the composition was baked at 270 ° C. for 1 hour, and the contrast during driving at 30 ° C. was measured in the same manner as in Example 14. As a result, the contrast was 29.5.

As is clear from Examples 17, 18 and 19, even when the element structure was changed, the element containing the ferroelectric liquid crystal composition according to the present invention showed high contrast as in Example 15. There is. Further, as a result of detailed examination even when the drive waveform was changed, it was found that a liquid crystal element containing the ferroelectric liquid crystal composition of the present invention similarly provided higher contrast.

[0202]

INDUSTRIAL APPLICABILITY According to the present invention, a novel compound (2-fluorocyclopentanone compound, 1,4-dioxa-6-fluorospiro [4,4]) having a large ability to impart spontaneous polarization is obtained.
A nonane compound) is obtained. The liquid crystal composition containing the compound of the present invention can be operated by utilizing the ferroelectricity of the liquid crystal composition. Moreover, even if it is a racemate, a composition with less temperature dependence of response speed can be obtained by adding it to the ferroelectric liquid crystal composition.

The ferroelectric liquid crystal device of the present invention that can be used in this manner has high contrast, good switching characteristics, and excellent characteristics such as high-speed response and reduction of temperature dependence of optical response speed. It can be a liquid crystal element.

A display device in which the liquid crystal device of the present invention is used as a display device in combination with a light source, a driving circuit, etc. is a good device.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view of an example of a liquid crystal element using a liquid crystal exhibiting a chiral smectic phase.

FIG. 2 is a perspective view schematically showing an example of an element cell for explaining the operation of a liquid crystal element utilizing the ferroelectricity of liquid crystal.

FIG. 3 is a perspective view schematically showing an example of an element cell for explaining the operation of a liquid crystal element utilizing the ferroelectricity of liquid crystal.

FIG. 4 is an explanatory diagram showing a tilt angle.

FIG. 5 is a waveform diagram of a driving method of a liquid crystal element used in the present invention.

6 is a schematic diagram of a display pattern when actual driving is performed with the time-series driving waveform shown in FIG.

FIG. 7 is a block configuration diagram showing a liquid crystal display device having a liquid crystal element utilizing ferroelectricity and a graphics controller.

FIG. 8 is a timing chart of image information communication between the liquid crystal display device and the graphics controller.

[Explanation of symbols]

1 Liquid Crystal Layer Having Chiral Smectic Phase 2 Glass Substrate 3 Transparent Electrode 4 Insulating Alignment Control Layer 5 Spacer 6 Lead Wire 7 Power Supply 8 Polarizing Plate 9 Light Source I ₀ Incident Light I Transmitted Light 21a Substrate 21b Substrate 22 Liquid Crystal Having Chiral Smectic Phase Layer 23 Liquid crystal molecule 24 Dipole moment (P⊥) 31a Voltage applying means 31b Voltage applying means 33a First stable state 33b Second stable state 34a Upward dipole moment 34b Downward dipole moment Ea Upward electric field Eb Downward Electric field 101 ferroelectric liquid crystal display device 102 graphics controller 103 display panel 104 scanning line driving circuit 105 information line driving circuit 106 decoder 107 scanning signal generating circuit 108 shift register 109 line memory 110 information signal generating circuit 111 Drive control circuit 112 GCPU 113 Host CPU 114 VRAM

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C07C 69/75 D 9546-4H 69/753 69/757 C 9546-4H 69/773 69/92 69 / 94 255/54 255/55 323/16 C07D 213/30 263/56 277/24 277/64 285/12 307/33 307/42 307/79 307/80 309/30 D 317/18 317/30 317 / 34 333/24 333/38 405/12 215 409/12 307 C09K 19/12 9279-4H 19/14 9279-4H 19/16 9279-4H 19/18 9279-4H 19/20 9279-4H 19/30 9279-4H 19/32 9279-4H 19/34 9279-4H 19/54 B 9279-4H // G02F 1/13 500 (72) Inventor Goji Kadono 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Incorporated (72) Inventor Shinichi Nakamura 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (54) [Title of Invention] 2-Fluorocyclope Thanong compounds, 1,4-dioxa-6-fluoro-spiro [4,4] non-emission compound, liquid crystal compositions containing them, a liquid crystal device using the same, a display method using the same, 及 Beauty display device

