JPH07149908A - New polymer, ferroelectric liquid crystal composition prepared therefrom, and raw material compound - Google Patents

Abstract

PURPOSE:To obtain a ferroelectric liq. crystal compsn. which has a good orientatability, quickly responds to an electric field, and exhibits a small temp. dependence of response speed by combining a specific polymer with a lowmolecular smectic liq. crystal compd. CONSTITUTION:A new polymer comprises repeating units of formula I (wherein m and n are each an integer of 2-5; a is an integer of 4-16; b is an integer of 0-3; c is an integer of 1-7; * indicates an asymmetric carbon; Y is a group of formula II; k is an integer of 1-13; and j is an integer of 1-4), exhibits a chiral smectic C phase in a wide temp. range including room temp., quickly responds to change in electric field, exhibits a small temp. dependence of response speed, and is derived from a diene compd. of formula N (wherein m, n, a, b, c, and * are each the same as described above). A ferroelectric liq. crystal compsn. is formed from the polymer and at least one low-molecular smectic liq. crystal compd.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel polymer compound, a ferroelectric liquid crystal composition using the same, and a raw material compound for the novel polymer compound. More specifically, the present invention relates to the field of optoelectronics, in particular, digital display devices such as calculators and watches, dot matrix type display devices, room temperature switching devices, electro-optical shutters, electro-optical diaphragms, optical modulators, optical communication optical path switching switches, The present invention relates to a novel polymer compound suitably used as a material for a liquid crystal element used in a memory, a liquid crystal printer head, a variable focal length lens, etc., and a ferroelectric liquid crystal composition using the same.

[0002]

2. Description of the Related Art Conventionally, a display device using a low molecular weight liquid crystal compound has been widely used for digital display of calculators, watches and the like. In these fields of use, conventional low molecular weight liquid crystal compounds are usually used by sandwiching them between two glass substrates whose spacing is controlled in the order of microns. However,
Such adjustment of the interval cannot be realized on a large screen or a curved screen.

As a means for solving this difficulty, it has been attempted to polymerize the liquid crystal so that the liquid crystal itself can be molded [J. Polym. Sci. , Polym. L
ett. , Ed. 13 , 243 (1975), Poly
m. Bull. 6 , 309 (1982), JP-A-56-
21479, etc.]. However, these conventional polymer liquid crystal compounds have the drawback that the polymer itself does not exhibit the properties as a liquid crystal at room temperature and must be heated to a liquid crystal at a temperature range not lower than the glass transition temperature and lower than the clearing temperature. is doing.

Further, Japanese Patent Application Laid-Open No. 63-99204 reports the synthesis of a polyacrylate-based ferroelectric polymer liquid crystal compound, and the ferroelectric polymer liquid crystal compound is prepared from the above polymer liquid crystal compound. Has also been shown to exhibit excellent performance. However, even in this conventional side chain type ferroelectric polymer liquid crystal compound, the response speed,
There is a problem with the usable temperature range.

Further, in JP-A-63-254529, a polyether type ferroelectric polymer liquid crystal compound obtained by polymerizing an epoxy monomer having an optically active group [for example, represented by the general formula (III)] A repeating unit obtained by polymerizing an epoxy compound and represented by the general formula (III ′) {in the formulas (III) and (III ′), u is 1 to
An integer of 30 is shown. } The polymeric liquid crystal compound consisting of] is disclosed.

[0006]

[Chemical 4] In addition, in WO 92/01731, a repeating unit having an aromatic ring in a side chain and a chain hydrocarbon skeleton and a siloxane skeleton in the main chain is used, for example, a compound represented by the following formula (IV): Molecular liquid crystal compounds are disclosed.

[0007]

[Chemical 5] However, although these conventional side-chain type ferroelectric polymer liquid crystal compounds have the advantage of responding to an external electric field stimulus in a wide temperature range including around room temperature, their response speed is slow and they are not suitable for practical use. Is still insufficient.

On the other hand, as a liquid crystal composition, a polymer liquid crystal composition comprising a polymer liquid crystal compound having asymmetric carbon and a low molecular weight liquid crystal compound has been proposed (Japanese Patent Laid-Open No. 63-284291).
Issue). However, since the side chain type polymer liquid crystal compounds exemplified are those having a normal acrylate or siloxane chain as the main chain, the side chain spacing is not sufficient, and if the molecular weight is increased, a low molecular weight liquid crystal compound can be sufficiently mixed. It becomes difficult to speed up because it disappears. Therefore, while maintaining the conventional high polymer,
There is a problem that it is difficult to obtain a composition having high-speed response.

Further, as an attempt to obtain a composition having a high-speed response while maintaining a high molecular weight by using a composition comprising a non-liquid crystal polymer compound and a low molecular liquid crystal compound, Japanese Patent Laid-Open No. 61-
Japanese Patent No. 47427 describes a composition in which a non-liquid crystalline polymer is blended with a low molecular weight liquid crystal compound to impart self-shape retention ability. In this composition, there is a liquid crystal region that is dispersed in the polymer compound (resin) matrix, so it may separate when left for a long time, and since the liquid crystal is dispersed in islands, the contrast It is difficult to control the orientation because it is a dispersion system. JP-A-62-260859, JP-A-62-260841
In the publication, a ferroelectric composite film containing a thermoplastic resin and a low-molecular liquid crystal compound is described, and a thermoplastic resin that is compatible is used. However, a low-molecular compound that is compatible with the thermoplastic resin is used. It is difficult to combine liquid crystal compounds, and it is difficult to control the alignment. Further, there is a problem that the low molecular weight liquid crystal compound used is limited to the ferroelectric liquid crystal. JP-A-1-19868
No. 3 discloses a polymer having a proton donor (or a proton acceptor) and a proton acceptor (or a proton donor).
Although a composition comprising a low molecular weight liquid crystal compound having is described, since both the polymer and the low molecular weight liquid crystal compound must have a proton donor (or a proton acceptor),
The problem is that both structures are quite limited.

[0010]

The present invention develops a chiral smectic C phase in a wide temperature range including room temperature,
It is an object of the present invention to provide a novel polymer compound that responds to electric field changes at high speed and has a small temperature dependence of its response speed.

Another object of the present invention is to provide a diene compound which is a raw material compound used in the production of this novel polymer compound.

Further, the present invention comprises the above-mentioned polymer compound and a low-molecular-weight smectic liquid crystal compound, and has a good alignment property (the alignment can be easily performed) and has a high-speed response to an electric field and a response speed. It is an object of the present invention to provide a ferroelectric liquid crystal composition having a low temperature dependency of.

