JP3315226B2 - Novel polymer compound, ferroelectric liquid crystal composition containing the same and raw material compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polymer compound, a ferroelectric liquid crystal composition containing the same, and a starting compound of the novel polymer compound. More specifically, the present invention relates to the field of optoelectronics, in particular, calculators, digital display elements such as watches, dot matrix display elements, room temperature switching elements, electro-optical shutters, electro-optical diaphragms,
The present invention relates to a novel polymer compound suitably used as a material of a liquid crystal element used for an optical modulator, an optical communication optical path switch, a memory, a liquid crystal printer head, a variable focal length lens, and a ferroelectric liquid crystal composition using the same. .

[0002]

2. Description of the Related Art Conventionally, display devices using low-molecular liquid crystal compounds have been widely used for digital displays such as calculators and watches. In these fields of application, conventional low-molecular liquid crystal compounds are usually used between two glass substrates whose spacing is controlled on 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, attempts have been made 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);
No. 21479, etc.]. However, these conventional polymer liquid crystal compounds have the disadvantage that the polymer itself does not exhibit the properties of a liquid crystal at room temperature, and must be converted into a liquid crystal by heating in a temperature range above the glass transition temperature and below the clearing temperature. are doing.

Japanese Patent Application Laid-Open No. 63-99204 reports the synthesis of a polyacrylate-based ferroelectric 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,
Problems remain in the usable temperature range.

Further, JP-A-63-254529 discloses a polyether-based 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 ′] {u in the formulas [III] and [III ′] is 1 to
Indicates an integer of 30. And a liquid crystal compound of the formula [1].

[0006]

Embedded image WO92 / 01731 pamphlet also discloses, for example, a compound represented by the following formula (IV) consisting of a repeating unit having an aromatic ring in the side chain and having a chain hydrocarbon skeleton and a siloxane skeleton in the main chain. A molecular liquid crystal compound is disclosed.

[0007]

Embedded image However, although these conventional side-chain 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 practical. Is still inadequate.

On the other hand, a polymer liquid crystal composition comprising a polymer liquid crystal compound having an asymmetric carbon and a low-molecular liquid crystal compound has been proposed as a liquid crystal composition (JP-A-63-284291).
No.). However, the side-chain type high-molecular liquid crystal compound exemplified has an ordinary acrylate or siloxane chain as the main chain, so the side-chain spacing is not sufficient, and when the molecular weight is increased, the low-molecular-weight liquid crystal compound can be sufficiently mixed. And speeding up becomes difficult. Therefore, while maintaining the conventional polymer properties,
There is a problem that it is difficult to obtain a composition having high-speed response.

An attempt to obtain a high-speed responsive composition while maintaining high polymerity with a composition comprising a non-liquid crystalline polymer compound and a low-molecular liquid crystal compound has been disclosed in Japanese Patent Application Laid-Open No.
No. 47427 discloses a composition in which a non-liquid crystalline polymer is blended with a low-molecular liquid crystal compound to impart a self-shape retention ability. In this composition, the liquid crystal region is dispersed in the polymer compound (resin) matrix, so that the liquid crystal region may be separated when left for a long time. In addition, since the liquid crystal is dispersed in an island shape, the contrast is high. However, since it is a dispersion system, it is difficult to control the orientation. JP-A-62-260859, JP-A-62-260841
Japanese Patent Application Laid-Open Publication No. H11-177,086 describes a ferroelectric composite film containing a thermoplastic resin and a low-molecular liquid crystal compound, in which a thermoplastic resin that becomes compatible is used, but a low-molecular compound that becomes compatible with this thermoplastic resin is used. It is difficult to combine liquid crystal compounds and control alignment. In addition, there is a problem that low-molecular liquid crystal compounds to be used are limited to ferroelectric liquid crystals. 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 liquid crystal compound having the following formula is described, both the polymer and the low-molecular liquid crystal compound must have a proton donor (or a proton acceptor).
The problem is that both structures are quite limited.

[0010]

SUMMARY OF THE INVENTION The present invention provides 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 quickly to electric field changes.

Another object of the present invention is to provide a diene compound which is a raw material compound used for producing the novel polymer compound.

Furthermore, the present invention provides a ferroelectric liquid crystal comprising the above-mentioned polymer compound and a low-molecular smectic liquid crystal compound, which has good alignment properties (alignment can be easily performed) and has high-speed response to an electric field. It is intended to provide a composition.

[0013]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have a specific mesogen group in the side chain and a flexible siloxane chain or A novel polymer compound having a carbon-silicon bond, a wide side chain interval, and a carbon-silicon bond having a low rotation barrier at the main chain-side chain bond is obtained by using a chiral smectic C in a wide temperature range including a room temperature range. The present inventors have found that a ferroelectric polymer liquid crystal exhibiting a phase (S _C ^* phase) and exhibiting high-speed response to an electric field change can be obtained, and the present invention has been completed based on these findings. .

