JP2001335524A - Acetylene compound, liquid crystal composition and liquid crystal element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid crystal composition capable of maintaining a book shelf structure and suppressed a layer structure change after a low temperature hysteresis. SOLUTION: This acetylene compound is expressed by formula (1) (wherein R1 and R2 express each an alkyl, alkenyl, alkoxyalkyl, alkenyloxyalkyl, aralkyl, aryloxyalkyl or cycloalkylalkyl and they may be substituted with a halogen atom; Y1 expresses O or COO; Y2 expresses a single bond, O, COO or C=C; n expresses 1-4 integer; X1 expresses H or a halogen). This liquid crystal composition contains the acetylene compound. This liquid crystal element uses the liquid crystal composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel acetylene compound. More specifically, the present invention relates to a novel acetylene compound useful as a component of a liquid crystal composition used for a liquid crystal display device, a liquid crystal composition containing the compound, and a liquid crystal device using the liquid crystal composition.

[0002]

2. Description of the Related Art Liquid crystal display devices are used as displays for various applications because they are thin and lightweight and have low power consumption. At present, a TN (twisted nematic) type display system is most widely used as a liquid crystal display device. The TN type display system is inferior to the light emitting type devices (cathode tube, electroluminescence, plasma display, etc.) in response time. STN (super twisted nematic) type display elements having a twist angle of 180 to 270 ° have been developed, but the response time is still inferior. Although various improvements have been made in this way, a TN type display element having a short response time has not been realized.

However, in a new display system using a ferroelectric liquid crystal, which has been actively studied in recent years, there is a possibility that the response time can be remarkably improved [NAClark].
Applied Phys.lett., 36, 899 (1980)]. This method is
This is a method utilizing a chiral smectic phase such as a chiral smectic C phase exhibiting ferroelectricity. It is known that not only the chiral smectic C phase but also the chiral smectic F, G, H and I phases are ferroelectric liquid crystal phases exhibiting ferroelectricity. These smectic liquid crystal phases belong to a tilt-type chiral smectic phase, but practically, use of a chiral smectic C phase, which has low viscosity and is expected to have high-speed response, is being studied. . Recently, a display system using a chiral smectic CA phase (antiferroelectric phase), which is a higher order phase of the chiral smectic C phase, has been actively studied in recent years [L. Chandani et al., Jpn. J.App.
Phys., 27.L719 (1988)].

Various liquid crystal compounds exhibiting the tilt-type smectic phase have been studied so far, and a large number of compounds have already been searched for and manufactured. However,
Numerous characteristics (high-speed response, alignment, high contrast ratio, threshold characteristics, memory stability, temperature dependence of these characteristics, etc.) required for application to the ferroelectric liquid crystal display device actually used At present, a single compound cannot be used to optimize the liquid crystal composition, and a ferroelectric liquid crystal composition obtained by mixing several liquid crystal compounds is used.

The tilt-type chiral smectic composition includes not only a liquid crystal composition comprising only a compound exhibiting a tilt-type chiral smectic liquid crystal phase, but also a compound or a composition exhibiting a non-chiral tilt-type smectic phase. One or more compounds exhibiting a tilt-type chiral smectic phase can be mixed with the mixture to obtain a tilt-type chiral smectic liquid crystal composition as a whole. Furthermore, a compound or composition exhibiting a tilt-based smectic phase is used as a basic substance, and is optically active but does not exhibit a tilt-based chiral smectic liquid crystal phase.
There have been reports that a kind or a plurality of compounds are mixed to form a tilt-type chiral smectic liquid crystal composition as a whole [Mol. Cryst. Liq. Cryst., 89, 327 (1982)]. In summary, regardless of whether it shows a tilt-based chiral smectic liquid crystal phase, by mixing one or more optically active compounds and a compound that shows a non-chiral tilt-based smectic liquid crystal phase, It turns out that a tilt type smectic liquid crystal composition can be constituted.

As described above, various compounds can be used as constituents of the liquid crystal composition, but practically, they exhibit a tilt-based smectic phase or a chiral smectic phase in a wide temperature range including room temperature. Liquid crystal compounds or mixtures are desirable. As the components of these liquid crystal compositions, phenylbenzoate-based liquid crystal compounds, biphenyl-based liquid crystal compounds, phenylpyrimidine-based liquid crystal compounds, and ester-based liquid crystal compounds are known. However, the liquid crystal compositions containing these compounds as constituents are still insufficient in the layer structure (ideally a bookshelf structure) in the smectic phase, viscosity and its temperature dependence, threshold characteristics, phase solubility and the like. It is hard to say that it has characteristics.

For example, a tilt-type smectic liquid crystal is
On the transition from the non-tilt smectic liquid crystal phase to the tilt smectic liquid crystal phase, volume shrinkage occurs,
There is a disadvantage that the layer structure is in a chevron state. Tilt-based smectic liquid crystal material with chevron structure has tilt angle (θ) and memory angle (θm) due to its layer structure.
Are not equal, which causes a problem that "leakage" of light transmittance occurs at the time of actual driving (Preliminary proceedings of the lecture meeting of the Liquid Crystal Society of Japan, 1999, p. 418, 2D12). For this reason,
A liquid crystal composition having a bookshelf structure in which θ-θm is reduced is desired. Techniques such as the use of a naphthalene-based liquid crystal material for the purpose of forming a bookshelf (JP-A-6-122875) have been disclosed, but the temperature dependence of the layer structure (particularly, the layer structure after a low-temperature history) has been disclosed. Changes) remain. In addition, smectic liquid crystals generally have a large temperature dependence of response characteristics, and therefore have a problem in that response characteristics in a low-temperature region are deteriorated. Thus, at present, as a smectic liquid crystal material, a bookshelf structure (lower (θ−θm)), lower viscosity (higher speed response, lower threshold voltage), and a reduction in their temperature dependence are desired. ing.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a smectic liquid crystal device for practical use, when blended in a smectic liquid crystal composition, various characteristics such as a threshold characteristic, a layer structure, an orientation and a contrast ratio. And a compound suitable for improving the temperature dependence thereof, a liquid crystal composition containing the compound, and a liquid crystal element using the composition.

[0009]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found a certain acetylene compound, and have reached the present invention. That is,
The present invention relates to an acetylene compound represented by the general formula (1) (Formula 3). Further, the present invention relates to a liquid crystal composition containing at least one acetylene compound represented by the general formula (1), and a liquid crystal element using the composition.

[0010]

Embedded image (Wherein, R ₁ and R _{2 each} represent a linear or branched alkyl group having 3 to 24 carbon atoms which may be substituted with a halogen atom, or 3 to 4 carbon atoms which may be substituted with a halogen atom.
24 straight-chain or branched-chain alkenyl groups, a straight-chain or branched-chain alkoxyalkyl group optionally having 3 to 24 carbon atoms, which may be substituted with a halogen atom, and 3 to 24 carbon atoms optionally substituted with a halogen atom. A linear or branched alkenyloxyalkyl group, an aralkyl group having 7 to 15 carbon atoms which may be substituted with a halogen atom, an aryloxyalkyl group having 7 to 15 carbon atoms which may be substituted with a halogen atom, Or a cycloalkylalkyl group having 4 to 15 carbon atoms which may be substituted with a halogen atom, Y ₁ represents a —O— group or a —COO— group, Y ₂ represents a single bond, a —O— group, Represents a —COO— group or a —C≡C— group, n represents an integer of 1 to 4, and X ₁ represents a hydrogen atom or a halogen atom.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The acetylene compound represented by the general formula (1) of the present invention has the following two structures (Formula 4) depending on the type of Y ₁ .

[0012]

Embedded image

In the acetylene compound represented by the general formula (1) of the present invention, R ₁ and R _{2 each} represent a linear or branched alkyl group having 3 to 24 carbon atoms which may be substituted with a halogen atom; A straight-chain or branched-chain alkenyl group having 3 to 24 carbon atoms which may be substituted by a halogen atom, a straight-chain or branched-chain alkoxyalkyl group having 3 to 24 carbon atoms which may be substituted by a halogen atom, halogen A linear or branched alkenyloxyalkyl group having 3 to 24 carbon atoms which may be substituted with an atom, an aralkyl group having 7 to 15 carbon atoms which may be substituted with a halogen atom, Represents an aryloxyalkyl group having 7 to 15 carbon atoms, or a cycloalkylalkyl having 4 to 15 carbon atoms which may be substituted with a halogen atom.

R ₁ and R ₂ are preferably a straight-chain or branched-chain alkyl group having 3 to 24 carbon atoms which may be substituted with a halogen atom, or 3 to 4 carbon atoms which may be substituted with a halogen atom. 24 linear or branched alkenyl groups, 7 to 15 carbon atoms which may be substituted with a halogen atom;
Represents an aralkyl group, an aryloxyalkyl group having 7 to 15 carbon atoms which may be substituted with a halogen atom, and a cycloalkylalkyl group which may be substituted with a halogen atom, more preferably 3 to 24 carbon atoms. Represents a linear or branched alkyl group, an aralkyl group having 7 to 15 carbon atoms, or an aryloxyalkyl group having 7 to 15 carbon atoms.

Specific examples of the groups represented by R ₁ and R ₂ include, for example, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group , N-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n
Heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, n-heneicosyl group, n-docosyl group, n-tricosyl group, n-tetracosyl group, 1
-Methylethyl group, 1,1-dimethylethyl group, 1-methylpropyl group, 1-ethylpropyl group, 1-n-propylpropyl group, 1-methylbutyl group, 1-ethylbutyl group, 1-n-propylbutyl group A 1-n-butylbutyl group, a 1-methylpentyl group, a 1-ethylpentyl group,
1-n-propylpentyl group, 1-n-butylpentyl group, 1-n-pentylpentyl group, 1-methylhexyl group, 1-ethylhexyl group, 1-n-propylhexyl group, 1-n-butylhexyl group , 1-n-pentylhexyl group, 1-n-hexylhexyl group, 1-methylheptyl group, 1-ethylheptyl group, 1-n-propylheptyl group, 1-n-butylheptyl group, 1-n-pentyl Heptyl group, 1-n-heptylheptyl group, 1-methyloctyl group, 1-ethyloctyl group, 1-n-propyloctyl group, 1-n-butyloctyl group, 1-n-pentyloctyl group, 1-n -Hexyloctyl group, 1-n
-Heptyloctyl group, 1-n-octyloctyl group,
1-methylnonyl group, 1-ethylnonyl group, 1-n-propylnonyl group, 1-n-butylnonyl group, 1-n-pentylnonyl group, 1-n-hexylnonyl group, 1-n-
Heptylnonyl group, 1-n-octylnonyl group, 1-n
-Nonylnonyl group, 1-methyldecyl group,