[0013]

As a result of intensive studies to solve the above problems, the present inventors have found that a siloxane chain having a specific mesogenic group in the side chain and having a flexible siloxane chain in the main chain. A novel polymer compound having a carbon-silicon bond, a wide side chain interval, and a flexible siloxane unit in a portion near the main chain of a spacer is a chiral smectic C phase (in a wide temperature range including room temperature range). Based on these findings, we have found that it can be an excellent ferroelectric polymer liquid crystal that exhibits a S _C ^* phase), exhibits a high-speed response to electric field changes, and has a small temperature dependence of response speed. The invention was completed.

That is, the present invention provides a novel polymer compound comprising a repeating unit [I] represented by the following general formula.

[0015]

[Chemical 6] (In the formula, m and n are integers of 2 to 5, a is an integer of 4 to 16,
b represents an integer of 0 to 3, c represents an integer of 1 to 7, * represents an asymmetric carbon atom, and Y represents

[0016]

[Chemical 7] Where k is a number from 1 to 13 and j is an integer from 1 to 4. The polymer compound of the present invention has a flexible siloxane chain or a carbon-silicon bond in the main chain, has a wide side chain interval, and further has a flexible siloxane unit in the portion near the main chain of the spacer, when showing the S _C ^* phase, high-speed response to an electric field change at S _C ^* phase. Further, since it has a structure with a wide side chain spacing, even when mixed with a low molecular weight liquid crystal compound, the mixture becomes a compatible system and phase separation does not occur. Therefore, regardless of whether the polymer compound exhibits liquid crystallinity or not, it is possible to obtain a ferroelectric liquid crystal composition having good orientation.

1. Novel polymer compound Weight average molecular weight (Mw) of the novel polymer compound of the present invention
Is usually 1,000 to 1,000,000, and preferably 1,000 to 100,000. When the Mw is less than 1,000, a film of the polymer compound,
Formability as a coating film may be impaired, while
If it exceeds 1,000,000, unfavorable effects such as a long response time may be exhibited.

The method for producing the polymer compound of the present invention is not particularly limited and may be produced by any method. For example, the diene compound represented by the following general formula [II] (Compound II) and a silicon compound (compound V) represented by the following general formula [V] in a predetermined ratio in a solvent, in the presence of a catalyst, by copolymerization by a hydrosilylation reaction. You can

[0019]

[Chemical 8] (However, m, n, a, b, c and * in the formula are the same as above.)

[0020]

[Chemical 9] (However, j and k in the formula are the same as above.) The ratio of the compound II and the compound V to be subjected to this copolymerization reaction depends on the degree of polymerization of the polymer compound to be obtained. That is, in order to obtain a high polymer, the molar ratio (compound II / compound V) should be close to 1, and conversely, to obtain a low degree of polymerization, it should be larger than 1 or smaller than 1. There is a need.

The solvent used in the copolymerization reaction of the compound II and the compound V is, for example, benzene, toluene,
An inert aromatic hydrocarbon such as xylene, an inert ether solvent such as tetrahydrofuran (THF), diisopropyl ether and the like are preferably used. The solvent may be a single solvent or a mixed solvent, but normally, one having a boiling point of 70 ° C. or higher is preferably used in view of the polymerization temperature. As the catalyst, one having hydrosilylation activity is used, and specifically, for example, chloroplatinic acid, platinum (II) acetylacetonate, bis (divinyltetramethyldisiloxane) platinum (0) complex, diamine Platinum-based catalysts such as cyclopentadienylplatinum chloride are preferably used.

There are no particular restrictions on the order and system of addition of the respective components when carrying out the copolymerization reaction, but, for example,
A preferred example is a method in which a solvent such as toluene or THF is added to compound II, and then a predetermined amount of compound V and an appropriate amount of a catalyst such as chloroplatinic acid are added. Regarding the method of adding the catalyst, the catalyst may be added alone or may be added by dissolving it in a solvent such as isopropyl alcohol or hexane.

The copolymerization reaction can be suitably carried out, for example, in an inert atmosphere such as nitrogen gas or argon at a temperature range of usually 60 to 120 ° C., preferably 80 to 100 ° C. The reaction time is usually about 3 to 30 hours.

The desired polymer compound can be synthesized as described above. The polymer compound thus obtained can be separated and recovered from the reaction mixture by a known method or the like to obtain a polymer compound having a desired degree of purification. The polymer compound of the present invention having a high degree of purification is obtained by, for example, filtering the reaction mixture after the completion of the polymerization reaction and distilling the solvent from the filtrate to obtain a residue, which is dissolved in a suitable solvent such as methylene chloride. Can be suitably obtained by purifying it by column chromatography using silica gel as a packing material.

The above-mentioned compound II and compound V, which are raw material compounds preferably used for producing the polymer compound of the present invention, will be described in detail below.

2. Example of synthesis of compound II Step

[0027]

[Chemical 10] (In the formula, X represents a halogen atom or a tosyl group.)

A mixture of compound VI and methyl p-hydroxybenzoate is subjected to an etherification reaction in a solvent in the presence of an alkaline reagent to give an etherified ester compound (compound V
II) is obtained. In the step, compound VI is reacted with methyl p-hydroxybenzoate, but p-hydroxybenzoic acid ester other than methyl ester can be used instead of the latter. In the etherification reaction of this step, compound VI, methyl p-hydroxybenzoate, an alkaline reagent and a solvent are mixed in any order,
Usually, it is suitably carried out by heating and stirring at 60 to 100 ° C. As the solvent in this step, for example, a ketone solvent such as acetone or 2-butanone, TH
An inert ether solvent such as F or diisopropyl ether, or a lower alcohol such as methanol or ethanol is preferably used. As the alkaline reagent in the step, for example, alkali metal carbonates such as potassium carbonate and sodium carbonate, alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, and the like are preferably used.

