JP2003012762A - Polymerizable liquid crystal compound, composition, and optically anisotropic product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymerizable liquid crystal compound low in temperature showing liquid crystal phase and highly compatible with other polymerizable liquid crystalline compound in combined use, a polymerizable liquid crystal composition including the above compound, exhibiting liquid crystalline character at room temperature and curable under the atmospheric conditions in the presence of oxygen, and an optically anisotropic product using the composition. SOLUTION: The polymerizable liquid crystal compound is represented by formula (1) [X is a 1-8C alkyl or a group: (Z-O-Z)p (Z is a 1-4C alkyl; and (p) is an integer of 1-3); and Y is a tolanbenzoate skeleton, biphenylbenzoate skeleton, phenylbenzoate skeleton, bisbenzoylbenzene skeleton or tolan skeleton each optionally bearing at least one substituent selected from the group consisting of halogen atom, cyano, OH, a 1-8C alkyl, 1-8C alkoxy and 1-8C alkanoyl groups]. The polymerizable composition includes the polymerizable liquid crystal compound. The optically anisotropic product using the composition is provided.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an optical film, a retardation plate, a polarizing plate, a polarizing prism, an optical anisotropic body such as various optical filters, an optical waveguide, a piezoelectric element, a non-linear optical element, and a selective reflection of a cholesteric liquid crystal phase. Liquid crystal pigment using
Liquid crystal-resin composite display, holographic liquid crystal display, polymer-stabilized liquid crystal (ferroelectric liquid crystal, antiferroelectric liquid crystal) display, polymerizable liquid crystal compound having an epoxy group and its compound useful as a coating agent for optical fibers, etc. And a polymerizable liquid crystal composition containing

[0002]

2. Description of the Related Art In recent years, liquid crystal substances have been TN (twisted
In addition to application to display media utilizing reversible motion of liquid crystal molecules such as display elements represented by nematic) type and STN (super twisted nematic) type,
Utilizing the orientation and the anisotropy of physical properties such as refractive index, dielectric constant and magnetic susceptibility, an optical film, a retardation plate, a polarizing plate,
Applications to optical anisotropic bodies such as polarizing prisms and various optical filters are being studied.

As described above, an optically anisotropic body having a liquid crystal substance as a constituent material is required to have stable and uniform optical characteristics. For that purpose, the alignment state structure of liquid crystal molecules in a liquid crystal state is fixed semipermanently. It is necessary to.

As a means for semi-permanently fixing the alignment state structure of liquid crystal molecules in the liquid crystal state, a liquid crystal compound having a polymerizable functional group or a polymerizable liquid crystal composition containing such a compound is used in the liquid crystal state. There is known a method of polymerizing by aligning and then irradiating with energy rays such as ultraviolet rays in that state.

A polymerizable liquid crystal composition utilizing such a method is disclosed in JP-A-58-102205 and JP-A-62-62.
No. 70406, Japanese Patent Publication No. 8-3586, Japanese Patent Laid-Open No. 4-227611, German Published Patent DE 4226.
No. 994, etc.

However, since these compositions have a high temperature of exhibiting a liquid crystal phase, undesired thermal polymerization is induced in the alignment step, and an optically anisotropic substance excellent in uniformity cannot be prepared, or the composition was prepared. There is a problem that the heat resistance of the optically anisotropic body is not sufficient.

On the other hand, demand for optical films such as image quality improving films and retardation films has increased in recent years as optical anisotropic bodies. In general, an optical film is a substrate in which a surface of a polymerizable liquid crystal composition is rubbed with a cloth or the like, a substrate in which a surface of an organic thin film is formed is rubbed with a cloth, or SiO ₂ is obliquely vapor-deposited. It is produced by carrying it on a substrate having a film or sandwiching it between the substrates, and then polymerizing and curing a polymerizable compound, but due to its convenience, the method of carrying it on the substrate is preferred. There is.
Therefore, a polymerizable liquid crystal composition that exhibits liquid crystallinity at room temperature and that easily cures under atmospheric conditions in the presence of oxygen is desired.

As a polymerizable liquid crystal composition exhibiting liquid crystallinity at room temperature, for example, JP-A-8-3111 describes a composition containing a liquid crystal compound having a polymerizable (meth) acrylate functional group. There is. However, this does not completely cure under atmospheric conditions in the presence of oxygen, and therefore a large amount of nitrogen is required when carrying it on a substrate to manufacture an optical film. Alternatively, it is produced by sandwiching between substrates and then polymerizing and curing the polymerizable compound.

Compounds and compositions having a cation-curable epoxy group are known to be photo-curable under atmospheric conditions in the presence of oxygen, and a liquid crystallinity having a polymerizable epoxy functional group having this as a functional group is known. The compounds and compositions are described in Macromolecules (1244,26 (1993)) and Polymers (Polymer, 622,35 (1994)).
However, the compound described in Macromolecules has a Tm = 45
° C, Tc = 61 ° C, and the compound described in the polymer has Tm = 46
C, Tc = 66 ° C, the phase transition temperature is still high, and no example of a polymerizable liquid crystal composition showing liquid crystallinity at room temperature has been reported.

Further, Japanese Patent Laid-Open No. 10-509726,
JP-A-5-61022, International Patent Application Publication No. 98
/ 52905 and International Patent Application Publication No. 98 /
A liquid crystal compound having a polymerizable epoxy functional group is described in Japanese Patent No. 00475 and the like. However, these only describe those having a structure in which a polymerizable epoxy functional group is bonded to a mesogen via a connecting chain such as an alkylene group containing an oxygen atom.

[0011]

The problem to be solved by the present invention is that the melting point and the temperature exhibiting an isotropic phase are low, and the polymerizability excellent in compatibility with other liquid crystal compounds having other polymerizability to be used together. A liquid crystal compound, and containing the compound,
(EN) It is intended to provide a polymerizable liquid crystal composition which exhibits liquid crystallinity at room temperature and is curable under atmospheric conditions in the presence of oxygen, and an optical anisotropic body using the same.

[0012]

In order to solve the above-mentioned problems, the present invention provides (A) general formula (1) [X is independently an alkyl group having 1 to 8 carbon atoms, or-
(Z-O-Z) _p- (Z represents an alkyl group having 1 to 4 carbon atoms, p represents an integer of 1 to 3),
G represents hydrogen, fluorine or a methyl group. ] The liquid crystal compound represented by these is provided.