That is, the present invention provides the following general formula [I]
Weight average molecule consisting of the repeating unit [I] represented by
It is intended to provide a novel polymer compound having an amount of 1,000 to 1,000,000 .

[0015]

Embedded image (Wherein, 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; p represents an integer of 0 or 1; * represents an asymmetric carbon atom;

[0016]

Embedded image Where k is a number from 1 to 13 and j is an integer from 1 to 4. )

1. Novel polymer compound The polymer compound of the present invention has a flexible siloxane chain or carbon-silicon bond in the main chain, has a wide side chain interval, and has a low rotation barrier at the main chain-side chain bond portion. Due to the coupling, when the S _C ^* phase is shown, the S _C ^* phase responds quickly to an electric field change. Further, since it has a structure with a wide side chain interval, even when mixed with a low-molecular liquid crystal compound, the mixture becomes a compatible system and phase separation does not occur. Accordingly, a ferroelectric liquid crystal composition having good orientation can be obtained irrespective of whether or not the polymer exhibits liquid crystallinity.

[0018] The weight average molecular weight of the novel polymer compound of the present invention (Mw) of, 1 is 000～1,000,000, preferably 1,000 to 100,000. M
If w is less than 1,000, the formability of the polymer compound as a film or coating film may be impaired. On the other hand, if it exceeds 1,000,000, the response time may be undesirably long. May appear.

The polymer compound of the present invention can be produced by any method without particular limitation. For example, a diene compound represented by the following general formula (II) (Compound II) and a silicon compound (compound V) represented by the following general formula (V) are preferably produced by copolymerizing at a predetermined ratio by a hydrosilylation reaction in a solvent in the presence of a catalyst. Can be.

[0020]

Embedded image (However, m, n, p, a, b, c and * in the formula are the same as described above.)

[0021]

Embedded image (However, j and k in the formula are the same as described above.) Ratio of compound II and compound V subjected to this copolymerization reaction
Depends on the degree of polymerization of the polymer compound to be obtained. Immediately
In order to obtain a high polymer, the molar ratio (compound II / compound
Compound V) is better to be close to 1 and conversely obtains a compound having a low degree of polymerization.
Need to be greater than 1 or less than 1
There is.

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

There is no particular limitation on the order and system of addition of each component in the above-mentioned copolymerization reaction.
Preferred examples include 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. The catalyst may be added singly or may be dissolved in a solvent such as isopropyl alcohol or hexane.

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

As described above, the desired polymer compound can be synthesized. The polymer compound thus obtained is separated and recovered from the reaction mixture by a known method or the like, and can be obtained as a polymer compound having a desired degree of purification. The polymer compound of the present invention having a high degree of purification can be obtained, for example, by filtering the reaction mixture after completion of the polymerization reaction, dissolving a residue obtained by distilling off the solvent from the filtrate, and dissolving the residue in an appropriate solvent such as methylene chloride. This can be suitably obtained by purifying this by column chromatography using silica gel or the like as a filler.

Hereinafter, the compound II and compound V, which are the starting compounds suitably used for producing the polymer compound of the present invention, will be described in detail.

2. Example of Synthesis of Compound II Step

[0028]

Embedded image (In the formula, X represents a halogen atom or a tosyl group.)

The mixture of compound VI and 4-bromophenol is subjected to an etherification reaction in a solvent in the presence of an alkali reagent to obtain an etherified bromo compound (compound VII). The etherification reaction of this step comprises the compound VI,
It is preferably carried out by mixing 4-bromophenol, an alkali reagent and a solvent in an arbitrary order, and usually heating and stirring at 60 to 100 ° C. As the solvent in this step, for example, a ketone-based solvent such as acetone and 2-butanone, and an ether-based inert solvent such as THF and diisopropyl ether are preferably used. As the alkali 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 suitably used.

Specific examples of compound VI include 4-bromo-1-butene, 4-iodo-1-butene, 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, 1-allyloxy-8-
Bromooctane, 1-allyloxy-8-iodooctane, 1-allyloxy-8-tosyloctane, 1-allyloxy-10-bromodecane, 1-allyloxy-1
0-iododecane, 1-allyloxy-10-tosyldecane and the like can be mentioned.

Further, by using the corresponding iodide or chloride in place of 4-bromophenol, the corresponding iodide or chloride may be obtained in place of compound VII which is a bromide and used in the subsequent step. .

Step

[0033]

Embedded image (I) A compound VIII is obtained by performing a hydrosilylation reaction between compound VII and dichloromethylsilane in a solvent in the presence of a catalyst. Compound VIII is unstable and used for the next reaction without isolation and purification.

(Ii) Compound VIII is reacted with Compound IX and then Compound X to give Compound XI.

The reaction conditions such as the method of adding the solvent, catalyst and reagent in (i) are the same as in the above-mentioned polymerization reaction of the polymer compound.