Claims (28)

[Claims] 1. A 2-fluorocyclopentanone compound represented by the following general formula (I): ## STR00001 ## R--A--Y--X (I) (In the formula, R represents a hydrogen atom, halogen, CN, or a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms. . However, -CH ₂ in the alkyl group - is -O under the condition that heteroatoms are not adjacent -, - S -, - CO
-, -CH = CH-, -C≡C-, -C ^(*) H (CN)
It may be replaced with-and a hydrogen atom in the alkyl group may be replaced with a fluorine atom. A is
_{-A 1 -, - A 1 -Z} 1 -A 2 -, - A 1 -Z 1 -A 2
--Z ₂ --A _3- , A ₁ , A ₂ and A ₃ are each independently unsubstituted or F, Cl, Br, CH ₃ , CF ₃
Or 1,4-phenylene having 1 or 2 substituents selected from CN, pyrimidine-2,5-diyl, pyridine-2,5-diyl, pyrazine-2,5-diyl,
Pyridazine-3,6-diyl, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 1,3-dithian-2,5-diyl, furan-2,5-diyl, thiadiazole-2 , 5-diyl, thiophene-2,5-
Diyl, thiazole-2,5-diyl, benzothiazole-2,6-diyl, benzothiazole-2,5-diyl, benzoxazole-2,5-diyl, benzoxazole-2,6-diyl, indane-2, 5-diyl, 2-alkylindan-2,5-diyl (the alkyl group is a linear or branched alkyl group having 1 to 18 carbon atoms), indanone-2,6-diyl, 2-alkylin Danone-2,6-diyl (the alkyl group is a linear or branched alkyl group having 1 to 18 carbon atoms),
Coumaran-2,5-diyl, 2-alkylcoumaran-
2,5-diyl (the alkyl group is a linear or branched alkyl group having 1 to 18 carbon atoms), 2,6-naphthylene, quinoxaline-2,6-diyl, quinoline-2,
It is selected from 6-diyl, benzofuran-2,5-diyl and benzofuran-2,6-diyl. Z ₁ and Z ₂ are each independently a single bond, —COO—, —OCO—, —C.
_{H 2 O -, - OCH 2} -, - CH 2 CH 2 -, - CH =
CH-, -C≡C-. Y is -OCO-,-
OCH ₂ — and X represents 2-fluorocyclopentanone-2-yl. ) 2. The 2-fluorocyclopentanone compound according to claim 1, wherein the compound represented by the general formula (I) is any of the following (Ia) to (Ic). (Ia) A represents -A _1- , A ₁ is unsubstituted or has 1,4-phenylene having 1 or 2 substituents selected from F, Cl, Br, CH ₃ , CF ₃ or CN. ,
A compound selected from 1,4-cyclohexylene, 2,6-naphthylene, quinoxaline-2,6-diyl and quinoline-2,6-diyl. (Ib) A is -A ₁ -Z ₁ -A ₂ - indicates, A _1, A
_At least one of ₂ is unsubstituted or F, Cl, Br,
1,4-phenylene having 1 or 2 substituents selected from CH ₃ , CF ₃ or CN, pyrimidine-2,
A compound selected from 5-diyl, pyridine-2,5-diyl and 1,4-cyclohexylene. (Ic) A is _{-A 1 -Z 1 -A 2 -Z 2} -A 3 - indicates, A _1, A _2, at least one unsubstituted or F of _{A 3, Cl, Br, CH} 3, CF 1,4-phenylene having 1 or 2 substituents selected from ₃ or CN, the rest being pyrimidine-2,5-diyl, pyridine-2,5-diyl, 1,4-cyclohexylene, Thiadiazole-2,5-diyl, thiazole-2,5-diyl, thiophene-2,5-diyl, indane-2,5-