In order to solve the above problems, the present invention provides (B) a general formula (2) [X is independently an alkyl group having 1 to 8 carbon atoms, or-
(Z-O-Z) _p- (Z represents an alkyl group having 1 to 4 carbon atoms, p represents an integer of 1 to 3),
Y is a halogen, a cyano group, a hydroxyl group, a C1-C8 alkyl group, a C1-C8 alkoxy group, and a C1-C1
8 represents a tranbenzoate skeleton, a biphenylbenzoate skeleton, a phenylbenzoate skeleton, a bisbenzoylbenzene skeleton, or a tolan skeleton, which may have at least one substituent selected from the group consisting of alkanoyl groups of 8] Provided is a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound.

In order to solve the above-mentioned problems, the present invention is an optical structure composed of a polymer of a polymerizable liquid crystal composition containing (C) a polymerizable liquid crystal compound represented by the above general formula (2). Provide an anisotropic body.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The polymerizable liquid crystal compound of the present invention is represented by the general formula (1).

[Chemical 1]

In the general formula (1), X is a methyl group,
Alkyl group such as ethyl group, or-(Z-O-Z) _p-
(Z represents an alkyl group having 1 to 4 carbon atoms, and p represents an integer of 1 to 3). Each X may be the same or different. The number of carbon atoms in the alkyl group is 1-8
Is preferred, and 4 to 6 is particularly preferred. G represents hydrogen, fluorine or a methyl group, and among them, a fluorine group is preferable. The polymerizable liquid crystal compound of the invention represented by the general formula (1) can be preferably used as one component of the polymerizable liquid crystal composition of the invention.

The polymerizable liquid crystal compound used in the polymerizable liquid crystal composition of the present invention is represented by the following general formula (2) containing the polymerizable liquid crystal compound of the general formula (1).

[Chemical 2]

In the above general formula (2), each X is independently an alkyl group such as a methyl group or an ethyl group, or-(Z
-O-Z) represents a connecting chain composed of a group represented by _p- . 1-8 are preferable and, as for carbon number of an alkyl group, 4-6 are especially preferable. Z represents an alkyl group having 1 to 4 carbon atoms, and p is 1
Represents an integer of 3;

In the above general formula (2), Y represents a liquid crystal ring skeleton. The liquid crystal skeleton is not particularly limited as long as it is a skeleton generally recognized as a liquid crystal ring skeleton in this technical field, and among them, a tranbenzoate skeleton, a biphenylbenzoate skeleton, a phenylbenzoate skeleton, a bisbenzoylbenzene skeleton, or a tolan skeleton is used. It is preferable. These skeletons include halogen such as chloro group and fluorine group, cyano group, hydroxyl group, alkyl group such as methyl group having 1 to 8 carbon atoms, ethyl group, alkoxy group such as methoxy group and ethoxy group having 1 to 8 carbon atoms. , And at least one substituent selected from the group consisting of alkanoyl groups having 1 to 8 carbon atoms.

Specific preferred examples of the compound of the present invention include compounds represented by the following general formulas (3) and (4).

[0021]

[Chemical 3] (X represents the same content as in general formula (1).)

[0022]

[Chemical 4] (X represents the same content as in general formula (1).)

The compound represented by the general formula (3) can be synthesized, for example, by the following method.

[Chemical 5]

(In the formula, X has the same meaning as in the general formula (3) above, and DMF represents dimethylformamide.) That is, the alcohol derivative represented by the general formula (6), and The target compound represented by the general formula (3) can be synthesized by subjecting 1.1 equivalents of the halogen derivative represented by the general formula (5) to substitution reaction in a DMF solvent of potassium carbonate.

The halogenated epoxy compound represented by the general formula (5), which is a raw material for synthesizing the compound represented by the general formula (3), can be synthesized, for example, by the following method.

[0026]

[Chemical 6] (In the formula, X represents the same content as in the general formula (3). TEA represents triethylamine.)

That is, the acid chloride represented by the general formula (7) is added dropwise to a tetrahydrofuran solution of TEA and 1.2 equivalents of the glycidyl alcohol represented by the general formula (8) at room temperature to carry out a substitution reaction. As a result, the desired compound represented by the general formula (5) can be synthesized.

The alcohol derivative represented by the general formula (6), which is a raw material for synthesizing the compound represented by the general formula (3), can be synthesized, for example, by the following method.

[0029]

[Chemical 7] (In the formula, X represents the same content as in the case of the general formula (3). Further, DCC represents dicyclohexylcarbodiimide.) That is, the alcohol derivative represented by the general formula (9) and 1.5 After an equivalent amount of the carboxylic acid derivative represented by the general formula (10) is subjected to an esterification reaction by using a condensing agent such as DCC (dicyclohexylcarbodiimide), the compound represented by the general formula (11) is synthesized, and then an acid catalyst is prepared. By deprotecting in the presence, the desired alcohol derivative represented by the general formula (6) can be obtained.

The alcohol derivative in which a hydrogen atom on an aromatic ring is substituted with a fluoro group (a compound represented by the general formula (9)), which is a raw material for synthesizing the compound represented by the general formula (6), is, for example, It can be synthesized by a method.

[0031]

[Chemical 8]

(In the formula, X represents the same content as in the above general formula (3), Base represents a base, and Ph represents
Represents a phenyl group. ) That is, 4 represented by the equation (12)
After protecting the hydroxyl group of -bromo-2-fluorophenol with tetrapyranyl ether, it was reacted with 2-methyl-3-butyn-2-ol in the presence of a palladium catalyst, and a t-butyl alcohol group was further added. Is removed to obtain an acetylene derivative represented by the general formula (15). An acetylene derivative represented by the general formula (15) and 4
-With iodophenol in the presence of a palladium catalyst,
A coupling reaction is performed to obtain the compound represented by the general formula (16). After reacting the compound represented by the general formula (16) with the bromine-containing alcohol derivative represented by the general formula (17), deprotection is performed in the presence of an acid catalyst to obtain the desired compound represented by the general formula (9). Alcohol derivatives can be obtained.

Next, the compound represented by the general formula (4) will be described. The compound represented by the general formula (4) is
For example, it can be synthesized by the following method.

[0034]

[Chemical 9]

(In the formula, X has the same meaning as in the case of the general formula (4). Further, DMF represents dimethylformamide.) That is, the alcohol derivative represented by the general formula (19) and On the other hand, the target compound represented by the general formula (4) can be synthesized by subjecting 1.1 equivalents of the halogen derivative represented by the general formula (5) to a substitution reaction in a DMF solvent of potassium carbonate.

The alcohol derivative represented by the general formula (19), which is a raw material for synthesizing the compound represented by the general formula (4), can be synthesized, for example, by the following method.

[0037]

[Chemical 10]

(In the formula, X has the same meaning as in the case of the general formula (4). Further, DCC represents dicyclohexylcarbodiimide.) That is, the alcohol derivative represented by the general formula (20) and On the other hand, 1.5 equivalents of the carboxylic acid derivative represented by the general formula (10) is subjected to an esterification reaction by using a condensing agent such as DCC (dicyclohexylcarbodiimide) to give the compound represented by the general formula (2
After synthesizing the compound represented by 1), in the presence of an acid catalyst,
By deprotecting, the desired alcohol derivative represented by the general formula (19) can be obtained.