The solvent used in (ii) is an ether-based inert solvent such as THF or a hydrocarbon-based inert solvent such as toluene or hexane, and the reaction is carried out in an atmosphere of an inert gas such as N ₂ or Ar. The reaction temperature can be arbitrarily set in the range of -70 ° C to 80 ° C, but is usually performed at room temperature or lower.

Compounds IX and X include vinyl lithium (M = Li), allyl lithium (M = Li), vinyl magnesium bromide (M = MgBr), vinyl magnesium chloride (M = MgCl), allyl magnesium bromide (M = M MgBr), allyl magnesium chloride (M = MgCl), 3-butenyl magnesium bromide (M = MgBr), 4-pentenyl magnesium bromide (M = MgBr) and the like. M = MgBr, MgCl
In the case of (1), in order to accelerate the reaction, copper (I) cyanide, copper (I) thiocyanate and the like are added in (ii).

Instead of dichloromethylsilane in (i), a corresponding alkoxysilane compound may be used.

Step

[0040]

Embedded image (I) reacting compound XI with magnesium in a solvent,
The compound XII is obtained by using a Grignard reagent and (ii) further reacting with carbon dioxide. As the solvent (i), an ether inert solvent such as THF is suitable. For promoting the reaction, I ₂ , 1,2-dibromoethane and the like may be added. The reaction is carried out by heating to an appropriate temperature of room temperature or 20 to 80 ° C. in an atmosphere of an inert gas such as nitrogen or argon. In (ii), carbon dioxide may be bubbled into the reaction solution of (i), or the reaction solution of (i) may be added to dry ice. Note that lithium may be used instead of magnesium.

Steps

[0042]

Embedded image Compound XII and compound XIII are reacted with a condensing agent such as DCC (dicyclohexylcarbodiimide) to obtain compound II. 4-
Dimethylaminopyridine or the like may be added. As the solvent, toluene, methylene chloride or the like is used. The reaction is
This is performed in an atmosphere of an inert gas such as nitrogen or argon. The reaction temperature can be arbitrarily set in the range of 0 to 80 ° C., but the reaction is usually performed at room temperature.

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

[0044]

Embedded image The optically active alcohol used here (HO-R¹)age
For example, (+)-2-methylbutanol, (-)
-2-methylbutanol, (+)-2-methylpentano
, (-)-2-methylpentanol, (+)-3-
Methylpentanol, (-)-3-methylpentanol
, (+)-4-methylhexanol, (-)-4-
Tylhexanol, (+)-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
Nol, (+)-2-octanol, (-)-2-oct
Tanol and the like can be mentioned.

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,

[0046]

Embedded image 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 compound 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 compound V include 1,1,3,3-tetramethyldisiloxane,
1,3,3,5,5-hexamethyltrisiloxane,
1,1,3,3,5,5,7,7-octamethyltetrasiloxane and α, ω- having 6 or 7 silicon atoms
Hydrogen oligodimethylsiloxane, and 1,
1-bis (dimethylsilyl) methane, 1,1,4,4-
Examples thereof include tetramethyldisylethylene, 1,3-bis (dimethylsilyl) propane, and 1,4-bis (dimethylsilyl) butane. One of these compounds V may be used alone in the copolymerization reaction, or two or more of them may be used in combination as needed.

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

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

The low-molecular smectic liquid crystal compound used in the present invention is not particularly limited, and one or more compounds selected from conventionally known compounds can be used. As the liquid crystal compound, for example,

[0051]

Embedded image

[0052]

Embedded image (R ² and R ³ in the formula are each a linear or branched alkyl group, alkoxy group, alkoxycarbonyl group or acyloxy group having 1 to 12 carbon atoms, which may be the same or May be different from each other, d, e
Is an integer of 2 to 5, 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 * represents an asymmetric carbon atom. )
And diene compounds represented by the general formula [II] used for the synthesis of the novel polymer compound of the present invention.

Further,

[0054]

Embedded image Etc. can be used. R ⁴ is an alkyl group having 7 to 12 carbon atoms, an alkoxy group having 6 to 15 carbon atoms, or
12 alkoxycarbonyl groups or acyloxy groups, R
⁵ is an alkyl group having 7 to 12 carbon atoms or an alkoxy group having 6 to 11 carbon atoms. R ⁶ and R ⁷ are an alkyl group or an alkoxy group having 4 to 14 carbon atoms, respectively, which may be the same or different from each other. On the other hand, R ⁸ is an alkyl group having 4 to 14 carbon atoms, and R ⁹ is an alkyl group having 5 to 14 carbon atoms or an alkoxy group having 4 to 14 carbon atoms. R ¹⁰ is an alkyl group having 7 to 12 carbon atoms or an alkoxy group having 6 to 20 carbon atoms. Part of the methylene group in R ⁴ and R ¹⁰ may be substituted with an ester group or an oxygen atom. However, ester groups and oxygen atoms do not continue. R ^{4 to} R ¹⁰ may be linear or branched.