Specific examples of compound VI include 4-bromo-1-butene, 4-iodo-1-butene and 4-tosyl-.
1-butene, 5-bromo-1-pentene, 5-iodo-
1-pentene, 5-tosyl-1-pentene, 6-bromo-1-hexene, 6-iodo-1-hexene, 6-tosyl-1-hexene, 7-bromo-1-heptene, 7-iodo-1 -Heptene, 7-tosyl-1-heptene, 8-
Bromo-1-octene, 8-iodo-1-octene, 8
-Tosyl-1-octene, 9-bromo-1-nonene, 9
-Iodo-1-nonene, 9-tosyl-1-nonene, 10
-Bromo-1decene, 10-iodo-1-decene, 10
-Tosyl-1-decene, 11-bromo-1-undecene, 11-iodo-1-undecene, 11-tosyl-1
-Undecene, 12-bromo-1-dodecene, 12-iodo-1-dodecene, 12-tosyl-1-dodecene, 1
3-bromo-1-tridecene, 13-iodo-1-tridecene, 13-tosyl-1-tridecene, 14-bromo-1-tetradecene, 14-iodo-1-tetradecene, 14-tosyl-1-tetradecene, 15- Bromo-
1-pentadecene, 15-iodo-1-pentadecene,
15-tosyl-1-pentadecene, 16-bromo-1-
Hexadecene, 16-iodo-1-hexadecene, 16
-Tosyl-1-hexadecene and the like.

Step

[0031]

[Chemical 11] In the step, only the ester bond of the ester form (compound VII) obtained in the step is selectively hydrolyzed to obtain the corresponding carboxylic acid (compound VIII). This hydrolysis can be carried out by various methods, but usually it is suitably carried out by heating Compound VII in the presence of an alkali in water or a mixed solution of water and an alcohol, if necessary, and treating it. The compound VIII is efficiently recovered by adding an appropriate acid to the obtained reaction solution and adjusting the pH to acidic. Note that this hydrolysis reaction may be heated only with an alkali catalyst and water, but by further adding alcohol, the solubility of the ester compound as a raw material is improved, and the reaction proceeds easily. here,
As the alkali, for example, alkali metal hydroxides such as potassium hydroxide and sodium hydroxide are preferably used, and as the alcohol, methanol, ethanol (E
Water-soluble lower alcohols such as tOH) are preferably used. Further, as the acid used for pH adjustment, for example,
Commonly used mineral acids such as hydrochloric acid and sulfuric acid are preferably used.

Step

[0033]

[Chemical 12] In the step, the carboxylic acid (compound VIII) obtained in the step is converted to an acid chloride (compound IX) without a solvent or with an acid halogenating agent in a suitable solvent. This acid halogenation reaction can be suitably performed according to a known method. For example, as the solvent, a commonly used solvent such as toluene may be appropriately selected and used, and as the acid halogenating agent, for example, known compounds such as thionyl chloride, phosphorus oxychloride, phosphorus pentachloride and the like can be used. Acid halogenating agents are used. Further, for example, it is preferable to add an appropriate amount of a reaction accelerator such as pyridine.

Step

[0035]

[Chemical 13] Compound XI is obtained by subjecting an acid chloride (Compound IX) and a hydroxy compound (Compound X) to an esterification reaction in a solvent in the presence of a suitable hydrogen halide acceptor.

Each of the above compounds X can be produced by a known method or the like. At that time, the optically active alkyl group at the terminal portion of the compound X can be easily introduced by utilizing an esterification reaction or the like using an optically active alcohol (HO-R ¹ ).

[0037]

[Chemical 14] Optically active alcohol used here (HO-R¹)age
Are, for example, (+)-2-methylbutanol, (-)
-2-methylbutanol, (+)-2-methylpentano
, (−)-2-methylpentanol, (+)-3-
Methylpentanol, (-)-3-Methylpentano
, (+)-4-methylhexanol, (−)-4-me
Chillhexanol, (+)-2-methylheptanol,
(−)-2-Methylheptanol, (+)-2-Methyl
Octanol, (-)-2-methyloctanol,
(+)-2-butanol, (-)-2-butanol,
(+)-2-Pentanol, (-)-2-Pentanol
(+)-2-hexanol, (-)-2-hexano
, (+)-2-heptanol, (-)-2-hepta
Knoll, (+)-2-octanol, (-)-2-oct
Tanol can be mentioned.

The esterification reaction of the step is, for example,
It can be suitably carried out by introducing a solution of the compound X, a hydrogen halide acceptor and a suitable solvent into the acid chloride (compound IX) obtained in the above step or a solution thereof and stirring the mixture. At that time, when the reactivity is low, it may be heated to an appropriate temperature, for example, 20 to 80 ° C. In this way, the desired compound XI is efficiently obtained.

The acid chloride (compound IX) used as a raw material for the esterification reaction may be an isolated one,
Alternatively, the reaction mixture obtained by appropriately removing the solvent, the acid halogenating agent and the like from the acid chloride-containing reaction mixture obtained in the above step may be continuously used. As a solvent for the esterification reaction in the step, for example, an ether-based inert solvent such as THF, a hydrocarbon-based inert solvent such as toluene and hexane, and the like are preferably used. Further, as the hydrogen halide acceptor, usually, for example, tertiary amines such as pyridine and triethylamine (Et ₃ N) can be preferably used.

In addition, the compound VI
Compound XI can also be obtained by reacting II and compound X in the presence of a condensing agent such as DCC (dicyclohexylcarbodiimide).

In this case, 4-dimethylaminopyridine or the like may be added to accelerate the reaction. As the solvent, toluene, methylene chloride or the like is used. The reaction temperature is 0 to 8
Although it can be arbitrarily set in the range of 0 ° C., it is usually performed at room temperature. Also, under an atmosphere of an inert gas such as nitrogen or argon,
Alternatively, use a salt calcium tube or the like to carry out the reaction to prevent water from entering.

Compound XI can be obtained by, for example, compound VI and the general formula [XII] in addition to the method described above.

[0043]

[Chemical 15] (In the formula, b, c and * are the same as described above.) The hydroxy compound (compound XII) can be produced by carrying out an etherification reaction in a solvent in the presence of an alkaline reagent. The reaction proceeds as follows, for example.

[0044]

[Chemical 16] (Solvent, reagents, reaction conditions are the same as the step.)

Step

[0046]

[Chemical 17] (I) By performing a hydrosilylation reaction between compound XI and chlorodimethylsilane in a solvent in the presence of a catalyst,
Compound XIII is obtained, (ii) Compound XIII is reacted with water to obtain Compound XIV, and (iii) Compound XIV is reacted with Compound XV in a solvent in the presence of a suitable hydrogen halide acceptor. Get II.

The solvent in (i), catalyst, temperature,
Reaction conditions such as a method for adding a reagent are the same as those used for the above-mentioned copolymerization reaction of the polymer compound.

