JP2000290315A - Polymerizable optically active compound - Google Patents

Abstract

(57) [PROBLEMS] To provide a polymerizable optically active compound which is useful for an optically anisotropic substance and provides a liquid crystal composition which becomes a liquid crystal phase in a wide temperature range including a low temperature range. SOLUTION: The polymerizable optically active compound of the present invention is a novel compound represented by the following general formula (I). Further, the polymerizable composition of the present invention contains the above-mentioned polymerizable optically active compound as an essential component. The polymer of the present invention is obtained from the above polymerizable composition. Embedded image

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polymerizable optically active compound, a polymerizable composition using the same, and a polymer obtained from the polymerizable composition.
The present invention relates to a compound having an 1,3-dimethylpropylene group as an optically active site and having an alkenyl group as a polymerizable site, a polymerizable composition using the compound, and a polymer thereof, which are useful for display materials and recording materials.

[0002]

2. Description of the Related Art Portable electronic devices such as a notebook type personal computer and a video camera are required to be lightweight and have a long battery life. There is a strong demand for low power consumption and low voltage driving.

[0003] In response to the above demands, there has been proposed a retardation plate, a polarizing plate, a light polarizing prism, a reflecting plate, etc., utilizing anisotropy of physical properties such as orientation, refractive index, dielectric constant and magnetic susceptibility of a liquid crystalline substance. Methods for increasing the light source utilization efficiency by applying various optical anisotropic bodies are being studied.

For example, Japanese Patent Application Laid-Open No. 6-281814 and Liquid Crystal Vol. 2 No. 1998 report an optically anisotropic substance using a cholesteric liquid crystal composition, and Japanese Patent Application Laid-Open No. 8-3111 discloses a nematic. An optical anisotropic body using a liquid crystal composition has been reported.

[0005] These optically anisotropic bodies are irradiated with energy rays such as ultraviolet rays while a liquid crystal compound having a polymerizable site or a polymerizable liquid crystal composition containing a liquid crystal compound having a polymerizable site is oriented. Obtained by a method of polymerizing.
In other words, the obtained optically anisotropic substance is a state in which the state of maintaining the molecular orientation is fixed, and when the optically active site is introduced into the raw material, the effect of the optically active site controlled in a higher-order structure, Properties can be given to optical properties. Therefore, it has been considered to control the optical characteristics by selecting the structure of the optically active site of the liquid crystal material as a raw material.

[0006] The polymerizable compound or polymerizable composition used for such an application is required to have not only a structure giving necessary optical characteristics after polymerization but also to exhibit a liquid crystal state in a wide temperature range including a low temperature range. Thus, a compound and a composition which can completely satisfy these requirements have not been obtained.

Accordingly, an object of the present invention is to provide a polymerizable optically active compound which is useful for an optically anisotropic substance and provides a liquid crystal composition which becomes a liquid crystal phase in a wide temperature range including a low temperature range.

[0008]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a specific compound having a 1,3-dimethylpropylene group as an optically active site and an alkenyl group as a polymerizable site is: It has been found that the above object can be achieved.

The present invention has been made based on the above findings, and provides a novel polymerizable optically active compound represented by the following general formula (I) of the following [Chemical formula 2] (same as the above [Chemical formula 1]). Things.

[0010]

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[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the compound represented by the above general formula (I) which is the polymerizable optically active compound of the present invention will be described in detail.

The compound represented by the general formula (I) has a 1,3-dimethylpropylene group as an optically active site and an alkenyl group as a polymerizable site in the molecule. In the general formula (I), examples of the halogen atom represented by X and Y include fluorine, chlorine, bromine, and iodine. Examples of the alkylene group having 1 to 8 carbon atoms represented by R include methylene. , Ethylene, propylene, 1-
Methyl ethylene, 2-methyl ethylene, butylene, 1-
Methylpropylene, 2-methylpropylene, 3-methylpropylene, 1,3-dimethylpropylene, butylene,
1-methylbutylene, 2-methylbutylene, 3-methylbutylene, 4-methylbutylene, 2,4-dimethylbutylene, 1,3-dimethylbutylene, pentylene, hexylene, heptylene, octylene, etc., and R ′ and R "
Examples of the alkyl group having 1 to 8 carbon atoms represented by are methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, tert-butyl, amyl, isoamyl, hexyl, cyclohexyl, heptyl, isoheptyl, n -Octyl, isooctyl, 2-ethylhexyl, and examples of the alkenyl group having 1 to 8 carbon atoms include vinyl, 1-methylethenyl, 2-methylethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl and the like. .

The compound represented by the above general formula (I), which is the polymerizable optically active compound of the present invention, is not particularly limited, but preferred specific examples thereof include the following [formula 3] to [formula 8].
Compound No. shown in 1 to No. 6 and the like.

