JP2003286319A - Optically active fumaric acid diester derivative and liquid crystal polymer made of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid crystal polymer made of a polymerizable and optically active fumaric diester, high in light resistance, heat resistance, and mechanical strength, and to provide a light compensation film, an optically writable recording material, a liquid crystal color filter, and a ferroelectric liquid crystal polymer display device, composed of the polymer. <P>SOLUTION: The optically active polymerizable compound is described by formula (1), and the polymer is obtained by polymerization of the compound, and the optical compensation film, the optically writable recording material, the liquid crystal color filter, and the ferroelectric liquid crystal polymer display device are made of the polymer. In formula (1), R<SP>1</SP>is a 3-15C alkyl wherein any hydrogen may be replaced by -CH<SB>3</SB>, -CH<SB>2</SB>CH<SB>3</SB>, -CF<SB>3</SB>, chlorine, or the like, for the alkyl to have asymmetric carbons; R<SP>2</SP>is a 1-20C alkyl: A<SP>1</SP>, A<SP>2</SP>and A<SP>3</SP>are each a ring like a 1,4-cyclohexylene ring; Z<SP>1</SP>is a single bond, -O-, -COO-, or the like; Z<SP>2</SP>and Z<SP>3</SP>are each a single bond, -COO-, or the like; and x is 1 or 0 and y is 1-20. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a liquid crystal optically active polymerizable compound, a polymer thereof, and uses thereof. These can be used for a liquid crystal composition, an optical compensation film, an optical writing recording material, a liquid crystal color filter, a ferroelectric liquid crystal polymer display device, and the like, which are components of a liquid crystal display device. In the present invention, the term liquid crystal compound is used as a general term for a compound having a liquid crystal phase and a compound having no liquid crystal phase but useful as a component of a liquid crystal composition. The optically active polymerizable compound represented by the formula (1) may be referred to as the compound (1). A polymer having at least one repeating unit represented by the formula (2) may be referred to as a polymer (2). A liquid crystal composition containing at least one compound (1) may be referred to as a composition. “(Meth) acrylate” means “acrylate in which hydrogen at the α-position may be replaced by methyl”, ie, “acrylate or methacrylate”. This usage also applies to "(meth) acrylic acid". The term "any" means "at least one selected without distinction".

[0002]

BACKGROUND OF THE INVENTION Many attempts have been made to utilize optically active liquid crystal polymers. Applications include optical compensation films such as retardation plates (JP-A 2000-144132), optical writing recording materials (JP-A-10-62740), liquid crystal color filters (JP-A 2001-242315), and ferroelectric liquid crystals. Examples include polymer displays (Ferroelectronics, Vol.122, p53-62, 1991). In the materials for these applications, an optically active liquid crystalline group (mesogen) is bonded to an acrylic acid polymer, a methacrylic acid polymer or a siloxane polymer by a spacer such as a methylene chain.

[0003]

The characteristics required for the optical compensation film and the liquid crystal color filter are strength and light resistance against stress such as twisting and pulling. The characteristics required for the optical writing recording material are light resistance to laser and heat resistance. The property required for a ferroelectric liquid crystal polymer display is strength against stress. The properties required for these materials are light resistance, heat resistance, and strength against stress.
However, these properties have not been sufficient in conventional materials.

The first object of the present invention is to provide fumaric acid diester which is polymerizable and optically active. The second object is to provide a polymer having excellent light resistance, heat resistance and mechanical strength, and having liquid crystallinity. A third object is to provide an optical compensation film made of this polymer, an optical writing recording material, a liquid crystal color filter, and a ferroelectric liquid crystal polymer display device.

[0005]

Means for Solving the Problems The present inventor has investigated an optically active fumaric acid diester derivative, and found that a polymer obtained by polymerizing a specific fumaric acid diester derivative has excellent light resistance, heat resistance and Has mechanical strength,
And they found that they have liquid crystallinity. Furthermore, they have found that this polymer is useful for an optical compensation film, an optical writing recording material, a liquid crystal color filter, a ferroelectric liquid crystal polymer display device, etc., and completed the present invention.

In order to achieve the above object, the present invention has the following constitution. [1] An optically active polymerizable compound represented by the formula (1). (In the formula, R ¹ is alkyl having 3 to 15 carbon atoms, and any hydrogen is —CH 2 such that the alkyl has an asymmetric carbon.
_{3, -CH 2 CH 3, -CF} 3, chlorine, fluorine or is replaced by -CN,; ^{R 2} is alkyl having 1 to 20 carbon ^atoms; A 1, ^{A 2} and ^{A 3} are independently ,
1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-cyclohexylene in which arbitrary hydrogen is replaced by fluorine, 1,3-dioxane-2,5-diyl,
1,4-phenylene, 1,4-phenylene in which arbitrary hydrogen is replaced by halogen, pyridine-2,5-diyl, pyridazine-3,6-diyl, pyrimidine-2,5
-Diyl, naphthalene-2,6-diyl, 1,2,3
4-tetrahydronaphthalene-2,6-diyl or fluorene-2,7-diyl; Z ¹ is a single bond,-
O-, -COO-, or -OOC-; Z ² and Z ³ are independently a single bond, -COO-, -OOC-,
_{-CF 2 O -, - OCF 2} -, - CH 2 O -, - OCH
_{2 -, - CH = CH -} , - CH 2 CH 2 -, or -C
≡ C-; x is 1 or 0, and y is an integer of 1-20. ) [2] In the formula (1) described in the item [1], x is 0.
The optically active polymerizable compound according to the item [1]. [3] In the formula (1) described in the item [1], x is 1
The optically active polymerizable compound according to the item [1]. [4] A composition containing at least one of the optically active polymerizable compounds described in the item [1] and at least one non-polymerizable compound having liquid crystallinity. [5] A composition containing at least one of the optically active polymerizable compounds described in the item [1] and at least one of other polymerizable compounds. [6] The composition according to the item [4], which further contains at least one other polymerizable compound.

[7] A polymer having at least one repeating unit represented by the formula (2). (R ¹ , R ² , A ^{1 to} A ³ , Z ¹ to in these formulas
The meanings of the symbols Z ³ , x, and y are the same as the meanings of the symbols described in the item [1]. [8] A polymer obtained by polymerizing the composition described in the item [4].

[9] A polymer obtained by polymerizing the composition described in the item [5]. [10] A polymer obtained by polymerizing the composition described in the item [6].