Since the compound XIII obtained in (i) is easily decomposed, it is used as it is in the next reaction (ii) without isolation. In (ii), an equimolar amount of water is dissolved in a solvent such as THF that is miscible with water and added to the reaction solution containing compound XIII. The reaction temperature can be arbitrarily set in the range of 0 to 80 ° C., but it is usually carried out at room temperature or under water cooling. Tertiary amines such as pyridine and triethylamine are added as hydrogen halide acceptors. Alternatively, XIV is obtained by diluting the reaction solution containing compound XIII with diethyl ether or the like, and then adding water containing sodium hydroxide or the like as a hydrogen halide receiving solvent and stirring. When this reaction solution is used as it is in the reaction (iii), it is dehydrated with magnesium sulfate or the like.

The compound XIV obtained in (ii) is purified by a silica gel column or the like and added with an ether inert solvent such as THF or diethyl ether, or a reaction solution in the reaction (ii) without purification, Alternatively, to a solution obtained by adding an ether-based inert solvent such as THF and diethyl ether or a hydrocarbon-based inert solvent such as toluene and hexane to the unpurified reaction solution, add the compound XV to an ether-based inert solvent such as THF and diethyl ether, or Compound II is prepared by dissolving it in a hydrocarbon-based inert solvent such as toluene or hexane and adding it, and further adding a tertiary amine such as pyridine or triethylamine as a hydrogen halide acceptor and stirring the mixture.
To get The reaction is performed at room temperature in an atmosphere of an inert gas such as N ₂ or Ar. When the reactivity is low, it may be heated to an appropriate temperature of 20 to 80 ° C.

Instead of chlorodimethylsilane, alkoxysilane compounds such as methoxydimethylsilane and ethoxydimethylsilane may be used.

Step Method for Synthesizing Compound XV

[0052]

[Chemical 18] (I) Compound XVI is reacted with magnesium in a solvent to obtain compound XVII (M = MgX) or metallic lithium to obtain compound XVII (M = Mg).
Li). Compound XVI can be obtained by halogenating the corresponding alcohol with N-bromosuccinimide / triphenylphosphine, N-chlorosuccinimide / triphenylphosphine, carbon tetrachloride / triphenylphosphine, or the like.

(Ii) Further, the compound XVII is reacted with tetrachlorosilane and then with twice the molar amount of methyllithium as tetrachlorosilane to obtain the compound XV. When M = Li, compound XVII can also be obtained by reacting compound XVII with dichlorodimethylsilane.

The solvent for the reaction of (i) and (ii) is T
Ether type inert solvents such as HF and diethyl ether are preferable. The reaction is carried out in the range of -70 to 80 ° C under an atmosphere of an inert gas such as nitrogen or argon.

In (i), iodine, 1,2-dibromoethane or the like may be added to accelerate the reaction.

Specific examples of the compound XVI include 3-chloromethyl-1,4-pentadiene and 3-chloromethyl-
1,5-hexadiene, 3-chloromethyl-1,6-heptadiene, 4-chloromethyl-1,6-heptadiene, 3-chloromethyl-1,7-octadiene, 4-chloromethyl-1,7-octadiene, 3-chloromethyl- 1,8-nonadiene, 5-chloromethyl-1,8-nonadiene, 4-chloromethyl-1,9-decadiene, 5
-Chloromethyl-1,9-decadiene, 3-chloromethyl-1,10-undecadiene, 6-chloromethyl-
Examples include 1,10-undecadiene and the corresponding bromomethyl compound.

Compound (II) thus obtained
Is useful not only as a raw material of the polymer compound of the present invention but also as a constituent element of a ferroelectric liquid crystal composition.

3. Compound V The silicon compound (compound V) used as a raw material for producing the polymer compound of the present invention is a compound having two Si—H bonds,

[0059]

[Chemical 19] In the case of, when the value of k is 1, 2 or 3, there is almost no distribution in the value of k and a single one is used, but a compound having a large value of k has a distribution in the degree of polymerization (value of k). Therefore, the value of k is represented by an average value. Therefore, k of the obtained polymer compound is also an average value. Specific examples of the compound V include 1,1,3,3-tetramethyldisiloxane, 1,
1,3,3,5,5-hexamethyltrisiloxane,
1,1,3,3,5,5,7,7-octamethyltetrasiloxane, and α, ω-with 6 or 7 silicon atoms
Hydrogen oligodimethyl siloxane, 1,
1-bis (dimethylsilyl) methane, 1,1,4,4-
Examples include tetramethyldisylethylene, 1,3-bis (dimethylsilyl) propane, 1,4-bis (dimethylsilyl) butane. These compounds V may be used alone in the above-mentioned copolymerization reaction, or may be used in combination of two or more kinds, if necessary.

The novel polymer compound of the present invention can be preferably obtained by using the compound II and compound V described in detail above as production raw materials and following the production examples of the polymer compound described above.

4. Ferroelectric Liquid Crystal Composition The present invention also provides a ferroelectric liquid crystal composition comprising the novel polymer compound and a low molecular weight smectic liquid crystal compound.

The ferroelectric liquid crystal composition of the present invention can be obtained by mixing the novel polymer compound and a low molecular weight smectic liquid crystal compound.

The low molecular weight smectic liquid crystal compound used in the present invention is not particularly limited, and one or more arbitrary compounds can be selected and used from conventionally known compounds. Examples of the liquid crystal compound include:

[0064]

[Chemical 20]

[0065]

[Chemical 21] (R ³ and R ⁴ in the formula are each a linear or branched alkyl group having 1 to 12 carbon atoms, an alkoxy group, an alkoxycarbonyl group or an acyloxy group, and they may be the same, They may be different from each other, d, e
Represents an integer of 2 to 5, g represents an integer of 8 to 12, h represents an integer of 0 to 3, i represents an integer of 1 to 7, and * represents an asymmetric carbon atom. )
And a diene compound represented by the general formula [II] used for the synthesis of the novel polymer compound of the present invention.

Furthermore,

[0067]

[Chemical formula 22] A compound represented by can also be used. R ⁵ is an alkyl group, an alkoxy group, an alkoxycarbonyl group or an acyloxy group having 6 to 15 carbon atoms, and R ⁶ is ⁶ to 1 carbon atoms.
2 is an alkyl group or an alkoxy group. R ⁷ and R ⁸ are each an alkyl group or an alkoxy group having 4 to 14 carbon atoms, and they may be the same or different from each other. On the other hand, R ⁹ has 4 to 14 carbon atoms.
Alkyl group, R ¹⁰ is an alkyl group or an alkoxy group having 4 to 14 carbon atoms. R ¹¹ is an alkyl group or an alkoxy group having 6 to 20 carbon atoms. Part of the methylene group in R ⁵ and R ¹¹ may be substituted with an ester group or an oxygen atom. However, ester groups and oxygen atoms are not continuous. R ^{5 to} R ¹¹ may be linear or branched.

