JPH05156025A - Liquid crystal copolymer, dienic compound used for its production and ferrodielectric liquid crystal composition - Google Patents

Abstract

PURPOSE:To provide a new liquid crystal copolymer having specific repeating units. capable of quickly responding to electric fields at a wide temperature range and permitting to readily control a phase transfer temperature by the adjustment of the composition. CONSTITUTION:The objective copolymer comprises repeating units of formula I and II {(p), (q), (s), (t) are 2-5; (m), (n) are 2-20; (a) is 0-3; (b) is 1-8; (r) is 0-5; R<1> is group of formula III or IV [R<2> is group of formula V or VI (R<3> is H, methyl; (c) is 0-4; (d) is 1-8], etc.} in an unit I/II molar ratio of 1/99 to 99/1. This copolymer is produced e.g. by copolymerizing a dienic compound of formula VIII and a dienic compound of formula VIII with a silicon compound such as 1,1,3,3-tetramethyldisiloxane in the presence of a catalyst such as platinic chloride by a hydrosilylation reaction.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a copolymer having liquid crystallinity, and more specifically, it exhibits a high-speed electric field response in a wide temperature range, and the phase transition temperature can be easily controlled by adjusting the composition. The present invention relates to a liquid crystal copolymer which is an excellent polymer liquid crystal having advantages such as being able to be used and can be suitably used in various fields of liquid crystal utilization such as liquid crystal display.

The present invention further relates to a diene compound used in the production of the liquid crystal copolymer and a ferroelectric liquid crystal composition using the liquid crystal copolymer.

[0003]

2. Description of the Related Art Conventionally, a display element using a low-molecular liquid crystal is
Widely used for digital displays such as calculators and clocks. In these fields of application, conventional low molecular weight liquid crystals 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 crystals have the disadvantage that the polymer itself does not exhibit the properties as a liquid crystal at room temperature and must be heated to a liquid crystal by heating in a temperature range above the glass transition temperature and below the clearing temperature. ing.

Further, Japanese Unexamined Patent Publication (Kokai) No. 63-99204 reports the synthesis of a polyacrylate-based ferroelectric polymer liquid crystal, which is superior to the above-mentioned polymer liquid crystals. It has been shown to show performance.
However, even in this conventional side chain type ferroelectric polymer liquid crystal, there still remain problems in response speed, usable temperature range and the like.

Further, in JP-A-63-254529, a polyether type ferroelectric polymer liquid crystal obtained by polymerizing an epoxy monomer having an optically active group [eg,
The repeating unit obtained by polymerizing the epoxy compound represented by the general formula (VI) and represented by the general formula (VI ') {u in the formulas (VI) and (VI') is an integer of 1 to 30). Indicates. } Polymeric liquid crystal].

[0007]

[Chemical 7] However, although this conventional side-chain type ferroelectric polymer liquid crystal has an advantage of responding to an external electric field stimulus in a wide temperature range including around room temperature, its response speed is slow and it is not yet ready for practical use. Is 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).
Publication). However, the side chain type polymer liquid crystal compounds exemplified are ordinary acrylate and siloxane chains, so the side chain spacing is not sufficient, and if the molecular weight is increased, low molecular weight liquid crystal compounds cannot be mixed sufficiently and it is difficult to increase the speed. Become. Therefore, there is a problem that it is difficult to obtain a high-speed composition while maintaining the conventional polymer property.

[0009]

DISCLOSURE OF THE INVENTION The present invention is a liquid crystal which is remarkably excellent in practical use because it shows an electric field response at a high speed in a wide temperature range and the phase transition temperature can be easily controlled by adjusting the composition. It is intended to provide a copolymer.

Another object of the present invention is to provide a diene compound used for producing the liquid crystal copolymer.

Further, the present invention comprises a ferroelectric liquid crystal comprising the liquid crystal copolymer and a low molecular weight smectic liquid crystal compound, having excellent compatibility with each other, having good orientation, and having high-speed response to an electric field. It is intended to provide a composition.

[0012]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a repeating unit [I] having a tricyclic side chain and a side chain of a divalent system. A copolymer having a novel structure containing a repeating unit [II] having a ratio of a certain range expresses a chiral smectic C phase (Sc ^* phase) in a wide temperature range including a room temperature range, and changes in electric field. On the other hand, an excellent ferroelectric polymer liquid crystal exhibiting high-speed response is obtained, and further, the liquid crystal temperature range can be easily controlled by adjusting the ratio of the repeating unit [I] and the repeating unit [II]. Also,
It has been found that the ratio can be easily adjusted by adjusting the use ratio of the trivalent monomer and the divalent monomer.
The present inventors have completed the present invention based on these findings.

That is, according to the present invention, the repeating unit [I] represented by the following general formula (I) and the repeating unit [II] represented by the following general formula (II):

[0014]

[Chemical 8] [However, in the formula, p, q, s, and t are integers of 2 to 5, m and n
Is an integer of 2 to 20, a is an integer of 0 to 3, b is an integer of 1 to 8, r is a number of 0 to 5, * represents an asymmetric carbon atom, and R ¹ is

[0015]

[Chemical 9] And R ² is an optically active alkyl group represented by the general formula (III) or an optically inactive alkyl group represented by the general formula (IV)

[0016]

[Chemical 10] (However, R ³ in the formula represents hydrogen or a methyl group, and c is 0.
Is an integer of 4 and d is an integer of 1 to 8, and * represents an asymmetric carbon atom. ) Is represented. ] And the molar ratio ([I] / [II]) of repeating units [I] and [II] is (1
/ 99) to (99/1). A liquid crystal copolymer is provided.

In the liquid crystal copolymer of the present invention, it is important that the ratio of the repeating unit [I] to the repeating unit [II] is within the above specific range, and the ratio is within such a specific range. As a result, it is possible to realize the expression of the Sc ^* phase in a sufficiently wide temperature range and a sufficient high-speed response to the electric field change. The preferable range of the molar ratio ([I] / [II]) is (98/2) to (50/50). The liquid crystal copolymer of the present invention has the repeating unit [I]
By adjusting the proportion of the repeating unit [II], the temperature range of the Sc ^* phase can be easily controlled. The liquid crystal copolymer of the present invention may contain other repeating units as long as the object of the present invention is not impaired.

The weight average molecular weight (Mw) of the liquid crystal copolymer of the present invention is usually 1,000 to 1,000,000, preferably 1,000 to 100,000.
When Mw is less than 1,000, moldability as a film or coating film of the liquid crystal copolymer may be impaired,
On the other hand, if it exceeds 1,000,000, unfavorable effects such as a long response time may appear.

The method for producing the liquid crystal copolymer of the present invention is not particularly limited and may be produced by any method. For example, the diene compound represented by the general formula (A) ( Compound A), a diene compound (Compound B) represented by the general formula (B) and a silicon compound (Compound C) represented by the general formula (C) in a predetermined ratio in a solvent in the presence of a catalyst, hydrosilyl It can be suitably produced by copolymerization by a chemical reaction.

[0020]

[Chemical 11] (However, a, b, m, n, p, q, s, t, r and R ¹ in the formula have the same meanings as described above.) The ratio of the compound A and the compound B to be subjected to the copolymerization reaction is
The repeating units [I] and [I
I] may be selected so that the ratio is within the above range.
For that purpose, the molar ratio (A / B) is usually (99/1)
To (1/99), preferably (98/2) to (50/5)
It is better to select the range of 0).

The ratio of the compound C to be used in this copolymerization reaction depends on the degree of polymerization of the copolymer to be obtained. That is, in order to obtain a high polymer, the molar ratio ((A + B) /
C) is preferably close to 1, and conversely, in order to obtain a polymer having a low degree of polymerization, it needs to be larger than 1 or smaller than 1.

Examples of the solvent used in the copolymerization reaction of the compound A, the compound B and the compound C include inert aromatic hydrocarbons such as benzene, toluene and xylene, inert solvents such as tetrahydrofuran (THF) and diisopropyl ether. A suitable ether solvent is 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. Further, as the catalyst, one having hydrosilylation activity is used, and specifically, for example, a platinum-based catalyst such as chloroplatinic acid, platinum (II) acetylacetonate, dicyclopentadienylplatinum chloride is preferably used. To be

There are no particular restrictions on the order and system of addition of each component when carrying out the copolymerization reaction, but for example,
A preferred example is a method of adding a solvent such as toluene or THF to a mixture of compound A and compound B in a predetermined ratio, and then adding a predetermined amount of compound C and an appropriate amount of a catalyst such as chloroplatinic acid. be able to.

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

The desired liquid crystal copolymer can be synthesized as described above. The liquid crystal copolymer thus obtained can be separated and recovered from the reaction mixture by a known method or the like to obtain a liquid crystal copolymer having a desired degree of purification. The liquid crystal copolymer of the present invention having a high degree of purification is obtained, for example, by 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. And purified by column chromatography using, for example, silica gel as a packing material.