2-methylpropyl, 2-methylbutyl, 2-ethylbutyl, 2-methylpentyl, 2-
Ethylpentyl group, 2-n-propylpentyl group, 2-
Methylhexyl group, 2-ethylhexyl group, 2-n-propylhexyl group, 2-n-butylhexyl group, 2-methylheptyl group, 2-ethylheptyl group, 2-n-propylheptyl group, 2-n-butyl Heptyl group, 2-n-
Pentylheptyl group, 2-methyloctyl group, 2-ethyloctyl group, 2-n-propyloctyl group, 2-n-
Butyloctyl group, 2-n-pentyloctyl group, 2-
n-hexyloctyl group, 2-methylnonyl group, 2-ethylnonyl group, 2-n-propylnonyl group, 2-n-butylnonyl group, 2-n-pentylnonyl group, 2-n-hexylnonyl group, 2-n -Heptylnonyl group, 2-methyldecyl group, 2,3-dimethylbutyl group, 2,3,3-
Trimethylbutyl group, 3-methylbutyl group, 3-methylpentyl group, 3-ethylpentyl group, 4-methylpentyl group, 4-ethylhexyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 2, 4,4-trimethylpentyl group, 2,3,3,4-tetramethylpentyl group, 3-methylhexyl group, 2,5-dimethylhexyl group, 3-ethylhexyl group, 3,5,5, -trimethylhexyl group An alkyl group such as a 4-methylhexyl group, a 6-methylheptyl group, a 3,7-dimethyloctyl group, a 6-methyloctyl group,

2-fluoro-n-propyl group, 3-fluoro-n-propyl group, 1,3-difluoro-n-propyl group, 2,3-difluoro-n-propyl group, 2-fluoro-n-butyl Group, 3-fluoro-n-butyl group,
4-fluoro-n-butyl group, 3-fluoro-2-methylpropyl group, 2,3-difluoro-n-butyl group,
2,4-difluoro-n-butyl group, 3,4-difluoro-n-butyl group, 2-fluoro-n-pentyl group, 3
-Fluoro-n-pentyl group, 5-fluoro-n-pentyl group, 2,4-difluoro-n-pentyl group, 2,5
-Difluoro-n-pentyl group, 2-fluoro-3-methylbutyl group, 2-fluoro-n-hexyl group, 3-fluoro-n-hexyl group, 4-fluoro-n-hexyl group, 5-fluoro-n- Hexyl group, 6-fluoro-n
-Hexyl group, 2-fluoro-n-heptyl group, 4-fluoro-n-heptyl group, 5-fluoro-n-heptyl group, 2-fluoro-n-octyl group, 3-fluoro-n
-Octyl group, 6-fluoro-n-octyl group, 4-fluoro-n-nonyl group, 7-fluoro-n-nonyl group,
3-fluoro-n-decyl group, 6-fluoro-n-decyl group, 4-fluoro-n-dodecyl group, 8-fluoro-
n-dodecyl group, 5-fluoro-n-tetradecyl group,
9-fluoro-n-tetradecyl group, 3-chloro-n-
Propyl group, 2-chloro-n-butyl group, 4-chloro-
n-butyl group, 2-chloro-n-pentyl group, 5-chloro-n-pentyl group, 5-chloro-n-hexyl group, 4
-Chloro-n-heptyl group, 6-chloro-n-octyl group, 7-chloro-n-nonyl group, 3-chloro-n-decyl group, 8-chloro-n-dodecyl group,

N-perfluoropropyl group, n-perfluorobutyl group, n-perfluoropentyl group, n-perfluorohexyl group, n-perfluoroheptyl group,
n-perfluorooctyl group, n-perfluorononyl group, n-perfluorodecyl group, n-perfluoroundecyl group, n-perfluorododecyl group, n-perfluorotetradecyl group, 1-hydro-n- Perfluoropropyl group, 1-hydro-n-perfluorobutyl group, 1
-Hydro-n-perfluoropentyl group, 1-hydro-
n-perfluorohexyl group, 1-hydro-n-perfluoroheptyl group, 1-hydro-n-perfluorooctyl group, 1-hydro-n-perfluorononyl group, 1-
Hydro-n-perfluorodecyl group, 1-hydro-n-
Perfluoroundecyl group, 1-hydro-n-perfluorododecyl group, 1-hydro-n-perfluorotetradecyl group, 1,1-dihydro-n-perfluoropropyl group, 1,1-dihydro-n- Perfluorobutyl group,
1,1-dihydro-n-perfluoropentyl group, 1,
1-dihydro-3-pentafluoroethyl perfluoropentyl group, 1,1-dihydro-n-perfluorohexyl group, 1,1-dihydro-n-perfluoroheptyl group, 1,1-dihydro-n-perfluoro Octyl group,
1,1-dihydro-n-perfluorononyl group, 1,1
-Dihydro-n-perfluorodecyl group, 1,1-dihydro-n-perfluoroundecyl group, 1,1-dihydro-n-perfluorododecyl group, 1,1-dihydro-
n-perfluorotetradecyl group, 1,1-dihydro-
n-perfluoropentadecyl group, 1,1-dihydro-
an n-perfluorohexadecyl group,

1,1,3-trihydro-n-perfluoropropyl group, 1,1,3-trihydro-n-perfluorobutyl group, 1,1,4-trihydro-n-perfluorobutyl group, 1,4-trihydro-n-perfluoropentyl group, 1,1,5-trihydro-n-perfluoropentyl group, 1,1,3-trihydro-n-perfluorohexyl group, 1,1,6-trihydro -N-perfluorohexyl group, 1,1,5-trihydro-n-
Perfluoroheptyl group, 1,1,7-trihydro-n
-Perfluoroheptyl group, 1,1,8-trihydro-
n-perfluorooctyl group, 1,1,9-trihydro-n-perfluorononyl group, 1,1,11-trihydro-n-perfluoroundecyl group, 2- (perfluoroethyl) ethyl group, 2- (N-perfluoropropyl) ethyl group, 2- (n-perfluorobutyl) ethyl group, 2- (n-perfluoropentyl) ethyl group, 2-
(N-perfluorohexyl) ethyl group, 2- (n-perfluoroheptyl) ethyl group, 2- (n-perfluorooctyl) ethyl group, 2- (n-perfluorodecyl) ethyl group, 2- (n -Perfluorononyl) ethyl group, 2- (n-perfluorododecyl) ethyl group, 2-
(Perfluoro-9′-methyldecyl) ethyl group,

2-trifluoromethylpropyl group, 3-
(N-perfluoropropyl) propyl group, 3- (n-
Perfluorobutyl) propyl group, 3- (n-perfluorohexyl) propyl group, 3- (n-perfluoroheptyl) propyl group, 3- (n-perfluorooctyl) propyl group, 3- (n-perfluoro Decyl) propyl group, 3- (n-perfluorododecyl) propyl group, 4- (perfluoroethyl) butyl group, 4- (n-
Perfluoropropyl) butyl, 4- (n-perfluorobutyl) butyl, 4- (n-perfluoropentyl) butyl, 4- (n-perfluorohexyl) butyl, 4- (n-perfluoro Heptyl) butyl group, 4
-(N-perfluorooctyl) butyl group, 4- (n-
Perfluorodecyl) butyl group, 4- (perfluoroisopropyl) butyl group, 5- (n-perfluoropropyl) pentyl group, 5- (n-perfluorobutyl) pentyl group, 5- (n-perfluoropentyl) Pentyl group, 5- (n-perfluorohexyl) pentyl group, 5
-(N-perfluoroheptyl) pentyl group, 5- (n
-Perfluorooctyl) pentyl group, 6- (perfluoroethyl) hexyl group, 6- (n-perfluoropropyl) hexyl group, 6- (n-perfluorobutyl) hexyl group, 6- (n-perfluorohexyl) ) Hexyl group, 6- (n-perfluoroheptyl) hexyl group, 6
-(N-perfluorooctyl) hexyl group, 6- (perfluoroisopropyl) hexyl group, 6- (perfluoro-7'-methyloctyl) hexyl group, 7- (perfluoroethyl) heptyl group, 7- (n An alkyl group substituted with a halogen atom such as -perfluoropropyl) heptyl group, 7- (n-perfluorobutyl) heptyl group, 7- (n-perfluoropentyl) heptyl group,

2-methoxyethyl, 3-methoxypropyl, 4-methoxybutyl, 5-methoxypentyl, 6-methoxyhexyl, 7-methoxyheptyl, 8-methoxyoctyl, 9-methoxynonyl ,
10-methoxydecyl group, ethoxymethyl group, 2-ethoxyethyl group, 3-ethoxypropyl group, 4-ethoxybutyl group, 5-ethoxypentyl group, 6-ethoxyhexyl group, 7-ethoxyheptyl group, 8-ethoxyoctyl Group, 9-ethoxynonyl group, 10-ethoxydecyl group, n-propyloxymethyl group, 2-n-propyloxyethyl group, 3-n-propyloxypropyl group, 4
-N-propyloxybutyl group, 5-n-propyloxypentyl group, 6-n-propyloxyhexyl group, 7
-N-propyloxyheptyl group, 8-n-propyloxyoctyl group, 9-n-propyloxynonyl group, 1
0-n-propyloxydecyl group, n-butyloxymethyl group, 2-n-butyloxyethyl group, 3-n-butyloxypropyl group, 4-n-butyloxybutyl group,
5-n-butyloxypentyl group, 6-n-butyloxyhexyl group, 7-n-butyloxyheptyl group, 8-
n-butyloxyoctyl group, 9-n-butyloxynonyl group, 10-n-butyloxydecyl group, n-pentyloxymethyl group, 2-n-pentyloxyethyl group,
3-n-pentyloxypropyl group, 4-n-pentyloxybutyl group, 5-n-pentyloxypentyl group,
6-n-pentyloxyhexyl group, 7-n-pentyloxyheptyl group, 8-n-pentyloxyoctyl group, 9-n-pentyloxynonyl group, 10-n-pentyloxydecyl group,

N-hexyloxymethyl group, 2-n-hexyloxyethyl group, 3-n-hexyloxypropyl group, 4-n-hexyloxybutyl group, 5-n-hexyloxypentyl group, 6-n- Hexyloxyhexyl group, 7-n-hexyloxyheptyl group, 8-n-hexyloxyoctyl group, 9-n-hexyloxynonyl group, 10-n-hexyloxydecyl group, n-heptyloxymethyl group, 2- n-heptyloxyethyl group,
3-n-heptyloxypropyl group, 4-n-heptyloxybutyl group, 5-n-heptyloxypentyl group,
6-n-heptyloxyhexyl group, 7-n-heptyloxyheptyl group, 8-n-heptyloxyoctyl group, 9-n-heptyloxynonyl group, 10-n-heptyloxydecyl group, octyloxymethyl group, 2-n
-Octyloxyethyl group, 3-n-octyloxypropyl group, 4-n-octyloxybutyl group, 5-n-
Octyloxypentyl group, 6-n-octyloxyhexyl group, 7-n-octyloxyheptyl group, 8-n
-Octyloxyoctyl group, 9-n-octyloxynonyl group, 10-n-octyloxydecyl group, n-nonyloxymethyl group, 2-n-nonyloxyethyl group,
3-n-nonyloxypropyl group, 4-n-nonyloxybutyl group, 5-n-nonyloxypentyl group, 6-n
-Nonyloxyhexyl group, 7-n-nonyloxyheptyl group, 8-n-nonyloxyoctyl group, 9-n-nonyloxynonyl group, 10-n-nonyloxydecyl group, n-decyloxymethyl group, 2 -N-decyloxyethyl group, 3-n-decyloxypropyl group, 4-n-
Decyloxybutyl group, 5-n-decyloxypentyl group, 6-n-decyloxyhexyl group, 7-n-decyloxyheptyl group, 8-n-decyloxyoctyl group,
9-n-decyloxynonyl group, 10-n-decyloxydecyl group, 2-n-undecyloxyethyl group, 4-
n-undecyloxybutyl group, 6-n-undecyloxyhexyl group, 8-n-undecyloxyoctyl group, 10-n-undecyloxydecyl group, 2-n-dodecyloxyethyl group, 4-n -Dodecyloxybutyl group, 6-n-dodecyloxyhexyl group, 8-n-dodecyloxyoctyl group, 10-n-dodecyloxydecyl group,