Specific examples of these liquid crystal compounds include:

[0069]

[Chemical formula 23]

[0070]

[Chemical formula 24] And so on.

Since the novel polymer compound is a comb-shaped polymer structurally, in the ferroelectric liquid crystal composition of the present invention, which is a mixed system, a low-molecular smectic liquid crystal compound is introduced between polymer side chains. It becomes a melting system. FIG. 1 is an explanatory view schematically showing this situation.

Since the ferroelectric liquid crystal composition of the present invention becomes a compatible system in this way, it has a good contrast ratio and responds quickly to external factors. In addition, since it contains a polymer compound, it has a good alignment property, alignment control is easy, and a liquid crystal optical element can be easily manufactured.

Further, since the optically active group is introduced into the comb polymer, even if the low molecular weight smectic liquid crystal compound to be mixed is a non-chiral smectic liquid crystal, the comb polymer functions as a chiral dopant, Ferroelectricity can be exhibited as the composition, and the liquid crystal composition can be a ferroelectric liquid crystal composition.

Further, in the ferroelectric liquid crystal composition of the present invention, the polymer compound may function as a chiral dopant, and may play a role of imparting moldability and good orientation to the composition. , Not necessarily S _C ^*
It does not have to have a phase.

The method for mixing the high molecular compound and the low molecular weight smectic liquid crystal compound is not particularly limited and may be direct mixing or solution mixing. For example, as the solution mixing, a method in which a predetermined amount of a high molecular compound and a low molecular weight smectic liquid crystal compound is placed in a container, dissolved in a solvent such as dichloromethane and mixed, and the solvent is evaporated is suitable.

The mixing ratio is preferably 5 to 99% by weight of the novel polymer compound. If the proportion of the polymer compound is less than 5% by weight, the film-forming property and the orientation of the liquid crystal composition may deteriorate. In addition, when the low-molecular-weight smectic liquid crystal compound to be mixed is non-chiral, it may cause inconvenience such as not expressing a ferroelectric phase. When the fraction of the polymer compound exceeds 99% by weight, the response time to changes in the electric field may be long. The mixture may contain a polymer compound other than the polymer compound of the present invention, a dye, an adhesive, etc. within a range that does not impair the characteristics of the composition of the present invention.

Examples of the polymer compound other than the polymer compound of the present invention which may be added to the composition of the present invention include a polymer compound composed of the following repeating unit [XVIII]. As a specific example, in the formula [XVIII], d = e = 3, f = 1, g = 10, h = 0, i =
There is a polymer compound having a repeating unit of 2.

[0078]

[Chemical 25] (In the formula, d and e are integers of 2 to 5, f is a number of 1 to 6, g is an integer of 8 to 12, h is an integer of 0 to 3, i is an integer of 1 to 7, and * is asymmetric. Represents a carbon atom.)

[0079]

EXAMPLES Next, the present invention will be explained based on examples, but the present invention is not limited to these examples.

The electric field response time (τ) is ± 10 V at 25 ° C.
The time required for changing the amount of transmitted light (10 → 90%) when a rectangular wave voltage of / μm is applied. All measuring methods were performed by the method of Example 6. Tilt angle 2θ is also 25
It is a value in ° C.

In the formula showing the phase transition behavior, each symbol has the following meaning. glass: glass phase, S _C ^* : chiral smectic C
Liquid crystal phase, Iso: isotropic liquid phase, S _A : smectic A
Phase, N ^* : chiral nematic phase, Cryst: crystalline state The phase transition temperature was determined by observation with a polarizing microscope. All measuring methods were performed by the method of Example 6. In the formula showing the phase transition behavior, the numbers represent ° C. In addition, in the following examples, Mw represents a weight average molecular weight, and is a polystyrene conversion value by GPC measurement.

Example 1 Synthesis of polymer compound A

[0083]

[Chemical formula 26] Synthesis of compound (1)

[0084]

[Chemical 27] 4- (9-decenyloxy) benzoic acid 8.
4 ml of thionyl chloride was added to 0 g, and the mixture was stirred at 65 ° C. for 4 hours. After distilling off excess thionyl chloride under reduced pressure, 20 ml of toluene was added. There, (s) -1-
Methylbutyl 4-hydroxybiphenyl-4'-carboxylate 9.1 g, pyridine 2.8 g toluene 2
The 0 ml solution was added dropwise at room temperature and the reaction was carried out at room temperature for 1 day. The generated insoluble material was removed by filtration, and the solvent was evaporated under reduced pressure. By recrystallization from ethanol, 11.7 g of the desired product (1)
Was obtained (yield 74%).

Synthesis of Monomer a

[0086]

[Chemical 28] 4.5 g of 4-chloromethyl-1,6-heptadiene (3
1 mmol), magnesium 1.5 g (62 mmo
l), 1.2 g of 1,2-dibromoethane (6.2 mmo
A solution of 1) in 100 ml of THF was refluxed under an argon atmosphere for 3 hours. After cooling to room temperature, this was added to a solution of tetrachlorosilane 5.3 g (31 mmol) in THF 50 ml, and the mixture was stirred for 8 hours under an argon atmosphere and water cooling conditions. 49 ml of 1.4M ethereal solution of methyllithium
(69 mmol) was added, and the mixture was stirred under an argon atmosphere and water cooling conditions for 7 hours to give 4-chlorodimethylsilylmethyl-.
An ether solution of 1,6-heptadiene (2) was obtained.

At the same time, 4.5 g (8.3 m) of compound (1)
mol) in 9 ml of toluene, and 1.6 g (17 mmol) of chlorodimethylsilane and 70 μl of a 4 wt% 2-propanol solution of chloroplatinic acid hexahydrate are added,
The mixture was stirred at 100 ° C. for 3 hours under an argon atmosphere to obtain a chlorosilane compound (3). 150 mg of water was added to this reaction solution.
(8.3 mmol), triethylamine 0.84 g
A solution of (8.3 mmol) in 50 ml of THF was added, and the mixture was stirred under an argon atmosphere and water cooling conditions for 10 minutes to obtain a silanol compound (4).

To this reaction solution was added the ether solution of 4-chlorodimethylsilylmethyl-1,6-heptadiene (2) and 2.5 g (25 mmol) of triethylamine.
18 mL of THF solution was added under water cooling under an argon atmosphere. Then, the reaction was carried out for 2 days at room temperature in an argon atmosphere. The extract was washed with brine and dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. After purification by silica gel column chromatography, 1.7 g (2.
2 mmol) was obtained (yield 27%). ¹ H of monomer a
The NMR chart is shown in FIG. 2 and the physical properties are shown in Table 1.