The liquid crystal copolymer of the present invention produced as described above exhibits a Sc ^* phase in a wide temperature range, usually including room temperature, and exhibits a rapid response to a change in an electric field. (Repeating unit [I] and repeating unit [II]
It is an excellent polymer liquid crystal having an advantage that the phase transition temperature can be easily controlled by adjusting the content ratio), and thus can be suitably used not only for liquid crystal displays but also for various liquid crystal application fields. ..

The compounds A, B and C, which are the respective monomers preferably used for the production of the liquid crystal copolymer of the present invention, will be described in detail below.

The compound A represented by the general formula (A) can be obtained, for example, as follows. First R ⁶ -OH
(D)

[0029]

[Chemical 12]Alcohol represented by (Compound D) and the following general formula
(E) X (CH₂)_mX (E) (where X is a chlorine atom, a bromine atom, an iodine atom
Or two tosyl groups and the like, and the two Xs may be the same kind
Or they may be different. Further, m has the same meaning as above.
Represent ) Dissolved with a bifunctional compound (compound E)
First etherification reaction in the presence of alkaline reagent in a medium
(Monoetherification) and purify the resulting reaction mixture.
To obtain compound F. Step a (eg in THF in the presence of NaH) R⁶-OH + X (CH₂)_m X → R⁶-O (CH₂)_mX (Compound F) Here, for example, the etherification reaction of step a is as follows.
Add a mixture of compound D (R⁶-OH ) Is added
At room temperature (however, compounds with low reactivity or alkaline reagents
If used, heat appropriately to perform alkoxide formation.
Then, add compound E such as dibromoalkane,
Suitably performed by heating and stirring at 60 to 100 ° C
Be done. As the solvent in this step a, for example,
THF , The I So The B Pi Le D - Te Ether type inert
Solvents can be mentioned, and especially THF is preferably used.
Used. In addition, as an alkaline reagent in step a
For example, sodium hydride, potassium hydride, etc.
Alkali metal hydrides and the like can be mentioned, especially N
aH and the like are preferably used.

Specific examples of the alcohol (compound D) include 1,4-pentadien-3-ol and 1,5-
Hexadiene-3-ol, 1,6-heptadiene-3
-All, 1,7-octadiene-3-ol, 1,7
-Octadien-4-ol, 1,6-heptadiene-
4-ol, 1,8-nonadiene-5-ol, 1,1
0-undecadiene-6-ol and the like can be mentioned.

Specific examples of the bifunctional compound (compound E) are, for example, α, ω-dibromoethane, diiodoethane, ditosylethane, dibromopropane, diiodopropane, ditosylpropane, dibromobutane, diiodobutane, Ditosylbutane, dibromopentane, diiodopentane, ditosylpentane, dibromohexane, diiodohexane, ditosylhexane, dibromoheptane, diiodoheptane, ditosylheptane,
Dibromooctane, diiodooctane, ditosyloctane, dibromononane, diiodononane, ditosylnonane, dibromodecane, diiododecane, ditosyldecane, dibromoundecane, diiodoundecane, ditosylundecane, dibromododecane, diiododecane,
Ditosyldodecane, dibromotridecane, diiodotridecane, ditosyltridecane, dibromotetradecane,
Diiodotetradecane, ditosyltetradecane, dibromopentadecane, diiodopentadecane, ditosylpentadecane, dibromohexadecane, diiodohexadecane, ditosylhexadecane, dibromoheptadecane, diiodoheptadecane, ditosylheptadecane, dibromooctadecane, diiodooctadecane , Ditosyl octadecane, dibromononadecane, diiodononadecane, ditosylnonadecane, dibromoeicosane, diiodoeicosane and ditosyleicosane. Note that C _{2 to} C ₂₀ bromoiodoalkanes, bromotosylalkanes, and iodotosylalkanes corresponding to these can also be used. These bifunctional compounds (Compound E) may be used alone or, if necessary,
Two or more kinds can be used in combination.

Then, the product (compound F) obtained in the above step a and methyl p-hydroxybenzoate (HO-Y-CO 3).
OCH ₃ , Y: paraphenylene group) in a solvent in the presence of an alkaline reagent in an etherification reaction, and the reaction mixture obtained is filtered to obtain a product (compound G), for example, in the presence of an alkali, water. Alternatively, it is hydrolyzed in a mixed solution of water and alcohol, and the obtained reaction solution is put into water, and a mineral acid is added to adjust the pH.
Of the carboxylic acid (compound H) obtained by removing the ether by filtering the solid product formed by filtration or extracting the product with ether, and acid chloride (compound J ) Get.

From the above compound F to acid chloride (compound
The series of reactions leading up to J) proceed as follows, for example:
To go.Step b (For example, K₂CO₃/ 2-butanone) R⁶-O (CH₂)_mX (Compound F) + HO-Y-COOCH₃ → R⁶-O (CH₂)_m O-
Y-COOCH₃ (Compound G) Step c (For example, ■ 1KOH / MeOH, H₂O; ■ 2H⁺ ) Compound G → R⁶-O (CH₂)_mO-Y-COOH (Compound H)Step d (For example, SOCl₂ , Pyridine / toluene) Compound H → R⁶-O (CH₂)_mO-Y-COCl (Compound J) In step b above, compound F and p-hydroxybenzoate were used.
Methyl perfume (HO-Y-COOCH₃) In a solvent,
Etherification reaction is performed in the presence of reagents,
And an ester compound (Compound G) is obtained. In step b,
Compound F and methyl p-hydroxybenzoate (HO-Y-COOCH₃)
, But other than methyl ester instead of the latter
It is also possible to use p-hydroxybenzoic acid ester of
Wear. The etherification reaction in step b is
Substance F, methyl p-hydroxybenzoate, alkaline reagent and
And the solvent are mixed in any order, usually at 60-100 ° C.
It is preferably carried out by heating and stirring. This step
Examples of the solvent in group b include acetone and 2-butane.
Ketone-based solvent such as Tanone, THF, diisopropyl ether
Ether-based inert solvent such as tellurium, or methanol,
Lower alcohols such as ethanol are preferably used.
It Further, as the alkaline reagent in step b,
For example, alkali metal such as potassium carbonate and sodium carbonate
Alcohols such as genus carbonate, potassium hydroxide, sodium hydroxide
Potassium metal hydroxide is preferably used.

In step c, only the ester bond of the ester (compound G) obtained in step b is selectively hydrolyzed to obtain the corresponding carboxylic acid (compound H). This hydrolysis can be done by various methods,
Usually, it is suitably carried out by heating Compound G in water or a mixed solution of water and alcohol in the presence of an alkali, if necessary, and treating Compound G with a suitable acid for the obtained reaction solution. Is added, and the pH is adjusted to be acidic, whereby it is efficiently recovered. 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, water-soluble lower alcohols such as methanol and ethanol (EtOH) are preferably used. used. Also,
As the acid used for pH adjustment, for example, commonly used mineral acids such as hydrochloric acid and sulfuric acid are preferably used.

In step d, the carboxylic acid (compound H) obtained in step c is converted to the acid chloride (compound J) without a solvent or with an acid halogenating agent in a suitable solvent. This acid halogenation reaction can be suitably carried out according to a known method. For example, the solvent is usually
A commonly used one such as toluene may be appropriately selected and used, and as the acid halogenating agent, for example, a known acid halogenating agent such as thionyl chloride, phosphorus oxychloride, phosphorus pentachloride and the like is used. .. Further, for example, it is preferable to add an appropriate amount of a reaction accelerator such as pyridine.

The acid chloride (compound
Object J) and the following general formula (K) HO-Y-Y- COOR⁷ (K) (However, Y is a p-phenylene group as described above, and R⁷Is below
The above-mentioned optically active alkyl group is shown. )

[0037]

[Chemical 13]And a hydroxy compound (compound K) represented by
Esterification reaction in the presence of a suitable hydrogen halide acceptor
Compound A can be produced by carrying out
This esterification reaction proceeds as follows, for example.Step e (For example, Et₃N / THF) R⁶-O (CH₂)_mO-Y-COCl + HO-Y-Y-COOR⁷ → R⁶-O (CH₂)_mO-Y-COO-Y-Y-COOR⁷ (Compound A) The compound K is produced by a known method or the like.
can do. At that time, before the end of the compound K
The optically active alkyl group is, for example, an optically active alcohol.
(HO-R⁷) Is used to facilitate the esterification reaction, etc.
You can enter. HO-Y-Y-COOH + HO-R ⁷ → HO-Y-Y-COOR⁷ HO-Y-Y-COCl + HO-R⁷ → HO-Y-Y-COOR⁷ Optically active alcohol (HO-R⁷)as,
For example, (+)-2-methylbutanol, (-)-2-
Methyl butanol, (+)-2-methyl pentanol,
(−)-2-methylpentanol, (+)-3-methyl
Pentanol, (−)-3-methylpentanol,
(+)-4-methylhexanol, (-)-4-methyl
Hexanol, (+)-2-methylheptanol,
(−)-2-Methylheptanol, (+)-6-methyl
Octanol, (-)-6-methyloctanol,
(+)-2-butanol, (-)-2-butanol,
(+)-2-Pentanol, (-)-2-Pentanol
(+)-2-hexanol, (-)-2-hexano
, (+)-2-octanol, (-)-2-octa
Mention may be made of nols and the like.