A compound selected from diyl and coumarane-2,5-diyl. 3. The 2-fluorocyclopentanone compound according to claim 1, wherein the compound represented by the general formula (I) is any of the following (Iba) to (Icb). (Iba) A ₁ represents -A ₁ -Z ₁ -A _2- ,
A ₁ and A ₂ are both unsubstituted or F, Cl, Br, CH
1,4 phenylene having 1 or 2 substituents selected from ₃ , CF ₃ or CN, Z ₁ is a single bond,
_{-CH 2 O -, - OCH 2} -, - CH 2 CH 2 -, - C
A compound that is ≡C-. (Ibb) A represents -A ₁ -Z ₁ -A _2- , A ₁ is unsubstituted or 1 or 2 substituents selected from F, Cl, Br, CH ₃ , CF ₃ or CN. Have 1,4
- phenylene, A ₂ is pyrimidine-2,5-diyl, pyridine-2,5-diyl, pyrazine-2,5-diyl, pyridazine-3,6-diyl, 1,4-cyclohexylene, thiadiazol-2 , 5-diyl, thiophene-2,5-diyl, thiazole-2,5-diyl, benzothiazole-2,6-diyl, benzoxazole-2,5-diyl, indane-2,5-diyl, coumaran-2 , 5-diyl, 2,6-naphthylene, quinoxaline-2,6-diyl, quinoline-2,6-diyl, and Z ₁ is a single bond. (Ibc) A is -A ₁ -Z ₁ -A ₂ - indicates, A ₁ is pyridine-2,5-diyl, A ₂ is 1,4-cyclohexylene, indan-2,5-diyl, coumaran −
Selected from 2,5-diyl and 2,6-naphthylene,
A compound in which Z ₁ is a single bond. (Ibd) A represents -A ₁ -Z ₁ -A _2- , A ₁ is pyrimidine-2,5-diyl, A ₃ is 1,4-cyclohexylene, indane-2,5-diyl, coumaran. A compound selected from 2,2,5-diyl and 2,6-naphthylene, wherein Z ₁ is a single bond. (Ica) A represents -A ₁ -Z ₁ -A ₂ -Z ₂ -A _3- , and A ₁ , A ₂ and A ₃ are both unsubstituted or F and C
1,4-phenylene having 1 or 2 substituents selected from 1, Br, CH ₃ , CF ₃ or CN,
One of Z ₁ and Z ₂ is a single bond, the other is a single bond, -C
_{H 2 O -, - OCH 2} -, - CH 2 CH 2 -, - C≡C
A compound that is any of: (Icb) A is _{-A 1 -Z 1 -A 2 -Z 2} -A 3 - indicates, A _1, two of A _2, A ₃ is unsubstituted or F,
1 selected from Cl, Br, CH ₃ , CF ₃ or CN
1,4-phenylene having 1 or 2 substituents, the remaining one is pyrimidine-2,5-diyl, pyridine-2,5-diyl, 1,4-cyclohexylene, thiadiazole-2,5 -Diyl, thiazole-2,5-diyl, thiophene-2,5-diyl, indane-2,5
-Choose from Diyl and Kumaran-2,5-diyl,
A compound in which Z ₁ and Z ₂ are single bonds. 4. The 2-fluorocyclopenta according to any one of claims 1 to 3, wherein R of the compound represented by the general formula (I) is any of the following (i) to (xvi). Non-compound. [Chemical 2] (In the formula, a is an integer of 1 to 16, d, g, and i are 0 to 7
, B, c, h, j, k are integers from 1 to 10, f,
w is 0 or 1, m, n, q, r, s, and t are integers from 0 to 10. However, b + d ≦ 16, e + f + g ≦ 16, h + i ≦
16 conditions are met. E represents CH ₃ or CF ₃ . Y
₁ represents a single bond, -O-, -COO-, -OCO-,
Y ₂ is _{-COO -, - CH 2 O -} , - CH 2 CH 2 O-,
_{-CH 2 CH 2 CH 2 O -} , - CH 2 CH 2 - shows a. Y ₃
Is a single _{bond, -COO -, - CH 2 O} -, - OCO -, -
OCH ₂ - shows the. It may be optically active. ) 5. The 2-fluorocyclopentanone compound according to any one of claims 1 to 3, wherein in the general formula (I), R is the following (xvii). Embedded image (xvii) n-C _a H _{2a + 1} —Y ₄ — (where a represents an integer of 1 to 17 and Y ₄ represents a single bond or —O—). 6. In the general formula (I), A is -A ₁