[0014]

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[0015]

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[0016]

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[0017]

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[0018]

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[0019]

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The polymerizable optically active compound of the present invention is useful for optical materials, display materials and recording materials, and particularly useful for optically anisotropic liquid crystal elements. When the polymerizable optically active compound of the present invention is used in a liquid crystal element by being mixed with another polymerizable compound, it may or may not show liquid crystallinity itself, and is a mixture with another polymerizable compound, that is, Any polymerizable composition may be used as long as it shows liquid crystallinity and gives an optically anisotropic substance (polymer) having excellent alignment properties.

Further, the polymerizable optically active compound of the present invention comprises:
One type or two or more types thereof may be used, or one type or more of other polymerizable compounds may be used.

The other polymerizable compound used together with the polymerizable optically active compound of the present invention is not particularly limited, and examples thereof include 4-acryloyloxy-4-decylbiphenyl and 4-acryloyloxy-4-cyano. Biphenyl, 4-acryloyl-4-amyltran, 4-acryloyl-4- (3,4-difluorophenyl) bicyclohexyl, 4- (2-acryloyloxyethyl) benzoic acid (4-amylphenyl), 4-
(2-acryloyloxyethyl) benzoic acid (4- (4
-Propylcyclohexyl) phenyl), 4- (6-
(Acryloyloxyhexyloxy) -4 ′ cyanobiphenyl, 4- (2-acryloyloxyethyl) phenyl 4-cyanobenzoate, 4- (6-acryloyloxyhexyloxy) phenyl 3,4-difluorophenylbenzoate, 1- Monoacrylate compounds such as (4- (2-acryloyloxyethyloxy) phenylcarbonyloxy) -4 (4-cyanophenylcarbonyloxy) benzene, and 1,4-bis (4- (6-acryloyloxyhexyloxy) benzoyloxy) benzene,
1,4-bis (4- (2-acryloyloxyethyloxy) benzoyloxy) benzene, bis (4- (2-
Symmetric diacrylate compounds such as acryloyloxyethyloxy) phenyl) terephthalate, 4- (4-acryloyloxyphenyl) carbonyloxy- (6-acryloyloxyhexyloxyphenyl) carbonyloxybenzene, 4- (4-acryloyloxyphenyl) carbonyl Oxy- (3-acryloyloxypropyloxyphenyl) carbonyloxybenzene, 4-
Acryloyloxybenzoic acid-4- (2-acryloyloxyethyl) phenyl, 4-acryloyloxybenzoic acid-4- (3-acryloyloxypropyl) phenyl, 4-acryloyloxyphenyl-4-acryloyloxybenzoic acid ester, 4- Asymmetric diacrylate compounds such as (2-acryloyloxyethyl) benzoic acid (4-acryloyloxy) phenyl ester and 4- (4-acryloyloxyphenyl) carbonyloxy (6-acryloyloxyhexyl) carbonyloxybenzene; Bis (acryloyloxy) benzoic acid 4- (4- (2-acryloyloxyethyloxy)
Phenylcarbonyloxy) phenyl, 4- (4- (3-acryloyloxypropyloxy) phenylcarbonyloxy) phenyl 3,4-bis (acryloyloxy) benzoate, 3,4-bis (acryloyloxy)
4- (4- (6-acryloyloxyhexyloxy) phenylcarbonyloxy) phenyl benzoate, 3,4
-Bis (acryloyloxy) benzoic acid 4- (4-acryloylphenylcarbonyloxy) phenyl, 3,4
Triacrylate compounds such as 4-acryloyloxyphenyl bis- (acryloyloxy) benzoate; and methacrylate compounds in which the acryloyloxy group of these acrylate compounds is substituted with a methacryloyloxy group.

When a polymerizable composition comprising the polymerizable optically active compound of the present invention and another polymerizable compound in combination is used, the amount of the polymerizable optically active compound of the present invention is not particularly limited. If the amount used is small, the effect of the optically active site is unlikely to appear, so the amount is preferably 3% by weight or more, more preferably 20% by weight or more.

The polymerizable optically active compound of the present invention is not limited by the production method, but the polymerization active site is a carboxylic acid having a double bond such as acrylic acid or methacrylic acid, an ester compound thereof, or a halide thereof. It can be introduced from an isoester-forming derivative, the optically active site can be introduced from 2,4-pentadione, and a ring structure such as a benzene ring or a cyclohexane ring is formed from an ester-forming derivative of the corresponding ring or an alcohol of the corresponding ring. Can be introduced. Using these as a raw material, a polymerizable optically active compound having a target structure can be obtained by an esterification reaction, a transesterification reaction, a halogenation reaction, an etherification reaction, or the like.