The esterification reaction of step e is, for example,
This can be suitably carried out by introducing a solution of compound K, a hydrogen halide acceptor and a suitable solvent into the acid chloride (compound J) obtained in step d or a solution thereof and stirring the mixture. At that time, when the reactivity is low, for example, 20
You may heat to suitable temperature, such as -80 degreeC. In this way, the desired monomer (compound A) is efficiently obtained.

The acid chloride (Compound J) used as a raw material for the esterification reaction may be an isolated one, or a solvent and acid halogen may be appropriately selected from the acid chloride-containing reaction mixture obtained in the above step d. The reaction mixture from which the agent and the like have been removed may be continuously used. As the solvent for the esterification reaction in step e, 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 to the method described above, the compound A is subjected to an etherification reaction in the presence of an alkaline reagent, for example, with an alcohol (compound D) and a bifunctional compound (compound E) in a solvent to obtain the reaction obtained. The product obtained by purifying the mixture and the compound of the general formula (L)

[0041]

[Chemical 14] (In the formula, a and b are the same as above.) And the hydroxy compound (compound L) 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.

[0042]

[Chemical 15] The production of compound F in step a is the same as described above. The solvent, reagent and reaction conditions in step f are the same as the solvent, reagent and reaction conditions in step b.

Compound B is

[0044]

[Chemical 16] In the case of, the compound M (HO-R ¹ ) was used instead of the compound L used in the synthesis of the compound A, and the compound F was used instead of the compound F.
In which n is replaced by m and R ⁶ is replaced by R ⁹

[0045]

[Chemical 17] Can be obtained by a method similar to the second synthetic method of compound A.

The alkyl group R ² in the compound M (hydroxy compound) is an optically active or optically inactive alcohol.
It is introduced by a conventional method using (R ² —OH).

[0047]

[Chemical 18]I) In the first synthetic example of compound A, compound J
In the compound J instead of n, R⁶R⁹Replaced with
In place of the compound K, the following general formula (Q) HO-Y-COOR² (Q) (However, Y is a p-phenylene group as described above, and R²Is before
The above-mentioned optically active or optically inactive alkyl group is shown. )
Using a hydroxy compound (compound Q)
You can This esterification reaction is, for example, as follows.
To proceed.Step e ′ (For example, Et₃N / THF) R⁹ -O (CH₂)_nO-Y-COCl + HO-Y-COOR² → R⁹ -O (CH₂)_nO-Y-COO-Y-COOR²(Compound B) (Compound P) (Compound Q) The compound Q can be synthesized by a known method.
Wear. At that time, the above-mentioned optically active or
Is an optically inactive alkyl group, for example, an optically active or optically
Inert alcohol (HO-R²) Is used for esterification reaction, etc.
Can be easily introduced by using. HO-Y-COOH + HO-R ² → HO-Y-COOR² HO-Y-COCl + HO-R² → HO-Y-COOR² The esterification reaction of step e ′ is carried out in place of compound J
Compound P is replaced by Compound Q instead of Compound K
Is preferably performed in the same manner as in the esterification reaction of step e.
I can.

Ii) Instead of the compound L used in the synthesis of the diene compound A, the compound M (HO-R ¹ ) was replaced, and in place of the compound F, m in compound F was replaced by n, and R ⁶ was replaced by R ⁹ . By using the compound N, the compound A can be obtained by a method similar to the second synthetic method.

The optically active alcohol (HO-R ² ) used for the synthesis of the compound B is, for example, (+)-2-methylbutanol, (-)-2-methylbutanol, (+)-.
2-methylpentanol, (-)-2-methylpentanol, (+)-3-methylpentanol, (-)-3-
Methylpentanol, (+)-4-methylhexanol, (−)-4-methylhexanol, (+)-2-methylheptanol, (−)-2-methylheptanol,
(+)-6-methyloctanol, (-)-6-methyloctanol, (+)-2-butanol, (-)-2-
Butanol, (+)-2-pentanol, (-)-2-
Pentanol, (+)-2-hexanol, (-)-2
-Hexanol, (+)-2-octanol, (-)-
2-octanol etc. can be mentioned.

Examples of the optically inactive alcohol used in the synthesis of compound B include 1-octanol, 1-heptanol, 1-hexanol, 1-pentanol, 1-butanol, 1-propanol and the like.

The silicon compound (compound C) used as a raw material for producing the copolymer of the present invention is a compound having two Si--H bonds, and those having r values of 0, 1, and 2 are r. The value of has almost no distribution and a single value is used.
Since the compound having a large value of has a distribution in the degree of polymerization (value of r), the value of r is represented by an average value. Therefore, r of the obtained liquid crystal copolymer is also an average value. Specific examples of the compound C include 1,1,3,3-tetramethyldisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, 1,1,3,3,5,5. Examples include 7,7-octamethyltetrasiloxane, and α, ω-hydrogenoligodimethylsiloxane having 6 or 7 silicon atoms. These compounds C may be used alone in the copolymerization reaction, or if necessary, 2
You may use together 1 or more types.

The copolymer of the present invention can be preferably obtained by using the compound A, the compound B and the compound C which have been described in detail above as the raw materials for production and following the above-mentioned production examples of the copolymer. ..

In the compound B used in the present invention, the following general formula (V)

[0054]

[Chemical 19] A diene compound represented by the formula [wherein s and t are 2 to 5
, N is an integer from 2 to 20, R ⁴ is

[0055]

[Chemical 20] And R ⁵ is an optically inactive alkyl group represented by the general formula (IV)

[0056]

[Chemical 21] (However, in the formula, R ³ represents hydrogen or a methyl group, and c is 0.
Is an integer of 4 and d is an integer of 1-8. ) Is represented. ]
Is a novel compound, and the present invention provides this novel compound.

The present invention also provides a ferroelectric liquid crystal composition comprising the above liquid crystal copolymer and a low molecular weight smectic liquid crystal compound.

The ferroelectric liquid crystal composition of the present invention can be obtained by mixing the above liquid crystal copolymer with 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 compounds selected from conventionally known compounds can be selected and used. Examples of the liquid crystal compound include:

[0060]

[Chemical formula 22]

[0061]

[Chemical formula 23] (In the formula, R ¹⁰ and R ¹¹ are each a linear or branched alkyl group having 1 to 12 carbon atoms, an alkoxy group or an acyloxy group, which may be the same or different from each other. Can be mentioned).

Further, the general formula

[0063]

[Chemical formula 24] A compound represented by can also be used. R ¹² in the general formula (a) is an alkyl group having 7 to ¹² carbon atoms,
An alkoxy group having 6 to 11 carbon atoms or an acyloxy group having 6 to 12 carbon atoms, and R ¹³ is an alkyl group having 7 to 12 carbon atoms or an alkoxy group having 6 to 11 carbon atoms. In addition, R ¹⁴ and R ¹⁵ in the general formula (b) each have 4 to ¹⁴ carbon atoms.
And alkyl groups or alkoxy groups, which may be the same or different from each other. On the other hand, R ¹⁶ in the general formula (c) is an alkyl group having 4 to 14 carbon atoms, and R ¹⁷ is an alkyl group having 5 to 14 carbon atoms or 4 to 14 carbon atoms.
14 alkoxy groups.

Specific examples of these liquid crystal compounds include:

[0065]

[Chemical 25] And so on.

Since the liquid crystal copolymer is a comb-shaped polymer in terms of structure, a smectic liquid crystal compound having a low molecular weight is introduced between the side chains of the polymer in the mixed system to form a compatible 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. Further, 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.

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

As a mixing ratio, it is preferable that the liquid crystal copolymer has a fraction of 5 to 99% by weight. If the fraction of the liquid crystal copolymer 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 liquid crystal copolymer exceeds 99% by weight, the response time to changes in the electric field may be long. Further, the mixture may contain a dye, an adhesive, and the like.

[0071]

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) was measured as follows.

20 × 10 mm glass substrate with ITO electrodes
Insert the test compound between two plates and adjust the thickness with a spacer.
The electric field Is applied, and the change in the amount of transmitted light at that time (10 → 9
0%), and measure this as the electric field response time τ
did.