[11] An optical compensation film containing the polymer described in the item [7]. [12] An optical compensation film containing the polymer described in any one of [8] to [10]. [13] A cholesteric liquid crystal polymer (polymer) type optical writing recording material containing the polymer described in the item [7]. [14] A cholesteric liquid crystal polymer (polymer) type optical writing recording material containing the polymer described in any one of [8] to [10]. [15] A ferroelectric liquid crystal polymer (polymer) display device containing the polymer described in the item [7]. [16] A ferroelectric liquid crystal polymer (polymer) display device containing the polymer described in any one of [8] to [10]. [17] A liquid crystal color filter containing the polymer described in the item [7]. [18] A liquid crystal color filter containing the polymer described in any one of [8] to [10].

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The compound (1) has the following characteristics. 1) The compound (1) is polymerizable and has liquid crystallinity. 2) Compound (1) is ^{R 1 -Z 1 -A 1 -Z 2} -A 2 -
Having a liquid crystal skeleton of _{^{- (Z 3 -A 3) x}} . This liquid crystal skeleton is rigid and contributes to the development of liquid crystallinity. This group is attached to the ester by an alkylene chain. 3) The bonding groups Z ¹ , Z ² and Z ³ in the liquid crystal skeleton are
It is not azo, diazo or azoxy which is unstable to light.

The polymer (2) obtained by homopolymerizing or copolymerizing the compound (1) has the following characteristics. 1) Since all carbon atoms of the polymethylene main chain in the polymer (2) have a substituent, the mechanical strength against heat and heat resistance are excellent. 2) Since the compound (1) is stable to light, the polymer (2)
Also has excellent light resistance. 3) The liquid crystal skeleton is less likely to be sterically constrained by the polymethylene main chain. Therefore, the polymer (2) has a large liquid crystallinity and a high clearing point.

Therefore, the polymer (2) has properties superior to those of the conventional materials as described above.
It is a material suitable for optical writing recording materials, liquid crystal color filters, and ferroelectric liquid crystal polymer display devices.

R ¹ , R ² , A ¹ in the compound (1),
The symbols of A ² , A ³ , Z ¹ , Z ² , Z ³ , x, and y will be described. R ¹ is alkyl having 3 to 15 carbon atoms, and any hydrogen is —C so that the alkyl has an asymmetric carbon.
_{H 3, -CH 2 CH 3,} -CF 3, have been replaced chlorine, fluorine or -CN,. Preferred R ¹ is 1-methylpropyl, 1-methylbutyl, 1-methylpentyl, 1-methylhexyl, 1-methylheptyl, 1-methyloctyl, 1-methylnonyl, 1-methyldecyl,
1-ethylbutyl, 1-ethylpentyl, 1-ethylhexyl, 1-ethylheptyl, 1-ethyloctyl, 1
-Ethylnonyl, 1-ethyldecyl, 5-methylheptyl, 6-methyloctyl, 2-methylbutyl, 1-trifluoromethylbutyl, 1-trifluoromethylpentyl, 1-trifluoromethylhexyl, 1-trifluoromethyloctyl, 1- Trifluoromethylnonyl, 2
-Fluorooctyl, 2-chlorooctyl, 2-cyanooctyl, and 1-cyanooctyl. These groups may have the (R) configuration or the (S) configuration.

R ² is alkyl having 1 to 20 carbons.
Preferred straight chain alkyls are methyl, ethyl, propyl,
Butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. Preferred branched alkyl is
Isopropyl, sec-butyl, t-butyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 4-
Methyl-2-pentyl, sec-heptyl, and se
It is c-octyl. Preferred cyclic alkyl is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclododecyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-propylcyclohexyl, 4-butylcyclohexyl, 4-pentylcyclohexyl, 4-hexylcyclohexyl,
4-heptylcyclohexyl, 4-octylcyclohexyl, 4-nonylcyclohexyl, 4-decylcyclohexyl, trans-4-cyclohexylcyclohexyl, trans-4- (4-methylcyclohexyl) cyclohexyl, trans-4- (4-ethylcyclohexyl) cyclohexyl , Trans-4- (4-n-propylcyclohexyl) cyclohexyl, trans-4-
(4-n-pentylcyclohexyl) cyclohexyl,
Trans-4- (4-n-hexylcyclohexyl) cyclohexyl, trans-4- (4-n-heptylcyclohexyl) cyclohexyl, trans-4- (4-n
-Octylcyclohexyl) cyclohexyl, norbornyl, camphenyl, tricyclodecyl, adamantyl, and dimethyladamantyl.

The bulkier R ² is, the higher the reactivity of the compound (1) is. High reactivity is cyclic alkyl> branched alkyl>
The order is straight-chain alkyl. When R ² is not bulky, the liquid crystallinity of the polymer (2) is higher. The liquid crystallinity is in the order of linear alkyl> branched alkyl> cyclic alkyl. R ² of the compound (1) having high reactivity and high liquid crystallinity is branched alkyl. A particularly preferred R ² is isopropyl.

A ¹ , A ² and A ³ are independently 1,4
-Cyclohexylene, 1,4-cyclohexenylene, 1,4-cyclohexylene in which arbitrary hydrogen is replaced by fluorine, 1,3-dioxane-2,5-diyl, 1,4
-Phenylene, 1,4-phenylene in which any hydrogen is replaced by halogen, pyridine-2,5-diyl, pyridazine-3,6-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl or fluorene-2,7-diyl. Preferred A ¹ , A ² or A ³ are the following divalent groups.

[0016]

Z¹Is a single bond, -O-, -COO-, or
Is -OOC-. Preferred Z¹Is a single bond, -COO
-, And -OOC-. Z^TwoAnd Z^ThreeIs independent
Single bond, -COO-, -OOC-, -CF_TwoO-,
-OCF_Two-, -CH_TwoO-, -OCH_Two-, -CH =
CH-, -CH_TwoCH_Two-, Or -C≡C-.
Preferred Z^TwoOr Z^ThreeIs a single bond, -COO- and
-OOC-. Z ^TwoOr Z^ThreeIs a single bond, -CO
In the case of O- and -OOC-, the liquid crystal skeleton is rigid.
Therefore, the liquid crystal property is easily exhibited. Z^TwoOr Z^ThreeIs -C
When ≡C-, the polymer (2) has a large refractive index anisotropy.
I hear Z^TwoOr Z^ThreeIs -CF_TwoO-, -OCF_Two
-, -CH_TwoO-, -OCH_Two-, And -CH_TwoCH
_TwoIn the case of-, the liquid crystal skeleton becomes flexible,
The viscosity of (2) becomes low.