Specific examples of these liquid crystal compounds include:

[0056]

Embedded image

[0057]

Embedded image And the like.

Since the novel polymer compound is a comb-shaped polymer in structure, in the mixed ferroelectric liquid crystal composition of the present invention, a low-molecular smectic liquid crystal compound is inserted between the side chains of the polymer to form a phase. It becomes a solution system. FIG. 1 is an explanatory diagram schematically showing this state.

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

Further, since an optically active group is introduced into the comb polymer, even if the low molecular smectic liquid crystal compound to be mixed is a non-chiral smectic liquid crystal, the comb polymer functions as a chiral dopant, The composition can exhibit ferroelectricity, 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 only has to function as a chiral dopant and play a role of imparting moldability and good orientation to the composition. , Not necessarily S _C ^*
It does not need to have a phase.

The method of mixing the high molecular compound and the low molecular 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 smectic liquid crystal compound are put in a container, dissolved in a solvent such as dichloromethane, mixed, and the solvent is evaporated is preferable.

The mixing ratio is preferably such that the fraction of the novel polymer compound is 5 to 99% by weight. When the fraction of the polymer compound is less than 5% by weight, the film forming property and the orientation of the liquid crystal composition may be reduced. In addition, when the low-molecular smectic liquid crystal compound to be mixed is non-chiral, inconvenience such as not exhibiting a ferroelectric phase may occur. When the proportion of the polymer compound exceeds 99% by weight, the response time to the electric field change may be long. The mixture may contain a polymer compound other than the polymer compound of the present invention, a chiral dopant, a dye, an adhesive, and the like.

[0064]

Next, the present invention will be described 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.
/ Μm rectangular wave voltage And changes in the amount of transmitted light at that time
(10 → 90%) required time. The measurement method is
All were performed by the method of Example 7. Also, the inclination angle 2θ
It is a value at 25 ° C.

In the formula showing the phase transition behavior, each symbol has the following meaning. glass: glass phase, S _C ^* : chiral smectic C
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 the measurement methods were performed by the method of Example 7. In the equation showing the phase transition behavior, the numbers represent ° C. Further, in the following examples, Mw represents a weight average molecular weight and is a value in terms of polystyrene measured by GPC.

Example 1 Synthesis of polymer compound A

[0068]

Embedded image Synthesis of compound (1)

[0069]

Embedded image 23 g (87 mmol) of 10-iodo-1-decene, 4
-15 g (87 mmol) of bromophenol, 36 g (0.26 mmol) of potassium carbonate in 2-butanone 150
The ml solution was refluxed for 9 hours under an argon atmosphere. After removing the solid, the solvent was distilled off under reduced pressure. The residue was purified by silica gel chromatography to obtain 18 g (58 mmol) of 4- (9-decenoxy) -bromobenzene (2) (yield 67%).

2.8 g of dichloromethylsilane was added to a solution of 4.0 g (13 mmol) of 4- (9-decenoxy) -bromobenzene (2) in 8 ml of toluene under an argon atmosphere.
(24 mmol) and 4 wt% of chloroplatinic acid hexahydrate 2
-40 µl of a propanol solution was added and reacted at 100 ° C for 4 hours to obtain a dichlorosilane compound (3). After cooling to room temperature, 20 ml of THF was added.

On the other hand, copper (I) cyanide 60 mg (0.6
8 mmol) was suspended in 20 ml of THF, and 38 ml of a 1M ether solution of allyl magnesium bromide (38 mm) was added.
ol) at room temperature. The atmosphere was changed to an argon atmosphere, and the above-mentioned solution of the dichlorosilane compound (3) was added thereto at -30 ° C. Thereafter, the mixture was stirred for 2 hours, and further stirred at room temperature for 4 hours. After washing with aqueous ammonia and brine, the extract was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. Purified by silica gel column chromatography, 3.4 g of bromo compound (1)
(7.7 mmol) was obtained (yield 59%).

Synthesis of Compound (4)

[0073]

Embedded image 4.0 g (9.2 mmol) of bromo compound (1), 0.44 g (18 mmol) of magnesium, and 0.34 g (1.8 mmol) of 1,2-dibromoethane in 100 m of THF.
The solution was refluxed for 6 hours under an argon atmosphere, poured into 68 g of dry ice, and allowed to stand until the temperature rose to room temperature. 200 ml of methylene chloride was added, and the mixture was washed with an aqueous hydrochloric acid solution and brine, and dried over magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 3.4 g (8.4 mmol) of compound (4). (Yield 91%).

