JP2008239873A - Biphenyl and terphenyl compound and polymerizable liquid composition containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymerizable compound which has excellent dissolvability with another liquid crystal compound when constituting a polymerizable liquid crystal composition and can form a polymer excellent in heat resistance when the polymerizable liquid crystal composition is cured. <P>SOLUTION: A polymerizable liquid crystal compound expressed by general formula (I) is provided. The polymerizable liquid crystal compound is useful as a constituent material of the polymerizable composition due to the good dissolvability with another liquid crystal compound. The polymerizable composition containing the polymerizable compound has a wide liquid phase temperature range and an optically anisotropic article using the polymerizable composition has high heat resistance and is useful for applications to a polarization plate, a retardation film and the like. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a polymerizable compound, a polymerizable liquid crystal composition containing the compound, and an optical anisotropic body using the polymerizable composition.

  In recent years, with the progress of the information society, the importance of optical compensation films used for deflecting plates, retardation plates and the like essential for liquid crystal displays has been increasing. In addition, there has been reported an example in which a polymerizable liquid crystal composition is polymerized in an optical compensation film that is highly durable and requires high functionality. Since the optical anisotropic body used for the optical compensation film or the like varies depending on the purpose, a compound having characteristics suitable for the purpose is required. In addition to the optical properties, the polymerization rate, solubility, melting point, glass transition point, transparency of the polymer, mechanical strength, surface hardness, heat resistance and the like are important factors.

  As a compound constituting the polymerizable liquid crystal composition, conventionally, a compound having a structure in which 1,4-phenylene groups are linked by an ester bond (see Patent Document 1) and a compound having a fluorene group (see Patent Document 2) have been proposed. Has been. However, the polymerizable compound described in the cited document has problems such as low solubility. On the other hand, a polymerizable compound having an asymmetric structure in order to improve solubility is disclosed (see Patent Document 3), which is sufficiently improved in terms of solubility compared to conventional polymerizable compounds. In addition, there were problems such as low heat resistance and low mechanical strength.

Japanese National Patent Publication No. 10-513457 JP 2005-60373 A JP-T-2001-527570

  The problem to be solved by the present invention is that when a polymerizable liquid crystal composition is constituted, it has excellent solubility with other liquid crystal compounds, and further, it has excellent heat resistance when the polymerizable liquid crystal composition is cured. It is to provide a polymerizable compound.

As a result of studying various substituents in the polymerizable compound, the present inventors have found that a polymerizable compound having a specific structure can solve the above-described problems, and have completed the present invention.
The present invention relates to the general formula (I)

(In the formula, R ¹ and R ² are polymerizable groups represented by the following formulas (R-1) to (R-15):

And S ¹ and S ² are each independently an alkylene group having 2 to 10 carbon atoms in which a carbon atom may be replaced with an oxygen atom, or a single atom. Represents a bond, and L ¹ , L ² , L ³ , and L ⁴ each independently represent —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO. _{^{-, - OCOO -, - CO}} -NR 11 -, - NR 11 -CO -, - SCH 2 -, - CH 2 S -, - CH = CH-COO -, - OOC-CH = CH -, - COOC 2 H ₄ —, —OCOC ₂ H ₄ —, —C ₂ H ₄ OCO—, —C ₂ H ₄ COO—, —OCOCH ₂ —, —CH ₂ COO—, —CH═CH—, —CF═CH—, represents a -CH = CF- or -C≡C- ^{(wherein, R 11} is TansoHara . Representing 1-4 alkyl group), ^{L 2,} and at least one of ^{L 3} is _{-COOC 2 H 4 -, - OCOC} 2 H 4 -, - C 2 H 4 OCO- or _-C 2 _H 4 COO M ¹ and M ² each independently represent 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene- 2,6-diyl group, tetrahydronaphthalene-2,6-diyl group or 1,3-dioxane-2,5-diyl group, wherein M ¹ and M ² are each independently unsubstituted or alkyl Group, a halogenated alkyl group, an alkoxy group, a halogen group, a cyano group, or a nitro group, X ^{1 to} X ⁸ may be a hydrogen atom or an alkyl group, a halogenated alkyl group, an alkoxy group, a halogen, Represents a group, a cyano group, or a nitro group, and p represents 1 or 2. And a polymerizable liquid crystal composition using the compound.

  The polymerizable compound of the present invention is useful as a constituent member of the polymerizable composition because it has excellent solubility with other liquid crystal compounds. In addition, the polymerizable composition containing the polymerizable compound of the present invention has a wide liquid crystal phase temperature range, and the optical anisotropic body using the polymerizable composition has high heat resistance, such as a deflector plate and a retardation plate. Useful for applications.

In General Formula (1), R ¹ and R ² each independently represent a polymerizable group represented by Formula (R-1) to Formula (R-15);
These polymerizable groups are cured by radical polymerization, radical addition polymerization, cationic polymerization, and anionic polymerization.

  In particular, when performing ultraviolet polymerization as a polymerization method, the formula (R-1), formula (R-2), formula (R-4), formula (R-5), formula (R-7), formula (R -11), formula (R-13) or formula (R-15) are preferred, and formula (R-1), formula (R-2), formula (R-7), formula (R-11) or formula ( R-13) is more preferable, and formula (R-1) or formula (R-2) is particularly preferable.

S ¹ and S ² are preferably alkylene groups having 2 to 10 carbon atoms in which the carbon atoms may be replaced by oxygen atoms as the oxygen atoms are not directly bonded to each other. From the viewpoint of compatibility, an alkylene group having 3 to 8 carbon atoms is more preferable.