X is 1 or 0. y is an integer of 1 to 20, but preferable y is 3 to 11. Furthermore, preferable y is 3 to 6. Preferred liquid crystal skeleton of compound (1), R ¹ -Z ¹ -A ¹ -Z ² -A ^2- (Z ³ -A ³ ).
_x − is equations (1-1) to (1-31).

[0019]

[0020]

[0021] (In the formula, the meanings of the symbols of R ¹ , Z ¹ , A ¹ , A ² , and A ³ are the same as the meanings of the symbols in the item [1].)

[Production Method of Compound (1)] Compound (1)
An example of the production method of is shown in the following scheme. The maleic acid monoester (a) is obtained by the esterification reaction of maleic anhydride and alcohol (R ² OH). This compound is isomerized to produce the raw material fumaric acid monoester (b). The optically active compound (MEG1) is reacted with the ω-bromoalkanol in the presence of a base such as potassium hydroxide, sodium hydroxide, potassium carbonate, or sodium hydride to give another raw material alcohol (c). obtain. This alcohol (c) and the above fumaric acid monoester (b) are combined with dicyclohexylcarbodiimide or 1
-Esterified with a condensing agent such as ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride,
The target compound (1) is produced.

[0023] (In the formula, R ¹ , R ² , A ¹ , A ² , A ³ , Z ¹ , Z ² ,
The symbols of Z ³ , x, and y have the same meanings as the symbols of the item [1]. )

The polymer (2) has a liquid crystallinity and has at least one repeating unit represented by the formula (2). The polymer (2) is obtained by polymerizing the compound (1). The form of polymerization of the compound (1) is as follows. One of the compounds (1) is homopolymerized. At least two of the compounds (1) are copolymerized. At least one of the compound (1) and another monomer are copolymerized. These polymerizations can also be carried out in the presence of non-polymerizable compounds. The obtained copolymer may be a random copolymer, an alternating copolymer, a block copolymer, a graft copolymer, or the like.

To carry out the polymerization reaction, a composition containing at least one compound (1) is prepared. This composition may contain other components such as a non-polymerizable compound having liquid crystallinity, a polymerizable compound different from the compound (1), a polyfunctional polymerizable compound, a polymerization reaction initiator and a solvent. Good. A polymerizable compound different from the compound (1) may be referred to as "compound (3)". A composition containing the compound (1) and the compound (3) may be referred to as a “polymerizable composition”.

The compound (3) is not particularly limited as long as it does not deteriorate the film forming property and mechanical strength and can be copolymerized with the compound (1). The compound (3) may or may not have liquid crystallinity. Preferred compound (3)
Are fumaric acid derivatives, acrylic acid derivatives, sorbic acid derivatives, crotonic acid derivatives, and maleimide derivatives. When the compound (3) has liquid crystallinity, the temperature range of the liquid crystal phase of the polymer (2) can be adjusted. Examples of the compound (3) having liquid crystallinity are as follows.

[0027]

[0028]

[0029]

(In the formula, R ³ is alkyl having 1 to 15 carbon atoms, and R ⁴ is methyl, ethyl, 2-methylbutyl, propyl, octyl, isopropyl, t-butyl, cyclohexyl, 4butylcyclohexyl, norbornyl, or It is adamantyl, and y is an integer of 1 to 20.)

The preferable addition amount of the liquid crystal compound (3) is 0.5 to 95% by weight based on the weight of the compound (1). Since the added amount is 0.5% by weight or more, the temperature range of the liquid crystal phase can be easily adjusted. 95% by weight
Since it is below, the polymer (2) can be easily obtained.

Preferred examples of the polymerizable compound having no liquid crystallinity are the fumaric acid diester represented by the formula (3) and a vinyl monomer. The fumaric acid diester represented by the formula (3) may be referred to as the compound (3-1). The polymer (2) copolymerized with these compounds easily forms a film.

[0033]

First, the compound (3-1) is exemplified. R
⁵ or R ⁶ is a monovalent aliphatic hydrocarbon group or aromatic hydrocarbon group. The hydrogen in these groups may be replaced by halogen. Instead of carbon, these groups are sulfur (S), nitrogen (N), phosphorus (P), and silicon (S).
It may have a heteroatom such as i). These hydrocarbon groups are acyclic, monocyclic, fused polycyclic, or bridged cyclic. The preferred carbon number of the aliphatic hydrocarbon group is 1 to 14
And the preferred carbon number of the aromatic hydrocarbon group is 6 to 20.
Is. Preferred examples of these monovalent groups are straight chain alkyl,
Branched alkyl, cycloalkyl, aryl, and alkyl having halogen or heteroatoms. A specific example will be shown in this order.

Specific examples of linear alkyl are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl. Specific examples of branched alkyl are isopropyl, sec-butyl, t-butyl, sec-amyl, isopentyl, neopentyl, t-pentyl, sec-hexyl, 4-methyl-2-pentyl, sec-heptyl, and sec-octyl. is there. Specific examples of cycloalkyl are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, and dimethyladamantyl. Specific examples of aryl are phenyl,
Benzyl, 1-phenyl-1-ethyl, 3-phenylpropyl, 1-phenyl-2-propyl, and 1-phenyl-1-propyl.

Specific examples of alkyl having a halogen include trifluoromethyl, trifluoromethylethyl, hexafluoroisopropyl, perfluoroisopropyl, perfluorobutylethyl, perfluorooctylethyl, 2-chloroethyl, and 1-butoxy-2-. It is propyl. Specific examples of alkyl having a hetero atom include
Alkoxy such as methoxy, ethoxy, propoxy, butoxy; alkoxyalkyl such as methoxymethyl, methoxyethyl, cyanoalkyl such as cyanomethyl, cyanoethyl, cyanobutyl; hydroxy, hydroxyethyl, hydroxyethylthioethyl (HO-CH
_{2 CH 2 -S-CH 2 CH} 2 -), hydroxyalkyl such as hydroxybutyl; and trimethylsilyl,
It is a silicon-containing group such as trimethylsiloxypropyl.

Compound (3-1) in which R ⁵ and R ⁶ are the same
Preferred examples of are: diethyl fumarate, diisopropyl fumarate, dibutyl fumarate, dicyclohexyl fumarate, di1-phenyl-2-propyl fumarate, disec-butyl fumarate, di-t-butyl fumarate, and difumarate fumarate. It is 2-ethylhexyl. Particularly preferred compound (3-1) is diisopropyl fumarate and disec-butyl fumarate. Since these compounds have good copolymerizability, they are suitable for copolymerization with the compound (1).