1-methyl-2-methoxyethyl group, 1-
Methyl-2-ethoxyethyl group, 1-methyl-2-n-
Propyloxyethyl group, 1-methyl-2-n-butyloxyethyl group, 1-methyl-2-n-pentyloxyethyl group, 1-methyl-2-n-hexyloxyethyl group, 1-methyl-2- n-heptyloxyethyl group, 1
-Methyl-2-n-octyloxyethyl group, 1-methyl-2-n-nonyloxyethyl group, 1-methyl-2-
n-decyloxyethyl group, 1-methyl-2-n-undecyloxyethyl group, 1-methyl-2-n-dodecyloxyethyl group, 2-methoxypropyl group, 2-ethoxypropyl group, 2-n- Propyloxypropyl group, 2
-N-butyloxypropyl group, 2-n-pentyloxypropyl group, 2-n-hexyloxypropyl group, 2
-N-heptyloxypropyl group, 2-n-octyloxypropyl group, 2-n-nonyloxypropyl group, 2
-N-decyloxypropyl group, 2-n-undecyloxypropyl group, 2-n-dodecyloxypropyl group,
1-methyl-3-methoxypropyl group, 1-methyl-3
-Ethoxypropyl group, 1-methyl-3-n-propyloxypropyl group, 1-methyl-3-n-butyloxypropyl group, 1-methyl-3-n-pentyloxypropyl group, 1-methyl-3- n-hexyloxypropyl group, 1-methyl-3-n-heptyloxypropyl group,
1-methyl-3-n-octyloxypropyl group, 1-
Methyl-3-n-nonyloxypropyl group, 1-methyl-3-n-decyloxypropyl group, 1-methyl-3-
n-undecyloxypropyl group, 1-methyl-3-n
-Dodecyloxypropyl group, 3-methoxybutyl group,
3-ethoxybutyl group, 3-n-propyloxybutyl group, 3-n-butyloxybutyl group, 3-n-pentyloxybutyl group, 3-n-hexyloxybutyl group, 3
-N-heptyloxybutyl group, 3-n-octyloxybutyl group, 3-n-nonyloxybutyl group, 3-n-
Decyloxybutyl group, 3-n-undecyloxybutyl group, 3-n-dodecyloxybutyl group,

Isopropyloxymethyl, 2-isopropyloxyethyl, 3-isopropyloxypropyl, 4-isopropyloxybutyl, 5-isopropyloxypentyl, 6-isopropyloxyhexyl, 7-isopropyloxyheptyl, 8-isopropyloxyoctyl group, 9-isopropyloxynonyl group, 10-isopropyloxydecyl group, isobutyloxymethyl group, 2-isobutyloxyethyl group, 3-
Isobutyloxypropyl, 4-isobutyloxybutyl, 5-isobutyloxypentyl, 6-isobutyloxyhexyl, 7-isobutyloxyheptyl, 8-isobutyloxyoctyl, 9-isobutyloxynonyl, 10-isobutyl Oxydecyl group, te
rt-butyloxymethyl group, 2-tert-butyloxyethyl group, 3-tert-butyloxypropyl group, 4-tert
-Butyloxybutyl group, 5-tert-butyloxypentyl group, 6-tert-butyloxyhexyl group, 7-tert
-Butyloxyheptyl group, 8-tert-butyloxyoctyl group, 9-tert-butyloxynonyl group, 10-te
rt-butyloxydecyl group, (2-ethylbutyloxy) methyl group, 2- (2′-ethylbutyloxy) ethyl group, 3- (2′-ethylbutyloxy) propyl group,
4- (2′-ethylbutyloxy) butyl group, 5-
(2′-ethylbutyloxy) pentyl group, 6- (2 ′
-Ethylbutyloxy) hexyl group, 7- (2′-ethylbutyloxy) heptyl group, 8- (2′-ethylbutyloxy) octyl group, 9- (2′-ethylbutyloxy) nonyl group, 10- ( 2'-ethylbutyloxy) decyl group,

A (3-ethylpentyloxy) methyl group,
2- (3′-ethylpentyloxy) ethyl group, 3-
(3′-ethylpentyloxy) propyl group, 4-
(3′-ethylpentyloxy) butyl group, 5- (3 ′
-Ethylpentyloxy) pentyl group, 6- (3'-ethylpentyloxy) hexyl group, 7- (3'-ethylpentyloxy) heptyl group, 8- (3'-ethylpentyloxy) octyl group, 9- ( 3′-ethylpentyloxy) nonyl group, 10- (3′-ethylpentyloxy) decyl group, 6- (1′-methyl-n-heptyloxy) hexyl group, 4- (1′-methyl-n-heptyl) An oxy) butyl group, a 2- (2′-methoxyethoxy) ethyl group, a 2- (2′-ethoxyethoxy) ethyl group,
(2′-n-propyloxyethoxy) ethyl group, 2-
(2′-isopropyloxyethoxy) ethyl group, 2-
(2′-n-butyloxyethoxy) ethyl group, 2-
(2′-isobutyloxyethoxy) ethyl group, 2-
(2′-tert-butyloxyethoxy) ethyl group, 2-
(2′-n-pentyloxyethoxy) ethyl group, 2-
[2 '-(2 "-ethylbutyloxy) ethoxy] ethyl group, 2- (2'-n-hexyloxyethoxy) ethyl group, 2- [2'-(3" -ethylpentyloxy) ethoxy] ethyl group 2- (2'-n-heptyloxyethoxy) ethyl group, 2- (2'-n-octyloxyethoxy) ethyl group, 2- (2'-n-nonyloxyethoxy) ethyl group, 2- (2 '-N-decyloxyethoxy) ethyl group, 2- (2'-n-undecyloxyethoxy) ethyl group, 2- (2'-n-dodecyloxyethoxy) ethyl group,

2- [2 '-(2 "-methoxyethoxy)
Ethoxy] ethyl group, 2- [2 '-(2 "-ethoxyethoxy) ethoxy] ethyl group, 2- [2'-(2" -n
-Propyloxyethoxy) ethoxy] ethyl group, 2-
[2 '-(2 "-isopropyloxyethoxy) ethoxy] ethyl group, 2- [2'-(2" -n-butyloxyethoxy) ethoxy] ethyl group, 2- [2 '-(2 "-
Isobutyloxyethoxy) ethoxy] ethyl group, 2-
[2 ′-(2 ″ -tert-butyloxyethoxy) ethoxy] ethyl group, 2- {2 ′-[2 ″-(2 ′ ″-ethylbutyloxy) ethoxy] ethoxy} ethyl group, 2-
[2 '-(2 "-n-pentyloxyethoxy) ethoxy] ethyl group, 2- [2'-(2" -n-hexyloxyethoxy) ethoxy] ethyl group, 2- {2 '-[2 "
-(3 "'-ethylpentyloxy) ethoxy] ethoxydiethyl group, 2- [2'-(2" -n-heptyloxyethoxy) ethoxy] ethyl group, 2- [2 '-(2 "
-N-octyloxyethoxy) ethoxy] ethyl group,
2- [2 '-(2 "-n-nonyloxyethoxy) ethoxy] ethyl group, 2- [2'-(2" -n-decyloxyethoxy) ethoxy] ethyl group, 2- [2 '-(2 "
-N-undecyloxyethoxy) ethoxy] ethyl group, 2- [2 '-(2 "-n-dodecyloxyethoxy) ethoxy] ethyl group,

2- {2 ′-[2 ″-(2 ′ ″-methoxyethoxy) ethoxy] ethoxy} ethyl group, 2- {2 ′
-[2 "-(2"'-n-dodecyloxyethoxy) ethoxy] ethoxy} ethyl group, 2- {2'-{2 "-
[2 '"-(2-methoxyethoxy) ethoxy] ethoxy {ethoxy} ethyl group, 2- {2'-{2"-
{2 ′ ″-[2- (2-methoxyethoxy) ethoxy]
Ethoxy {ethoxy} ethoxy} ethyl group, 1-methyl-2- (1′-methyl-2′-methoxyethoxy) ethyl group, 1-methyl-2- (1′-methyl-2′-ethoxyethoxy) ethyl group A 1-methyl-2- (1′-methyl-2′-n-propyloxyethoxy) ethyl group, 1
-Methyl-2- (1′-methyl-2′-isopropyloxyethoxy) ethyl group, 1-methyl-2- (1′-methyl-2′-n-butyloxyethoxy) ethyl group, 1
-Methyl-2- (1'-methyl-2'-isobutyloxyethoxy) ethyl group, 1-methyl-2- (1'-methyl-2'-tert-butyloxyethoxy) ethyl group, 1
-Methyl-2- (1′-methyl-2′-n-pentyloxyethoxy) ethyl group, 1-methyl-2- (1′-methyl-2′-n-hexyloxyethoxy) ethyl group,
1-methyl-2- (1′-methyl-2′-n-heptyloxyethoxy) ethyl group, 1-methyl-2- (1′-
Methyl-2'-n-octyloxyethoxy) ethyl group, 1-methyl-2- (1'-methyl-2'-n-nonyloxyethoxy) ethyl group, 1-methyl-2- (1 '
-Methyl-2'-n-decyloxyethoxy) ethyl group, 1-methyl-2- (1'-methyl-2'-n-undecyloxyethoxy) ethyl group, 1-methyl-2-
(1′-methyl-2′-n-dodecyloxyethoxy)
Ethyl group,

1-methyl-2- [1'-methyl-2'-
(1 "-methyl-2" -methoxyethoxy) ethoxy]
Ethyl group, 1-methyl-2- [1′-methyl-2′-
(1 "-methyl-2" -ethoxyethoxy) ethoxy]
Ethyl group, 1-methyl-2- [1′-methyl-2′-
(1 "-methyl-2" -n-propyloxyethoxy)
Ethoxy] ethyl group, 1-methyl-2- [1′-methyl-2 ′-(1 ″ -methyl-2 ″ -isopropyloxyethoxy) ethoxy] ethyl group, 1-methyl-2- [1 ′
-Methyl-2 '-(1 "-methyl-2" -n-butyloxyethoxy) ethoxy] ethyl group, 1-methyl-2-
[1'-methyl-2 '-(1 "-methyl-2" -isobutyloxyethoxy) ethoxy] ethyl group, 1-methyl-2- [1'-methyl-2'-(1 "-methyl-2") −
tert-butyloxyethoxy) ethoxy] ethyl group, 1
-Methyl-2- [1'-methyl-2 '-(1 "-methyl-2" -n-pentyloxyethoxy) ethoxy] ethyl group, 1-methyl-2- [1'-methyl-2'-( 1 "
-Methyl-2 "-n-hexyloxyethoxy) ethoxy] ethyl group, 1-methyl-2- [1'-methyl-2 '
-(1 "-methyl-2" -n-heptyloxyethoxy) ethoxy] ethyl group, 1-methyl-2- [1'-methyl-2 '-(1 "-methyl-2" -n-octyloxyethoxy) ) Ethoxy] ethyl group, 1-methyl-2-
[1'-methyl-2 '-(1 "-methyl-2" -n-nonyloxyethoxy) ethoxy] ethyl group, 1-methyl-2- [1'-methyl-2'-(1 "-methyl- 2 "-
n-decyloxyethoxy) ethoxy] ethyl group, 1-
Methyl-2- [1′-methyl-2 ′-(1 ″ -methyl-
2 "-n-undecyloxyethoxy) ethoxy] ethyl group, 1-methyl-2- [1'-methyl-2 '-(1"
-Methyl-2 "-n-dodecyloxyethoxy) ethoxy] ethyl group,