Synthesis of Monomer a

[0075]

Embedded image 3.4 g (8.4 mmol) of compound (4), (s) -1
-Methylbutyl 4-hydroxybiphenyl-4'-carboxylate 2.4 g (8.4 mmol), DCC
1.9 g (9.2 mmol), DMAP (N, N-dimethyl
Chill aminopyridine) 0.20 g of (1.6 mmol) was dissolved in toluene 40 ml, and stirred at room temperature for 12 hours. After the precipitate was separated by filtration, the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography and further recrystallized from ethanol to give 2.8 g of monomer a (4.1 m
mol) was obtained (yield 49%). Table 1 shows the various physical properties of the monomer a. The ¹ H-NMR (TMS / CDCl ₃ ) data (p
pm) are shown below.

-0.02 (3H, s), 0.37-0.
67 (2H, b), 0.96 (3H, bt), 1.09
-2.22 (27H, m), 4.05 (2H, t),
4.68-5.00 (4H, m), 5.06-5.36
(1H, m), 5.51-6.05 (2H, m), 6.
84-8.23 (12H, m)

Polymerization Monomer a 0.12 g (0.18 mmol) was added to toluene
The system dissolved in 2.5 ml of argon gas was replaced with argon. 1,
1,3,3-tetramethyldisiloxane 21 mg (0.
16 mmol) and a catalytic amount of chloroplatinic acid hexahydrate,
The reaction was performed at 85 ° C. for 3 hours. Then, 1,1,3,3-
15 mg of tetramethyldisiloxane (0.11 mmol
l) was added, and the mixture was further reacted for 14 hours. Solvent distillation under reduced pressure
And purified by silica gel column chromatography.
Thus, 0.11 g of polymer compound A was obtained (yield: 71%).
Of polymer compound A¹H -NMR charts are shown in FIG.
The properties are shown in Table 2.

Example 2 Synthesis of polymer compound B

[0079]

Embedded image0.30 g (0.45 mmol) of monomer a was dissolved in toluene
The system dissolved in 4 ml was replaced with argon. 1,1,
44 mg of 4,4-tetramethyldisylethylene (0.3 mg)
0 mmol) and 4 wt% of 2-chloroplatinic acid hexahydrate
Add 20 μl of a panol solution and react at 85 ° C. for 5 hours.
Was. After the activated carbon treatment, the solvent was distilled off under reduced pressure, and the residue was silica gel
Purified by column chromatography
0.22 g of B was obtained (64% yield). Polymer compound B
of¹H FIG. 3 shows an NMR chart and Table 2 shows various physical properties.
You.

Example 3 Synthesis of Polymer Compound C

[0081]

Embedded image Synthesis of compound (5)

[0082]

Embedded image 5.7 g of 11-chloro-1-undecene (30 mmol
l), 11 g (75 mmol) of sodium iodide in 2-
The butanone 40 ml solution was refluxed for 5 hours. After cooling to room temperature, solids were removed and this was added to 4-bromophenol5.
8 g (33 mmol), potassium carbonate 13 g (90 mm
ol) in 40 ml of 2-butanone and refluxed for 6 hours under an argon atmosphere. After removing the solid, the solvent was distilled off under reduced pressure. The residue was purified by silica gel chromatography to obtain 8.4 g (26 mmol) of 4- (10-undecenoxy) -bromobenzene (6) (yield: 87).
%).

4- (10-undecenoxy) -bromobenzene (6) 5.0 g (15 mmol) of toluene 8 m
2. Dichloromethylsilane was added to the solution under an argon atmosphere.
5 g (31 mmol) and 4 wt% of chloroplatinic acid hexahydrate
50 μl of a 2-% propanol solution at 100 ° C.
The reaction was carried out for an hour to obtain a dichlorosilane compound (7). After cooling to room temperature, 25 ml of THF was added.

On the other hand, 69 mg (0.7%) of copper (I) cyanide
7 mmol) was suspended in 25 ml of THF, and 40 ml of a 1M ether solution of allyl magnesium bromide (40 mm
ol) at room temperature. Under an argon atmosphere, the above dichlorosilane compound (7) solution was added at −30 ° C. Thereafter, the mixture was stirred for 1 hour, and further stirred at room temperature for 4 hours. After washing with aqueous ammonia and brine, the extract was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. Purified by silica gel column chromatography, 3.5 g of bromo compound (5)
(7.8 mmol) was obtained (yield 52%).

Synthesis of Compound (8)

[0086]

Embedded image 3.5 g (7.8 mmol) of bromo compound (5), 0.38 g (16 mmol) of magnesium, and 0.29 g (1.5 mmol) of 1,2-dibromoethane in THF80m
The solution was refluxed for 5 hours under an argon atmosphere, poured into 40 g of dry ice, and allowed to stand until the temperature rose to room temperature. Methylene chloride was added to make a total of 200 ml, washed with aqueous hydrochloric acid and brine, and dried over magnesium sulfate.
The solvent was distilled off under reduced pressure, and 2.8 g of compound (8) (6.8 mm) was obtained.
ol) was obtained (yield 87%).