Compound (3-1) in which R ⁵ and R ⁶ are not the same
The preferred examples of are as follows. The symbol = was used to clearly distinguish R ⁵ and R ⁶ . More preferred compounds are marked with a # after their name. Preferred examples are isopropyl fumarate = methyl, isopropyl fumarate = ethyl #, isopropyl fumarate = propyl,
Isopropyl fumarate = butyl #, isopropyl fumarate = sec-butyl #, isopropyl fumarate = t-butyl #, isopropyl fumarate = amyl #, isopropyl fumarate = isoamyl, isopropyl fumarate = se
c-amyl, isopropyl fumarate = sec-hexyl, isopropyl fumarate = 4-methyl-2-pentyl, isopropyl fumarate = 2-ethylhexyl, isopropyl fumarate = octyl, isopropyl fumarate =
Nonyl, t-butyl fumarate = sec-butyl, t-butyl fumarate = cyclohexyl, t-butyl fumarate =
4-methyl-2-pentyl, t-butyl fumarate = 2-
Ethylhexyl, isopropyl fumarate = cyclohexyl #, and isopropyl fumarate = cyclopentyl #
Is a dialkyl ester such as.

A preferred example is isopropyl fumarate = 2-
Phenyl-1-ethyl, isopropyl fumarate = 3-phenylpropyl, isopropyl fumarate = 1-phenyl-2-propyl #, and isopropyl fumarate = 1-
An ester having an aryl such as phenyl-1-propyl. Preferred examples are isopropyl fumarate = (trimethylsilyl) propyl, t-butyl fumarate = (trimethylsilyl) propyl, cyclohexyl fumarate =
Silicon-containing esters such as (trimethylsilyl) propyl, isopropyl fumarate = (3-tris (trimethylsiloxy) silyl) propyl, and isopropyl fumarate = 3-((pentamethyl) disiloxanyl) propyl. Preferred examples are N, N-dimethylaminoethyl fumarate = isopropyl, t-butyl fumarate =
1-butoxy-2-propyl, 2-cyanoethyl fumarate = isopropyl, 2-hydroxyethyl fumarate isopropyl, glycidyl fumarate isopropyl, isopropyl fumarate = diethylphosphomethyl, 2-methylthioethyl fumarate isopropyl, and Esters having a hetero atom such as isopropyl fumarate = 2-hydroxyethylthioethyl = isopropyl.
Preferred examples are halogens such as isopropyl fumarate = perfluoroisopropyl #, perfluorooctylethyl fumarate isopropyl, trifluoromethyl fumarate isopropyl, pentafluoroethyl fumarate isopropyl, and hexafluoroisopropyl fumarate isopropyl. It is an ester having. R ⁵ and R
Particularly preferred examples of compound (3-1) in which ⁶ are not the same are:
Isopropyl fumarate = 2-hydroxyethyl and isopropyl fumarate = 2-cyanoethyl.

Next, vinyl monomers will be exemplified. The vinyl-based monomer is not particularly limited as long as it can be copolymerized with the compound (1) and can give the film-forming property and mechanical strength to the polymer (2) produced. A preferred vinyl-based monomer is a vinyl-based monomer mainly containing an olefinic hydrocarbon. Preferred examples are vinyl acetate, vinyl pivalate, 2,
With vinyl esters such as vinyl 2-dimethylbutanoate, vinyl 2,2-dimethylpentanoate, vinyl 2-methyl-2-butanoate, vinyl propionate, vinyl stearate, and vinyl 2-ethyl-2-methylbutanoate. is there. A preferred example is vinyl acetamide, such as N-vinyl acetamide. Preferred examples are vinyl aromatic monomers such as pt-butyl vinyl benzoate, vinyl N, N-dimethylaminobenzoate, and vinyl benzoate. Preferred examples are styrene, styrene derivatives such as o-, m-, p-chlorostyrene, o-, m-, p-chloromethylstyrene, and α-methylstyrene. Preferred examples are vinyl chloride and vinyl halides such as vinyl fluoride.

Preferred examples are vinyl ethers such as ethyl vinyl ether, hydroxybutyl monovinyl ether, t-amyl vinyl ether, and cyclohexanedimethanol methyl vinyl ether. A preferred example is a naphthalene derivative such as α, β-vinylnaphthalene. Preferred examples are methyl vinyl ketone and alkyl vinyl ketones such as isobutyl vinyl ketone. Preferred examples are butadiene and dienes such as isoprene. Preferred examples are (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and phenyl (meth) acrylate. Preferred examples are itaconates such as dimethyl itaconate, diethyl itaconate, dibutyl itaconate, and diisopropyl itaconate.

The film-forming ability of the crosslinked polymer (2) is high. A polyfunctional polymerizable compound for crosslinking may be added as a component of the composition. A preferred polyfunctional polymerizable compound is a polyfunctional acrylate derivative. Preferred polyfunctional acrylates are 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate. , Tripropylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylol EO addition triacrylate, pentaerythritol triacrylate, trisacryloxyethyl phosphate, bisphenol A EO addition diacrylate, bisphenol A glydidiene Luther diacrylate (trade name: Viscoat 700 manufactured by Osaka Organic Chemical Co., Ltd.), and polyethylene glycol It is an acrylate.

The preferred addition amount of the non-liquid crystalline vinyl monomer or polyfunctional polymerizable compound is 0.5 to 50% by weight based on the weight of the liquid crystalline derivative. Since the addition amount is 0.5% by weight or more, a sufficient film forming power can be obtained, and the addition amount is 50% by weight or less, the polymer (2) can be easily obtained. The liquid crystal derivative is the compound (1), a specific gravity synthetic compound having liquid crystallinity, and the liquid crystal compound (3).

[Production Method of Polymer (2)] In order to obtain the polymer (2), various polymerization reaction modes can be used.
Polymerization reaction types that can be used include a radical polymerization method, an anionic polymerization method, a cationic polymerization method, a coordination polymerization method and a living polymerization method. In order to produce the polymer (2) using the compound (1), a heat or light polymerization method is preferable. In the thermal polymerization, the compound (1) and the polymerizable compound are mixed with each other at a reaction temperature of 0 to 150 ° C. for 1 to 1 in the presence of a radical polymerization initiator.
Polymerize for about 100 hours. Examples of radical polymerization initiators include benzoyl peroxide, diisopropyl peroxydicarbonate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxypivalate, t-butyl peroxydiisobutyrate, and peroxide. Lauroyl,
Dimethyl 2,2'-azobisisobutyrate (MAIB), di-t-butyl peroxide (DTBPO), azobisisobutyronitrile (AIBN), and azobiscyclohexanecarbonitrile (ACN).