The alcohol derivative (the compound represented by the general formula (20)), which is a raw material for synthesizing the compound represented by the general formula (19), can be synthesized, for example, by the following method.

[0040]

[Chemical 11]

(In the formula, X has the same meaning as in the general formula (4), and DMF represents dimethylformamide.) That is, 1,4-dihydroquinone and 2.
Compound (22) is synthesized by subjecting 0 equivalent of 4-hydroxybenzoic acid to a dehydration esterification reaction in the presence of an acid catalyst. Subsequently, the phenol derivative represented by the general formula (22) and 2.0 equivalents of the halogen derivative represented by the general formula (17) were added to DMF in the presence of potassium carbonate.
By carrying out a substitution reaction in a solvent, the desired compound represented by the general formula (20) can be synthesized.

The polymerizable liquid crystal compound of the present invention can be used alone, or a known polymerizable liquid crystal compound can be mixed to form a composition. Examples of the known polymerizable liquid crystal compound include a polymerizable liquid crystal compound having a skeleton generally recognized as a liquid crystal ring skeleton in this technical field and a polymerizable functional group in the molecule. The liquid crystal ring skeleton particularly preferably has at least two or three 6-membered rings. As the polymerizable functional group, an acryloyloxy group, a methacryloyloxy group, an epoxy group, a vinyloxy group,
Examples thereof include a cinnamoyl group, a vinyl group, an ethynyl group and a maleimide group.

In the case of a compound having a plurality of polymerizable functional groups in one molecule, the kinds of polymerizable functional groups may be different. For example, in the case of a compound having two polymerizable functional groups,
One may be a methacryloyl group and the other a vinyloxy group.

The polymerizable liquid crystal composition of the present invention may be any composition which exhibits a phase generally recognized as a liquid crystal phase in this technical field. Among such compositions, the liquid crystal phase includes a nematic phase, a smectic A phase, and a (chiral) smectic C.
Those expressing a phase and a cholesteric phase are preferable. Among them, the nematic phase is particularly preferable because it has good orientation. Further, in the case of exhibiting a (chiral) smectic C phase, a smectic A phase is present in a temperature range higher than the temperature range of the (chiral) smectic C phase, and a nematic phase is presented in a temperature range higher than the temperature range of the smectic A phase. Liquid crystal compositions that exhibit the respective properties are preferable because they tend to obtain good alignment properties.

The polymerizable liquid crystal composition of the present invention further has the general formula (23)

[Chemical 12] (In the formula, D represents a hydrogen atom or a methyl group, r represents 0 or 1, and the 6-membered rings K, L, and M are each independently

[0046]

[Chemical 13]

Represents a ring structure selected from the group consisting of:
p represents an integer of 1 to 4, Y ₁ and Y ₂ are each independently a single bond, —CH ₂ CH ₂ —, —CH ₂ C (CH ₃ ).
_{H -, - C (CH 3} ) HCH 2 -, - CH 2 O -, - OC
_{H 2 -, - CF 2 O} -, - OCF 2 -, - COO -, - O
CO-, -C≡C-, -CH = CH-, -CF = CF
_{-, - (CH 2) 4} -, - CH 2 CH 2 CH 2 O -, - OC
_{H 2 CH 2 CH 2 -,} - CH = CH-CH 2 CH 2 - and -
CH ₂ CH ₂ CH: represents a connecting chain selected from the group consisting of CH-, Y ₃ is a single bond, -O-, -COO- or-.
Represents OCO-, and Z represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms or 2 carbon atoms.
Represents an alkenyl group of 20. It is also possible to contain a liquid crystal (meth) acrylate represented by).

The liquid crystallinity (meta) represented by the general formula (23) that can be contained in the polymerizable liquid crystal composition of the present invention.
Acrylate compounds are especially represented by the general formula (24)

[0049]

[Chemical 14] (In the formula, D represents a hydrogen atom or a methyl group, and R is
It represents an alkyl group having 1 to 10 carbon atoms. ) Or a compound represented by the general formula (25)

[0050]

[Chemical 15]

A compound represented by the formula (wherein D represents a hydrogen atom or a methyl group, and R represents an alkyl group having 1 to 10 carbon atoms) is preferable. The compound represented by the general formula (24) and the compound represented by the general formula (25) may be used alone or in combination. When used in combination, the general formula (24)
It is preferable to make the concentrations of the compounds represented by the general formula (25) equal. However, the compounds that can be used in the polymerizable liquid crystal composition of the present invention are not limited to these compounds.

A liquid crystal compound having no polymerizable functional group may be added to the polymerizable liquid crystal composition of the present invention depending on the use. However, from the viewpoint of ensuring the heat resistance of the polymer produced using the liquid crystal composition, the addition amount is 8
It is preferably 0% by weight or less, more preferably 30% by weight or less, particularly preferably 10% by weight or less.

Further, to the polymerizable liquid crystal composition of the present invention, a compound having a polymerizable functional group, which does not exhibit liquid crystallinity, can be added. As such a compound, any compound generally recognized as a polymer-forming monomer or polymer-forming oligomer in this technical field can be used without particular limitation.

The polymerizable liquid crystal composition of the present invention is intended to polymerize the polymerizable compound containing an epoxy group in the composition by irradiating with active energy rays in the temperature range of the liquid crystal phase. Therefore, in the active energy ray irradiation step,
The polymerizable liquid crystal composition of the present invention has liquid crystallinity at or near room temperature (typically 25 ° C.) in order to produce a polymer having excellent uniformity while avoiding undesired thermal polymerization. Is preferred. For example, in the (chiral) smectic C phase, when the polymerizable liquid crystal composition of the present invention is irradiated with an active energy ray to polymerize the polymerizable compound in the composition, the (chiral) smectic C phase is obtained at or near room temperature. What expresses is preferable.

A chiral (optically active) compound may be added to the polymerizable liquid crystal composition of the present invention for the purpose of obtaining a polymer having a helical structure of the liquid crystal skeleton therein. The chiral compound used for such a purpose does not need to exhibit liquid crystallinity by itself, and may or may not have a polymerizable functional group. Further, the direction of the helix of the chiral compound can be appropriately selected depending on the intended use of the polymer. Examples of such a chiral compound include cholesterol pelargonate having a cholesteryl group as a chiral group, cholesterol stearate, and "CB-" manufactured by BHD (BDH; UK) having a 2-methylbutyl group as a chiral group. 1
5 "," C-15 "," S- "from Merck GmbH (Germany)
1082 "," CM-19 "and" CM-2 "manufactured by Chisso Corporation.
0 ”,“ CM ”;“ S-811 ”manufactured by Merck Co., which has a 1-methylheptyl group as a chiral group,“ CM-21 ”,“ CM-22 ”manufactured by Chisso Co., and the like.