In the formula showing the phase transition behavior, each symbol has the following meaning. glass: glass phase, Sc ^* : chiral smectic C liquid crystal phase, Iso: isotropic liquid phase, Sm1: unidentified smectic liquid crystal phase, and the numbers represent ° C. In the following examples, Mw represents the weight average molecular weight measured by GPC.

Synthesis Example 1 A compound represented by the following formula (monomer A1) was produced by the following series of operations.

[0076]

[Chemical formula 26] [Operation 1]

[0077]

[Chemical 27] According to the above Reaction 1, the compound was synthesized as follows.

With flowing argon gas, dry THF
1.1 mol NaH (purity 60%) was gradually added to 200 ml and stirred. Next, 1 mol of 1,5-hexadiene-3-ol dissolved in 200 ml of THF was added dropwise with stirring. The reaction solution was stirred for about 2 hours, and after confirming that the generation of hydrogen gas had stopped, 2 mol of 1,10-dibromodecane dissolved in 200 ml of anhydrous THF was added at once, and the mixture was stirred under reflux for 8 hours.

The obtained reaction solution was filtered and then at 50 ° C. for 3 To
The mixture was concentrated under rr for 1 hour, then diluted 3-fold with hexane, and then purified by liquid chromatography to obtain a compound. The yield was about 50%.

[Operation 2]

[0081]

[Chemical 28] According to the above Reaction 2, the compound was synthesized as follows.

80 g of compound, 45.8 g of methyl 4-hydroxybenzoate, potassium carbonate (anhydrous) 124
g and 2-butanone (400 ml) were charged in a 4-liter flask having a volume of 1 liter, and the mixture was refluxed and stirred for 14 hours while flowing an argon gas.

The reaction mixture cooled to room temperature was filtered to remove salts such as potassium carbonate, and the obtained filtrate was put on a rotary evaporator and 2-butanone was distilled off at a bath temperature of 50 ° C. under reduced pressure with an electric aspirator. Next, about 300 ml of methylene chloride was added to the obtained residue, the mixture was stirred, and then filtered again to remove insoluble salts. The obtained filtrate was put on a rotary evaporator, and methylene chloride was distilled off under reduced pressure at a bath temperature of 50 ° C. to obtain a crude product of the compound 91.
g was obtained.

45 g of this crude product was diluted with 30 ml of methylene chloride to give a homogeneous solution, and liquid chromatography was carried out using a precolumn (volume 270 ml) packed with activated alumina and a main column (volume 1 liter) packed with silica gel. Was collected in. The eluate containing the target substance was put on a rotary evaporator, and the solvent was distilled off at 50 ° C. under reduced pressure. The remaining crude product was also fractionated and purified under the same conditions as above, and both fractionated and purified products were combined. The yield of the highly pure compound thus obtained was 84.4 g (yield: about 87%).

[Operation 3]

[0086]

[Chemical 29] According to the above Reaction 3, the compound was synthesized as follows.

Compound 42.4 g, potassium hydroxide 24
g, 20 ml of water and 60 ml of methanol (MeOH) were charged into a 4-necked flask having a capacity of 1 liter, and heated and stirred at 70 ° C. for 30 minutes while flowing an argon gas.

Then, after cooling to bring the temperature of the reaction mixture to 40 ° C. or lower, 600 ml of water was added to the reaction mixture. Then, the temperature was raised to 90 ° C. and stirring was continued for 4 hours. After confirming that the reaction mixture became light blue and transparent, the reaction was terminated and the mixture was cooled to room temperature.

The obtained reaction mixture was transferred to a 2 liter beaker, and pure water was added to make it 1.5 liter. After uniformly dissolving, the pH of the system was adjusted to 2 by adding 3N hydrochloric acid aqueous solution.
I chose The suspension in which the white solid had precipitated in this way was filtered, and the collected white solid was suction filtered and washed several times with pure water. Transfer this solid to a 2 liter beaker and add pure water 1
It was washed for 10 minutes by adding liter and stirring in suspension. The suspension was filtered again by suction, washed with pure water several times, and then dried overnight in a vacuum dryer at 50 ° C. to obtain a compound. The yield was 36.8 g (yield 90%).

[Operation 4]

[0091]

[Chemical 30] According to the above Reaction 4, the desired monomer A1 was synthesized as follows.

The above carboxylic acid (compound) 27.5
g, 21 ml of thionyl chloride, and 80 ml of toluene were charged into a 4-necked flask having a capacity of 500 ml equipped with a reflux condenser and stirred to obtain a uniform solution. Next, after adding 0.02 ml of pyridine, the reaction temperature was raised to 65 ° C. and heating and stirring were continued for 4 hours. Argon gas was constantly passed through the flask.

Thereafter, in order to remove excess thionyl chloride and toluene as a solvent in the reaction mixture, an aspirator with a dry ice trap in the middle was used.
Most of the thionyl chloride and toluene were distilled off over 1 hour while heating to ℃. Finally, the temperature was raised to 80 ° C. and the remaining thionyl chloride was removed over 30 minutes.

The reaction mixture thus obtained is cooled to room temperature and 160 ml of toluene and 7.5 ml of pyridine are added thereto.
Was added to form a uniform solution, and 160 ml of a toluene solution containing 21.1 g of the compound [(S) form], which is an optically active 1-methylbutyl ester of 4'-hydroxybiphenyl-4-carboxylic acid, was added thereto over 30 minutes. It was added dropwise with stirring. Then, the mixture was stirred overnight at room temperature to complete the reaction. During the reaction, an argon gas was flown to prevent water from entering the reaction vessel.

The reaction mixture thus obtained was filtered to remove the precipitated pyridine salt. Next, it was subjected to a rotary evaporator and the solvent was distilled off under reduced pressure at a bath temperature of 50 ° C. to obtain 48.5 g of a concentrate containing the monomer A1.

Next, 50 g of methylene chloride was added to this concentrate and stirred to obtain a uniform and transparent solution. This solution
Pre-column packed with activated alumina (capacity 270 m
l) and a silica gel-packed main column (capacity: 1 liter) were used for preparative liquid chromatography. The eluate containing the target substance was applied to a rotary evaporator, and the solvent was distilled off under reduced pressure at a bath temperature of 50 ° C. The yield of the crude product (crude monomer A1) thus obtained was 35.0 g (yield about 74%).

The crude product obtained above was transferred to a flask having a volume of 1 liter, and 500 ml of ethanol was added. Then, a reflux condenser was attached to the thruster and stirred at 70 ° C. for 10 minutes. After confirming that the white solid was completely dissolved into a uniform solution, the flask was naturally cooled to near room temperature. Next, stopper the flask, keep it out of moisture, put it in the refrigerator,
Let stand for 4 hours or more. Then, the flask was taken out, the precipitated white solid was collected by suction filtration, and the collected solid was washed with cold ethanol several times. Finally, this solid was dried in a vacuum dryer at 50 ° C. overnight to obtain the desired monomer A1. The yield was 30.7 g (69% yield).

The structure of the monomer A1 is ¹ H-NM
It was confirmed by R and the like. The ¹ H-NMR chart is shown in FIG.

Synthesis Example 2 The following formula

[0100]

[Chemical 31] In the method of synthesizing the monomer A1 of Synthesis Example 1, the compound represented by

[0101]

[Chemical 32] A compound represented by [4'-hydroxybiphenyl-4
-Optically active 1-methylheptyl ester of carboxylic acid:
(S) -form] was used in the same manner by using the same molar amount. The structure of the monomer A2 is ¹ H—N
Confirmed by MR etc. The ¹ H-NMR chart is shown in FIG.

Synthesis Example 3

[0103]

[Chemical 33] Synthesis of Monomer A3 [Operation 1]

[0104]

[Chemical 34] Synthesis of 4- (10-bromodecyloxy) -1,6-heptadiene (compound) Sodium hydride (content 60
%) 4.1 g of tetrahydrofuran (THF) 50 ml
And the system was purged with argon. 50 ml of a THF solution containing 11.2 g of 1,6-heptadien-4-ol
Was dripped. Stir at room temperature until the evolution of hydrogen gas subsides. Then, T containing 75 g of 1,10-dibromodecane
100 ml of HF solution was added and refluxed for 7 hours. After removing the resulting non-solution by filtration, THF was distilled off under reduced pressure. Purification by silica gel column chromatography gave 11.6 g of the desired bromine product (yield 35%). [Operation 2] Synthesis of compound

[0105]

[Chemical 35] Bromine product 10.0 g, methyl 4-hydroxybenzoate 4.6 g, and potassium carbonate 4.2 g were refluxed in 50 ml of 2-butanone for 12 hours. The generated insoluble material was removed by filtration, and the solvent was evaporated under reduced pressure. Purification by silica gel column chromatography gave a methyl ester form. [Operation 3] Synthesis of compound

[0106]

[Chemical 36] The above methyl ester and potassium hydroxide 6.0
g and 1.6 g of water were refluxed in 20 ml of methanol for 1 hour. 50 ml of water was added and the mixture was refluxed for 1 hour. Water 300
It was diluted with ml and diluted hydrochloric acid was added dropwise to adjust the pH to 2. The resulting precipitate was collected by filtration, washed with water and dried to give 4- {10-
7.4 g of (1,6-heptadiene-4-yloxy) decyloxy} benzoic acid was obtained. [Operation 4] Synthesis of Monomer A3 3.5 g of thionyl chloride was added to 7.4 g of the above carboxylic acid.
Was added and heated at 85 ° C. for 2 hours. After distilling off excess thionyl chloride under reduced pressure, 40 ml of toluene was added to give an acid chloride solution. There (S) -1-methylbutyl 4-
Hydroxybiphenyl-4'-carboxylate 5.4
40 ml of a toluene solution containing 1 g of pyridine and 1.6 g of pyridine 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. Purification by silica gel column chromatography gave 8.7 g of the desired monomer A3 (yield 44% from bromine).