In the polymerization method of irradiating energy such as light or electron beam, the compound (1) and the polymerizable compound are generally polymerized in the presence of a photoradical polymerization initiator during the polymerization. Examples of the photo-radical polymerization initiator include 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Darocur 1173), 1-hydroxycyclohexyl phenyl ketone (Ciba Specialty Chemicals Co., Ltd. Product name: Irgacure 184), 2, 2
-Dimethoxy-1,2-diphenylethan-1-one (trade name: Irgacure 651), the following trade names: Irgacure 500, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 1300, Irgacure 819, Irgacure 17
00, Irgacure 1800, Irgacure 185
0, Darocur 4265, and Irgacure 78
It is 4. Examples of the photo-radical polymerization initiator are p-methoxyphenyl-2,4-bis (trichloromethyl) -s-triazine, 2- (p-butoxystyryl) -5-trichloromethyl 1,3,4-oxadiazole. , 9-phenylacridine, 9,10-benzphenazine, benzophenone / Michler's ketone mixture, hexaarylbiimidazole / mercaptobenzimidazole mixture, 1
-(4-Isopropylphenyl) -2-hydroxy-2
-Methylpropan-1-one, benzyldimethylketal, and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1,2,4-diethylxanthone / methyl p-dimethylaminobenzoate mixture Is.

The method for producing the polymer (2) may be an anionic polymerization method, a coordination polymerization method or a living polymerization method.
Preferred initiators used in the anionic polymerization method, the coordination polymerization method and the living polymerization method are alkali metal alkyls such as n-butyllithium and t-butyllithium-trialkylaluminum, aluminum compounds, and transition metal compounds.

A solvent can be used in the polymerization. Examples of preferred solvents are benzene, toluene, xylene, mesitylene, pentane, hexane, heptane, octane, nonane, decane, tetrahydrofuran, 1,4-
Dioxane, N-methylpyrrolidone, dimethylformamide, dimethylsulfoxide, and a mixed solvent thereof.

The isolated polymer (2) can be molded by dissolving it in a solvent. A preferred solvent is N-methyl-2
-Pyrrolidone, dimethyl sulfoxide, N, N-dimethylacetamide, N, N-dimethylformamide, N,
N-dimethylacetamide dimethyl acetal, tetrahydrofuran, chloroform, 1,4-dioxane, bis (methoxyethyl) ether, γ-butyrolactone,
Tetramethylurea, trifluoroacetic acid, ethyl trifluoroacetate, and hexafluoro-2-propanol. However, the solvent is not limited to these,
It may be a mixture with common organic solvents such as acetone, benzene, toluene, heptane and methylene chloride.

The cholesteric liquid crystal film is manufactured by the following method. That is, a solution in which the polymer (2) obtained above is dissolved in an organic solvent is prepared. A glass plate or triacetyl cellulose film obtained by pre-orienting this solution, or Apel manufactured by Mitsui Chemicals, Inc., ZEONOR or ZEONEX manufactured by Nippon Zeon Co., Ltd., JS
Applied to a norbornene-based polymer film such as Arton manufactured by R Co., Ltd. using a method such as a microgravure coating method, a gravure coating method, a wire barcode method, a dip coating method, a spray coating method, or a meniscus coating method. To do. Then, it is heated to a temperature not lower than the glass transition point of the polymer (2). Then, the polymer (2) is uniformly oriented by allowing it to cool to obtain a cholesteric liquid crystal polymer film having a uniform film thickness. An optically active compound may be added to the polymer (2) to adjust the pitch of the cholesteric phase to produce a cholesteric liquid crystal film. The optically active compound used for pitch adjustment may be a chiral compound or a compound having a cholesterol skeleton. A specific example is shown below. Preferred compounds are short pitch compounds. This compound can be added in a small amount in terms of pitch adjustment.

[0050]

The thickness of the optically anisotropic thin film depends on the desired retardation value. The retardation value depends on the birefringence of the optically anisotropic thin film. The preferred thickness of the optically anisotropic thin film is 0.
05 to 50 μm, more preferably 0.1 to 20 μm, still more preferably 0.5 to 10 μm.

The haze value of the optically anisotropic thin film is 1.5% or less, preferably 1.0% or less. The transmittance of the optically anisotropic thin film is 80% or more, preferably 85% or more. Preferred transmittances are these ratios in the visible light region. If the haze value is higher than these ratios, there may be a problem in polarization performance. Particularly, when the transmittance is low, the brightness may be lost when used in a liquid crystal display element.

[Use of Polymer (2)] The polymer (2) obtained by thermal polymerization can be applied to various protective films, photowriting recording materials, color filters of liquid crystal display devices, and the like. Since the polymer (2) has optical anisotropy, it can be used alone as a retardation plate or in combination with another retardation plate to obtain a polarizing plate, a circular polarizing plate, an elliptic polarizing plate, a color compensating plate, It can be used as an optically anisotropic thin film such as a visual compensator. When the polymer (2) has ferroelectricity, it can be used for a ferroelectric liquid crystal polymer display. The polymer (2) obtained by photopolymerization can also be used as in the case of thermal polymerization. This polymer can be further used for a rubbingless alignment film by using polarized light.

[0054]

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. At the phase transition temperatures described in the examples, C is a crystal, Ch is a cholesteric phase, SmC ^* is a ferroelectric liquid crystal phase, SmX is an unidentified smectic phase, I is an isotropic liquid, and Tm is the melting point of a polymer. Indicates. The unit of the phase transition temperature is ° C. The obtained compound was identified based on the nuclear magnetic resonance spectrum. In the nuclear magnetic resonance spectrum, s is a singlet, d is a doublet, t is a triplet, q is a quartet, and m is a multiplet. Weight average molecular weight of polymer (M
w) and polydispersity (Mw / Mn) are measured by GPC (gel permeation chromatography) (Shimadzu LC-
9A, column: Shodex GF-7MHQ, developing solvent: DMF). The pencil hardness is JI
S standard "JIS K5400 8.4 pencil scratch test"
It measured based on the method of.

[Production of Optically Active Polymerizable Compound] Example 1 (First Step) Production of Mono (trans-4-n-butylcyclohexyl) Maleic Acid 63 g of maleic anhydride, trans-4-n-butylcyclohexanol 100 g and 5 g of sodium acetate were added to the flask, and the mixture was heated with stirring at 70 ° C. for 3 hours. After cooling to room temperature, 200 ml of water was added and stirred vigorously to obtain a slurry containing crystals. The crystals obtained by filtration are air dried and recrystallized from cyclohexane to give 110 g.
Of mono (trans-4-n-butylcyclohexyl) maleate was obtained. When proton NMR was measured, δ
= 6.39 ppm, a doublet (double line) with a J value of 1.8 Hz derived from the double bond of maleic acid was observed, and thus the product was identified as the target product. The melting point was 66 ° C.