The preferred addition amount of the chiral compound depends on the use of the polymerizable liquid crystal composition, but the thickness (d) of the polymer obtained by polymerization is divided by the helical pitch (P) in the polymer. The amount (d / P) is preferably in the range of 0.1 to 100, more preferably 0.1 to 20.

When the polymerizable liquid crystal composition of the present invention is polymerized and cured, a cationic polymerization initiator is used. Examples of the cationic polymerization initiator include triphenylsulfonium salt derivatives such as UVI6990 (manufactured by Union Carbide), diphenyliodonium derivatives such as PI2074 (manufactured by Rhone Poulenc), aryldiazonium salt derivatives, sulfonylacetophenones, and arenes of organometallic compounds. An ionic complex etc. are mentioned. Further, other polymerization initiators such as a thermal polymerization initiator and a photopolymerization initiator can be added for the purpose of improving the polymerization reactivity. Examples of the thermal polymerization initiator include benzoyl peroxide and bisazobutyronitrile. Examples of the photopolymerization initiator include radical polymerization initiators such as benzoin ethers, benzophenones, acetophenones, and benzyl ketals, and the addition amount thereof is 10% by weight or less based on the polymerizable liquid crystal composition. Is preferable, 5% by weight or less is particularly preferable, and the range of 0.5 to 2.5% by weight is further preferable.

A stabilizer may be added to the polymerizable liquid crystal composition of the present invention in order to improve its storage stability. Examples of the stabilizer that can be used include hydroquinone, hydroquinone monoalkoxys, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, β-naphthylamines, β-naphthols and the like. When using a stabilizer, the amount added is
It is preferably 1% by weight or less with respect to the liquid crystal composition, and 0.5
A weight percentage of less than or equal to is especially preferable.

As described above, the polymerizable liquid crystal composition of the present invention contains not only the polymerizable liquid crystal compound represented by the general formula (2) but also a liquid crystal compound having a polymerizable functional group and a polymerizable functional group. No liquid crystal compounds, polymerizable compounds that do not show liquid crystallinity,
A polymerization initiator and a stabilizer may be appropriately combined and added, but it is necessary to adjust the addition amount of each component so that at least the liquid crystallinity of the obtained liquid crystal composition is not lost.

When the polymerizable liquid crystal composition of the present invention is used as a raw material for a polarizing film or an alignment film, or as a printing ink and paint, a protective film, etc., a metal or a metal complex may be used depending on the purpose. , Dyes, pigments, dyes, fluorescent materials, phosphorescent materials, surfactants, leveling agents, thixotropic agents, gelling agents,
It is also possible to add a polysaccharide, an ultraviolet absorber, an infrared absorber, an antioxidant, an ion exchange resin, a metal oxide such as titanium oxide, and the like.

The polymerizable liquid crystal composition containing the polymerizable liquid crystal compound of the present invention is polymerized into a polymer to obtain an optical film, a retardation plate, a polarizing plate, a polarizing prism,
Liquid crystal pigments that utilize selective reflection of waveguides, piezoelectric elements, nonlinear optical elements, various optical filters, cholesteric liquid crystal phases, liquid crystal-resin composite displays, holographic liquid crystal displays, polymer-stabilized liquid crystals (ferroelectric liquid crystals,
It can be applied to various applications such as antiferroelectric liquid crystal) displays and coatings for optical fibers. Above all,
In a state where the polymerizable liquid crystal composition of the present invention is aligned,
The polymerized polymer has anisotropy in physical properties, and includes an optical film, a retardation plate, a polarizing plate, a polarizing prism,
It is particularly useful for optical anisotropic bodies such as various optical filters.

Such a polymer is, for example, a substrate obtained by rubbing the surface of the polymerizable liquid crystal composition of the present invention with a cloth or the like, a substrate obtained by rubbing the surface of a substrate having an organic thin film formed thereon with a cloth, or the like. It can be manufactured by supporting SiO ₂ on a substrate having an orientation film obliquely vapor-deposited or sandwiching it between substrates and then polymerizing a polymerizable compound. The polymerizable liquid crystal composition of the present invention has an epoxy group and is well cured under atmospheric conditions in the presence of oxygen. Therefore, only polymerization is carried out in a state of being supported on a substrate. The body can be manufactured well.

The method for supporting the polymerizable liquid crystal composition on the substrate is, for example, spin coating, die coating, extrusion coating, roll coating, wire bar coating, gravure coating, spray coating, dipping, printing, And so on. In addition, an organic solvent may be added to the polymerizable liquid crystal composition during coating. Examples of the organic solvent that can be used for such a purpose include ethyl acetate, tetrahydrofuran, toluene, hexane, methanol, ethanol, dimethylformamide, methylene chloride, isopropanol, acetone, methyl ethyl ketone, acetonitrile, cellosolves, and the like. To be These organic solvents may be used alone or in combination of two or more, and may be appropriately selected in consideration of the vapor pressure and the solubility of the polymerizable liquid crystal composition. The amount of organic solvent added is
90% by weight or less of the coating material is preferred. When it is 90% by weight or more, the obtained film thickness tends to be thin, which is not preferable.

As a method for volatilizing the added organic solvent, natural drying, heat drying, reduced pressure drying, or reduced pressure heating drying can be used. In order to further improve the coatability of the polymerizable liquid crystal material, a method of providing an intermediate layer such as a polyimide thin film on the substrate and a method of adding a leveling agent to the polymerizable liquid crystal material are also effective. In particular, the method of providing an intermediate layer such as a polyimide thin film on the substrate is effective as a means for improving the adhesiveness when the adhesiveness between the polymer obtained by polymerizing the polymerizable liquid crystal material and the substrate is not good. .

As a method for sandwiching the polymerizable liquid crystal material between the substrates, there is an injection method utilizing a capillary phenomenon.
A means for reducing the pressure in the space formed between the substrates and then injecting the polymerizable liquid crystal material is also effective.

Examples of the alignment treatment other than the rubbing treatment or the SiO ₂ oblique vapor deposition include a method utilizing the flow orientation of the liquid crystal material and a method utilizing an electric field or a magnetic field.
These orientation means can be used alone or in combination of two or more methods. Furthermore, a photo-alignment method can be used as an alignment treatment method instead of rubbing. This method, for example, an organic thin film having a functional group that undergoes a photodimerization reaction in the molecule such as polyvinyl cinnamate, an organic thin film having a functional group that is isomerized by light or an organic thin film such as polyimide, polarized light, preferably The alignment film is formed by irradiating polarized ultraviolet rays. By applying a photomask to this photo-alignment method, alignment patterning can be easily achieved, so that the molecular alignment inside the polymer can also be precisely controlled.