Synthesis Example 4

[0108]

[Chemical 37] Synthesis of Monomer A4 To 4.0 g of carboxylic acid obtained in the same manner as in [Operation 3] of Synthesis Example 3, 10.0 g of thionyl chloride was added, and the temperature was changed to 75 ° C.
And reacted for 4 hours. Excess thionyl chloride was distilled off under reduced pressure, and 8 ml of toluene was added.

Instead of (S) -1-methylbutyl 4-hydroxybiphenyl-4'-carboxylate, 3.4 g of (S) -1-methylpentyl 4-hydroxybiphenyl-4'-carboxylate and 1.
Using 0 g, the same reaction procedure as in [Operation 4] of Synthesis Example 3 was carried out to obtain 5.2 g of the desired monomer A4 (yield from carboxylic acid: 75%).

Synthesis Example 5 The following formula

[0111]

[Chemical 38] In the method of synthesizing the monomer A1 of Synthesis Example 1, the compound represented by

[0112]

[Chemical Formula 39] Was similarly prepared by using the same molar amount of the compound [optically active 1-methylheptyl ester of p-hydroxybenzoic acid: (S) -form] represented by In addition,
The structure of the monomer B1 was confirmed by ¹ H-NMR and the like. The ¹ H-NMR chart is shown in FIG.

Synthesis Example 6

[0114]

[Chemical 40] Synthesis of Monomer B2 1.5 g of bromide obtained in Procedure 1 of Synthesis Example 3, (s)-
1-methylbutyl 4-hydroxybiphenyl-4'-
2 g of 1.5 g of carboxylate and 2.2 g of potassium carbonate
Refluxed in 15 ml of butanone for 8 hours. The generated insoluble material was removed by filtration, and the solvent was evaporated under reduced pressure. Purified by silica gel column chromatography, monomer B2
1.0 g was obtained (yield 42%).

Synthesis Example 7

[0116]

[Chemical 41] Synthesis of Monomer B3 1.5 g of bromide obtained in Procedure 1 of Synthesis Example 3, (s)-
2-methylbutyl 4-hydroxybiphenyl-4'-
2 g of 1.5 g of carboxylate and 2.2 g of potassium carbonate
Refluxed in 20 ml butanone for 8 hours. The generated insoluble material was removed by filtration, and the solvent was evaporated under reduced pressure. Purified by silica gel column chromatography, monomer B3
1.3 g was obtained (53% yield).

Synthesis Example 8

[0118]

[Chemical 42] Synthesis of Monomer B4 0.2 g of sodium hydride (content 60%) was suspended in 12 ml of dimethylformamide, and 2- (4-hydroxyphenyl) -5-((s) -1-methylbutyloxycarbonyl) was suspended therein. 1.3 g of pyrimidine was added, and then 1.5 g of the brominated product obtained in Procedure 1 of Synthesis Example 3 was added. Reflux for 8 hours at 80 ° C. under an argon atmosphere. The generated insoluble material was removed by filtration, and the solvent was evaporated under reduced pressure. Purified by silica gel column chromatography, monomer B40.
44 g was obtained (yield 18%).

Synthesis Example 9

[0120]

[Chemical 43] Synthesis of Monomer B5 0.2 g of sodium hydride (content 60%) was suspended in 12 ml of dimethylformamide, and 2- (4-hydroxyphenyl) -5-((s) -2-methylbutyloxycarbonyl) was suspended therein. 1.3 g of pyrimidine was added, and then 1.5 g of the brominated product obtained in Procedure 1 of Synthesis Example 3 was added. It stirred at 80 degreeC under argon atmosphere for 12 hours. The generated insoluble material was removed by filtration, and the solvent was evaporated under reduced pressure. Purified by silica gel column chromatography, monomer B5
0.74 g was obtained (yield 31%).

Synthesis Example 10

[0122]

[Chemical 44] Synthesis of Monomer B6 4- {10 obtained by the method described in operation 3 of synthesis example 3
2.5 ml of thionyl chloride was added to 1.0 g of-(1,6-heptadiene-4-yloxy) decyloxy} benzoic acid, and the mixture was stirred at 65 ° C for 4 hours. After distilling off excess thionyl chloride under reduced pressure, 4 ml of toluene was added. 4 ml of a toluene solution containing 0.59 g of (s) -1-methylbutyl 4-hydroxybenzoate and 0.26 g of pyridine was added thereto at room temperature, and the mixture was reacted at room temperature for one day. The generated insoluble material was removed by filtration, and the solvent was evaporated under reduced pressure. Purification by silica gel column chromatography gave 1.0 g of monomer B6 (yield 67%).

Synthesis Example 11

[0124]

[Chemical 45] Synthesis of Monomer B7 4- {10 obtained by the method described in operation 3 of synthesis example 3
2.5 ml of thionyl chloride was added to 1.0 g of-(1,6-heptadiene-4-yloxy) decyloxy} benzoic acid, and the mixture was stirred at 65 ° C for 4 hours. After distilling off excess thionyl chloride under reduced pressure, 4 ml of toluene was added. 4 ml of a toluene solution containing 0.59 g of (s) -2-methylbutyl 4-hydroxybenzoate and 0.26 g of pyridine was added thereto at room temperature, and the mixture was reacted at room temperature for one day. The generated insoluble material was removed by filtration, and the solvent was evaporated under reduced pressure. Purification by silica gel column chromatography gave 1.0 g of monomer B7 (yield 67%).

Synthesis Example 12

[0126]

[Chemical 46] Synthesis of Monomer B8 1.1 g of bromide obtained in Procedure 1 of Synthesis Example 3, (s)-
3-methylpentyl 4-hydroxybiphenyl-4'-
Carboxylate 1.0g, potassium carbonate 1.4g 2
Refluxed in 20 ml butanone for 8 hours. The generated insoluble material was removed by filtration, and the solvent was evaporated under reduced pressure. Purified by silica gel column chromatography, monomer B8
1.3 g was obtained (69% yield).

Synthesis Example 13

[0128]

[Chemical 47] Synthesis of Monomer B9 4- {10 obtained by the method described in operation 3 of synthesis example 3
5 ml of thionyl chloride was added to 0.94 g of-(1,6-heptadiene-4-yloxy) decyloxy} benzoic acid, and the mixture was stirred at 65 ° C for 5 hours. After distilling off excess thionyl chloride under reduced pressure, 5 ml of toluene was added. 10 ml of a toluene solution containing 0.59 g of (s) -3-methylpentyl 4-hydroxybenzoate and 0.23 g of pyridine was added thereto at room temperature, and the mixture was reacted at room temperature for one day. The generated insoluble material was removed by filtration, and the solvent was evaporated under reduced pressure. Purification by silica gel column chromatography gave 1.0 g of monomer B9 (yield 72%).

Example 1 <Synthesis of Copolymer> Synthesis Example 1 was added to 20 ml of dry toluene.
Monomer A1 obtained in [[2.02 g (3.15 mmo
l)] and the monomer B1 obtained in Synthesis Example 5 [0.48 g
(0.79 mmol)] and 0.35 g (2.63 mmol) of 1,1,3,3-tetramethyldisiloxane were stirred while flowing an argon gas and uniformly dissolved. Next, after adding 2.5 mg of hexahydrate of chloroplatinic acid, at 80 ° C
The mixture was heated and stirred for 20 hours. During stirring, a very small amount of argon gas was kept flowing so that moisture and oxygen did not enter the reaction vessel.

After the polymerization reaction was completed, the reaction mixture was filtered,
Toluene was distilled off from the filtrate. The obtained residue was diluted with 5 g of methylene chloride, separated and purified by column chromatography using silica gel as a packing material to obtain a target copolymer. The yield was 2.00 g.