-Z ₁ -A _2- , wherein A ₁ is pyrimidine-2,5-diyl, A ₂ is 1,4-phenylene, and Z ₁ is a single bond. Compound. 7. The 2-fluorocyclopentanone compound according to claim 1, wherein in the general formula (I), X is optically active. 8. 1,4-Dioxa-6-fluorospiro [4, which is represented by the following general formula (II):
4] Nonane compound. R-A-Y-X '(II) (In the formula, R represents a hydrogen atom, halogen, CN or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. shown, however, -CH ₂ in the alkyl group -. is -O under the condition that heteroatoms are not adjacent -, - S -, - CO
-, -CH = CH-, -C≡C-, -C ^(*) H (CN)
It may be replaced with-and a hydrogen atom in the alkyl group may be replaced with a fluorine atom. A is
_{-A 1 -, - A 1 -Z} 1 -A 2 -, - A 1 -Z 1 -A 2
--Z ₂ --A _3- , A ₁ , A ₂ and A ₃ are each independently unsubstituted or F, Cl, Br, CH ₃ , CF ₃
Or 1,4-phenylene having 1 or 2 substituents selected from CN, pyrimidine-2,5-diyl, pyridine-2,5-diyl, pyrazine-2,5-diyl,
Pyridazine-3,6-diyl, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 1,3-dithian-2,5-diyl, furan-2,5-diyl, thiadiazole-2 , 5-diyl, thiophene-2,5-
Diyl, thiazole-2,5-diyl, benzothiazole-2,6-diyl, benzothiazole-2,5-diyl, benzoxazole-2,5-diyl, benzoxazole-2,6-diyl, indane-2, 5-diyl, 2-alkylindan-2,5-diyl (the alkyl group is a linear or branched alkyl group having 1 to 18 carbon atoms), indanone-2,6-diyl, 2-alkylin Danone-2,6-diyl (the alkyl group is a linear or branched alkyl group having 1 to 18 carbon atoms),
Coumaran-2,5-diyl, 2-alkylcoumaran-
2,5-diyl (the alkyl group is a linear or branched alkyl group having 1 to 18 carbon atoms), 2,6-naphthylene, quinoxaline-2,6-diyl, quinoline-2,
It is selected from 6-diyl, benzofuran-2,5-diyl and benzofuran-2,6-diyl. Z ₁ and Z ₂ are each independently a single bond, —COO—, —OCO—, —C.
_{H 2 O -, - OCH 2} -, - CH 2 CH 2 -, - CH =
CH-, -C≡C-. Y is -OCO-,-
OCH ₂ — and X ′ represents 1,4-dioxa-6-fluorospiro [4,4] nonan-6-yl. ) 9. The 1,4-dioxa-6-fluorospiro [4,4] according to claim 8, wherein the compound represented by the general formula (II) is any of the following (IIa) to (IIc). Nonane compound. (IIa) A represents -A _1- , A ₁ is unsubstituted or has 1,4-phenylene having 1 or 2 substituents selected from F, Cl, Br, CH ₃ , CF ₃ or CN. , 1,4-cyclohexylene, 2,6-naphthylene,
A compound selected from quinoxaline-2,6-diyl and quinoline-2,6-diyl. (IIb) A represents -A ₁ -Z ₁ -A _2- , A ₁ ,
At least one of A ₂ is unsubstituted or F, Cl, B
1 or 2 selected from r, CH ₃ , CF ₃ or CN
1,4-phenylene having 1 substituent, pyrimidine-
2,5-diyl, pyridine-2,5-diyl, 1,4-