(Second Step) Fumarate mono (trans-4
-N-Butylcyclohexyl) 90 g of maleic acid mono (trans-4-n-butylcyclohexyl) and 50 ml of water were added to a 300 ml flask and heated to 80 ° C and stirred. 2 g of tetraethylammonium bromide and 2 g of potassium peroxide were added thereto, and the mixture was further stirred for 2 hours. Stop heating and return to room temperature,
Crystals were obtained by pouring the reaction mixture into 400 ml of water. The crystals obtained by filtration were air-dried and recrystallized from cyclohexane to obtain 80 g of mono (trans-4-n-butylcyclohexyl) fumarate. Proton N
When MR was measured, δ = 6.86 ppm, and doublet (2 J value 1.8 Hz derived from double bond of fumaric acid)
Since it was observed, the product was identified as the target product.
The melting point was 68 ° C.

In the same manner as in the first and second steps, monocyclohexyl fumarate (melting point 85-87)
C), monocyclopentyl fumarate, monoadamantyl fumarate, monoisopropyl fumarate, mono-fumarate
t-butyl, fumaric acid monotrans, trans-4-
n-Pentyl-cyclohexyl-4-cyclohexyl was obtained.

(Third stage) Production of (S) -4- (6-hydroxyhexyloxy) -4 '-(2-methylbutyloxy) biphenyl (S) -4'-hydroxy-4- (2-methyl) Butyloxy) biphenyl 10 g, 6-bromohexanol 8.
4 g, potassium carbonate 9.7 g and dimethylformamide 2
It was added to 00 ml and stirred at 90 ° C. for 3 hours. When the reaction mixture was poured into 500 L of 3N hydrochloric acid, colorless crystals were precipitated, which were filtered and collected. The crystals obtained were thoroughly washed with water, dried thoroughly, and recrystallized from ethyl acetate to give 13 g of (S) -4- (6-hydroxyhexyloxy) -4 '-(2-methylbutyloxy). Biphenyl was obtained. Melting point: 114-115 ° C

The following compounds were produced by the same method as described above. (S) -4- (3-hydroxypropyloxy) -4 '
-(1-Methylheptyloxy) biphenyl Melting point: 6
7 to 68 ° C. (S) -2-Methylbutyl 4 ′-(9-hydroxynonyloxy) biphenyl-4-carboxylate Melting point: 74 ° C. (R) -1-Methylheptyl 4 ′-(9-hydroxynonyloxy) biphenyl -4-carboxylate Melting point: 83-85 ° C (S) -4 '-(2-methylbutyloxy) biphenyl 4- (6-hydroxyhexyloxy) benzoate Phase transition temperature: C 130 SmX 180 I (R) -3 -Fluoro-4- (1-methylheptyloxycarbonyl) phenyl 4- (6-hydroxyhexyloxy) benzoate Oil (R) 2- (9-hydroxynonyl) -6-[(1-methylheptyloxy) phenyl] Naphthalene melting point: 1
17 ° C

(Step 4) Preparation of (S) -isopropyl fumarate [4 '-(2-methylbutyloxy) biphenyl-4-yloxy] hexyl (compound [7]) Monoisopropyl fumarate 3.4 g, ( S) -4-
7.7 g of (6-hydroxyhexyloxy) -4 '-(2-methylbutyloxy) biphenyl was added to methylene chloride 1
It was dissolved in 50 ml and cooled to 5 ° C., 1 g of dimethylaminopyridine and 4.5 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride were added thereto, and the mixture was stirred at room temperature for 12 hours. 50 ml of water was added, the layers were separated, and the organic layer was dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent was purified by silica gel chromatography and recrystallized from ethanol to give 5.3 g of (S) -isopropyl fumarate [4 '-(2-methylbutyloxy)].
Biphenyl-4-yloxy] hexyl [7] was obtained.

C 60.5 (SmX 50.7) I ¹ H-NMR (CDCl ₃ , 90 MHz): δ (pp
m): 0.99 (3H, t), 1.02 (3H, d, J
= 6.3 Hz), 1.29 (6H, d, J = 6.3H)
z) 1.4 to 2.0 (m), 3.80 (2H, dd)
3.99 (2H, t, J = 6.3Hz), 4.21 (2
H, t, J = 6.3 Hz), 5.11 (1H, m),
6.83 (2H, s), 6.93 (4H, d, J = 8.
3Hz), 7.45 (4H, d, J = 8.3Hz)

The following optically active polymerizable compounds were produced in the same manner as in Example 1. Example 2 Compound [17]: (S) -isopropyl fumarate isopropyl
[4 '-(1-methylheptyloxy) biphenyl-4
-Iloxy] propyl Melting point: 70-72 ° C ¹ H-NMR (CDCl ₃ , 90 MHz): δ (pp
m): 0.88 (3H, t), 1.29 (6H, d, J
= 6.3 Hz) 1.2 to 1.5 (m), 2.18 (2
H, m) 4.09 (2H, t, J = 6.3Hz), 4.
42 (2H, t, J = 6.3 Hz), 5.11 (1H,
m), 6.83 (2H, s), 6.92 (4H, d, J
= 8.3 Hz), 7.45 (4H, d, J = 8.3H)
z)

Example 3 Compound [28]: (R) -isopropyl fumarate
4 '-(2-Methylbutyloxycarbonyl) biphenyl-4-yloxy) nonyl Melting point: 49-55 ° C ¹ H-NMR (CDCl ₃ , 90 MHz): δ (pp
m): 0.99 (3H, t), 1.02 (3H, d, J
= 6.3 Hz), 1.29 (6H, d, J = 6.3H)
z) 1.4 to 2.0 (m), 4.00 (2H, t, J =
6.3 Hz), 4.10 to 4.30 (4H, m), 5.
11 (1H, m), 6.82 (2H, s), 6.98
(2H, d, J = 8.8 Hz), 7.56 (2H, d,
J = 8.8 Hz), 7.61 (2H, d, J = 8.6H
z), 8.08 (2H, d, J = 8.6Hz)