The shape of the substrate may be a flat plate or a curved surface. The material forming the substrate may be an organic material or an inorganic material. Examples of the organic material for the substrate material include polyethylene terephthalate, polycarbonate, polyimide, polyamide, polymethylmethacrylate, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polychlorotrifluoroethylene, polyarylate, polysulfone,
Triacetyl cellulose, cellulose, polyether ether ketone and the like can be mentioned, and as the inorganic material,
Examples include silicon, glass, calcite and the like.

When proper orientation cannot be obtained by rubbing these substrates with a cloth or the like, an organic thin film such as a polyimide thin film or a polyvinyl alcohol thin film is formed on the surface of the substrate according to a known method, and this is wiped with a cloth or the like. You can rub it. In addition, the usual twisted nematic (T
N) element or super twisted nematic (S)
The polyimide thin film used in the TN) device for providing a pretilt angle is particularly preferable because the molecular orientation structure inside the polymer can be controlled more precisely. Also,
When controlling the orientation state by an electric field, a substrate having an electrode layer is used. In this case, it is preferable to form an organic thin film such as the above-mentioned polyimide thin film on the electrode.

The alignment state of the liquid crystal composition may be various alignment states generally known in the technical field of liquid crystals,
For example, there may be mentioned a homogeneous (horizontal) orientation, a tilted homogeneous orientation, a homeotropic (vertical) orientation, a tilted homeotropic orientation, a hybrid orientation, a twisted nematic orientation, and a super twisted nematic orientation state. Further, a pattern may be formed by combining these orientations or changing the orientation state for each place.

In both cases of tilted homogeneous alignment and tilted homeotropic alignment, it means that the angle between the substrate surface and the long axis of the liquid crystal molecule is not 0 or 90 degrees. The angle between the substrate surface and the long axis of the liquid crystal molecule may be selected depending on the use and function of the polymer to be obtained. When the angle between the substrate surface and the long axis of the liquid crystal molecule is set in the range of 10 to 80 degrees, more preferably 20 to 70 degrees, the obtained polymer is an optical member for improving the viewing angle of a liquid crystal display. Can be used as

Also, when the liquid crystal composition has an alignment state of hybrid alignment, the obtained polymer can be used as an optical member for widely improving the viewing angle of a liquid crystal display. When the angle between the substrate surface and the long axis of the liquid crystal molecule is set to 30 to 60 degrees, more preferably 40 to 50 degrees, and particularly preferably 45 degrees, the obtained polymer has
The polarized light separating ability can be efficiently imparted. Such a polymer is useful as a polarization separation element or an optical low pass filter. Further, even when the liquid crystal composition has an alignment state of hybrid alignment, the obtained polymer is useful as a polarizing optical element or an optical low pass filter.

On the other hand, an oriented structure having a helical structure represented by twisted nematic orientation, super twisted nematic orientation and cholesteric orientation is also useful. When the twist angle is set to 60 to 270 degrees, the resulting polymer is useful for optical compensation of liquid crystal display devices. Further, when the helical pitch is adjusted and set so as to selectively reflect a specific wavelength region, the obtained polymer is useful as a notch filter or a reflective color filter.

When the wavelength range for selective reflection is set in the infrared range, the resulting polymer is useful as a heat ray cut filter. Further, in the case of a homogeneous alignment, in the homeotropic alignment state, the resulting polymer is compared with that obtained by stretching the plastic,
Since the anisotropy of the refractive index is large, there is an advantage that those exhibiting the same anisotropy of the refractive index can be designed thin. There is also a possibility that an optical compensator can be built inside the liquid crystal cell. When used for optical compensation of a reflection type liquid crystal display element, this characteristic is important, and particularly useful as a quarter wavelength plate.

As a method for polymerizing the polymerizable liquid crystal composition of the present invention, a method of polymerizing by irradiating with active energy rays such as ultraviolet rays or electron beams is preferable from the viewpoint of rapid polymerization. When ultraviolet rays are used, a polarized light source or a non-polarized light source may be used. Further, when the liquid crystal composition is sandwiched between two substrates to carry out the polymerization in a state, at least the substrate on the irradiation surface side must be provided with appropriate transparency for active energy rays. Further, after polymerizing only a specific portion using a mask at the time of light irradiation, by changing conditions such as an electric field, a magnetic field, or temperature, the orientation state of the unpolymerized portion is changed,
Further, a means of irradiating with active energy rays for polymerization may be used.

The temperature during irradiation is preferably within a temperature range in which the liquid crystal state of the polymerizable liquid crystal composition of the present invention is maintained. In particular, when a polymer is produced by photopolymerization, polymerization is performed at a temperature close to room temperature, that is, typically at a temperature of 25 ° C., as far as possible in order to avoid unintended induction of thermal polymerization. It is preferable. The intensity of the active energy ray is 0.1 mW / cm ^{2 to 2} W / cm ^2.
Is preferred. When the intensity is less than 0.1 mW / cm ² , it takes a lot of time to complete the photopolymerization,
Since the productivity tends to deteriorate and the strength exceeding ² W / cm ² , the polymerizable liquid crystal composition tends to deteriorate.
Not preferable.

After irradiating the polymerizable liquid crystal composition of the present invention with an active energy ray, a heat treatment may be carried out for the purpose of reducing changes in initial characteristics of the obtained polymer and achieving stable characteristics. it can. The temperature of the heat treatment is 50 to 250
The heat treatment time is preferably in the range of 30 ° C to 12 hours in the range of ° C.

The polymer comprising the polymerizable liquid crystal composition of the present invention produced by such a method can be used alone after peeling it from the substrate, or can be used as it is without being peeled from the substrate. In addition, the polymer comprising the polymerizable liquid crystal composition of the present invention can be used by laminating two or more or by laminating it on another substrate.

[0078]

EXAMPLES The present invention will be described in more detail with reference to examples. However, the invention is not limited to these examples.

Example 1 [Synthesis of Polymerizable Liquid Crystal Compound] To a solution of 48.0 g of 4-bromo-2-fluorophenol and 250 m of dichloromethane was added 6.3 g of pyridinium p-toluenesulfonic acid, and then, in an ice bath. A solution of 42.0 g of dihydropyran and 75 ml of dichloromethane was gradually added dropwise from the dropping funnel over about 1 hour. After completion of dropping, the reaction temperature was brought to room temperature and the mixture was stirred for about 4 hours. After confirming the reaction by gas chromatography and terminating the reaction, the mixture was washed once with 250 ml of a saturated sodium hydrogen carbonate aqueous solution and once with 250 ml of saturated saline. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure to give the compound of the formula (S-1) 67.0 g.