Further, the polymerizable optically active compound of the present invention comprises
By using the polymer, an optically anisotropic body having optical characteristics can be obtained. In this polymer,
The polymerizable optically active compound of the present invention is immobilized while maintaining the molecular orientation, and optical properties are imparted by the effect of the optically active site controlled in a higher-order structure. As a method for obtaining such a polymer, for example, a photopolymerization initiator is added to the polymerizable composition containing the polymerizable optically active compound of the present invention as an essential component, and irradiation with energy such as ultraviolet light is performed. Examples of the method include polymerization.

[0026]

The present invention will be described below in more detail with reference to Production Examples and Examples. However, the present invention is not limited by the following Production Examples and Examples.

(Production Example 1) Synthesis of 4-((1S, 3R) -3-hydroxy-1,3-dimethylpropyloxy) benzoic acid Synthesis of (S, S)-in a 500 ml flask purged with argon.
5.46 g of 2,4-pentanediol (0.0525 m
ol), 7.6 g of methyl 4-hydroxybenzoate (0.
0500 mol), 14.4 g of triphenylphosphine
(0.0550 mol) and 150 m of diethyl ether
12.1 g (0.0600 mol) of diisopropyl azodicarboxylate while stirring and mixing at room temperature.
The mixture was added dropwise in 5 minutes and reacted at room temperature for 3 hours. After the precipitate was separated by filtration and the solvent was removed from the filtrate, the residue was purified by column separation with a silica gel column and an ethyl acetate / hexane = 1/4 solvent to obtain a methyl ester. 3.4 g (0.0600 mol) of potassium hydroxide and 100 m of ethanol
l, 50 ml of water was added and the mixture was refluxed for 3 hours, concentrated, acidified with dilute hydrochloric acid, filtered and washed with water to obtain 6.2 g (yield 55%) of the desired alcohol compound.

Synthesis of Acrylic Ester 5.6 g (0.0250 mol) of alcohol compound obtained in a reaction flask equipped with a Dean-Stark trap
l), acrylic acid 18.0 g (0.0250 mol),
While charging 1.40 g of paratoluenesulfonic acid monohydrate and 0.3 g of hydroquinone, and distilling off generated water,
The reaction was performed for 8 hours. After the reaction, the solvent was removed, and water and diethyl ether were added in 100 ml portions to separate oil and water. The ether phase was washed with a 1% aqueous sodium hydrogen carbonate solution and distilled water, concentrated, and then purified with a silica gel column using chloroform / methanol = 50/1. By doing, acrylic acid ester 4.
08 g (58% yield) was obtained.

Compound No. Synthesis of 1 Acrylic ester 3.0 in a 100 ml reaction flask
6 g (0.011 mol), dimethylformamide 0.
08 g (0.0011 mol) and 3,5-ditert-butyl-4-hydroxytoluene 0.02 g (0.00
011 mol) and toluene 10.5 g, and stirring and mixing at room temperature 1.65 g (0.013 mol) of thionyl chloride.
2 mol) was added dropwise and reacted at room temperature for 2 hours. After confirming the completion of the reaction by gas chromatography, the solvent and excess thionyl chloride were distilled off to obtain an acid chloride compound. In a 300 ml flask purged with argon, 0.606 g (0.00550 mol) of hydroquinone, 0.918 g (0.0116 mol) of pyridine, and 7.00 g of tetrahydrofuran were charged, and the above acid chloride was dissolved in 3.5 g of tetrahydrofuran while stirring and mixing. The solution was added dropwise in 15 minutes, and after completion of the addition, the mixture was reacted at 50 ° C. for 2 hours. After adding 50 ml of chloroform and water each time, separating oil and water, mixing a chloroform phase and a phase extracted from the aqueous phase again with 50 ml of chloroform, washing with water twice, drying with magnesium sulfate, desolvating, and silica gel with a chloroform solvent. After column purification, the desired compound No. 1.20 g (34.7 g) of Compound 1 was obtained. The structure of the obtained compound was confirmed by IR measurement and ¹ H-NMR.

IR analysis results (unit: cm ^-1 ) 2970, 2920, 1720, 1630, 1600,
1570, 1500, 1455, 1405, 1380,
1250, 1160, 1065 ¹ H-NMR analysis result 1.3 ppm: (d; 6H), 1.5 ppm: (d; 6)
H), 2.0 ppm: (m; 4H), 4.6 ppm
(M; 2H), 5.2 ppm (m; 2H), 5.8-
6.5 (m; 6H), 6.9-8.2 (m; 12H)

(Production Example 2) Synthesis of 2 In a 100 ml flask, 0.78 g (0.0028 mol) of the acrylate obtained in Production Example 1, 4- (4
-Hydroxyphenyl) -4'-propylcyclohexane 0.73 g (0.00335 mol) and 10 ml of dichloromethane were charged, and 0.69 g (0.00335 mol) of N, N'-dichlorohexylcarbodiimide dissolved in 2 ml of dichloromethane with stirring and mixing. 10
The reaction was allowed to proceed at room temperature for 5 hours. The precipitate was separated by filtration, the filtrate was desolvated, and hexane / ethyl acetate = 4/1.
A silica gel column was purified using a solvent, and the target compound No. showing a cholesteric liquid crystal phase at room temperature. 0.70 g (yield 53.8%) of Compound 2 was obtained. The structure of the obtained compound was confirmed by IR measurement and ¹ H-NMR.