Example 4 Compound [38]: (R) -isopropyl fumarate
4 '-( ¹ -Methylheptyloxycarbonyl) biphenyl-4-yloxy) nonyl Melting point: 36-37 ° C ¹ H-NMR (CDCl ₃ , 90 MHz): δ (pp
m): 0.87 (3H, t), 1.02 (3H, d, J
= 6.3 Hz), 1.2 to 2.0 (m), 4.00 (2
H, t, J = 6.3 Hz), 4.19 (2H, t, J =
6.3 Hz), 5.12 (2H, m), 6.83 (2
H, s), 6.97 (2H, d, J = 8.8 Hz),
7.56 (2H, d, J = 8.8Hz), 7.61 (2
H, d, J = 8.6 Hz), 8.08 (2H, d, J =
8.6 Hz)

Example 5 Compound [77]: (R) -isopropyl fumarate
[3-Fluoro-4- (1-methylheptyloxycarbonyl) phenyl benzoate-4-yloxy] hexyl ¹ H-NMR (CDCl ₃ , 90 MHz): δ (pp
m): 0.87 (3H, t), 1.02 (3H, d, J
= 6.3 Hz), 1.2 to 2.0 (m), 3.98 (2
H, t, J = 6.3 Hz), 4.14 (2H, t, J =
6.3 Hz), 5.11 (2H, m), 6.50-6.
80 (m), 6.83 (2H, s), 6.20 (m),
7.80-8.00 (m) oil

Example 6 Compound [88]: (R) -isopropyl fumarate
6- [4- (1-Methylheptyloxy) phenyl] naphthalen-2-yloxy) nonyl C 124 SX 157 I ¹ H-NMR (CDCl ₃ , 90 MHz): δ (pp
m): 0.88 (6H, t), 1.29 (6H, d, J
= 6.3 Hz) 1.4-2.0 (m), 4.00-4.
30 (4H, m), 4.40 (1H, m), 5.11.
(1H, m), 6.83 (2H, s), 6.90 to 7.
23 (m), 7.55 to 7.93 (m)

Example 7 Compound [107]: (S) -isopropyl fumarate
[4 '-(2-Methylbutyloxy) biphenyl benzoate-4-yloxy] hexyl delta (ppm): 0.99 (3H, t), 1.02 (3
H, d, J = 6.3 Hz), 1.29 (6H, d, J =
6.3 Hz) 1.4 to 2.0 (m), 3.82 (2H,
dd) 4.06 (2H, t, J = 6.3Hz), 4.2
2 (2H, t, J = 6.3 Hz), 5.11 (1H,
m), 6.83 (2H, s), 6.97 (2H, d, J
= 8.8 Hz), 7.23 (2H, d, J = 8.8H)
z) 7.50 (4H, d, J = 8.8Hz), 7.58
(2H, d, J = 9.0 Hz), 8.16 (2H, d,
J = 9.0Hz) Oil

[Production of Fumarate Diester Homopolymer] Example 8 <Polymerization of (S) -isopropyl fumarate [4 '-(2-methylbutyloxy) biphenyl-4-yloxy] hexyl [7]> (S ) -Isodium fumarate [4 '-(2-methylbutyloxy) biphenyl-4-yloxy] hexyl (0.7 g) and azobiscyclohexanecarbonitrile (hereinafter abbreviated as ACN) 0.017 g were placed in a glass ampoule and once at -60 ° C. After cooling to room temperature and degassing with a vacuum pump for 1 hour, the tube was sealed. The sealed glass ampoule was reacted at 80 ° C. for 18 hours. Dissolve the contents in a glass ampoule in 8 ml of tetrahydrofuran and
It was poured into 00 ml and precipitated. After performing this operation 3 times, it was sufficiently washed with methanol and dried under reduced pressure to 0.3
g of poly- (S) -isopropyl fumarate isopropyl [4'-
(2-Methylbutyloxy) biphenyl-4-yloxy] hexyl [P1] was obtained. This polymer exhibited a cholesteric liquid crystal phase at room temperature. Tm 128 (Ch 120) I weight average molecular weight _(M W) 40000 Polydispersity (Mw / Mn) 1.88

Example 9 Using 0.7 g of compound [28] and 0.015 g of ACN,
0.25 g of a polymer [P2] was obtained by the same operation as in Example 8 except that the reaction was carried out at 80 ° C. for 15 hours. This polymer exhibited a cholesteric liquid crystal phase. Tm 106 Ch 122 I Weight average molecular weight (Mw) 51000 Polydispersity (Mw / Mn) 1.89

Example 10 0.34 g of polymer [P3] was obtained by the same procedure as in Example 8 except that 0.87 g of compound [107] and 0.017 g of ACN were used and the reaction was carried out at 80 ° C. for 24 hours. It was This polymer exhibited a cholesteric liquid crystal phase. Tm 50 Ch 65 I Weight average molecular weight (Mw) 10700 Polydispersity (Mw / Mn) 1.48

Example 11 Using 1 g of compound [117] and 0.01 g of ACN, 80
0.74 g of a polymer [P4] is obtained by the same operation as in Example 8 except that the reaction is performed at 24 ° C. for 24 hours. This polymer exhibits a ferroelectric liquid crystal phase.

[Production of Fumarate Diester Copolymer] Example 12 <(S) -isopropyl fumarate [4 ′-(2-
Methylbutyloxy) biphenyl-4-yloxy] hexyl [7] and isopropyl fumarate 6- (4'-
Copolymerization with cyano-1,1′-biphenyl-4-yloxy) hexyl [FCB]>

(S) -Isopropyl fumarate [4 '
0.57 g of-(2-methylbutyloxy) biphenyl-4-yloxy] hexyl [7], isopropyl 6- (4'-cyano-1,1'-biphenyl-4-yloxy) hexyl fumarate [FCB] 0. 5g, ACN0.02
7 g was put in a glass ampoule, cooled to −60 ° C., sufficiently deaerated with a vacuum pump, and then sealed. The sealed glass ampoule was reacted at 80 ° C. for 16 hours. The obtained reaction mixture was dissolved in 20 ml of tetrahydrofuran and poured into 150 ml of methanol to precipitate the copolymer. After performing this operation 3 times, it was sufficiently washed with methanol and dried under reduced pressure to obtain 0.5 g of a copolymer [CP1].
It showed a clearing point higher than that of the homopolymer [P1]. Tm 170 Ch 175 I The weight average molecular weight _(M W) 46000 Polydispersity (Mw / Mn) 1.90