[0080]

[Chemical 16] 1H-NMR (300 MHz, CDCl3); δ = 1.50 to 2.08 (m, 6H), 3.56 to 3.
63 (m, 1H), 3.84 to 3.92 (m, 1H),
5.38-5.40 (m, 1H), 7.00-7.32.
(M, 3H)

(S-1) Compound 3 obtained by the above synthesis
4.4 g, trimethylsilylacetylene 14.7 g, dimethylformamide 120 ml and triethylamine 4
1.73 g of tetrakistriphenylphosphine palladium and 0.57 g of copper iodide were added to a 5 ml solution, and the mixture was heated at 80 ° C. for 8 hours while stirring. After confirming the reaction by thin layer chromatography (hexane: dichloromethane = 2: 1) and terminating the reaction, 300 m of ethyl acetate
The reaction solution was diluted with 1. Wash once with 200 ml of saturated ammonium chloride aqueous solution and 2 with 200 ml of saturated saline.
Washed twice. The organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the crude product was purified by column chromatography (hexane: dichloromethane = 2: 1) to give the compound of the formula (S-2) 32. 8 g
Got

[0082]

[Chemical 17]

A solution of 34.5 g of 75% tetra-n-butylammonium fluoride and 60 ml of dichloromethane was cooled in an ice bath, and then a solution of 30.7 g of the compound represented by the formula (S-2) synthesized above and 60 ml of dichloromethane was added. It dripped gradually from the dropping funnel over about 1 hour. After completion of dropping, the reaction temperature was raised to room temperature and the mixture was stirred for about 3 hours. After confirming the reaction by thin layer chromatography (toluene) and terminating the reaction, the mixture was washed twice with 150 ml of saturated saline. After dehydrating the organic layer with anhydrous magnesium sulfate,
The solvent was distilled off under reduced pressure, and the crude product was purified by column chromatography (toluene) to obtain 22.1 g of the compound represented by the formula (S-3).

[0084]

[Chemical 18] 1H-NMR (300 MHz, CDCl3); δ = 1.50 to 2.09 (m, 6H), 3.01 (s,
1H), 3.60 to 3.65 (m, 1H), 3.85
3.93 (m, 1H), 5.46-5.48 (m, 1
H), 7.10 to 7.35 (m, 3H)

(S-3) Compound 2 obtained by the above synthesis
2.5 g, 4-bromophenol 19.9 g, dimethylformamide 120 ml and triethylamine 35 ml
1.25 g of tetrakistriphenylphosphine palladium and 0.41 g of copper iodide were added to the above solution and heated at 90 ° C. for 12 hours while stirring. After confirming the reaction by thin layer chromatography (toluene: ethyl acetate = 10: 1) and terminating the reaction, the reaction solution was diluted with 200 ml of ethyl acetate. Saturated ammonium chloride aqueous solution 15
It was washed once with 0 ml and twice with 150 ml of saturated saline. The organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the crude product was purified by column chromatography (toluene: ethyl acetate = 10: 1) to give compound 17 of the formula (S-4). 0.5 g was obtained.

[0086]

[Chemical 19] 1H-NMR (300 MHz, CDCl3); δ = 1.60 to 2.06 (m, 6H), 3.62 to 3.
66 (m, 1H), 3.90 to 3.98 (m, 1H),
5.11 (s, 1H), 5.47-5.49 (m, 1
H), 6.70 to 7.41 (m, 7H)

(S-4) Compound 1 obtained by the above synthesis
1 g of potassium carbonate was added to a solution of 4.4 g, 16.7 g of 6-bromohexanol and 140 ml of dimethylformamide.
2.7 g was added and the mixture was heated with stirring at 85 ° C. for about 4 hours. After confirming the reaction by thin layer chromatography (toluene: ethyl acetate = 4: 1) and terminating the reaction, the reaction solution was diluted with 200 ml of ethyl acetate. It was washed 3 times with 100 ml of saturated saline. The organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the crude product was separated by column chromatography (toluene: ethyl acetate = 4: 1). After evaporating the solvent under reduced pressure, the residue was purified by recrystallization (chloroform: hexane = 1: 3) to obtain 17.0 g of the compound represented by the formula (S-5).

[0088]

[Chemical 20] White crystal, melting point: 96.5-97.0 ° C. 1H-NMR (300 MHz, CDCl 3); δ = 1.32-2.12 (m, 14H), 3.61-
3.69 (m, 3H), 3.88 to 3.99 (m, 3
H), 5.46-5.48 (m, 1H), 6.84-
7.45 (m, 7H)

10 g of a solution of 7.6 g of the (S-5) compound obtained in the above synthesis and 70 ml of tetrahydrofuran was added.
% Hydrochloric acid (35 ml) was added and the reaction was carried out at room temperature for about 4 hours with stirring. After confirming the reaction by thin layer chromatography (toluene: ethyl acetate = 4: 1) and terminating the reaction, the reaction solution was diluted with 200 ml of ethyl acetate. It was washed twice with 100 ml of saturated saline. The organic layer was dried over anhydrous magnesium sulfate, the solvent was evaporated under reduced pressure, and the crude product was purified by recrystallization (chloroform) to obtain 5.5 g of the compound represented by the formula (S-6).

[0090]

[Chemical 21] White crystal, melting point: 127.0 to 128.0 ° C. 1H-NMR (300 MHz, CDCl 3); δ = 1.42 to 1.83 (m, 8H), 3.00 (b
r. s, 1H) 3.56 (t, 2H), 4.02 (t,
2H), 6.92 to 7.45 (m, 7H)

Glycidyl alcohol 10.4 g, triethylamine 28.2 g and tetrahydrofuran 400 m
1-solution, 6-bromohexanoyl chloride 25.0
A solution of g and tetrahydrofuran (170 ml) was gradually added dropwise from the dropping funnel, and the reaction was carried out at room temperature for about 5 hours while stirring. After confirming the reaction by thin layer chromatography (toluene: ethyl acetate = 4: 1) and terminating the reaction, the reaction solution was diluted with 500 ml of ethyl acetate. It was washed twice with 200 ml of saturated saline. The organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the crude product was separated by column chromatography (toluene: ethyl acetate = 4: 1) to give compound 22 of the formula (S-7). 0.5 g was obtained.