Polymerization A system in which 0.20 g (0.26 mmol) of monomer a was dissolved in 4 ml of toluene was replaced with argon. 1, 1,
38 mg of 3,3-tetramethyldisiloxane (0.28
mmol) and 1 mg of chloroplatinic acid hexahydrate, and added at 85 ° C.
And reacted for 3 hours. Further, 22 mg (0.16 mmol) of 1,1,3,3-tetramethyldisiloxane and a catalytic amount of chloroplatinic acid hexahydrate were added and reacted at 85 ° C. for 4 hours. The solvent was distilled off under reduced pressure and the residue was purified by silica gel column chromatography to obtain 0.23 g of polymer compound A (yield 98%). The ¹ H-NMR chart of polymer compound A is shown in FIG. 3, and its physical properties are shown in Table 2.

Example 2 Synthesis of polymer compound B

[0091]

[Chemical 29] Monomer a 0.15 obtained in the same manner as in Example 1
A system in which g (0.19 mmol) was dissolved in 3 ml of toluene was replaced with argon. α, ω-hydrogenoligodimethylsiloxane (weight average molecular weight 670) 68 mg
And 1 mg of chloroplatinic acid hexahydrate were added and reacted at 85 ° C. for 18 hours. After the treatment with activated carbon, the solvent was distilled off under reduced pressure and the residue was purified by silica gel column chromatography to obtain 0.15 g of polymer compound B (yield 69%). FIG. 4 shows the ¹ H-NMR chart of polymer compound B, and Table 2 shows its physical properties.

Example 3 Synthesis of polymer compound C

[0093]

[Chemical 30] A system in which 0.15 g (0.19 mmol) of monomer a was dissolved in 3 ml of toluene was replaced with argon. 1, 1,
16 mg of 4,4-tetramethyldisylethylene (0.1
1 mmol) and 1 mg of chloroplatinic acid hexahydrate were added, and 85
The reaction was carried out at 0 ° C for 4 hours. After the treatment with activated carbon, the solvent was distilled off under reduced pressure and the residue was purified by silica gel chromatography to obtain 0.15 g of polymer compound C (yield 90%). FIG. 5 shows the ¹ H-NMR chart of polymer compound C, and Table 2 shows its physical properties.

Example 4. Synthesis of polymer compound D

[0095]

[Chemical 31] Synthesis of compound (5)

[0096]

[Chemical 32] To 4.0 g of 4- (10-undecenyloxy) benzoic acid was added 3 ml of thionyl chloride, and the mixture was heated to 70 ° C.
It was stirred for 4 hours. After distilling off excess thionyl chloride under reduced pressure, 30 ml of toluene was added. There, (s)-
1-methylbutyl 4-hydroxybiphenyl-4'-
A solution of 3.7 g of carboxylate and 1.3 g of pyridine in 15 ml of toluene was added dropwise at room temperature, and the mixture was reacted at room temperature for 1 day. The generated insoluble material was removed by filtration, and the solvent was evaporated under reduced pressure. By recrystallization from ethanol, the desired product (5) 4.
3 g was obtained (yield 55%).

Synthesis of Monomer b

[0098]

[Chemical 33] 2.3 g of 4-chloromethyl-1,6-heptadiene (1
6 mmol), 0.76 g of magnesium (31 mmo
l), 0.59 g of 1,2-dibromoethane (3.1 mm
45 ml of THF solution of ol) was refluxed for 4 hours under an argon atmosphere. After cooling to room temperature, this was added to a solution of tetrachlorosilane (2.7 g, 16 mmol) in THF (20 ml) under water cooling conditions, and the mixture was further stirred at room temperature for 2 hours in an argon atmosphere. 22 ml (31 mmol) of a 1.4 M ether solution of methyllithium was added thereto, and the mixture was stirred under an argon atmosphere and water cooling for 1 hour to obtain an ether solution of 4-chlorodimethylsilylmethyl-1,6-heptadiene (2). .

At the same time, 3.5 g (6.3 m) of compound (5)
mol) in 7 ml of toluene, and 1.2 g (13 mmol) of chlorodimethylsilane and 55 μl of a 4 wt% 2-propanol solution of chloroplatinic acid hexahydrate are added,
The mixture was stirred at 100 ° C. for 3 hours under an argon atmosphere to obtain a chlorosilane compound (6). 110 mg of water was added to this reaction solution.
(6.3 mmol), 0.63 g of triethylamine
A solution of (6.2 mmol) in 35 ml of THF was added, and the mixture was stirred under an argon atmosphere and water cooling conditions for 10 minutes to obtain a silanol compound (7).

To this reaction solution, an ether solution of 4-chlorodimethylsilylmethyl-1,6-heptadiene (2) and 1.6 g (16 mmol) of triethylamine were added.
25 ml of THF solution was added under water cooling in an argon atmosphere. Then, the reaction was carried out for 2 days at room temperature in an argon atmosphere. The extract was washed with brine and dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. Purified by silica gel column chromatography, 0.70 g of target monomer b
(0.88 mmol) was obtained (14% yield). FIG. 6 shows the ¹ H-NMR chart of the monomer b, and Table 1 shows its physical properties.

Polymerization The system in which 0.15 g (0.19 mmol) of the monomer b was dissolved in 3 ml of toluene was replaced with argon. 1, 1,
4,4-Tetramethyldisylethylene 17 mg (0.1
2 mmol) and 1 mg of chloroplatinic acid hexahydrate,
The reaction was carried out at 0 ° C for 6 hours. After the treatment with activated carbon, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel chromatography to obtain 0.13 g of polymer compound D (yield 78%). FIG. 7 shows the ¹ H-NMR chart of polymer compound D, and Table 2 shows its physical properties.

Example 5 Synthesis of polymer compound E

[0103]

[Chemical 34] Synthesis of compound (8)

[0104]

[Chemical 35] (S) -1-Methylbutyl 4-of Example 1
The target product (8) was obtained by using (s) -1-methylhexyl 4-hydroxybiphenyl-4′-carboxylate instead of hydroxybiphenyl-4′-carboxylate (yield 73%).