2-ethoxyethoxymethyl group, 2-n-
Butyloxyethoxymethyl group, 2-n-hexyloxyethoxymethyl group, 3-ethoxypropyloxymethyl group, 3-n-propyloxypropyloxymethyl group, 3-n-pentyloxypropyloxymethyl group,
3-n-hexyloxypropyloxymethyl group, 2-
Methoxy-1-methylethoxymethyl group, 2-ethoxy-1-methylethoxymethyl group, 2-n-butyloxy-1-methylethoxymethyl group, 4-methoxybutyloxymethyl group, 4-ethoxybutyloxymethyl group, 4
-N-butyloxybutyloxymethyl group, 2- (3 ′
-Methoxypropyloxy) ethyl group, 2- (3'-ethoxypropyloxy) ethyl group, 2- (1'-methyl-2'-methoxyethoxy) ethyl group, 2- (1'-methyl-2'-ethoxy) Ethoxy) ethyl group, 2- (1 ′
-Methyl-2'-n-butyloxyethoxy) ethyl group, 2- (4'-methoxybutyloxy) ethyl group, 2
-(4'-ethoxybutyloxy) ethyl group, 2-
[4 '-(2 "-ethylbutyloxy) butyloxy]
Ethyl group, 2- [4 '-(3 "-ethylpentyloxy) butyloxy] ethyl group, 3- (2'-methoxyethoxy) propyl group, 3- (2'-ethoxyethoxy)
Propyl group, 3- (2′-n-pentyloxyethoxy) propyl group, 3- (2′-n-hexyloxyethoxy) propyl group, 3- (3′-ethoxypropyloxy) propyl group, 3- (3 '-N-propyloxypropyloxy) propyl group, 3- (3'-n-butyloxypropyloxy) propyl group, 3- (4'-ethoxybutyloxy) propyl group, 3- (5'-ethoxypentyloxy ) Propyl, 4- (2′-methoxyethoxy) butyl, 4- (2′-ethoxyethoxy) butyl, 4- (2′-isopropyloxyethoxy) butyl, 4- (2′-isobutyloxyethoxy) ) Butyl group, 4- (2′-n-butyloxyethoxy) butyl group, 4- (2′-n-hexyloxyethoxy) butyl group, 4- (3′-n-propyloxypropyl) Oxy)
Butyl group, 4- (2'-n-propyloxy-1'-methylethoxy) butyl group, 4- [2 '-(2 "-methoxyethoxy) ethoxy] butyl group, 4- [2'-(2"
-N-butyloxyethoxy) ethoxy] butyl group, 4
-[2 '-(2 "-n-hexyloxyethoxy) ethoxy] butyl group, 5- (2'-n-hexyloxyethoxy) pentyl group, 2- [2'-(2" -n-butyloxyethoxy) ) Ethoxy] ethyl;

A (2-ethylhexyloxy) methyl group,
(3,5,5-trimethylhexyloxy) methyl group,
(3,7-dimethyloctyloxy) methyl group, 2-
(2′-ethylhexyloxy) ethyl group, 2-
(3 ′, 5 ′, 5′-trimethylhexyloxy) ethyl group, 2- (3 ′, 7′-dimethyloctyloxy) ethyl group, 3- (2′-ethylhexyloxy) propyl group, 3- (3 ′ , 5 ', 5'-trimethylhexyloxy) propyl group, 3- (3', 7'-dimethyloctyloxy) propyl group, 4- (2'-ethylhexyloxy) butyl group, 4- (3 ', 5' , 5'-trimethylhexyloxy) butyl group, 4- (3 ', 7'-dimethyloctyloxy) butyl group, 5- (2'-ethylhexyloxy) pentyl group, 5- (3', 5 ', 5' -Trimethylhexyloxy) pentyl group, 5- (3 ', 7'
-Dimethyloctyloxy) pentyl group, 6- (2'-
Ethylhexyloxy) hexyl group, 6- (3 ′,
5 ′, 5′-trimethylhexyloxy) hexyl group,
An alkoxyalkyl group such as a 6- (3 ′, 7′-dimethyloctyloxy) hexyl group,

2- (2'-trifluoromethylpropyloxy) ethyl group, 4- (2'-trifluoromethylpropyloxy) butyl group, 6- (2'-trifluoromethylpropyloxy) hexyl group, 8- (2′-trifluoromethylpropyloxy) octyl group, 2- (2 ′
-Trifluoromethylbutyloxy) ethyl group, 4-
(2′-trifluoromethylbutyloxy) butyl group,
6- (2′-trifluoromethylbutyloxy) hexyl group, 8- (2′-trifluoromethylbutyloxy)
Octyl group, 2- (2'-trifluoromethylheptyloxy) ethyl group, 4- (2'-trifluoromethylheptyloxy) butyl group, 6- (2'-trifluoromethylheptyloxy) hexyl group, 8- (2′-trifluoromethylheptyloxy) octyl group, 2- (2 ′
-Fluoroethyloxy) ethyl group, 4- (2'-fluoroethyloxy) butyl group, 6- (2'-fluoroethyloxy) hexyl group, 8- (2'-fluoroethyloxy) octyl group, 2- ( 2'-fluoro-n-propyloxy) ethyl group, 4- (2'-fluoro-n-propyloxy) butyl group, 6- (2'-fluoro-n-
Propyloxy) hexyl group, 8- (2′-fluoro-
n-propyloxy) octyl group, 2- (3'-fluoro-n-propyloxy) ethyl group, 4- (3'-fluoro-n-propyloxy) butyl group, 6- (3'-fluoro-n- Propyloxy) hexyl group, 8- (3 ′
-Fluoro-n-propyloxy) octyl group, 2-
(3′-fluoro-2′-methylpropyloxy) ethyl group, 4- (3′-fluoro-2′-methylpropyloxy) butyl group, 6- (3′-fluoro-2′-methylpropyloxy) hexyl Group, 8- (3′-fluoro-
2′-methylpropyloxy) octyl group,

2- (2 ', 3'-difluoro-n-propyloxy) ethyl group, 4- (2', 3'-difluoro-n-propyloxy) butyl group, 6- (2 ', 3'-
Difluoro-n-propyloxy) hexyl group, 8-
(2 ′, 3′-difluoro-n-propyloxy) octyl group, 2- (2′-fluoro-n-butyloxy) ethyl group, 4- (2′-fluoro-n-butyloxy) butyl group, 6- ( 2'-fluoro-n-butyloxy) hexyl group, 8- (2'-fluoro-n-butyloxy)
Octyl group, 2- (3′-fluoro-n-butyloxy) ethyl group, 4- (3′-fluoro-n-butyloxy) butyl group, 6- (3′-fluoro-n-butyloxy) hexyl group, 8- (3′-fluoro-n-butyloxy) octyl group, 2- (4′-fluoro-n-butyloxy) ethyl group, 4- (4′-fluoro-n-butyloxy) butyl group, 6- (4′-fluoro -N-butyloxy) hexyl group, 8- (4'-fluoro-n-butyloxy) octyl group, 2- (2 ', 3'-difluoro-n-butyloxy) ethyl group, 4- (2', 3'- Difluoro-n-butyloxy) butyl group, 6- (2 ′,
3'-difluoro-n-butyloxy) hexyl group, 8
— (2 ′, 3′-difluoro-n-butyloxy) octyl group, perfluoro (2-n-hexyloxyethyl) group,

1,1-dihydro-perfluoro (2-methoxyethyl) group, 1,1-dihydro-perfluoro (3-n-propyloxypropyl) group, 1,1-dihydro-perfluoro (2-ethoxy) group Ethyl) group, 1,1
-Dihydro-perfluoro (2-n-pentyloxyethyl) group, 2- (2'-n-perfluorobutyloxyethoxy) ethyl group, 3- (n-perfluorobutyloxy) -3,3-difluoroethyl Group, 4- (1,1,
7-trihydro-n-perfluoroheptyloxy) butyl group, 2- (n-perfluoropropyloxy) -2
-Trifluoromethyl-2-fluoroethyl group, 2-
(2′-trichloromethylpropyloxy) ethyl group,
4- (2'-trichloromethylpropyloxy) butyl group, 6- (2'-trichloromethylpropyloxy) hexyl group, 8- (2'-trichloromethylpropyloxy) octyl group, 2- (2'-trichloromethyl Butyloxy) ethyl group, 4- (2′-trichloromethylbutyloxy) butyl group, 6- (2′-trichloromethylbutyloxy) hexyl group, 8- (2′-trichloromethylbutyloxy) octyl group, (2′-trichloromethylheptyloxy) ethyl group, 4- (2′-trichloromethylheptyloxy) butyl group, 6- (2′-trichloromethylheptyloxy) hexyl group, 8-
(2′-trichloromethylheptyloxy) octyl group, 2- (2′-chloroethoxy) ethyl group, 4-
(2'-chloroethoxy) butyl group, 6- (2'-chloroethoxy) hexyl group, 8- (2'-chloroethoxy) octyl group, 2- (2'-chloro-n-propyloxy) ethyl group, 4- (2′-chloro-n-propyloxy) butyl group, 6- (2′-chloro-n-propyloxy) hexyl group, 8- (2′-chloro-n-propyloxy) octyl group,

2- (3'-chloro-n-propyloxy) ethyl group, 4- (3'-chloro-n-propyloxy) butyl group, 6- (3'-chloro-n-propyloxy) hexyl group 8- (3'-chloro-n-propyloxy) octyl group, 2- (3'-chloro-2'-methylpropyloxy) ethyl group, 4- (3'-chloro-2 '
-Methylpropyloxy) butyl group, 6- (3'-chloro-2'-methylpropyloxy) hexyl group, 8-
(3′-chloro-2′-methylpropyloxy) octyl group, 2- (2 ′, 3′-dichloro-n-propyloxy) ethyl group, 4- (2 ′, 3′-dichloro-n-propyloxy) ) Butyl group, 6- (2 ′, 3′-dichloro-)
n-propyloxy) hexyl group, 8- (2 ′, 3′-
Dichloro-n-propyloxy) octyl group, 2-
(2′-chloro-n-butyloxy) ethyl group, 4-
(2′-chloro-n-butyloxy) butyl group, 6-
(2′-chloro-n-butyloxy) hexyl group, 8-
(2′-chloro-n-butyloxy) octyl group, 2-
(3′-chloro-n-butyloxy) ethyl group, 4-
(3′-chloro-n-butyloxy) butyl group, 6-
(3′-chloro-n-butyloxy) hexyl group, 8-
(3′-chloro-n-butyloxy) octyl group, 2-
(4′-chloro-n-butyloxy) ethyl group, 4-
(4′-chloro-n-butyloxy) butyl group, 6-
(4′-chloro-n-butyloxy) hexyl group, 8-
(4′-chloro-n-butyloxy) octyl group, 2-
(2 ′, 3′-dichloro-n-butyloxy) ethyl group, 4- (2 ′, 3′-dichloro-n-butyloxy)
Butyl group, 6- (2 ′, 3′-dichloro-n-butyloxy) hexyl group, 8- (2 ′, 3′-dichloro-n-)
An alkoxyalkyl group substituted by a halogen atom such as butyloxy) octyl group,