[0092]

[Chemical formula 22] 1H-NMR (300 MHz, CDCl3); δ = 1.42 to 1.93 (m, 6H), 2.38 (t,
2H) 2.65 (m, 1H) 2.83 (m, 1H),
3.20 (m, 1H), 3.43 (t, 2H), 3.9
1 (dd, 1H), 4.41 (dd, 1H)

Ethyl 4-hydroxybenzoate 33.2 g
After adding 5.02 g of pyridinium p-toluenesulfonic acid to a solution of 200 m of dichloromethane, a solution of 33.6 g of dihydropyran and 60 ml of dichloromethane was gradually added dropwise from an addition funnel over about 1 hour in an ice bath. After completion of the dropping, the reaction temperature was brought to room temperature and the mixture was stirred for about 2 hours. After confirming the reaction by gas chromatography and terminating the reaction, the mixture was washed once with 250 ml of saturated aqueous sodium hydrogen carbonate solution and once with 250 ml of saturated saline. After dehydrating the organic layer with anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain a crude product of the compound of the formula (S-8) 50.
0 g was obtained.

[0094]

[Chemical formula 23]

Crude product represented by the formula (S-8) 50.
0 g, sodium hydroxide 15.0 g, methanol 300
A mixture of ml and 150 ml of water was heated to reflux with stirring for 1 hour. Subsequently, after removing methanol, the reaction solution was cooled to room temperature and diluted hydrochloric acid was added to the reaction solution to neutralize it. The precipitated solid was filtered, washed thoroughly with water, and dried to give the compound of the formula (S-9) 42.7 g.
Got

[0096]

[Chemical formula 24] 1H-NMR (300 MHz, CDCl3); δ = 1.57 to 2.17 (m, 6H), 3.63 (m,
1H) 3.87 (m, 1H) 5.55 (m, 1H),
7.15 (d, 2H), 8.08 (d, 2H)

(S-6) Compound 1 obtained by the above synthesis
3.1 g, a benzoic acid derivative of the (S-9) compound 26.6
1-Ethyl-in a solution of 4 g and 500 ml of methylene chloride.
23.0 g of 3- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminipyridine 14.
64 g was added and the reaction was carried out at room temperature for about 5 hours with stirring. After confirming the reaction by thin layer chromatography (toluene: ethyl acetate = 4: 1), the reaction was terminated, and then washed with 200 ml of saturated saline three times. The organic layer was dried over anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure, followed by column chromatography (toluene: ethyl acetate = 4:
It was separated by 1) to obtain 29.0 g of the compound represented by the formula (S-10).

[0098]

[Chemical 25] 1H-NMR (300 MHz, CDCl3); δ = 1.54 to 2.10 (m, 20H), 3.62
(M, 2H), 3.85 (m, 2H) 3.97 (t, 2
H), 4.30 (t, 2H), 5.54 (m, 2H),
6.84-7.46 (m, 11H), 7.97 (d, 2
H), 8.15 (d, 2H)

150 ml of 10% hydrochloric acid was added to a solution of 29.4 g of the (S-10) compound obtained by the above synthesis and 300 ml of tetrahydrofuran, and the reaction was carried out at room temperature for about 2 hours while stirring. After confirming the reaction by thin layer chromatography (toluene: ethyl acetate = 4: 1) and terminating the reaction, the reaction solution was diluted with 350 ml of ethyl acetate. It was washed twice with 200 ml of saturated saline. The organic layer was dehydrated with anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the crude product was purified by recrystallizing from toluene to give the compound of the formula (S-11) 20.5 g.
Got

[0100]

[Chemical formula 26] 1H-NMR (300 MHz, CDCl3); δ = 1.43 to 1.73 (m, 8H), 4.00 (t,
2H), 4.20 (t, 2H), 6.81 to 7.61.
(M, 11H), 7.83 (d, 2H), 7.99
(D, 2H), 10.48 (br.s, 2H)

15.9 g of the (S-11) compound obtained by the above synthesis and the bromo compound of the epoxide (S-7) compound 1
8.5 g of potassium carbonate was added to a solution of 5.5 g and 450 ml of dimethylformamide, and the mixture was heated at 40 ° C. for about 7 hours while stirring. After confirming the reaction by thin layer chromatography (toluene: ethyl acetate = 4: 1) and terminating the reaction, the reaction solution was diluted with 500 ml of ethyl acetate. It was washed twice with 300 ml of saturated saline. The organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the crude product was separated by column chromatography (toluene: ethyl acetate = 3: 1) to obtain the compound of formula (S-1
16.0 g of the compound represented by 2) was obtained. The formula (S
As for the phase transition temperature of the polymerizable liquid crystal compound having an epoxy group of -12) at the time of temperature rise, the crystal phase-liquid crystal phase is 37 ° C., the liquid crystal phase-isotropic liquid phase is 54 ° C., and the phase transition temperature when the temperature is lowered. Had an isotropic liquid phase-liquid crystal phase of 54 ° C and a liquid crystal phase-crystal phase of 25 ° C or less.

[0102]

[Chemical 27]

1 H-NMR (300 MHz, CDCl
3); δ = 1.53 to 1.87 (m, 20H), 2.40
(M, 4H), 2.64 (m, 2H), 2.84 (m,
2H), 3.20 (m, 2H), 3.93 to 4.07.
(M, 8H), 4.29 to 4.41 (m, 4H), 6.
83-7.44 (m, 11H), 7.96-8.12.
(M, 4H)

Example 2 [Preparation (1) of Polymerizable Liquid Crystal Composition] Liquid crystalline acrylate compound 50 represented by formula (b1)
Parts by weight

[Chemical 28]

Then, a composition (A) comprising 50 parts by weight of the liquid crystal acrylate represented by the formula (b2) was prepared.

[Chemical 29]

The composition (A) exhibited a nematic liquid crystal phase at room temperature (25 ° C.). The nematic phase-isotropic liquid phase transition temperature was 46 ° C. Also, ne measured at 589 nm
The (refractive index of extraordinary light) was 1.662, the no (refractive index of ordinary light) was 1.510, and the birefringence was 0.152.

A composition (B) consisting of 10 parts by weight of the polymerizable liquid crystal compound having an epoxy group represented by the formula (S-12) obtained in Example 1 and 90 parts by weight of the composition (A) was prepared. The composition (B) exhibited a nematic liquid crystal phase at room temperature (25 ° C). Nematic phase-isotropic liquid phase transition temperature is 4
It was 7 ° C. Further, ne (refractive index of extraordinary light) measured at 589 nm is 1.661, and no (refractive index of ordinary light) is 1.
514, the birefringence was 0.147.

<Example 3> [Preparation of liquid crystal composition (2)] 30 parts by weight of the polymerizable liquid crystal compound having an epoxy group represented by the formula (S-12) obtained in Example 1 and the composition (A).
A composition (C) consisting of 70 parts by weight was prepared. The composition (C) exhibited a nematic liquid crystal phase at room temperature (25 ° C). The nematic phase-isotropic liquid phase transition temperature was 48 ° C. Also, ne (refractive index of extraordinary light) measured at 589 nm is 1.659, and no (refractive index of ordinary light) is 1.52.
0, the birefringence was 0.139.