Synthesis of Monomer c

[0106]

[Chemical 36] By using the compound (8) in place of the compound (1) in Example 1, 1.4 g of a monomer c was obtained (yield 20%). The physical properties of the monomers c in Table 1, ¹ H-
The NMR (TMS / CDCl ₃ ) data (ppm) is shown below. -0.04-0.15 (12H, m), 0.4
5-0.62 (4H, m), 0.90 (3H, t),
1.22-1.91 (28H, m), 2.02-2.1
4 (4H, m), 4.06 (2H, t), 4.95-
5.06 (4H, m), 5.12-5.25 (1H,
m), 5.67-5.87 (2H, m), 6.94-
8.20 (12H, m)

Polymerization A system in which 0.20 g (0.25 mmol) of monomer c was dissolved in 4 ml of toluene was replaced with argon. 1, 1,
27 mg (0.20) of 3,3-tetramethyldisiloxane
mmol) and 20 μl of a 4 wt% 2-propanol solution of chloroplatinic acid hexahydrate and reacted at 85 ° C. for 9 hours. After treatment with activated carbon, the solvent was distilled off under reduced pressure and the residue was purified by silica gel column chromatography to obtain polymer compound E.
0.15 g was obtained (yield 66%). Table 2 shows various physical properties of the polymer compound E, and ¹ H-NMR (TMS / CDCl ₃ ) data (ppm) is shown below.

-0.03-0.14 (20H, m),
0.42-0.60 (6H, m), 0.90 (3H,
t), 1.11-1.86 (34H, m), 2.00-
2.08 (1.8H, m), 4.25 (2H, t),
4.92-5.02 (1.8H, m), 5.12-5.
22 (1H, m), 5.68-5.81 (0.9H,
m), 6.94-8.18 (12H, m)

[0109]

[Table 1]

[0110]

[Table 2]

Example 6 The polymer compound D obtained in Example 4 and the ferroelectric liquid crystal CS-1015 manufactured by Chisso Petrochemical Co., Ltd. were mixed at a weight ratio of 8: 2.
To obtain a composition. Mixing method 40 mg of polymer compound D of Example 4 and CS-1015
Weigh 10 mg and use 5 ml of solvent (dichloromethane).
, And well stirred with each other, the solvent was evaporated at about 100 ° C.

The above composition was sandwiched between glass substrates with an ITO electrode (electrode area: 0.2 cm ² , ITO thickness: 1000 Å) and observed under a polarizing microscope (magnification: 400 times) to identify phases. (Cell thickness, 3 μm). A voltage of ± 10 V was applied between the upper and lower electrodes as needed. In the liquid crystal state, the island-like structure peculiar to the dispersion system was not observed, and it was confirmed that the liquid crystal phase was uniform and that the system was a compatible system. Subsequently, the liquid crystal was aligned in the above cell at 97 ° C. by applying shear stress between the upper and lower substrates several times (alignment by the shearing method). A rectangular wave voltage of ± 30 V was applied to this at 25 ° C., and the response time was measured and found to be 1.93 ms.

Example 7 The polymer compound A obtained in Example 1 and the following liquid crystal P100
8 (manufactured by Midori Kagaku Co., Ltd.) were mixed at a weight ratio of 8: 2.

[0114]

[Chemical 37] The mixing method was the same as in Example 6. Response time at 25 ° C. 0.42 ms Phase transition, response time measurement method and conditions were the same as in Example 6. (However, the orientation temperature is 86 ° C.) In the liquid crystal state, the island-like structure peculiar to the dispersion system was not observed, and it was confirmed that the liquid crystal phase was uniform and the system was compatible.

Example 8 The polymer compound B obtained in Example 2 and the following liquid crystal P908
(Midori Kagaku Co., Ltd.) were mixed at a weight ratio of 8: 2.

[0116]

[Chemical 38] The mixing method was the same as in Example 6. Response time at 25 ° C. 0.35 ms Phase transition, response time measurement method and conditions were the same as in Example 6. (However, the orientation temperature is 91 ° C.) In the liquid crystal state, the island-like structure peculiar to the dispersion system was not observed, and it was confirmed that the liquid crystal phase was uniform and the system was compatible.

Example 9 The polymer compound E obtained in Example 5 and the following low-molecular ferroelectric liquid crystal (generally known and synthesized by a conventional method)

[0118]

[Chemical Formula 39] (S _X ^* is a smectic phase higher than the S _C ^* phase) was mixed at a polymerization ratio of 8: 2. The mixing method was the same as in Example 6. Response time at 25 ° C. 0.41 ms 3 Phase transition, response time measurement method and conditions were the same as in Example 6. (However, the alignment temperature is 85 ° C.) In the liquid crystal state, the island-like structure peculiar to the dispersion system was not observed, and it was confirmed that the liquid crystal phase was uniform and the system was a compatible system.

Example 10 A liquid crystal optical element was produced using the liquid crystal composition having the same composition as in Example 7. A 20 wt% toluene solution of the above composition was used to form a film having a thickness of 3 μm on the electrode surface of a polyether sulfone (PES) substrate with an ITO electrode using a microgravure coater. Immediately after the solvent was dried, a substrate of the same type with nothing applied was laminated so that the liquid crystal layer and the electrode surface were in contact with each other, and the unaligned element raw material (width 150 mm,
A length of 3 m) was produced.

Then, the unorientation element 4 was subjected to bending orientation treatment using an orienting device composed of a group of four heating rolls as shown in FIG. Each heating roll 3 has a diameter of 80 mm
Was made of chrome-plated iron and had a width of 300 mm. Surface temperature is T ₁ = 89 ° C, T ₂ = 87 ° C, T
_The line speed was set to v = 8 m / min by controlling ₃ = 85 ° C. and T ₄ = 81 ° C. By this aligning device, the liquid crystal of the unaligned element 4 is cooled from the isotropic phase to the liquid crystal phase while being sheared by the bending deformation, and finally it is uniaxially horizontally aligned in the direction perpendicular to the substrate longitudinal direction, and the aligned element 5 was gotten.

Polarizing plates were arranged above and below the above element so that the polarization axes were orthogonal to each other, a voltage of ± 20 V was applied between the electrodes, and the contrast ratio was measured to be 26, showing that good contrast was obtained. It was

Therefore, it was demonstrated that this composition is suitable for continuous production of liquid crystal optical elements using the above-mentioned simple method.

Example 11 Synthesis of Monomer a by Alternative Method Synthesis of Compound (1) (Alternative Method) 4- (9-decenyloxy) benzoic acid
5 g (20 mmol), (S) -1-methylbutyl 4
-Hydroxybiphenyl-4'-carboxylate 5.
Dichloromethane 6 was added with 7 g (20 mmol), 4-dimethylaminopyridine 0.24 g (2 mmol) and dicyclohexylcarbodiimide 6.2 g (30 mmol).
It was dissolved in 0 ml and stirred at room temperature for 4 hours. The resulting insoluble solid was removed by filtration, washed with water, and the solvent was distilled off under reduced pressure. Target compound (1) by recrystallization from ethanol
9.3 g was obtained (yield 86%).