Example 13 [Production of vinyl ether copolymer] <(S) -isopropyl fumarate [4 '-(2-
Copolymerization of methylbutyloxy) biphenyl-4-yloxy] hexyl [7] and cyclohexyl vinyl ether> cyclohexyl fumarate 6- (4'-cyano-
1,1'-biphenyl-4-yloxy) hexyl 1
g, cyclohexyl vinyl ether 0.26 g, ACN
0.05 g was put into a glass ampoule, cooled to −60 ° C., sufficiently deaerated with a vacuum pump, and then sealed. The sealed glass ampoule was reacted at 80 ° C. for 17 hours. The obtained reaction mixture was dissolved in 10 ml of tetrahydrofuran and added to 150 ml of methanol to precipitate the copolymer. After performing this operation 3 times, it was sufficiently washed with methanol and dried under reduced pressure to obtain 0.7 g of a copolymer [CP2]. This copolymer exhibited a cholesteric liquid crystal phase. Tm 63 Ch 80 I The weight average molecular weight _(M W) 39000 Polydispersity (Mw / Mn) 1.46

Example 14 [Production and evaluation of retardation film] The copolymer [CP1] was dissolved in chloroform to prepare a 10% by weight solution. This solution was spin-coated on a polyethylene terephthalate substrate having a rubbed polyimide alignment film and then sufficiently dried to obtain a thin film (film thickness 30 nm). Then, after heating in an oven at 150 ° C. for 30 minutes, it was left to cool and oriented.
It was confirmed by observation with a polarizing microscope that the copolymer was oriented. It was confirmed that even if the sheet was pulled at room temperature and subjected to a twisting stress, the liquid crystal orientation was not disturbed, and the sheet was strong against mechanical stress.

[Strength, hardness test] The pencil hardness of the cholesteric liquid crystal polymer film [CP1] was 2H. It was found that the surface hardness was higher than that of the acrylic polymer. [Light resistance test] Polymer 1 [P1]
A light resistance test was conducted by leaving it outdoors for a month. Light resistance test After one month, the polymer was clouded and had no color. No deterioration of the polymer due to light was confirmed.

Example 15 [Production of Ferroelectric Liquid Crystal Polymer Display Element] Ferroelectric liquid crystal polymer [P4] and 4 μm beads were sandwiched between a polyethylene terephthalate substrate having an ITO transparent electrode and an alignment film, and 1
What was pressure-bonded while being heated to 30 ° C. was returned to room temperature to prepare a film-like ferroelectric liquid crystal polymer display device. It was confirmed that voltage can be applied to this element to switch it. Pulling on this film-like liquid crystal display element at room temperature,
It was confirmed that the liquid crystal orientation was not disturbed even when a twisting stress was applied, and it was strong against mechanical stress.

Example 16 [Production of Optically Active Polymerizable Compound] Compound Nos. [1] to [130] are produced in the same manner as in Example 1.

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

The optically active fumaric acid diester which is the compound of the present invention exhibits polymerizability, and the polymer obtained by polymerizing the same has excellent light resistance, heat resistance and mechanical strength, and Has liquid crystallinity. Therefore, the polymer of the present invention can be used for an optical compensation film such as a retardation film, an optical writing recording material, a liquid crystal color filter, and a ferroelectric liquid crystal polymer display.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G02B 5/30 G02B 5/30 G02F 1/13 500 G02F 1/13 500 F term (reference) 2H048 AA05 AA18 AA24 AA28 2H049 BA06 BA42 BB44 BC22 4H006 AA01 AB64 BJ50 BM30 BM71 BP30 4H027 BA02 BA06 BA11 BB08 BD01 4J100 AL08Q AL39P AL39Q AM47Q BA04P BA04Q BA40Q BC04P BC04Q BC49P BC43Q BC44P BC32P BC73Q BC49Q

Claims (18)

[Claims] 1. An optically active polymerizable compound represented by formula (1). (In the formula, R ¹ is alkyl having 3 to 15 carbon atoms, and any hydrogen is —CH 2 such that the alkyl has an asymmetric carbon.
_{3, -CH 2 CH 3, -CF} 3, chlorine, fluorine or is replaced by -CN,; ^{R 2} is alkyl having 1 to 20 carbon ^atoms; A 1, ^{A 2} and ^{A 3} are independently ,
1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-cyclohexylene in which arbitrary hydrogen is replaced by fluorine, 1,3-dioxane-2,5-diyl,
1,4-phenylene, 1,4-phenylene in which arbitrary hydrogen is replaced by halogen, pyridine-2,5-diyl, pyridazine-3,6-diyl, pyrimidine-2,5
-Diyl, naphthalene-2,6-diyl, 1,2,3
4-tetrahydronaphthalene-2,6-diyl or fluorene-2,7-diyl; Z ¹ is a single bond,-
O-, -COO-, or -OOC-; Z ² and Z ³ are independently a single bond, -COO-, -OOC-,
_{-CF 2 O -, - OCF 2} -, - CH 2 O -, - OCH
_{2 -, - CH = CH -} , - CH 2 CH 2 -, or -C
≡ C-; x is 1 or 0, and y is an integer of 1-20. ) 2. In the formula (1) described in claim 1,
The optically active polymerizable compound according to claim 1, wherein x is 0. 3. In the formula (1) described in claim 1,
The optically active polymerizable compound according to claim 1, wherein x is 1. 4. A composition containing at least one optically active polymerizable compound according to claim 1 and at least one non-polymerizable compound having liquid crystallinity. 5. A composition containing at least one optically active polymerizable compound according to claim 1 and at least one other polymerizable compound. 6. The composition according to claim 4, further containing at least one other polymerizable compound. 7. A polymer having at least one repeating unit represented by the formula (2). (R ¹ , R ² , A ^{1 to} A ³ , Z ¹ to in these formulas
The meanings of the symbols Z ³ , x, and y are the same as the meanings of the symbols described in claim 1. ) 8. A polymer obtained by polymerizing the composition according to claim 4. 9. A polymer obtained by polymerizing the composition according to claim 5. 10. A polymer obtained by polymerizing the composition according to claim 6. 11. An optical compensation film containing the polymer according to claim 7. 12. An optical compensation film containing the polymer according to claim 8. 13. A cholesteric liquid crystal polymer type photo-writing recording material containing the polymer according to claim 7. 14. A cholesteric liquid crystal polymer type optical writing recording material containing the polymer according to any one of claims 8 to 10. 15. A ferroelectric liquid crystal polymer display device containing the polymer according to claim 7. 16. A ferroelectric liquid crystal polymer display device containing the polymer according to claim 8. 17. A liquid crystal color filter containing the polymer according to claim 7. 18. A liquid crystal color filter containing the polymer according to claim 8.