2-propenyl group, 2-butenyl group, 3-
Butenyl group, 2-pentenyl group, 3-pentenyl group, 4
-Pentenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 2-heptenyl group, 3-heptenyl group, 4-heptenyl group, 5-heptenyl group, 6-heptenyl group, 2 -Octenyl group, 3
-Octenyl group, 4-octenyl group, 5-octenyl group, 6-octenyl group, 7-octenyl group, 2-nonenyl group, 3-nonenyl group, 4-nonenyl group, 5-nonenyl group, 6-nonenyl group, 7 -Nonenyl group, 8-nonenyl group, 2-decenyl group, 3-decenyl group, 4-decenyl group, 5-decenyl group, 6-decenyl group, 7-decenyl group, 8-decenyl group, 9-decenyl group, 3 Alkenyl groups such as 7,7-dimethyl-6-octenyl group, 3-n-perfluoropropyl-2-propenyl group, 3-n-perfluorobutyl-2-propenyl group, 3-n-perfluoropentyl-2- Propenyl group, 3-n-perfluorohexyl-2-propenyl group, 3-n-perfluoroheptyl-2-propenyl group, 3-n-perfluorooctyl-2-propenyl group, etc. An alkenyl group substituted with a halogen atom,

2-propenyloxymethyl group, 2-
(2′-propenyloxy) ethyl group, 2- [2′-
(2 "-propenyloxy) ethoxy] ethyl group, 3-
(2′-propenyloxy) propyl group, 4- (2′-
Propenyloxy) butyl group, 5- (2′-propenyloxy) pentyl group, 6- (2′-propenyloxy)
Hexyl group, 7- (2′-propenyloxy) heptyl group, 8- (2′-propenyloxy) octyl group, 9-
(2′-propenyloxy) nonyl group, 10- (2′-
Alkenyloxyalkyl groups such as propenyloxy) decyl group, 2- (2′-propenyloxy) -perfluoroethyl group, 3- (2′-propenyloxy) -perfluoropropyl group, 4- (2′-propenyloxy )-
A perfluorobutyl group, a 5- (2′-propenyloxy) -perfluoropentyl group, a 6- (2′-propenyloxy) -perfluorohexyl group, a 7- (2′-propenyloxy) -perfluoroheptyl group, 8-
An alkenyloxyalkyl group substituted with a halogen atom such as (2′-propenyloxy) -perfluorooctyl group,

Benzyl, 2-phenylethyl, 3-
Aralkyl groups such as phenylpropyl group, 4-phenylbutyl group, 5-phenylpentyl group, 2-naphthylethyl group, 3-naphthylpropyl group, 2-phenyloxyethyl group, 2- (4′-methylphenyloxy) ethyl Group,
2- (3′-methylphenyloxy) ethyl group, 2-
(4′-chlorophenyloxy) ethyl group, 2- (4 ′
-Bromophenyloxy) ethyl group, aryloxyalkyl group such as 4-phenyloxybutyl group, cyclopropylmethyl group, 2-cyclopropylethyl group, cyclopentylmethyl group, 2-cyclopentylethyl group, 3-cyclopentylpropyl group, cyclohexyl Methyl group, 2
-Cyclohexylethyl group, 3-cyclohexylpropyl group, cycloheptylmethyl group, 2-cycloheptylethyl group, cyclooctylmethyl group, 2-cyclooctylethyl group, 4-isopropenyl-2-cyclohexenylmethyl group (perillyl group) And the like.

In the acetylene compound represented by the general formula (1) of the present invention, Y ₁ represents —O— or —COO—, and Y ₂ represents a single bond, —O—, —COO— or Represents a —C≡C— group. Y ₂ is preferably a single bond, -O
Group or a -COO- group, more preferably -O
— Group or —COO— group. X ₁ represents a hydrogen atom or a halogen atom, preferably a hydrogen atom, a fluorine atom or a chlorine atom. Specific examples of the acetylene compound represented by the general formula (1) of the present invention include the compounds shown in Table 1 below (Tables 1 to 3).

[0039]

[Table 1]

[0040]

[Table 2]

[0041]

[Table 3] In the table, the substitution position of X ₁ is ortho to the Y ₂ group, and Ph, Ph-CH ₃ , Ph-Cl, CycHex, CycPen, CycPr
o and peri represent the following groups (Chemical Formula 5).

[0042]

Embedded image The acetylene compound represented by the general formula (1) of the present invention is
For example, it can be manufactured through the following steps. -Manufacturing process of acetylene compound (Chem. 6)-

[0043]

Embedded image

A compound represented by the general formula (5) (Formula 6) (L ₁ represents a halogen atom such as a bromine atom or an iodine atom or a leaving group such as a trifluoromethanesulfonyloxy group) is added to a palladium catalyst [ For example, palladium / carbon, dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium], copper iodide, triphenylphosphine and bases (eg, organic bases such as triethylamine, diisopropylamine, etc., sodium carbonate, potassium carbonate, etc.) The acetylene compound represented by the general formula (6) (Chemical formula 6) is reacted in the presence of an inorganic base) to obtain a compound represented by the general formula (7). Next, the compound represented by the general formula (7) and the carboxylic acid represented by the general formula (8) and the alkylation represented by the general formula (9) Agent (L2
Represents a leaving group such as a halogen atom or a p-toluenesulfonyloxy group), whereby an acetylene compound represented by the general formula (1-A) or (1-B) can be produced.

The reaction between the compound represented by the general formula (7) and the carboxylic acid represented by the general formula (8) is carried out by converting the carboxylic acid represented by the general formula (8) into thionyl chloride, oxalyl chloride and the like. A carboxylic acid halide with a halogenating agent such as
A compound represented by the general formula (7), a dehydration condensing agent such as N, N'-dicyclohexylcarbodiimide (hereinafter abbreviated as DCC), etc. And a catalyst (eg, 4-N, N-dimethylaminopyridine,
-Pyrrolidinopyridine) in the presence of a compound represented by the general formula (7) and a carboxylic acid represented by the general formula (8) in diethylazodicarboxylic acid (hereinafter, referred to as
DEAD) and reacting in the presence of triphenylphosphine.

Further, a compound represented by the general formula (7):
The reaction with the alkylating agent represented by the general formula (9) is performed in the presence of a base (eg, sodium hydride, potassium hydride, sodium) in a polar solvent (eg, tetrahydrofuran, dimethoxyethane, N, N-dimethyl). Formamide). The compound of the formula (1) in which Y ₂ is an —O— group can be produced, for example, by using a protecting group by the following step (Formula 7).

[0047]

Embedded image

That is, a compound represented by the general formula (10) (Chemical formula 7) (L ₁ represents a halogen atom such as an iodine atom or a bromine atom, a leaving group such as a trifluoromethanesulfonyloxy group, and P represents tetrahydropyrani And a compound represented by the general formula (6) in the presence of a palladium catalyst, copper iodide, triphenylphosphine and a base to obtain a compound represented by the general formula (11) Is obtained. Next, a carboxylic acid represented by the general formula (8) or an alkylating agent represented by the general formula (9) (L ₂ is a p-toluenesulfonyloxy group) is added to the compound represented by the general formula (11). Represents a leaving group such as a halogen atom) to obtain a compound represented by the general formula (12) (Formula 7). Further, the protecting group of the compound represented by the general formula (12) was removed (for example, in the case of a tetrahydropyranyl group, an acid such as hydrochloric acid or p-toluenesulfonic acid was allowed to act), and then the obtained compound was obtained. A compound represented by the general formula (13) (Chemical formula 7) and an alkylating agent represented by the general formula (14) (Chemical formula 7) (L ₃ is a halogen atom, a p-toluenesulfonyloxy group, a HO— group, etc.) With a leaving group) to produce a compound represented by the general formula (1).

A compound represented by the general formula (13):
The reaction of the alkylating agent represented by the general formula (14) is carried out, for example, by reacting the compound represented by the general formula (13) (when L ₃ is a halogen atom or a p-toluenesulfonyloxy group) with the compound represented by the general formula (14) ) Is a base (for example,
In the presence of sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide), a polar solvent (eg, N, N-dimethylformamide, dimethyl sulfoxide, N, -methyl-2)
(Wherein L ₃ is a HO— group) by subjecting the compound represented by the general formula (13) and the compound represented by the general formula (14) to DEA.
A reaction in the presence of D and triphenylphosphine.

The acetylene compound of the present invention includes a compound showing liquid crystallinity by itself and a compound not showing liquid crystallinity. Compounds exhibiting liquid crystallinity include compounds exhibiting chiral smectic C phase (hereinafter abbreviated as S _C ^* phase) and compounds exhibiting liquid crystallinity but exhibiting no S _C ^* phase. Each of these compounds can be effectively used as a component of a liquid crystal composition.

Next, the liquid crystal composition of the present invention will be described. The liquid crystal composition generally comprises two or more components,
The liquid crystal composition of the present invention contains at least one acetylene compound of the present invention as an essential component. The liquid crystal composition of the present invention preferably includes a liquid crystal composition exhibiting a phase such as chiral smectic C, C _A , F, G, H, or I, and more preferably an S _C ^* phase or a chiral smectic C. _A liquid crystal composition exhibiting an _A ^* phase. The liquid crystal composition of the present invention is prepared by combining a plurality of compounds selected from the acetylene compound of the present invention, a liquid crystal compound exhibiting a chiral smectic phase other than the acetylene compound of the present invention, a liquid crystal compound exhibiting a smectic phase, and an optically active compound. And at least one acetylene compound of the present invention.

The liquid crystal compound exhibiting a chiral smectic phase other than the acetylene compound of the present invention is not particularly limited. Liquid crystal compounds, optically active phenylnaphthalene liquid crystal compounds, optically active tolan liquid crystal compounds, optically active phenylpyrimidine liquid crystal compounds, optically active naphthylpyrimidine liquid crystal compounds, and optically active tetralin liquid crystal compounds.

The liquid crystal compound exhibiting a smectic phase is not particularly limited. For example, non-optically active phenylbenzoate liquid crystal compounds, non-optically active biphenylbenzoate liquid crystal compounds, non-optically active naphthalene liquid crystal compounds, Examples include optically active phenylnaphthalene-based liquid crystal compounds, non-optically active tolanic liquid crystal compounds, non-linearly active phenylpyrimidine-based liquid crystal compounds, non-optically active naphthylpyrimidine-based liquid crystal compounds, and non-optically active tetralin-based liquid crystal compounds. Specific examples of these compounds exhibiting a chiral smectic phase or a smectic phase include, for example, a compound represented by the general formula (2), (3) or (4) (Formula 8).