Synthesis of Monomer a (Alternative Method) 1.9 g (280 mmol) of lithium foil was put in 50 ml of dry ether and cooled with ice water. While stirring vigorously, 4-chloromethyl-1,6-heptadiene 1 was added thereto.
A solution of 0.1 g (70 mmol) in 50 ml of ether was added over 1.5 hours, and then the mixture was further stirred under ice-water cooling for 1 hour. This was placed in another flask, and 10.3 g (80 mmol) of dimethyldichlorosilane was added to ether 5
The solution was added dropwise to a 0 ml solution under ice-water cooling for 30 minutes, further returned to room temperature and stirred for 1 hour. The resulting white solid was removed by filtration with glass wool, the solvent was distilled off under atmospheric pressure, and the residue was distilled under reduced pressure to give 4-chlorodimethylsilylmethyl-
11.4 g of 1,6-heptadiene (2) was obtained. (Yield 80%, bp 57-58 ° C / 3 Torr).

5.4 g (10 mmol) of the compound (1) and 1.9 g (20 mmol) of chlorodimethylsilane were added to 10 ml of anhydrous toluene. 0.1 ml of 0.1 M chloroplatinic acid / 2-propanol solution (0.01 m
mol) was added and the mixture was heated with stirring at 80 ° C. for 3 hours to obtain a chlorosilane compound (3) solution. After distilling off excess chlorodimethylsilane, the temperature was returned to room temperature, and the amount of diethyl ether was 30 m.
1 was added to dilute, and the mixture was cooled with ice water. A 1 M sodium hydroxide aqueous solution was added to the solution over 10 minutes to the neutral point with vigorous stirring. The ether layer was separated, washed with a solubilized saline solution, dried over magnesium sulfate, and then the solvent was distilled off with an evaporator. The residue was purified by silica gel column chromatography to obtain silanol compound (4) 5.
3 g (yield 85%) was obtained. This was dissolved in 5 ml of anhydrous THF and 2.0 g of triethylamine (20.0 mmo
l) was added. In this, 1.8 g (8.7 mm) of 4-chlorodimethylsilylmethyl-1,6-heptadiene (2)
ol) in 5 ml of anhydrous THF was added, and the mixture was stirred for 5 hours at room temperature. After that, water was added to stop the reaction, and the mixture was extracted with methylene chloride and washed with water. After drying with magnesium sulfate,
The solvent was distilled off with an evaporator, and the residue was purified by silica gel column chromatography to obtain 4.5 g of a crude product. Ethanol was added to this, and it melt | dissolved by heating, it cooled to room temperature and the target object was reprecipitated. The solvent is decanted and removed, and the desired monomer a3.
6 g (yield 54%) was obtained. It was confirmed by ¹ H-NMR measurement that the monomer a obtained in this example was the same as the monomer a obtained in example 1.

Example 12 Polymer compound A obtained in Example 1, P1008 shown in Example 7, P908 shown in Example 8, and the following compounds

[0127]

[Chemical 40] Were mixed in a ratio of 6: 1: 1: 2 to obtain a composition. The mixing method was the same as in Example 6. (However, the orientation temperature is 78
℃) Response time at 25 ° C. 0.48 ms Tilt angle at 25 ° C. 2θ 47 ° (Response time at 0 ° C.) / (Response time at 40 ° C.) 2
5

Comparative Example Polymer compound A in Example 12 was prepared by repeating the following repeating unit.

[0129]

[Chemical 41] A composition having the same composition as in Example 12 was obtained except that the polymer compound (Mw = 4700) was substituted.
The mixing method was the same as in Example 6. (However, the orientation temperature is 85 ℃) Response time at 25 ° C 1.0 ms Tilt angle at 25 ° C 2θ 51 ° (Response time at 0 ° C) / (Response time at 40 ° C) 4
Two

[0130]

INDUSTRIAL APPLICABILITY The novel polymer compound of the present invention is an excellent chiral dopant, and when a chiral smectic C phase is expressed, the chiral smectic C phase is expressed in a wide temperature range including room temperature, and the electric field changes rapidly. Respond to.

Further, the ferroelectric liquid crystal composition of the present invention has a good alignment property which allows easy alignment, and also has a high speed response to an electric field.

The diene compound which is the starting material compound of the present invention is a novel compound useful as a starting material for the novel polymer compound of the present invention.

[Brief description of drawings]

FIG. 1 is an explanatory view showing a state in which a high molecular compound and a low molecular weight smectic liquid crystal compound form a compatible system in a ferroelectric liquid crystal composition of the present invention.

FIG. 2 is a ¹ H-NMR chart of Monomer a obtained in Example 1.

FIG. 3 ¹ H-NMR of polymer compound A obtained in Example 1.
chart.

FIG. 4 ¹ H-NMR of polymer compound B obtained in Example 2
chart.

FIG. 5 ¹ H-NMR of polymer compound C obtained in Example 3
chart.

FIG. 6 is a ¹ H-NMR chart of Monomer b obtained in Example 4.

FIG. 7 ¹ H-NMR of polymer compound D obtained in Example 4
chart.

FIG. 8 is an explanatory diagram of an alignment device used in Example 10.

Claims (5)

[Claims] 1. A novel polymer compound comprising a repeating unit [I] represented by the following general formula [I]. [Chemical 1] (In the formula, m and n are integers of 2 to 5, a is an integer of 4 to 16,
b represents an integer of 0 to 3, c represents an integer of 1 to 7, * represents an asymmetric carbon atom, and Y represents Where k is a number from 1 to 13 and j is an integer from 1 to 4. ) 2. The novel polymer compound according to claim 1, which exhibits a chiral smectic C phase. 3. A diene compound represented by the following general formula [II]. [Chemical 3] (In the formula, m and n are integers of 2 to 5, a is an integer of 4 to 16,
b represents an integer of 0 to 3, c represents an integer of 1 to 7, and * represents an asymmetric carbon atom. ) 4. A ferroelectric liquid crystal composition comprising the novel polymer compound according to claim 1 and one or more low molecular weight smectic liquid crystal compounds. 5. The ferroelectric liquid crystal composition according to claim 4, wherein at least one of the low molecular weight smectic liquid crystal compounds is a ferroelectric liquid crystal compound.