A compound selected from cyclohexylene. (IIc) A is _{-A 1 -Z 1 -A 2 -Z 2} -A 3 - indicates, A _1, A _2, at least one unsubstituted or F of _{A 3, Cl, Br, CH} 3, CF 1,4-phenylene having 1 or 2 substituents selected from ₃ or CN, the rest being pyrimidine-2,5-diyl, pyridine-2,5-diyl, 1,4-cyclohexylene, Thiadiazole-2,5-diyl, thiazole-2,5-diyl, thiophene-2,5-diyl, indane-2,5
-A compound selected from diyl and coumarane-2,5-diyl. 10. The 1,4-dioxa-6-fluorospiro [4,4] according to claim 8, wherein the compound represented by the general formula (II) is any of the following (IIba) to (IIcb). Nonane compound. (IIba) A ₁ represents -A ₁ -Z ₁ -A _2- , and A
₁ and A ₂ are both unsubstituted or F, Cl, Br, C
1,4-phenylene having 1 or 2 substituents selected from H ₃ , CF ₃ or CN, Z ₁ is a single bond, —CH ₂ O—, —OCH ₂ —, —CH ₂ CH. _2- ,
A compound wherein -C≡C-. (IIbb) A represents -A ₁ -Z ₁ -A _2- , and A ₁
Is unsubstituted or has 1 or 2 substituents selected from F, Cl, Br, CH ₃ , CF ₃ or CN 1,
4-phenylene, A ₂ is pyrimidine-2,5-diyl, pyridine-2,5-diyl, pyrazine-2,5-
Diyl, pyridazine-3,6-diyl, 1,4-cyclohexylene, thiadiazole-2,5-diyl, thiophene-2,5-diyl, thiazole-2,5-diyl,
Benzothiazole-2,6-diyl, benzoxazole-2,5-diyl, indane-2,5-diyl, coumaran-2,5-diyl, 2,6-naphthylene, quinoxaline-2,6-diyl, quinoline- A compound selected from 2,6-diyl and Z ₁ is a single bond. (IIbc) A represents -A ₁ -Z ₁ -A _2- , and A ₁
Is pyridine-2,5-diyl, A ₂ is selected from 1,4-cyclohexylene, indane-2,5-diyl, coumarane-2,5-diyl, 2,6-naphthylene, and Z ₁ Is a compound that is a single bond. (IIbd) A represents -A ₁ -Z ₁ -A _2- , and A ₁
Is pyrimidine-2,5-diyl and A ₃ is 1,4-
A compound selected from cyclohexylene, indane-2,5-diyl, coumarane-2,5-diyl and 2,6-naphthylene, wherein Z ₁ is a single bond. (IICA) A is _{-A 1 -Z 1 -A 2 -Z 2} -A 3 -
Where A ₁ , A ₂ and A ₃ are all unsubstituted or F and C
1,4-phenylene having 1 or 2 substituents selected from 1, Br, CH ₃ , CF ₃ or CN,
One of Z ₁ and Z ₂ is a single bond, the other is a single bond, -C
_{H 2 O -, - OCH 2} -, - CH 2 CH 2 -, - C≡C
A compound that is any of: (IIcb) A is _{-A 1 -Z 1 -A 2 -Z 2} -A 3 -
Wherein _{two of} A ₁ , A ₂ and A ₃ are unsubstituted or have 1 or 4 1 or 2 substituents selected from F, Cl, Br, CH ₃ , CF ₃ or CN. Phenylene, the other one is pyrimidine-2,5-diyl, pyridine-2,5-diyl, 1,4-cyclohexylene, thiadiazole-2,5-diyl, thiazole-2,5-
Diyl, thiophene-2,5-diyl, indane-2,
A compound selected from 5-diyl and coumarane-2,5-diyl, wherein Z ₁ and Z ₂ are single bonds. 11. The 1,4-dioxa according to claim 8, wherein R of the compound represented by the general formula (II) is any of the following (i) to (xvi). -6-Fluorospiro [4,4] nonane compound. [Chemical 5] (In the formula, a is an integer of 1 to 16, d, g, and i are 0 to 7
, B, c, h, j, k are integers from 1 to 10, f,
w is 0 or 1, m, n, q, r, s, and t are integers from 0 to 10. However, b + d ≦ 16, e + f + g ≦ 16, h + i ≦