<Confirmation of Structure of Copolymer> The above copolymer has a molar ratio of the monomer A1 unit and the monomer B1 unit of 77:23 by ¹ H-NMR analysis and the like, and the distance between these monomer units is It was found to be a copolymer linked with tetramethyldisiloxane units. The calculation of the above molar ratio was performed by ¹ H-NMR of 8.25 ppm and 7.6.
This was done using the integrated intensity of the 5 ppm peak. The ¹ H-NMR chart of this copolymer is shown in FIG.

The weight average molecular weight of this copolymer measured by GPC was 3,100.

<Characteristics of Liquid Crystal of Copolymer> Further, the characteristics of the above copolymer as liquid crystal were as follows. Electric field response time (10 → 90%; 25 ° C., ± 20 V / 1.
5 μm) τ = 2.4 ms As described above, this copolymer, which is an example of the copolymer of the present invention, is a monomer A1 homopolymer (monomers A1 and 1) having the same level of molecular weight as shown in the following Reference Example 1. , 1, 3,
It is possible to lower the transition temperature from the isotropic phase (Iso) to the chiral smectic C ^* phase (Sc ^* ) as compared with a polymer obtained by polymerization with 3-tetramethyldisiloxane), and It was found to be a copolymer having excellent liquid crystal properties such that the response speed can be remarkably improved.

Reference Example 1 Monomer A1 Homopolymer Monomer A1 obtained in Synthesis Example 1 was added to 60 ml of dry toluene.
[21 g (32.76 mmol)] and 1,1,3,3-
Tetramethyldisiloxane 3.15 g (23.40 mm
ol) was stirred while flowing an argon gas, and uniformly dissolved. Then, after adding 21 mg of hexahydrate of chloroplatinic acid,
The mixture was heated and stirred at 80 ° C. for 20 hours. During stirring, a very small amount of argon gas was kept flowing so that moisture and oxygen did not enter the reaction vessel.

After the polymerization reaction was completed, the reaction mixture was filtered,
Toluene was distilled off from the filtrate. 40 g of the obtained residue
Was diluted with methylene chloride, and separated and purified by column chromatography using silica gel as a packing material to obtain a target monomer A1 homopolymer. The yield was 21.80g.

From the ¹ H-NMR analysis and the like, it was found that the polymer obtained above was a polymer composed of repeating units in which a monomer A1 unit and a tetramethyldisiloxane unit were linked. In addition, ¹ H- of this homopolymer
The NMR chart is shown in FIG. The weight average molecular weight of this homopolymer was 4,100 (GPC measurement),
The characteristics of the liquid crystal were as follows. Electric field response time (10 → 90%; 25 ° C., ± 10 V / 1.
5 μm) τ = 50 ms

Example 2 <Synthesis of Copolymer> Synthesis Example 2 was added to 20 ml of dry toluene.
Monomer A2 obtained in [2.45 g (3.82 mmo
l)] and the monomer B1 obtained in Synthesis Example 5 [0.55 g
(0.95 mmol)] and 1,1,3,3-tetramethyldisiloxane (0.40 g, 2.98 mmol) were stirred while flowing an argon gas and uniformly dissolved. Next, after adding 2.5 mg of hexahydrate of chloroplatinic acid, at 80 ° C
The mixture was heated and stirred for 20 hours. During stirring, a very small amount of argon gas was kept flowing so that moisture and oxygen did not enter the reaction vessel.

After the polymerization reaction was completed, the reaction mixture was filtered,
Toluene was distilled off from the filtrate. The obtained residue was diluted with 5 g of methylene chloride, separated and purified by column chromatography using silica gel as a packing material to obtain a target copolymer. The yield was 2.39g.

<Confirmation of Structure of Copolymer> The above-mentioned copolymer has a molar ratio of the monomer A2 unit and the monomer B1 unit of 79:21 by ¹ H-NMR analysis and the like, It was found to be a copolymer linked with tetramethyldisiloxane units. Note that the above molar ratio was calculated by ¹ H-NMR of 8.15 ppm and 7.6.
This was done using the integrated intensity of the 5 ppm peak. The ¹ H-NMR chart of this copolymer is shown in FIG. 7.

The weight average molecular weight of this copolymer measured by GPC was 3,600.

<Characteristics of Liquid Crystal of Copolymer> The characteristics of the above copolymer as liquid crystal were as follows. Electric field response time (10 → 90%; 25 ° C., ± 20 V / 1.
5 μm) τ = 2.5 ms As described above, this copolymer, which is an example of the copolymer of the present invention, is a monomer A2 homopolymer (monomers A2 and 1) having the same level of molecular weight as shown in Reference Example 2 below. , 1, 3,
It is possible to lower the transition temperature from the isotropic phase (Iso) to the chiral smectic C ^* phase (Sc ^* ) as compared with a polymer obtained by polymerization with 3-tetramethyldisiloxane), and It was found to be a copolymer having excellent liquid crystal properties such that the response speed can be remarkably improved.

Reference Example 2 4 Monomer A2-based homopolymer In 60 ml of dry toluene, the monomer A2 [23.97 g (35.10 mmol)] obtained in Synthesis Example 2 above and 1,
3.15 g of 1,3,3-tetramethyldisiloxane (2
(3.40 mmol) was stirred while flowing an argon gas and uniformly dissolved. Next, chloroplatinic acid hexahydrate 24.
After adding 0 mg, the mixture was heated with stirring at 80 ° C. for 20 hours. During stirring, a very small amount of argon gas was kept flowing so that moisture and oxygen did not enter the reaction vessel.

After the polymerization reaction was completed, the reaction mixture was filtered,
Toluene was distilled off from the filtrate. 40 g of the obtained residue
Was diluted with methylene chloride, and separated and purified by column chromatography using silica gel as a packing material to obtain the target monomer A2 homopolymer. The yield was 19.20 g.

From the ¹ H-NMR analysis and the like, it was found that the polymer obtained above was a polymer composed of repeating units in which a monomer A2 unit and a tetramethyldisiloxane unit were linked. In addition, ¹ H- of this homopolymer
The NMR chart is shown in FIG. Further, the weight average molecular weight of this homopolymer was 3,700 (GPC measurement),
The characteristics of the liquid crystal were as follows. However, Sm1
Represents an unidentified Sm phase. Electric field response time (10 → 90%; 25 ° C., ± 20 V / 1.
5 μm) τ = 7.1 ms

Example 3 <Synthesis of Copolymer> Synthesis Example 2 was added to 14 ml of dry toluene.
Monomer A2 obtained in 1.8 [1.82 g (2.66 mmo
l)] and the monomer B1 obtained according to Synthesis Example 5 [0.18 g
(0.30 mmol)] and 0.26 g (1.94 mmol) of 1,1,3,3-tetramethyldisiloxane were stirred while flowing an argon gas and uniformly dissolved. Next, after adding 2.0 mg of hexahydrate of chloroplatinic acid, 80 ° C
The mixture was heated and stirred for 20 hours. During stirring, a very small amount of argon gas was kept flowing so that moisture and oxygen did not enter the reaction vessel.

After the polymerization reaction was completed, the reaction mixture was filtered,
Toluene was distilled off from the filtrate. The obtained residue was diluted with 3 g of methylene chloride, separated and purified by column chromatography using silica gel as a packing material to obtain a target copolymer. The yield was 1.74g.

<Confirmation of Structure of Copolymer> The above-mentioned copolymer has a molar ratio of the monomer A2 unit and the monomer B1 unit of 86:14 by ¹ H-NMR analysis and the like, and the distance between these monomer units is It was found to be a copolymer linked with tetramethyldisiloxane units. Note that the above molar ratio was calculated by ¹ H-NMR of 8.15 ppm and 7.6.
This was done using the integrated intensity of the 5 ppm peak. The ¹ H-NMR chart of this copolymer is shown in FIG.

The weight average molecular weight of this copolymer measured by GPC was 4,100.

<Characteristics of Liquid Crystal of Copolymer> Further, the characteristics of the above copolymer as liquid crystal are as follows. Electric field response time (10 → 90%; 25 ° C., ± 20 V / 1.
5 μm) τ = 5.6 ms As described above, this copolymer, which is an example of the copolymer of the present invention, has a monomer A2 homopolymer (monomers A2 and 1) having the same level of molecular weight as in Reference Example 2 above. , 1,
It is possible to lower the transition temperature from the isotropic phase (Iso) to the chiral smectic C ^* phase (SmC ^* ) as compared with the polymer obtained by the polymerization with 3,3-tetramethyldisiloxane), and It was found to be a copolymer having excellent liquid crystal properties such that the response speed to changes can be improved.

Example 4 <Synthesis of Monomer B10> A compound represented by the following formula (monomer B10) was synthesized as follows.