[0054]

Embedded image (Wherein, R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ and R ₃₂ each independently represent a linear or branched chain having 3 to 24 carbon atoms which may have an optically active asymmetric carbon atom. An alkyl group, a linear or branched alkenyl group having 3 to 24 carbon atoms, or a linear or branched alkoxyalkyl group having 3 to 24 carbon atoms, and Y ₁₁ , Y ₁₂ , Y ₂₁ , and Y ₂₂ , Y ₃₁ and Y ₃₂ each independently represent a single bond, a -COO- group or-
Represents a bonding group selected from O- groups)

The compounds represented by formulas (2) and (4) can be produced, for example, according to the method described in JP-A-62-10045 or JP-A-63-32748. The compound represented by the general formula (3) can be produced, for example, according to the operation described in JP-A-60-32748.

The optically active compound does not exhibit liquid crystallinity by itself, but has the ability to exhibit a chiral smectic phase when mixed with a liquid crystal compound exhibiting a smectic phase or a liquid crystal composition exhibiting a smectic phase. Examples of the compound include, but are not particularly limited to, an optically active compound, for example, an optically active phenylbenzoate-based non-liquid crystal compound, an optically active biphenylbenzoate-based non-liquid crystal compound, an optically active naphthalene-based non-liquid crystal compound, an optically active phenyl Examples include a naphthalene-based non-liquid crystal compound, an optically active trans-based non-liquid crystal compound, an optically active phenylpyrimidine-based non-liquid crystal compound, an optically active naphthylpyrimidine-based non-liquid crystal compound, and an optically active tetralin-based non-liquid crystal compound.

The liquid crystal composition of the present invention may further comprise, as an optional component, a nematic liquid crystal compound,
Compounds that do not exhibit liquid crystallinity other than the acetylene compound of the present invention (for example, anthraquinone dyes, azo dyes,
A coloring dye, a conductivity-imparting agent, a life-improving agent, etc.). The content of the acetylene compound of the present invention in the liquid crystal composition of the present invention is not particularly limited, but is usually 1 to 90% by weight, preferably 1 to 90% by weight.
60% by weight. Further, the acetylene compound of the present invention can be mixed with the above-mentioned components for a liquid crystal composition at a desired compounding ratio, and has high compatibility. The liquid crystal composition containing at least one acetylene compound of the present invention has a threshold characteristic, a response time, a layer structure in a smectic phase, an alignment characteristic on an alignment film, and a liquid crystal material as compared with a conventional liquid crystal composition. Excellent in compatibility.

Next, the liquid crystal device of the present invention will be described. The liquid crystal element of the present invention is obtained by disposing the liquid crystal composition of the present invention between a pair of electrode substrates. FIG. 1 is a schematic cross-sectional view illustrating an example of a liquid crystal element having a chiral smectic phase for describing the configuration of a liquid crystal element utilizing ferroelectricity. In the liquid crystal element, a liquid crystal layer 1 exhibiting a chiral smectic phase is disposed between a pair of substrates 2 provided with a transparent electrode 3 and an insulating alignment control layer 4 respectively, and the thickness of the liquid crystal layer 1 is set by a spacer 5. And a pair of transparent electrodes 3
A connection is made so that a voltage can be applied from a power supply 7 via a lead wire 6 therebetween. Further, the pair of substrates 2 is sandwiched by a pair of polarizing plates 8 arranged in a crossed Nicols state, and a light source 9 is arranged outside one of them.

Examples of the material of the substrate 2 include glass such as soda lime glass and borosilicate glass, and transparent polymers such as polycarbonate, polyether sulfone, and polyacrylate. As the transparent electrode 3 provided on the two substrates 2, for example, In ₂ O ₃ , SnO _2, or ITO (indium tin oxide; Indi)
um Tin Oxide).

The insulating alignment control layer 4 is for rubbing a thin film of a polymer such as polyimide with a flocked cloth such as nylon, acetate, rayon or the like to align the liquid crystal. Examples of the material of the insulating orientation control layer 4 include silicon nitride, silicon nitride containing hydrogen, silicon carbide, silicon carbide containing hydrogen, silicon oxide, boron nitride, and boron nitride containing hydrogen. , Cerium oxide, aluminum oxide, zirconium oxide, inorganic substance insulating layer such as titanium oxide and magnesium fluoride, polyvinyl alcohol, polyimide, polyamide imide, polyester imide, polyether imide,
Organic materials such as polyether ketone, polyether ether ketone, polyether sulfone, polyparaxylene, polyester, polycarbonate, polyvinyl acetal, polyvinyl chloride, polyvinyl acetate, polyamide, polystyrene, cellulose resin, melamine resin, urea resin, and acrylic resin An insulating orientation control layer having a two-layer structure in which an organic insulating layer is formed on an inorganic insulating layer, or an insulating orientation control layer consisting only of an inorganic insulating layer or an organic insulating layer. You may.

When the insulating orientation control layer is an inorganic insulating layer, it can be formed by an evaporation method or the like. In the case of an organic insulating layer, an organic insulating layer material or a solution of a precursor thereof is applied by a spinner coating method, a penetration coating method, a screen printing method, a spray coating method, a roll coating method, or the like,
The solvent can be removed under a predetermined condition (for example, under heating) and, if desired, calcination can be performed. When forming the organic insulating layer, if necessary, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-
Glycidyloxypropyltrimethoxysilane, γ-glycidyloxypropylmethyldiethoxysilane, γ-
Glycidyloxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-
Methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, N-β-
(Aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl)-
Surface treatment is performed using a silane coupling agent such as γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and the like, and then an organic insulating layer material or a precursor thereof May be applied. The thickness of the insulating orientation control layer 4 is
Usually, 10 angstroms to 1 μm, preferably 1
0-3000 angstroms, more preferably 1
0 to 1000 angstroms.

The two substrates 2 are kept at an arbitrary interval by the spacer 5. For example, silica beads and alumina beads having a predetermined diameter are sandwiched between the substrates 2 as spacers, and the periphery of the two substrates 2 is sealed with a sealant (for example, an epoxy-based adhesive) so as to have an arbitrary interval. Can be kept. Further, a polymer film or glass fiber may be used as the spacer. A liquid crystal exhibiting a chiral smectic phase is sealed between the two substrates. The thickness of the liquid crystal layer 1 is generally set to 0.5 to 20 μm, preferably 1 to 5 μm, and more preferably 1 to 3 μm. The transparent electrode 3 is connected to an external power supply 7 by a lead wire. Outside the substrate 2, a pair of polarizing plates 8 whose polarization axes are in, for example, a crossed Nicols state are arranged. The example in FIG. 1 is a transmission type,
A light source 9 is provided. Further, the liquid crystal device using the liquid crystal composition of the present invention can be applied not only as a transmissive device shown in FIG. 1 but also as a reflective device.

The display mode of the liquid crystal device using the liquid crystal composition of the present invention is not particularly limited,
For example, (a) helical distortion type, (b) SSFLC (surface stabilized ferroelectric liquid crystal) type, (c) TSM (transient scattering mode) type, (d) GH ( (E.g., guest-host) type and (e) field sequential color type display method can be used.

The driving method of the liquid crystal device using the liquid crystal composition of the present invention may be a passive driving type such as a segment type or a simple matrix type, a TFT (thin film transistor) type, a MIM (metal-insulator-metal). ) Type or the like. Further, the acetylene compound of the present invention and a liquid crystal composition containing the compound may be used in a field other than a liquid crystal element for display (for example, an electronic material such as a nonlinear optical function element, a capacitor material, a limiter, a memory, an amplifier, and a modulator). It can be applied to electronic devices such as, for example, conversion devices and sensors for converting heat, light, pressure, and mechanical deformation and voltage, power generation devices such as thermoelectric power generation devices, spatial light modulation devices, and photoconductive materials.

[0065]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples. The symbols I, S _A and S _C ^* in each example and table have the following meanings. I: Isotropic liquid S _A : Smectic A phase S _C ^* : Chiral smectic C phase The phase transition temperature in the examples was measured using a polarizing microscope equipped with a temperature controller and a DSC (differential scanning calorimeter). It was measured.

Production Example 1: Production of 4-tetrahydropyranyloxy-3-fluorobromobenzene 57.3 g (0.4 g) of 4-bromo-2-fluorophenol
3 mol), 3,4-dihydro-2H-pyran 30.2
g (0.36 mol) and 120 g of chloroform were cooled to 3 ° C. with an ice bath, and 0.03 g of p-toluenesulfonic acid monohydrate was added thereto, followed by stirring at the same temperature for 15 minutes. Thereafter, 2 g of sodium hydrogen carbonate and 30 g of water were added to the reaction mixture to stop the reaction, and the chloroform phase was separated. Chloroform was distilled off under reduced pressure to obtain 80.9 g of 4-tetrahydropyranyloxy-3-fluorobromobenzene as a colorless oil.

Production Example 2: Production of 4-n-decyloxy-3-fluorobromobenzene 19.1 g of 4-bromo-2-fluorophenol, n-
22.1 g of decyl bromide, 13.8 g of potassium carbonate
And a mixture of 50 g of N, N-dimethylformamide was heated to 70 ° C. with stirring, and heated and stirred at the same temperature for 6 hours. Thereafter, the mixture was cooled to room temperature, and 1/2 N hydrochloric acid and toluene were added to neutralize the mixture. After separating the toluene layer and washing with water, toluene was distilled off under reduced pressure, and the residue was distilled under reduced pressure to obtain a fraction of 174 to 176 ° C / 5.5 mmHg. 1 g was obtained as a colorless oil.

Production Example 3: Production of 4-n-decyloxybromobenzene Except that in Preparation Example 2, 17.3 g of 4-bromophenol was used instead of 19.1 g of 4-bromo-2-fluorophenol. According to the procedure described in Production Example 2, as a fraction of 181 to 182 ° C./5 mmHg,
2-6.6 g of 4-n-decyloxybromobenzene were obtained as a colorless oil.

Production Example 4: 4- (4'-tetrahydropyranyloxy-3'-fluorophenyl) -3-butyne-
Production of 1-ol 4-tetrahydropyranyloxy-3-fluorobromobenzene 55.0 g (0.2 mol), 3-butyne-1
-A mixture of 21.0 g (0.3 mol) of all, 2.0 g of triphenylphosphine, 0.4 g of dichlorobis (triphenylphosphine) palladium and 100 g of diisopropylamine was added under a nitrogen atmosphere to 0.8 g of copper iodide and 10 ml of tetrahydrofuran. Was added and the temperature was raised to 75 ° C. over 1 hour. After heating and stirring at the same temperature for 5 hours, diisopropylamine was distilled off, toluene was added to the residue, and the precipitated inorganic salt was separated by filtration. After the filtrate was neutralized and washed with water, toluene was distilled off.
-(4'-Tetrahydropyranyloxy-3'-fluorophenyl) -3-butyn-1-ol was obtained as pale brown crystals (40.1 g).