Synthesis of monomer b

[0088]

Embedded image 2.8 g (6.8 mmol) of compound (8), (s) -1
-Methylbutyl 4-hydroxybiphenyl-4'-carboxylate 1.6 g (5.5 mmol), DCC
1.6 g (7.5 mmol), DMAP 0.17 g
(1.4 mmol) was dissolved in 25 ml of toluene and stirred at room temperature for 12 hours. After the precipitate was separated by filtration, the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography, and further recrystallized from ethanol to obtain a monomer b (0.77 g, 1.1 mmol) (20%). FIG. 4 shows the ¹ H-NMR chart of the monomer b, and Table 1 shows various physical properties thereof.

Polymerization 0.20 g (0.29 mmol) of monomer b was added to toluene
The system dissolved in 3 ml of argon gas was replaced with argon. 1,1,
47 mg of 3,3-tetramethyldisiloxane (0.35
mmol) and 4 wt% 2-propa of chloroplatinic acid hexahydrate
Then, 15 μl of the phenol solution was added and reacted at 85 ° C. for 8 hours.
Was. The solvent was distilled off under reduced pressure, and the silica gel column chromatography was used.
Purification by filtration yielded 0.18 g of polymer compound C.
(Yield 73%). Of polymer compound C¹H -NMR char
Is shown in FIG. 5 and various physical properties are shown in Table 2.

Example 4 Synthesis of polymer compound D

[0091]

Embedded image0.20 g (0.29 mmol) of monomer b
The system dissolved in 3 ml of argon gas was replaced with argon. 1,1,
28 mg of 4,4-tetramethyldisilethylene (0.1
9mmol) and 4wt% 2-pro of chloroplatinic acid hexahydrate
Add 15 μl of a panol solution and react at 85 ° C. for 5 hours.
Was. The solvent is distilled off under reduced pressure, and the residue is purified by silica gel column chromatography.
Purified by chromatography to obtain 0.22 g of polymer compound D
Was obtained (96% yield). Of polymer compound D¹H -NMR
The chart is shown in FIG. 6, and various physical properties are shown in Table 2.

Example 5 Synthesis of Polymer Compound E

[0093]

Embedded image Synthesis of compound (9)

[0094]

Embedded image Under a argon atmosphere, 3.4 g of dichloromethylsilane (29 g) was added to a solution of 5.0 g (15 mmol) of 4- (8-allyloxyoctanoxy) -bromobenzene in 5 ml of toluene.
mmol) and 50 μl of a 4 wt% solution of chloroplatinic acid hexahydrate in 2-propanol were added and reacted at 100 ° C. for 5 hours to obtain a dichlorosilane compound (10). T after cooling to room temperature
25 ml of HF was added.

On the other hand, 65 mg (0.7%) of copper (I) cyanide
3 mmol) was suspended in 25 ml of THF, and 44 ml of a 1M ether solution of allylmagnesium bromide (44 mm) was added.
ol) at room temperature. The atmosphere was changed to an argon atmosphere, and the above solution of the dichlorosilane (10) was added at -30 ° C. Thereafter, the mixture was stirred for 1 hour, and further stirred at room temperature for 4 hours. After washing with aqueous ammonia and brine, the extract was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. Purified by silica gel column chromatography to obtain the bromo compound (9) 4.2.
g (9.1 mmol) were obtained (61%).

Synthesis of Compound (11)

[0097]

Embedded image 80 g of THF containing 4.2 g (9.1 mmol) of bromo compound (9), 0.44 g (18 mmol) of magnesium and 0.34 g (1.8 mmol) of 1,2-dibromoethane
The solution was refluxed for 4 hours under an argon atmosphere, poured into 31 g of dry ice, and left until the temperature rose to room temperature.
Methylene chloride was added to make a total of 200 ml, washed with aqueous hydrochloric acid and brine, and dried over magnesium sulfate. The solvent was distilled off under reduced pressure, and 3.5 g of compound (11) (8.1 mmol) was obtained.
1) was obtained (89% yield).

Synthesis of monomer c

[0099]

Embedded image 3.5 g (8.1 mmol) of compound (11), (s)-
1-methylbutyl 4-hydroxybiphenyl-4'-
1.8 g (6.5 mmol) of carboxylate, DCC
1.8 g (8.9 mmol), DMAP 0.20 g
(1.6 mmol) was dissolved in 30 ml of toluene and stirred at room temperature for 12 hours. After the precipitate was separated by filtration, the solvent was distilled off under reduced pressure. The residue was purified by silica gel chromatography and further recrystallized from ethanol to give monomer c1.
5 g (2.2 mmol) was obtained (34% yield). Table 1 shows various physical properties of the monomer c, and ¹ H-NMR (TMS / CDC
l ₃ ) Data (ppm) are shown below.