[0151]

[Chemical 48] 15.0 g (40.0 mmol) of carboxylic acid (compound) obtained by the method of synthesizing monomer A1 of Synthesis Example 1, 9.52 g (80.0 mmol) of thionyl chloride and dry toluene 5
0 ml was collected in a flask and stirred to make a uniform solution.
Next, 0.02 ml of pyridine was added and stirred to form a uniform solution. Then, the temperature was raised to 65 ° C., and the mixture was heated with stirring for 4 hours. Then, toluene and excess thionyl chloride were distilled off under reduced pressure, and 130 ml of toluene and 3.60 g of pyridine were added. Next, 7.86 g (35.4 m) of 1-n-hexyl 4-hydroxybenzoate dissolved in 130 ml of toluene.
(mol) was added dropwise over 30 minutes. After this, at room temperature 18
Stir for hours. The reaction mixture was filtered and concentrated, and the target compound was obtained by column chromatography using silica gel and alumina as a packing material. The yield was 14.7 g.

The structure of the monomer B10 is¹ H- N M R Etc.
Yo Ri Sure Approval Shi Was . ¹The H-NMR chart is shown in FIG.

<Synthesis of Copolymer> 20 ml of dry toluene
2.45 g (3.82 g) of the monomer A1 obtained in Synthesis Example 1
mmol) and monomer B10 0.55 g (0.95 m
mol) and 0.43 g (3.18 mmol) of 1,1,3,3-tetramethyldisiloxane were stirred while flowing an argon gas, and uniformly dissolved. Next, after adding 2.5 mg of chloroplatinic acid hexahydrate, the mixture was heated and stirred at 80 ° C. for 20 hours. During the stirring, a very small amount of argon gas was kept flowing to prevent moisture and oxygen from entering the reaction vessel. After completion of the polymerization reaction, the reaction mixture was filtered and toluene was distilled off from the filtrate. The residue was diluted with 5 g of methylene chloride and purified by column chromatography using silica gel as a packing material to obtain a target copolymer. The yield was 2.84g.

<Confirmation of Structure of Copolymer> From the ¹ H-NMR analysis and the like obtained in the above Production Example, the copolymer in which the molar ratio of the monomer A1 and the monomer B2 was 77:23 and the monomers were linked by disiloxane It was found to be a polymer. The calculation of the molar ratio was performed using the integrated intensity of the peaks at 8.15 ppm and 7.65 ppm. ¹ H-NM of this copolymer
The R chart is shown in FIG.

The weight average molecular weight of the copolymer measured by GPC was 3,800. <Characteristics of Liquid Crystal of Copolymer> The characteristics of the copolymer of the present invention as liquid crystal are as follows, as compared with the homopolymer of the monomer A1 having the same level of molecular weight (Reference Example 1). The phase transition temperature from the one phase to the chiral SmC ^* phase could be lowered and the response speed could be improved. Electric field response time (10 → 90%; 25 ° C., ± 20 V / 1.
5 μm) τ = 5.0 ms

Example 5 <Synthesis of Copolymer> Synthesis Example 2 was added to 14 ml of dry toluene.
Monomer A2 obtained in 1.65 g (2.42 mmol)
And 0.35 g of the monomer B10 obtained in Example 4 (0.
60 mmol) and 0.27 g (2.01 mmol) of 1,1,3,3-tetramethyldisiloxane were stirred while flowing an argon gas and uniformly dissolved. Next, after adding 2.0 mg of hexahydrate of chloroplatinic acid, the mixture was heated and stirred at 80 ° C. for 20 hours. During the stirring, a very small amount of argon gas was kept flowing to prevent moisture and oxygen from entering the reaction vessel. After completion of the polymerization reaction, the reaction mixture was filtered and toluene was distilled off from the filtrate. The residue was diluted with 3 g of methylene chloride and purified by column chromatography using silica gel as a packing material to obtain a target copolymer. Yield 1.51
It was g.

<Confirmation of Structure of Copolymer>
^{By 1} H-NMR analysis, etc., monomer A2 and monomer B
It was found that the molar ratio of 10 was 81:19 and the copolymer was a copolymer in which monomers were linked by disiloxane. The calculation of the molar ratio was performed using the integrated intensity of the peaks at 8.15 ppm and 7.65 ppm. The ¹ H-NMR chart of the copolymer is shown in FIG.

The weight average molecular weight of the copolymer measured by GPC was 3,700.

<Characteristics of Liquid Crystal of Copolymer> The characteristics of the above copolymer as liquid crystal are as follows.
It was possible to lower the transition temperature from the isotropic phase to the chiral SmC ^* phase and to improve the response speed, as compared with the homopolymer of the monomer A2 having the same level of molecular weight (Reference Example 2). Phase transition behavior Iso → Sc ^* → glass 77 ° C.-20 ° C. electric field response time (10 → 90%; 25 ° C., ± 20 V / 1.
5 μm) τ = 5.4 ms

Example 6

[0161]

[Chemical 49] Synthesis of Copolymer Monomer A3 0.5 obtained by the method described in Synthesis Example 3
8 g, monomer B2 obtained by the method described in Synthesis Example 6
The system in which 0.12 g was dissolved in 7 ml of toluene was replaced with argon. 0.12 g of 1,1,3,3-tetramethylsilidoxane and 25 μl of a 4 wt% isopropyl alcohol solution of chloroplatinic acid hexahydrate were added, and the mixture was polymerized at 85 ° C. for 14 hours. The solvent was distilled off under reduced pressure and the residue was purified by silica gel column chromatography to obtain 0.72 g of the copolymer having the above copolymer ratio. (Yield 88%). Table 3 shows the physical properties
Shown in. Further, an NMR chart is shown in FIG.

Examples 7 to 21

[0163]

[Chemical 50]

Synthesis of Copolymer One kind of monomer selected from Monomer A3 and Monomers B2 to B9, 1,1,3,3-tetrolamethyldisiloxane, was charged as shown in Table 1 below. Example 6
Copolymerization was carried out in the same manner as in. Table 3 shows the physical property values.

[0165]

[Table 1] Example 22

[0166]

[Chemical 51] Synthesis of Copolymer Monomer A3 0.5 obtained by the method described in Synthesis Example 3
8 g, monomer B2 obtained by the method described in Synthesis Example 6
The system in which 0.12 g was dissolved in 7 ml of toluene was replaced with argon. 0.39 g of α, ω-hydrogen oligodimethylsiloxane (weight average molecular weight 730) and a 4% by weight isopropyl alcohol solution of chloroplatinic acid hexahydrate 2
5 μl was added, and the mixture was polymerized at 85 ° C. for 14 hours. The solvent was distilled off under reduced pressure and the residue was purified by silica gel column chromatography to obtain 1.0 g of a copolymer. (Yield 93%).
Table 3 shows the physical property values. A ¹ H-NMR chart is shown in FIG.

Examples 23 to 25

[0168]

[Chemical 52] Synthesis of Copolymer Monomer A3, one kind of monomer selected from monomers B6 to B8, α, ω-hydrogenoligodimethylsiloxane (weight average molecular weight 730) was changed as shown in Table 2 below. Copolymerization was carried out in the same manner as in Example 22. Table 3 shows the physical property values.

[0169]

[Table 2]

Example 26

[0171]

[Chemical 53] Synthesis of Copolymer Monomer A4 0.5 obtained by the method described in Synthesis Example 4
8 g, monomer B7 obtained by the method described in Synthesis Example 11
The system in which 0.13 g was dissolved in 7 ml of toluene was replaced with argon. 0.39 g of α, ω-hydrogenoligodimethylsiloxane (weight average molecular weight 730) and 25 μl of a 4% by weight isopropyl alcohol solution of chloroplatinic acid hexahydrate were added, and the mixture was polymerized at 85 ° C. for 15 hours. The solvent was distilled off under reduced pressure and the residue was purified by silica gel column chromatography to obtain 1.0 g of the copolymer having the above copolymerization ratio.
(Yield 91%). Table 3 shows the physical property values. Also, ¹ H-N
The MR chart is shown in FIG.

[0172]

[Table 3] The phase transition temperature was determined by observation with a polarization microscope. The response time is a value when a cell thickness of 2 μm and a voltage of 20 V is applied at 25 ° C. The phase transition temperature and the response time are measured in Example 2
The same measurement method as in 7 was used. Mw represents a weight average molecular weight, and is a PS (polystyrene) conversion value by GPS measurement.