Preparation Example 5: Preparation of 4- (4'-n-decyloxy-3'-fluorophenyl) -3-butyn-1-ol 9.93 g of 4-n-decyloxy-3-fluorobromobenzene (0.9%). 03 mol), 4.2 g (0.06 mol) of 3-butyn-1-ol, 0.78 g of triphenylphosphine, 5% by weight palladium / carbon (50% by weight)
A mixture of 3.2 g of water (containing 3.2 g), 0.072 g of copper iodide, 10.35 g of potassium carbonate, 33 g of 1,2-dimethoxyethane and 37.5 g of water was heated to 70 ° C. over 30 minutes in a nitrogen atmosphere. . After heating and stirring at the same temperature for 6 hours, the palladium carbon was filtered off, toluene was added, and the mixture was neutralized and washed with water. After separating the organic phase, toluene and 1,2-dimethoxyethane were distilled off under reduced pressure, and the residue was recrystallized from n-hexane to give 4- (4'-decyloxy-3'-fluorophenyl) -3-. 9.10 g of butyn-1-ol was obtained as pale brown crystals.

Production Example 6 Production of 4- (4′-n-decyloxyphenyl) -3-butyn-1-ol In Production Example 5, 9.93 g of 4-n-decyloxy-3-fluorobromobenzene was used. Instead of doing
According to the procedure described in Production Example 5, except that 9.39 g of n-decyloxybromobenzene was used, 4- (4′-n
8.24 g of -decyloxyphenyl) -3-butyn-1-ol was obtained as pale brown crystals.

Production Example 7 Production of 3- (4′-n-decyloxy-3′-fluorophenyl) -2-propyn-1-ol In Production Example 5, 4.2 g of 3-butyn-1-ol was used. Instead of 2-propin-1-ol 3.36
g in accordance with the procedure described in Production Example 5 except that g was used.
(4'-n-decyloxy-3'-fluorophenyl)
7.-2-propyn-1-ol as pale brown crystals
13 g were obtained.

Production Example 8 Preparation of 4- (4'-tetrahydropyranyl-3'-fluorophenyl) -3-butyn-1-yl laurate 4- (4'-tetrahydropyranyl-3'-fluoro A mixture of 2.65 g of phenyl) -3-butyn-1-ol, 2.00 g of lauric acid, 2.06 g of DCC and 30 ml of dichloromethane was stirred at room temperature for 30 minutes.
Thereafter, a catalytic amount of 4-N, N-dimethylaminopyridine was added, and the mixture was further stirred at room temperature for 8 hours. Toluene was added to the reaction mixture, the generated N, N'-dicyclohexylurea was filtered off, and toluene and dichloromethane were distilled off under reduced pressure. The residue was purified by silica gel column chromatography to obtain 3.2 g of 4- (4′-tetrahydropyranyl-3′-fluorophenyl) -3-butyn-1-ol laurate as a pale brown oil.

Production Example 9 Lauric acid 4- (4′-hydroxy-3′-fluorophenyl) -3-butyne-1-
Production of yl ester Lauric acid 4- (4'-tetrahydropyranyl-3 '
A mixture of 3.0 g of -fluorophenyl) -3-butyn-1-yl ester, 20 ml of toluene, 20 ml of methanol and 1 ml of concentrated hydrochloric acid was stirred at room temperature for 3 hours. Thereafter, water was added to the reaction mixture, and the toluene phase was washed until neutral. The toluene was distilled off under reduced pressure, and the residue was recrystallized from n-hexane.
(4′-hydroxy-3′-fluorophenyl) -3-
1.9 g of butyn-1-yl ester were obtained.

Example 1 Preparation of Exemplified Compound 9 A mixture comprising 306 mg of 3- (4'-n-decyloxy-3'-fluorophenyl) -2-propyn-1-ol, 200 mg of lauric acid, 206 mg of DCC and 5 ml of dichloromethane was prepared. After stirring at room temperature for 30 minutes, a catalytic amount of 4-N, N-dimethylaminopyridine was added to the reaction mixture, and the mixture was further stirred at room temperature for 6 hours.
Dichloromethane was distilled off from the reaction mixture under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: toluene).
The compound was recrystallized twice to give Exemplified Compound 9 as colorless crystals (380 m).
g was obtained. The melting point of this compound was 51 ° C.

Example 2 Preparation of Exemplified Compound 24 Exemplified compound 24 was prepared in the same manner as in Example 1, except that 228 mg of myristic acid was used instead of 200 mg of lauric acid. 466 mg were obtained as crystals. The melting point of this compound was 50 ° C.

Example 3 Preparation of Exemplified Compound 38 In Example 1, 3- (4′-n-decyloxy-
Instead of using 306 mg of 3'-fluorophenyl) -2-propyn-1-ol and 200 mg of lauric acid, 4- (4'-n-decyloxyphenyl) -3-
302 mg of butyn-1-ol and 130 of enanthic acid
According to the procedure described in Example 1 except that mg was used,
239 mg of Exemplified Compound 38 was obtained as colorless crystals. The melting point of this compound was 41 ° C.

Example 4: Preparation of Exemplified Compound 56 In Example 1, 3- (4'-n-decyloxy-
Instead of using 306 mg of 3'-fluorophenyl) -2-propyn-1-ol and 200 mg of lauric acid, 4- (4'-n-decyloxyphenyl) -3-
302 mg of butyn-1-ol and pelargonic acid 15
Except that 8 mg was used, 346 mg of Exemplified Compound 56 was obtained as colorless crystals according to the procedure described in Example 1. The melting point of this compound was 47 ° C.

Example 5: Preparation of Exemplified Compound 74 In Example 1, 3- (4'-n-decyloxy-
Instead of using 306 mg of 3′-fluorophenyl) -2-propyn-1-ol and 200 mg of lauric acid, 320 mg of 4- (4′-n-decyloxy-3′-fluorophenyl) -3-butyn-1-ol 288 mg of Exemplified Compound 74 as colorless crystals was obtained according to the procedure described in Example 1 except that 158 mg of pelargonic acid was used. The melting point of this compound was 36 ° C.

Example 6: Preparation of Exemplified Compound 80 In Example 1, 3- (4'-n-decyloxy-
Instead of using 306 mg of 3′-fluorophenyl) -2-propyn-1-ol, instead of using 306 mg of 4- (4′-n-decyloxyphenyl) -3-butyn-1-ol 302 m
Except for using g, according to the procedure described in Example 1, 435 mg of Exemplified Compound 80 was obtained as colorless crystals. The melting point of this compound was 65 ° C.

Example 7 Preparation of Exemplified Compound 82 4- (4'-hydroxy-3'-fluorophenyl) -3-butyn-1-yl laurate 362m
g, a mixture of 96.8 mg of (S) -2-methyl-1-butanol [(S) -amyl alcohol], 288 mg of triphenylphosphine and 5 ml of tetrahydrofuran was added with diethyl azodicarboxylic acid (40%
Toluene solution (478.5 mg) was added, and the mixture was stirred at room temperature for 6 hours. Tetrahydrofuran was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 309 mg of Exemplified Compound 82 as a colorless oil.

Example 8: Preparation of Exemplified Compound 85 In Example 1, 3- (4'-n-decyloxy-
Instead of using 306 mg of 3'-fluorophenyl) -2-propyn-1-ol and 200 mg of lauric acid, 4- (4'-n-decyloxyphenyl) -3-
According to the procedure described in Example 1, except that 302 mg of butyn-1-ol and 187 mg of 10-undecenoic acid were used, 329 mg of Exemplified Compound 85 as colorless crystals was obtained.
Obtained. The melting point of this compound was 46 ° C.

Example 9: Preparation of Exemplified Compound 87 In Example 7, (S) -amyl alcohol 96.8
According to the procedure described in Example 7 except that 167 mg of (S) -perillyl alcohol was used instead of using mg, 254 mg of Exemplified Compound 87 was obtained as colorless crystals. This compound was prepared in methanol / ethanol (5/1
vol / vol) Recrystallized from a mixed solvent. The melting point of this compound was 34 ° C.

Example 10: Preparation of Exemplified Compound 94 In Example 1, 3- (4'-n-decyloxy-
Instead of using 306 mg of 3'-fluorophenyl) -2-propyn-1-ol, 4- (4'-n-decyloxy-3'-fluorophenyl) -3-butyne-1
-Exemplified compound 94 was converted into colorless crystals according to the procedure described in Example 1 except that 320 mg of all was used.
7 mg were obtained. The melting point of this compound was 46 ° C.

Example 11: Preparation of Exemplified Compound 109 0.9 g of 60% by weight sodium hydride was added to n-hexane 5
Washed twice with ml. Here, 5 ml of N, N-dimethylformamide and 4- (4′-n-decyloxy-
3'-fluorophenyl) -3-butyn-1-ol 6
40 mg was added, and the mixture was stirred at room temperature for 30 minutes and at 60 ° C. for 1 hour. The mixture was cooled to room temperature, to which 498 mg of n-dodecyl bromide was added and further heated at 60 ° C. for 6 hours. The reaction mixture was cooled to room temperature, 1 / 2N hydrochloric acid and toluene were added, and the toluene layer was separated and washed with water.
The toluene was distilled off under reduced pressure. The residue was purified by silica gel column chromatography, and the obtained solid was recrystallized twice from ethanol to obtain 366 mg of Exemplified Compound 109 as colorless crystals. The melting point of this compound was 34 ° C.

Example 12: Preparation of Exemplified Compound 111 In Example 11, 4- (4'-n-decyloxy-
3'-fluorophenyl) -3-butyn-1-ol 6
Instead of using 40 mg, 604 mg of 4- (4′-n-decyloxyphenyl) -3-butyn-1-ol
Except for using, 389 mg of Exemplified Compound 111 as colorless crystals was obtained according to the procedure described in Example 11. The melting point of this compound was 33 ° C.

Example 13: Preparation of Exemplified Compound 115 In Example 7, (S) -amyl alcohol 96.8
mg instead of 3-phenylpropanol 1
Except that 50 mg was used, 236 mg of Exemplified Compound 115 as colorless crystals was obtained according to the procedure described in Example 7. This compound was prepared in methanol / ethanol (5/1
vol / vol) Recrystallized from a mixed solvent. The melting point of this compound was 46 ° C.

Example 14: Preparation of Exemplified Compound 118 In Example 7, (S) -amyl alcohol 96.8
Exemplified compound 118 was converted into colorless crystals according to the procedure described in Example 7, except that 156 mg of 3-cyclohexylpropanol was used instead of using mg.
mg. This compound was recrystallized from a mixed solvent of methanol / ethanol (5/1 vol / vol). The melting point of this compound was 31 ° C.

Example 15: Preparation of Exemplified Compound 136 In Example 7, (S) -amyl alcohol 96.8
Example 7 except that 190 mg of 2- (4'-chlorophenoxy) ethanol was used instead of using mg.
In accordance with the procedure described in, 219 mg of Exemplified Compound 136 was obtained as colorless crystals. This compound was recrystallized from a mixed solvent of methanol / ethanol (5/1 vol / vol).
The melting point of this compound was 74 ° C.

Reference Example 1 Preparation of Liquid Crystal Composition The following compound group (Chemical Formula 9) was mixed at the ratio shown below, and heated and melted at 100 ° C. to obtain a liquid crystal composition (ferroelectric liquid crystal composition). Prepared.

[0091]

Embedded image

Example 16: Preparation of liquid crystal composition The liquid crystal composition prepared in Reference Example 1 was added with 10% by weight of Exemplified Compound 24 prepared in Example 2 to prepare a liquid crystal composition.