-0.02 (3H, s), 0.49-0.
58 (2H, b), 0.96 (3H, bt), 1.25
-1.90 (25H, m), 3.28-3.43 (4
H, m), 4.04 (2H, bt), 4.78-4.9
2 (4H, m), 5.10-5.24 (1H, m),
5.67-5.86 (2H, m), 6.93-8.20
(12H, m)

Polymerization Monomer c (0.30 g, 0.43 mmol) was added to toluene.
The system dissolved in 4 ml of argon gas was replaced with argon. 1,1,
42 mg of 4,4-tetramethyldisilethylene (0.2 mg
9mmol) and 4wt% 2-pro of chloroplatinic acid hexahydrate
Add 20 μl of a panol solution and react at 85 ° C. for 5 hours.
Was. The solvent is distilled off under reduced pressure, and the residue is purified by silica gel column chromatography.
Purified by chromatography, 0.17 g of polymer compound E was obtained.
(50%). Of polymer compound E¹H -NMR char
7 is shown in FIG. 7, and various physical properties are shown in Table 2.

Example 6 Synthesis of polymer compound F

[0103]

Embedded image Synthesis of monomer d

[0104]

Embedded image 3.8 g of compound (4) obtained in the same manner as in Example 1
(9.5 mmol), (s) -1-methylhexyl 4
-Hydroxybiphenyl-4'-carboxylate3.
0 g (9.6 mmol), DCC 2.2 g (11 mmol
l), 0.23 g (1.9 mmol) of DMAP was dissolved in 30 ml of toluene, and the mixture was stirred at room temperature for 12 hours. After the precipitate was separated by filtration, the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography, and further recrystallized from ethanol to give 3.6 g (5.2 mmol) of monomer d.
Was obtained (55% yield). Table 1 shows various physical properties of the monomer d.
^{The 1} H-NMR (TMS / CDCl ₃ ) data (ppm) is shown below.

-0.02 (3H, s), 0.36-0.
65 (2H, b), 0.97 (3H, bt), 1.08
-2.20 (31H, m), 4.04 (2H, t),
4.65-5.00 (4H, m), 5.08-5.36
(1H, m), 5.52-6.03 (2H, m), 6.
82-8.20 (12H, m)

Polymerization 0.30 g (0.43 mmol) of monomer d was added to toluene.
The system dissolved in 5 ml of argon gas was replaced with argon. α, ω-
Hydrogen oligodimethylsiloxane (weight average
670) 0.15g and 4wt of chloroplatinic acid hexahydrate
Add 25 μl of a 2-propanol solution at 85 ° C. for 8 hours
Reaction. The solvent is distilled off under reduced pressure.
Purified by chromatography, high molecular compound F0.3
4 g were obtained (76% yield). Of polymer compound F Various physical properties
In Table 2,¹H-NMR (TMS / CDCl_Three) Data (p
pm) are shown below.

-0.11-0.17 (20.9H, b
m), 0.42-0.65 (4.1H, b), 0.96
(3H, t), 1.15-1.89 (31H, m),
4.03 (2H, t), 4.77-4.90 (2.2
H, m), 5.14-5.26 (1H, m), 5.72
-5.84 (1.1H, m), 6.93-8.18 (1
2H, m)

[0108]

[Table 1]

[0109]

[Table 2]

Example 7 The polymer compound A obtained in Example 1 and a low-molecular ferroelectric liquid crystal CS-1015 manufactured by Chisso Petrochemical Co., Ltd. were mixed at a weight ratio of 8: 2, and the composition was mixed. Obtained. CS-1015 glass ← −S _C ^* ← −S _A ← −N ^* ← −Iso phase transition −17 ° C. 57.6 ° C. 67.9 ° C. 78.1 ° C. Mixing method Polymer of Example 1 Compound A 40 mg and CS-1015
Weigh 10mg, 5ml solvent (dichloromethane)
And stirred well with each other before evaporating the solvent at about 100 ° C.

The above composition was sandwiched between glass substrates with ITO electrodes (electrode area: 0.2 cm ² , thickness of ITO: 1000 Å), and observed under a polarizing microscope (400 × magnification) 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, an island structure peculiar to the dispersion system was not observed, and the liquid crystal phase was uniformly formed, confirming that it was a compatible system. Subsequently, the liquid crystal was aligned in the cell at 92 ° C. by applying a shear stress between the upper and lower substrates several times (alignment by a shearing method). A rectangular wave voltage of ± 30 V was applied thereto at 25 ° C., and the response time was measured to be 0.50 ms.

Example 8 The polymer compound B obtained in Example 2 and the following liquid crystal P100
8 (Midori Chemical Co., Ltd.) were mixed at a weight ratio of 8: 2.

[0113]

Embedded image The mixing method was the same as in Example 7. The method and conditions for measuring the phase transition and response time were the same as in Example 7.

In the liquid crystal state, the island structure peculiar to the dispersion system was not observed, and it was confirmed that the liquid crystal phase was uniformly formed and was a compatible system.