Example 27 The liquid crystal copolymer obtained in Example 4 and the ferroelectric liquid crystal CS-1015 manufactured by Chisso Petrochemical Co., Ltd. were mixed in a weight ratio of 8: 2.
To obtain a composition. CS-1015 glass ← Sc ^* ← S _A ← N ^* ← Iso phase transition -17 ° C 57.6 ° C 67.9 ° C 78.1 ° C (S _A : smectic A liquid crystal phase, N ^* : chiral nematic liquid crystal phase) Mixing method Example 14 40 mg of the liquid crystal copolymer of CS-1015
10 mg was weighed, dissolved in 5 cc of solvent (dichloromethane), well stirred with each other, and then 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. Phase transition of the composition glass ← Sc ^* ← S _A ← Iso -25 ℃ 75 ℃ 86 ℃ In the liquid crystal state, the island-like structure peculiar to the dispersion system is not observed, and the liquid crystal phase is uniform and becomes a compatible system. I was able to confirm that Subsequently, at 84 ° C., a shearing stress was applied between the upper and lower substrates in the above cell several times (alignment by the shearing method) to align the liquid crystal. A rectangular wave voltage of ± 30 V was applied to this at 25 ° C and the response time was measured to be 1.3 ms.
Met.

Example 28 The liquid crystal copolymer obtained in Example 25 and the following liquid crystal P100
8 (manufactured by Midori Kagaku Co., Ltd.) were mixed at a weight ratio of 8: 2.

[0176]

[Chemical 54] Phase transition Cryst ← Sc ^* ← S _A ← Iso 20 ° C. 64 ° C. 68 ° C. (Cryst: crystalline state) The mixing method was the same as in Example 27. Phase transition of composition glass ← Sc ^* ← S _A ← Iso -25 ° C 76 ° C 81 ° C 25 ° C Response time 0.63 ms Phase transition, response time measurement method and conditions were the same as in Example 27. (However, the orientation temperature is 78 ° 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 29 The liquid crystal copolymer obtained in Example 12 and the following low-molecular ferroelectric liquid crystal (generally known and synthesized by a conventional method):

[Chemical 55] Phase transition Cryst ← Sx ^* ← Sc ^* ← S _A ← Iso 45 ° C. 53 ° C. 107 ° C. 132 ° C. (Sx ^* is a smectic phase higher than the Sc ^* phase) were mixed in the proportions shown in Table 4. The mixing method is described in Example 27.
Same as.

[0178]

[Table 4] The method of measuring the phase transition and the response time was the same as in Example 27. However, the orientation temperature was 90 ° C. for 8: 2 and 106 ° C. for 6: 4.

Example 30 A liquid crystal optical element was produced using the liquid crystal composition having the same composition as in Example 28. Polyethersulfone (PES) with ITO electrode was prepared by using the above composition as a 20 wt% toluene solution.
A film having a thickness of 3 μm was formed on the electrode surface of the substrate using a microgravure coater. Immediately after the solvent is dried, a substrate of the same type with no coating is laminated so that the liquid crystal layer and the electrode surface are in contact with each other.
50 mm, length 3 mm) was produced.

Then, using the orienting device composed of four heating rolls as shown in FIG.
Was subjected to bending orientation treatment. Each heating roll 3 has a diameter of 80 m
An iron plate having a width of 300 mm was used. Surface temperature is T ₁ = 82 ° C, T ₂ = 78 ° C,
T ₃ = 74 ° C. and T ₄ = 70 ° C. were controlled, and the line speed was v = 8 m / min. 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-mentioned element so that their 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 21. Good contrast was obtained. It was

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

[0183]

INDUSTRIAL APPLICABILITY The liquid crystal copolymer of the present invention is a polymer having a novel structure and composition having a specific repeating unit in a specific ratio, showing a Sc ^* liquid crystal phase in a wide temperature range including room temperature, and It exhibits a remarkably high response speed to changes in the electric field, and has an advantage that the phase transition temperature can be easily controlled by adjusting the composition.

Further, since the ferroelectric liquid crystal composition of the present invention uses a polymer compound having a wide structural upper chain interval as the polymer compound, it becomes a compatible system with the low molecular weight liquid crystal compound and does not undergo phase separation and has an orientation property. It is a practically excellent ferroelectric liquid crystal composition exhibiting excellent and extremely excellent liquid crystal characteristics.

[Brief description of drawings]

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

FIG. 2 ¹ H-of Monomer A1 obtained in Synthesis Example 1 of Example
NMR chart

FIG. 3 ¹ H-of the monomer A2 obtained in Synthesis Example 2 of Example.
NMR chart.

FIG. 4 ¹ H-of Monomer B1 obtained in Synthesis Example 5 of Example
NMR chart.

FIG. 5 is a ¹ H-NMR chart of the copolymer obtained in Example 1.

FIG. 6 is a ¹ H-NMR chart of the homopolymer obtained in Reference Example 1.

FIG. 7 is a ¹ H-NMR chart of the copolymer obtained in Example 2.

FIG. 8 is a ¹ H-NMR chart of the homopolymer obtained in Reference Example 2.

FIG. 9 is a ¹ H-NMR chart of the copolymer obtained in Example 3.

FIG. 10 ¹ H—N of Monomer B10 obtained in Example 4
MR chart.

FIG. 11 is a ¹ H-NMR chart of the copolymer obtained in Example 4.

FIG. 12 is a ¹ H-NMR chart of the copolymer obtained in Example 5.

FIG. 13 is a ¹ H-NMR chart of the copolymer obtained in Example 6.

FIG. 14 is a ¹ H-NMR chart of the copolymer obtained in Example 7.

FIG. 15 is a ¹ H-NMR chart of the copolymer obtained in Example 8.

16 is a ¹ H-NMR chart of the copolymer obtained in Example 9. FIG.

FIG. 17 is a ¹ H-NMR chart of the copolymer obtained in Example 10.

FIG. 18 is a ¹ H-NMR chart of the copolymer obtained in Example 11.

FIG. 19 is a ¹ H-NMR chart of the copolymer obtained in Example 12.

20 is a ¹ H-NMR chart of the copolymer obtained in Example 13. FIG.

FIG. 21 is a ¹ H-NMR chart of the copolymer obtained in Example 14.

22 is a ¹ H-NMR chart of the copolymer obtained in Example 15. FIG.

FIG. 23 is a ¹ H-NMR chart of the copolymer obtained in Example 16.

FIG. 24 is a ¹ H-NMR chart of the copolymer obtained in Example 17.

FIG. 25 is a ¹ H-NMR chart of the copolymer obtained in Example 18.

FIG. 26 is a ¹ H-NMR chart of the copolymer obtained in Example 19.

FIG. 27 is a ¹ H-NMR chart of the copolymer obtained in Example 20.

28 is a ¹ H-NMR chart of the copolymer obtained in Example 21. FIG.

FIG. 29 is a ¹ H-NMR chart of the copolymer obtained in Example 22.

FIG. 30 is a ¹ H-NMR chart of the copolymer obtained in Example 23.

FIG. 31 is a ¹ H-NMR chart of the copolymer obtained in Example 24.

FIG. 32 is a ¹ H-NMR chart of the copolymer obtained in Example 25.

FIG. 33 is a ¹ H-NMR chart of the copolymer obtained in Example 26.

34 is an explanatory view showing the orienting device used in Example 30. FIG.

[Explanation of symbols] 1 polymer compound 2 low-molecular smectic liquid crystal compound 3 heating roll 4 unaligned element 5 aligned element

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Fumio Moriwaki 1280 Kamizumi, Sodegaura-shi, Chiba Idemitsu Kosan Co., Ltd.

Claims (4)

[Claims] 1. A repeating unit [I] represented by the following general formula (I) and a repeating unit [II] represented by the following general formula (II): [However, in the formula, p, q, s, and t are integers of 2 to 5, m and n
Is an integer of 2 to 20, a is an integer of 0 to 3, b is an integer of 1 to 8, r is a number of 0 to 5, * represents an asymmetric carbon atom, and R ¹ is And R ² is an optically active alkyl group represented by the general formula (III) or an optically inactive alkyl group represented by the general formula (IV) (However, R ³ in the formula represents hydrogen or a methyl group, and c is 0.
Is an integer of 4 and d is an integer of 1 to 8, and * represents an asymmetric carbon atom. ) Is represented. ] And the molar ratio ([I] / [II]) of repeating units [I] and [II] is (1
/ 99) to (99/1), a liquid crystal copolymer. 2. A diene compound represented by the following general formula (V): [Chemical 4] {However, in the formula, s and t are integers of 2 to 5, n is an integer of 2 to 20, and R ⁴ is And R ⁵ is an optically inactive alkyl group represented by the general formula (IV) (However, R ³ in the formula represents hydrogen or a methyl group, and c is 0.
Is an integer of 4 and d is an integer of 1-8. ) Is represented. ]. 3. A ferroelectric liquid crystal composition comprising the liquid crystal copolymer according to claim 1 and a low molecular weight smectic liquid crystal compound. 4. The ferroelectric liquid crystal composition according to claim 3, wherein the low molecular weight smectic liquid crystal compound is a ferroelectric liquid crystal compound.