IR analysis results (unit: cm ^-1 ) 2920, 2850, 1725, 1635, 1600,
1505, 1405, 1255, 1200, 1165,
1075 ¹ H-NMR analysis result 0.9 ppm: (t; 3H), 1.1-2.4 ppm:
(M; 22H), 4.6 ppm (m; 1H), 5.2 p
pm (m; 1H), 5.7-6.5 (m; 3H), 6.
8-8.1 (m; 8H)

(Production Example 3) Synthesis of 3 4- (4-hydroxyphenyl) in a 100 ml flask
1.10 g (0.005 mol) of butyl acrylate,
4-carboxyl-4 ′-[(1R, 3R) -3-chloro-1,3-dimethylpropyloxy] biphenyl
59 g (0.005 mol), 0.06 g (0.0005 mol) of 4-dimethylaminopyridine and 20 ml of dichloromethane were charged and dissolved in 3 ml with stirring and mixing. N, N'-dichlorohexylcarbodiimide 1.
08 g (0.00525 mol) was added dropwise in 10 minutes, and the mixture was reacted at room temperature for 6 hours. The precipitate was separated by filtration, the filtrate was desolvated, and the residue was purified by a silica gel column with a chloroform solvent. 1.70 g of 3
(65.4% yield). The structure of the obtained compound is represented by I
It was confirmed by R measurement and ¹ H-NMR.

IR analysis results (unit: cm ^-1 ) 2960, 2925, 2850, 1725, 1630,
1595, 1500, 1400, 1260, 1180,
1070 ¹ H-NMR analysis result 1.3 ppm: (d; 3H), 1.4 ppm: (d; 3)
H) 1.6-2.2 ppm: (m; 6H), 2.6:
(T; 2H), 4.2 ppm (m; 3H), 4.7 pp
m1 (m; 1H), 5.8-6.7 (m; 3H), 7.
0-8.2 (m; 12H)

Example 1 Production of Polymerizable Composition 2, 50 parts by weight, 4- (2-acryloyloxyethyl) benzoic acid (4-acryloyloxy)
A composition was prepared by mixing 25 parts by weight of phenyl and 25 parts by weight of 4- (4-acryloyloxyphenyl) carbonyloxy (6-acryloyloxyhexyl) carbonyloxybenzene. Compound No. 3 and 60 parts by weight of 4- (4-acryloyloxyphenyl) carbonyloxy (6-acryloyloxyhexyl) carbonyloxybenzene were mixed at a ratio of 40 parts by weight to prepare a composition. Compound No. 3, 50 parts by weight of 4- (2-acryloyloxyethyl) benzoic acid (4-acryloyloxy)
A composition was prepared by mixing 20 parts by weight of phenyl and 30 parts by weight of 4- (4-acryloyloxyphenyl) carbonyloxy (6-acryloyloxyhexyl) carbonyloxybenzene. All three polymerizable compositions described above exhibited a cholesteric liquid crystal phase at room temperature.

Example 2 Production of Polymer A polymerization test was carried out on the polymerizable compositions (1) to (4) of Example 1 above. To the polymerizable composition, a photopolymerization initiator: α, α-dimethoxydeoxybenzoin 0.5% by weight was added, sandwiched between glass cells, and irradiated with light of 356 nm at 25 ° C. to perform polymerization. For the polymer, selective reflection specific to the liquid crystal phase similar to that of the polymerizable composition before polymerization was observed, and it was confirmed that the liquid crystal state was fixed.

[0037]

The polymerizable optically active compound of the present invention provides a polymerizable liquid crystal composition useful for an optically anisotropic substance.

Continued on the front page (72) Inventor Takahiro Otsuka 5-2-13-Shirahata, Urawa-shi, Saitama F-term (reference) in Asahi Denka Kogyo Co., Ltd. 4H006 AA01 AB46 BJ20 BJ50 BM10 BP20 BP30 4J100 AL08P AL65P BA02P BA15P BB01P BC04P BC43P CA01 DA66

Claims (3)

[Claims] 1. A polymerizable optically active compound represented by the following general formula (I). Embedded image 2. A polymerizable composition comprising the polymerizable optically active compound according to claim 1 as an essential component. 3. A polymer obtained from the polymerizable composition according to claim 2.