Example 9 Polymer compound D obtained in Example 4 and the following low-molecular ferroelectric liquid crystal (generally known and synthesized by a conventional method)

[0116]

Embedded image (S _X ^* is a smectic phase higher than the S _C ^* phase) was mixed at a ratio as shown in Table 3. The mixing method was the same as in Example 7.

[0117]

[Table 3] The method of measuring the phase transition and response time was the same as in Example 7.
However, the orientation temperature was set to 110 ° C. for 8: 2 and 115 ° C. for 6: 4.

Example 10 A liquid crystal optical element was produced using a liquid crystal composition having the same composition as in Example 8. The above composition was made into a 20% by weight toluene solution, and a film was formed to a thickness of 3 μm on the electrode surface of a polyethersulfone (PES) substrate with an ITO electrode using a microgravure coater. Immediately after drying the solvent, the same type of substrate on which nothing was applied was laminated so that the liquid crystal layer and the electrode surface were in contact with each other.
3 m in length).

Next, the above-described non-aligned element 4 was subjected to the bending alignment process using an alignment apparatus including a group of four heating rolls as shown in FIG. Each heating roll 3 has a diameter of 80 mm
Of chrome-plated iron having a width of 300 mm. The surface temperature is T ₁ = 95 ° C., T ₂ = 93 ° C., T
₃ = 91 ° C., T ₄ = 87 ° C., and the line speed was v = 8 m / min. The liquid crystal of the unaligned element 4 is cooled from the isotropic phase to the liquid crystal phase while being subjected to shearing by bending deformation by this alignment device, and is finally uniaxially horizontally aligned in a direction perpendicular to the longitudinal direction of the substrate. was gotten.

A polarizing plate was arranged above and below the device so that the polarization axes were orthogonal to each other, and a voltage of ± 20 V was applied between the electrodes. The contrast ratio was measured. The result was 24. A good contrast was obtained. Was.

Thus, it was proved that this composition was suitable for continuously producing a liquid crystal optical element by using the above simple method.

[0122]

Industrial Applicability The novel polymer compound of the present invention is an excellent chiral dopant. When a chiral smectic C phase is developed, it exhibits a chiral smectic C phase in a wide temperature range including room temperature, and has a high speed in electric field change. Respond to

Further, the ferroelectric liquid crystal composition of the present invention has a good alignment property that alignment can be easily performed, and has a high-speed response to an electric field.

The diene compound as the starting 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 the drawings]

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

FIG. 2 shows the relationship between the polymer compound obtained in Example 1 and FIG.¹H -NMR
Art.

FIG. 3 shows a graph of the polymer compound obtained in Example 2.¹H -NMR
Art.

FIG. 4 shows the relationship between the monomer obtained in Example 3 and¹H -NMR char
G.

FIG. 5 shows the relationship between the molecular weight of the polymer compound obtained in Example 3.¹H -NMR
Art.

FIG. 6 shows the relationship between the polymer compound obtained in Example 4 and¹H -NMR
Art.

FIG. 7 shows the relationship between the polymer compound obtained in Example 5 and¹H -NMR
Art.

FIG. 8 is an explanatory diagram of an orientation device used in the examples.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI C09K 19/38 C09K 19/38 G02F 1/13 500 G02F 1/13 500 (56) References JP-A-2-180845 (JP, A) JP-A-5-132558 (JP, A) JP-A-5-170912 (JP, A) JP-A-5-194744 (JP, A) JP-A-5-194745 (JP, A) JP-A-5-156025 ( JP, A) JP-A-6-73179 (JP, A) JP-A-7-149908 (JP, A) JP-A-4-268389 (JP, A) JP-A-4-314784 (JP, A) JP JP-A-5-202358 (JP, A) JP-A-4-320218 (JP, A) JP-A-1-271431 (JP, A) WO 92/1731 (WO, A1) (58) Fields investigated (Int. Cl ^7, DB name) C08G 77/00 -. 77/62 C08L 83/00 - 83/16 C09K 19/38 - 19/40 G02F 1/13 500 CA (STN) REGISTRY (STN)

Claims (5)

(57) [Claims] A weight average molecular weight of the repeating unit [I] represented by the following general formula [I] is from 1,000 to 1,000.
A novel polymer compound of 1,000,000 . Embedded image (Wherein, 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, p represents an integer of 0 or 1, * 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]. Embedded image (Wherein, 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, p represents an integer of 0 or 1, and * represents an asymmetric carbon atom. ) Wherein Ri Do claims 1 novel polymer compound and a smectic liquid crystal compound of one or more low molecular according novel
Fraction is 5 to 99 wt% der Ru ferroelectric liquid crystal composition of the polymer compound. 5. The ferroelectric liquid crystal composition according to claim 4, wherein at least one of the low-molecular smectic liquid crystal compounds is a ferroelectric liquid crystal compound.