Example 17: Production of liquid crystal element Two glass plates having a thickness of 1.1 mm were prepared, an ITO film was formed on each of the glass plates, and a surface treatment was further performed. An insulating orientation control layer (CRD-8616 manufactured by Sumitomo Bakelite Co., Ltd.) was spin-coated on the glass plate with the ITO film, and the film was baked at 90 ° C. for 5 minutes and at 200 ° C. for 30 minutes. The alignment film was subjected to a rubbing treatment, and silica beads having an average particle size of 1.9 μm were sprayed on one glass plate. Thereafter, a glass plate was adhered using a sealant so that the respective rubbing treatment axes were antiparallel to each other, thereby producing a cell. The cell was heated to 120 ° C. and heated (1
(20 ° C.), the liquid crystal composition prepared in Example 16 was injected, and then cooled at a rate of 3 ° C./min to produce a liquid crystal element. When this liquid crystal element was sandwiched between two polarizing plates arranged in a crossed Nicols state and a rectangular wave of ± 20 V and 10 Hz was applied, a clear switching phenomenon was observed. In addition, under a polarizing microscope, a favorable uniform alignment state was observed, and no alignment defects such as zigzag defects were observed. 2
The driving characteristics at 5 ° C., 15 ° C., and 5 ° C. are summarized in Table 2 (Table 4). Further, as a measure of the stability of the layer structure, θ-θm at 25 ° C. after the 0 ° C. history and θ at 25 ° C. in the initial state
The difference between -θm was determined and is shown in Table 3 (Table 5) as Δ (θ-θm).

The driving characteristics were measured by the following methods.・ Response time (τ10-90): ± 20 V, 1
A 0 Hz rectangular wave was applied, and the response under a polarizing microscope was detected with a photomultiplier tube, and the response time (transmission light amount 10% -90%) was determined with a digital oscilloscope. Tilt angle: ± 20 V, 1 Hz rectangular wave was applied to the liquid crystal element, and the angle (2θ) of the extinction position at two points was visually determined under a polarizing microscope, and calculated (2θ / 2). Spontaneous polarization: A triangular wave of ± 20 V, 120 Hz was applied to the liquid crystal element, and the spontaneous polarization was determined by a triangular wave method. That is, the current accompanying the polarization inversion is converted into a voltage change by the current-voltage converter,
The integral value of the polarization reversal current was obtained from a digital oscilloscope. Threshold voltage: a rectangular wave of 180 Hz is applied to the liquid crystal element,
The voltage is changed from ± 20V to 0V, and the amount of transmitted light is ± 2
A value that is 95% or less at 0 V is defined as the threshold voltage. Θ-θm: Calculated from the difference between θ determined by the tilt angle and the memory angle (θm) when no electric field was applied. The smaller this value is,
It indicates that the layer structure is close to the bookshelf structure. Δ (θ−θm): initial alignment state, θ−θm at 25 ° C.
And θ−θm at 25 ° C. after the 0 ° C. history.
The smaller the value, the smaller the change in the layer structure due to the low-temperature history.

Example 18: Preparation of liquid crystal composition A liquid crystal composition was prepared by adding 10% by weight of the exemplified compound 38 prepared in Example 3 to the liquid crystal composition prepared in Reference Example 1.

Example 19: Preparation of liquid crystal element Example 17 was repeated except that the liquid crystal composition prepared in Example 18 was used instead of the liquid crystal composition prepared in Example 16. A liquid crystal element was manufactured according to the operation described. When this liquid crystal element was held between two polarizing plates arranged in a crossed Nicols state and a rectangular wave of ± 20 V and 10 Hz was applied, a clear switching phenomenon was observed. In addition, under a polarizing microscope, a favorable uniform alignment state was observed, and no alignment defects such as zigzag defects were observed. The driving characteristics at 25 ° C., 15 ° C., and 5 ° C. are summarized in Table 2. Table 3 shows .DELTA. (. Theta .-. Theta.m) as an index of the change in the layer structure due to the low-temperature history.

Reference Example 2 Preparation of Liquid Crystal Composition The following compound group (Chemical Formula 10) was mixed at the ratio shown below, and heated and melted at 100 ° C. to obtain a liquid crystal composition (ferroelectric liquid crystal composition). Prepared.

[0098]

Embedded image

Example 20: Preparation of liquid crystal composition A liquid crystal composition was prepared by adding 10% by weight of the exemplified compound 94 prepared in Example 10 to the liquid crystal composition prepared in Reference Example 2.

Example 21: Preparation of a liquid crystal device Example 17 was repeated except that the liquid crystal composition prepared in Example 20 was used instead of the liquid crystal composition prepared in Example 16. According to the operation described, a liquid crystal element was manufactured. When this liquid crystal element was held between two polarizing plates arranged in a crossed Nicols state and a rectangular wave of ± 20 V and 10 Hz was applied, a clear switching phenomenon was observed. In addition, under a polarizing microscope, a favorable uniform alignment state was observed, and no alignment defects such as zigzag defects were observed. The driving characteristics at 25 ° C., 15 ° C. and 5 ° C. are summarized in Table 2. Table 3 shows .DELTA. (. Theta .-. Theta.m) as an index of the change in the layer structure due to the low-temperature history.

Example 22: Preparation of a liquid crystal composition A liquid crystal composition was prepared by adding 10% by weight of the exemplified compound 115 prepared in Example 13 to the liquid crystal composition prepared in Reference Example 2.

Example 23: Preparation of liquid crystal device Example 17 was repeated except that the liquid crystal composition prepared in Example 22 was used instead of the liquid crystal composition prepared in Example 16. A liquid crystal element was manufactured according to the operation described. When this liquid crystal element was held between two polarizing plates arranged in a crossed Nicols state and a rectangular wave of ± 20 V and 10 Hz was applied, a clear switching phenomenon was observed. In addition, under a polarizing microscope, a favorable uniform alignment state was observed, and no alignment defects such as zigzag defects were observed. The driving characteristics at 25 ° C., 15 ° C. and 5 ° C. are summarized in Table 2. Table 3 shows .DELTA. (. Theta .-. Theta.m) as an index of the change in the layer structure due to the low-temperature history.

Comparative Example 1 The liquid crystal composition prepared in Reference Example 1 was injected into a liquid crystal cell prepared in the same manner as in Example 17 to prepare a liquid crystal device. This liquid crystal element was sandwiched between two polarizing plates arranged in a crossed Nicols state, and ± 20 V, 1
When a rectangular wave of 0 Hz was applied, a clear switching phenomenon was observed. In addition, under a polarizing microscope, a substantially uniform alignment state was observed, and no alignment defects such as zigzag defects were observed. The driving characteristics at 15 ° C. and 5 ° C. are summarized in Table 2. Table 3 shows .DELTA. (. Theta .-. Theta.m) as an index of the change in the layer structure due to the low-temperature history.

Comparative Example 2 The liquid crystal composition prepared in Reference Example 2 was injected into a liquid crystal cell prepared in the same manner as in Example 17 to prepare a liquid crystal element. This liquid crystal element was sandwiched between two polarizing plates arranged in a crossed Nicols state, and ± 20 V, 1
When a rectangular wave of 0 Hz was applied, a clear switching phenomenon was observed. In addition, under a polarizing microscope, a substantially uniform alignment state was observed, and no alignment defects such as zigzag defects were observed. The driving characteristics at 15 ° C. and 5 ° C. are summarized in Table 2. Table 3 shows .DELTA. (. Theta .-. Theta.m) as an index of the change in the layer structure due to the low-temperature history.

[0105]

[Table 4]

[0106]

[Table 5] Comparison of Example 17, Example 19, Example 21 and Example 23 shown in Table 2 with Comparative Example 1 and Comparative Example 2 shows that the acetylene compound of the present invention is used as a component of the liquid crystal composition. This shows that the response speed of the liquid crystal composition can be improved, θ-θm can be reduced, and the threshold voltage can be reduced. In addition, a large improvement can be confirmed in the driving characteristics (response speed, threshold voltage) at a low temperature (5 ° C.). In addition, Table 3 shows that the use of the acetylene compound of the present invention can greatly suppress the change in the layer structure after low-temperature hysteresis.

[0107]

According to the present invention, it has become possible to provide an acetylene compound useful as a component of a liquid crystal composition.

[Brief description of the 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.

[Description of Signs] 1: Liquid crystal layer having chiral smectic phase 2: 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

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07C 69/24 C07C 69/24 69/533 69/533 C09K 19/20 C09K 19/20 19/32 19 / 32 19/54 19/54 Z 19/56 19/56 G02F 1/13 500 G02F 1/13 500 (72) Inventor Teruo Muraishi 580 Takuji, Nagaura, Sodegaura City, Chiba Prefecture 32 Mitsui Chemicals, Inc. (72 ) Inventor Hideo Hama 580-32 Takuji Nagaura, Sodegaura-shi, Chiba Prefecture Inside Mitsui Chemicals, Inc. (72) Inventor Masakatsu Nakatsuka 580-32 Takuji Nagaura, Sodegaura-shi, Chiba Prefecture 32 F-term in Mitsui Chemicals, Inc. 4H006 AA01 AA03 AB64 GP01 4H027 BA03 BD05 BD12 BD20 BD24 BE04 BE07 CA02 CA03 CA05 CC07 DK07

Claims (4)

[Claims] 1. An acetylene compound represented by the general formula (1) (formula 1). Embedded image (Wherein, R ₁ and R ₂ are a straight-chain or branched-chain alkyl group having 3 to 24 carbon atoms which may be substituted with a halogen atom, and 3 to ₂ carbon atoms which may be substituted with a halogen atom.
4 linear or branched alkenyl groups, 3 to 24 carbon atoms which may be substituted with a halogen atom, linear or branched alkoxyalkyl groups, 3 to 24 carbon atoms which may be substituted with a halogen atom A linear or branched alkenyloxyalkyl group, an aralkyl group having 7 to 15 carbon atoms which may be substituted with a halogen atom, an aryloxyalkyl group having 7 to 15 carbon atoms which may be substituted with a halogen atom, Alternatively, represents a cycloalkylalkyl group having 4 to 15 carbon atoms which may be substituted with a halogen atom, Y ₁ represents an —O— group or a —COO— group, Y ₂ represents a single bond, an —O— group, Represents a —COO— group or a —C≡C— group, n represents an integer of 1 to 4, and X ₁ represents a hydrogen atom or a halogen atom. 2. A liquid crystal composition comprising at least one acetylene compound according to claim 1. 3. An acetylene compound represented by the general formula (1) and at least one compound represented by the following general formula (2), (3) or (4) The liquid crystal composition according to claim 2, comprising: Embedded image (Wherein, R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ and R ₃₂ are each independently a linear or branched chain having 3 to 24 carbon atoms which may have an optically active asymmetric carbon atom. An alkyl group, a linear or branched alkenyl group having 3 to 24 carbon atoms, or a linear or branched alkoxyalkyl group having 3 to 24 carbon atoms, and Y ₁₁ , Y ₁₂ , Y ₂₁ , and Y ₂₂ , Y ₃₁ and Y ₃₂ each independently represent a single bond, a -COO- group or-
Represents a bonding group selected from O- groups) 4. A liquid crystal device comprising the liquid crystal composition according to claim 2 or 3.