16 conditions are met. E represents CH ₃ or CF ₃ . Y
₁ represents a single bond, -O-, -COO-, -OCO-,
Y ₂ is _{-COO -, - CH 2 O -} , - CH 2 CH 2 O-,
_{-CH 2 CH 2 CH 2 O -} , - CH 2 CH 2 - shows a. Y ₃
Is a single _{bond, -COO -, - CH 2 O} -, - OCO -, -
OCH ₂ - shows the. It may be optically active. ) 12. The 1,4-dioxa-6-fluorospiro [4,4] according to any one of claims 8 to 10, wherein in the general formula (II), R is the following (xvii). Nonane compound. Embedded image (xvii) n—C _a H _{2a + 1} —Y ₄ — (however, a represents an integer of 1 to 17 and Y ₄ represents a single bond or —O—). 13. In the general formula (II), A is −
A ₁ -Z ₁ -A _2- , wherein A ₁ is pyrimidine-2,5
13. A 1,4-dioxa-6-fluorospiro [4,4] nonane compound according to claim 12, wherein -diyl, A ₂ is 1,4-phenylene, and Z ₁ is a single bond. 14. The 1,4-dioxa-6-fluorospiro [4,4] nonane compound according to claim 8, wherein X in the general formula (II) is optically active. 15. A liquid crystal composition comprising at least one compound according to any one of claims 1 to 14. 16. A liquid crystal composition comprising at least one compound which is optically active among the compounds according to any one of claims 1 to 14. 17. The compound according to any one of claims 1 to 14 containing 1 to 80% by weight.
The liquid crystal composition described. 18. A compound containing 1 to 60% by weight of the compound according to any one of claims 1 to 14.
The liquid crystal composition described. 19. The compound according to claim 1, which contains 1 to 40% by weight of the compound.
The liquid crystal composition described. 20. The liquid crystal composition according to claim 15, wherein the liquid crystal composition has a chiral smectic phase. 21. A liquid crystal device comprising the liquid crystal composition according to claim 15 disposed between a pair of electrode substrates. 22. The liquid crystal element according to claim 21, further comprising an alignment control layer provided on the side of the electrode substrate which is in contact with the liquid crystal composition. 23. The liquid crystal device according to claim 22, wherein the alignment control layer is a layer subjected to a rubbing treatment. 24. The liquid crystal element according to any one of claims 21 to 23, wherein the pair of electrode substrates are arranged with a film thickness in which a helix formed by alignment of liquid crystal molecules is released. 25. A display device comprising the liquid crystal element according to claim 21 as a display element. 26. The display device according to claim 24, further comprising a drive circuit for the liquid crystal element. 27. The display device according to claim 25, further comprising a light source. 28. A display method comprising displaying by controlling the liquid crystal composition according to any one of claims 15 to 20.