<Example 4> [Preparation of liquid crystal composition (3)] 50 parts by weight of the polymerizable liquid crystal compound having an epoxy group represented by the formula (S-12) obtained in Example 1 and the composition (A).
A composition (D) consisting of 50 parts by weight was prepared. The composition (D) exhibits a smectic liquid crystal phase at room temperature (25 ° C.),
It exhibited a nematic liquid crystal phase at 45 ° C. The nematic phase-isotropic liquid phase transition temperature was 50 ° C. Thus, the polymerizable liquid crystal compound having an epoxy group represented by the formula (S-12) obtained in Example 1 showed good compatibility with the composition (A) up to 50 parts by weight or more.

Example 5 [Preparation of Optically Anisotropic Body (1)] 98 parts by weight of the composition (C) prepared in Example 3, photocationic polymerization initiator "UVI-6990" (manufactured by Union Carbide Co.). A composition (E) consisting of 2 parts by weight was prepared. The composition (E) was injected at room temperature into an anti-parallel alignment liquid crystal glass cell having a cell gap of 50 μm (a glass cell in which an alignment treatment was performed so that liquid crystal was uniaxially aligned). After the injection, it could be confirmed that uniform uniaxial orientation was obtained. Next, at room temperature (25 ° C.), UVGL-2 produced by UVP
The composition (E) was polymerized by irradiating 1 mW / cm ² of ultraviolet light for 10 minutes using the No. 5 polymer to obtain a polymer. It was confirmed that the obtained polymer had a different refractive index depending on the direction, and functioned as an optically anisotropic body.

Example 6 [Preparation of Optically Anisotropic Body (2)] 98 parts by weight of the composition (C) prepared in Example 3, light cation
Polymerization Initiator "UVI-6990" (Union Carbide
2 parts by weight and a photo-radical polymerization initiator "IRGAKI"
651 "(manufactured by Ciba Geigy) from 1.4 parts by weight
The following composition (F) was prepared. Cell gap of 50 μm
Anti-parallel alignment liquid crystal glass cell (aligns liquid crystal uniaxially
To the glass cell which has been subjected to the orientation treatment so that the composition (F)
Was injected at room temperature. A uniform uniaxial orientation is obtained after injection
I was able to confirm that. Next, at room temperature (25
1 mW / c using UVGL-25 from UVP at
m ^TwoUV irradiation of 10 minutes to polymerize composition (F)
Then, a polymer was obtained. The obtained polymer is
Have different refractive indices, and can function as an optically anisotropic body.
I was able to confirm.

Example 7 The composition (F) prepared in Example 6 was coated on the surface of an acrylic plate using a # 4 bar coater so that the dry film thickness was about 5 μm.
Light intensity 1000 J / m ² through a cold mirror using a metal halide lamp with a light intensity of 160 W / cm ^{2 in} the atmosphere.
Of light was irradiated four times. About 1 hour after irradiation, the cured coating film was tack free as a result of a finger touch test.

<Comparative Example 1> A composition (G) comprising 98 parts by weight of the composition (A) prepared in Example 2 and 2.0 parts by weight of a radical photopolymerization initiator "IRGACURE 651" (manufactured by Ciba Geigy). Was prepared. The prepared composition (G) was applied onto the surface of the acrylic plate so that the dry film thickness was about 5 μm.
Coated using a 4 bar coater. In the atmosphere, a metal halide lamp with a light intensity of 160 W / cm ² was used to irradiate light with a light intensity of 1000 J / m ² four times through a cold mirror. About one hour after the irradiation, the cured coating film was subjected to a finger touch test. As a result, tack was recognized and the surface remained in a liquid state.

From the results of Examples 2 to 7 and Comparative Example 1, the polymerizable liquid crystal composition containing the polymerizable liquid crystal compound of the general formula (2) of the present invention showed a smectic liquid crystal phase at room temperature (25 ° C.). In addition, it can be seen that it exhibits good curability under atmospheric conditions.

[0115]

According to the present invention, it is possible to provide a polymerizable liquid crystal compound having a low melting point and a temperature exhibiting an isotropic phase, and having excellent compatibility with other polymerizable liquid crystal compounds used in combination therewith.
As a polymerizable liquid crystal composition containing the compound, a polymerizable liquid crystal composition that exhibits liquid crystallinity at room temperature and is curable under atmospheric conditions in the presence of oxygen, and an optical anisotropic body using the same can be provided. .

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H049 BA02 BA05 BA06 BA42 BB44                       BB45 BB46 BB47 BC04 BC09                 2H091 FA08 FA11 FB02 GA01 JA01                       LA11                 4C048 AA01 BB13 CC02 UU03 XX04                 4J036 AB01 AB05 AB08 AC01 AC06                       AC09 AC11 EA03 EA06 JA15

Claims (4)

[Claims] 1. The general formula (1) [X is independently an alkyl group having 1 to 8 carbon atoms, or-
(Z-O-Z) _p- (Z represents an alkyl group having 1 to 4 carbon atoms, p represents an integer of 1 to 3),
G represents hydrogen, fluorine or a methyl group. ] It is represented by these, The polymeric liquid crystal compound characterized by the above-mentioned. 2. X is an alkyl group having 4 to 6 carbon atoms,
The polymerizable liquid crystal compound according to claim 1. 3. The general formula (2) [X is independently an alkyl group having 1 to 8 carbon atoms, or-
(Z-O-Z) _p- (Z represents an alkyl group having 1 to 4 carbon atoms, p represents an integer of 1 to 3),
Y is a halogen, a cyano group, a hydroxyl group, a C1-C8 alkyl group, a C1-C8 alkoxy group, and a C1-C1
8 represents a tranbenzoate skeleton, a biphenylbenzoate skeleton, a phenylbenzoate skeleton, a bisbenzoylbenzene skeleton, or a tolan skeleton, which may have at least one substituent selected from the group consisting of alkanoyl groups of 8] A polymerizable liquid crystal composition comprising a polymerizable liquid crystal compound. 4. The general formula (2) [X is independently an alkyl group having 1 to 8 carbon atoms, or-
(Z-O-Z) _p- (Z represents an alkyl group having 1 to 4 carbon atoms, p represents an integer of 1 to 3),
Y may have at least one substituent selected from the group consisting of halogen, cyano group, hydroxyl group, alkyl group having 1 to 8 carbon atoms, alkoxy group having 1 to 8 carbon atoms, and alkanoyl group, A tran benzoate skeleton, a biphenyl benzoate skeleton, a phenyl benzoate skeleton, a bisbenzoylbenzene skeleton, or a tolan skeleton] is included in the polymerizable liquid crystal compound. An optical anisotropic body.