L ¹ , L ² , L ³ and L ⁴ are independently of each other —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, —OCOO. _{^{-, - CO-NR 11 -}} , - NR 11 -CO -, - SCH 2 -, - CH 2 S -, - CH = CH-COO -, - OOC-CH = CH -, - COOC 2 H 4 -, _{-OCOC 2 H 4 -, - C} 2 H 4 OCO -, - C 2 H 4 COO -, - OCOCH 2 -, - CH 2 COO -, - CH = CH -, - CF = CH -, - CH = CF — Or —C≡C— (wherein R ¹¹ represents an alkyl group having 1 to 4 carbon atoms), —O—, —COO—, —OCO—, —OCOC ₂ H ₄ —, — C ₂ H ₄ OCO—, —C ₂ H ₄ COO—, —OCOCH ₂ — or —CH ₂ COO— are preferred, A combination in which L ² represents —C ₂ H ₄ OCO— and L ³ represents —OCOC ₂ H ₄ — is particularly preferable.

M ¹ and M ² are each independently 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6- Represents a diyl group, a tetrahydronaphthalene-2,6-diyl group or a 1,3-dioxane-2,5-diyl group, wherein M ¹ and M ² are each independently unsubstituted or an alkyl group, halogenated An alkyl group, an alkoxy group, a halogen group, a cyano group, or a nitro group, which may be substituted, represents a 1,4-phenylene group, a 1,4-cyclohexylene group, or a naphthalene-2,6-diyl group Is preferable, it preferably represents a 1,4-phenylene group or a 1,4-cyclohexylene group, and particularly preferably represents a 1,4-phenylene group.

X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ and X ⁸ represent hydrogen or an alkyl group, a halogenated alkyl group, an alkoxy group, a halogen group, a cyano group, or a nitro group. , X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ and X ⁸ preferably represent a methyl group, an ethyl group, a fluoro group, a chloro group, a methoxy group or a cyano group. And more preferably a methyl group, a fluoro group, a chloro group or a methoxy group, and particularly preferably a methyl group.

  Although p represents 1 or 2, it is more preferable that p is 2 from a viewpoint of liquid crystallinity and heat resistance.

  More specifically, the compound represented by the general formula (I) is represented by the following general formula (I-1) to general formula (I-17).

The compound of the present invention can be synthesized by the following synthesis method.
(Production Method 1) Production of Compound Represented by General Formula (I-7) After trans-p-coumaric acid and 6-chlorohexanol are etherified in the presence of a suitable base such as sodium hydroxide, an acid catalyst is used. The coumarin acid derivative (S-3) is obtained by an esterification reaction with 3-chloropropionic acid used. Furthermore, an unsaturated bond can be hydrogenated by hydrogenation reaction using palladium carbon as a catalyst, and dehydrochlorinated with excess triethylamine to obtain a phenylpropionic acid derivative (S-5).

一方、（ｐ−ヒドロキシフェニル）ボロン酸と４−ブロモ−２−フルオロフェノールの鈴木−宮浦カップリング反応によりビフェノール化合物（Ｓ−７）を得る。

On the other hand, a biphenol compound (S-7) is obtained by Suzuki-Miyaura coupling reaction of (p-hydroxyphenyl) boronic acid and 4-bromo-2-fluorophenol.

  The obtained phenylpropionic acid derivative (S-5) and biphenol compound (S-7) can be esterified using a dehydration condensing agent such as dicyclohexylcarbodiimide to obtain the target compound (I-7).

(Production Method 2) Production of Compound Represented by General Formula (I-11) After trans-p-coumaric acid and diethylene glycol monochlorohydrin are etherified in the presence of a suitable base such as sodium hydroxide, an acid catalyst is used. The coumarin acid derivative (S-9) is obtained by esterification with the 3-chloropropionic acid used. Furthermore, an unsaturated bond can be hydrogenated by hydrogenation reaction using palladium carbon as a catalyst, and dehydrochlorinated with excess triethylamine to obtain a phenylpropionic acid derivative (S-11).

一方、（ｐ−ヒドロキシフェニル）ボロン酸と１，４−ジブロモ−２−フルオロベンゼンの鈴木−宮浦カップリング反応によりテルフェノール化合物（Ｓ−１２）を得る。

On the other hand, a terphenol compound (S-12) is obtained by Suzuki-Miyaura coupling reaction of (p-hydroxyphenyl) boronic acid and 1,4-dibromo-2-fluorobenzene.

  The obtained phenylpropionic acid derivative (S-11) and terphenol compound (S-12) can be esterified using a dehydration condensing agent such as dicyclohexylcarbodiimide to obtain the target compound (I-11).

本願発明の化合物は、ネマチック液晶、スメクチック液晶、キラルネマチック、キラルスメクチック、およびコレステリック液晶組成物に使用できる。本願発明の化合物を用いる液晶組成物において、本発明以外の重合性化合物を添加しても構わない。

The compounds of the present invention can be used in nematic liquid crystals, smectic liquid crystals, chiral nematics, chiral smectics, and cholesteric liquid crystal compositions. In the liquid crystal composition using the compound of the present invention, a polymerizable compound other than the present invention may be added.

  The polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition of the present invention preferably has an acryloyloxy group or a methacryloyloxy group as a polymerizable functional group. As the polymerizable liquid crystal compound, those having two or more polymerizable functional groups in the molecule are preferable. Such bifunctional or higher functional compounds include those represented by the general formula (II)

Wherein W ¹ and W ² each independently represent a single bond, —O—, —COO— or —OCO—, and Y ³ and Y ⁴ each independently represent —COO— or —OCO—. , R and s each independently represents an integer of 2 to 18, and the 1,4-phenylene group in the formula is an alkyl group having 1 to 7 carbon atoms, an alkoxy group, an alkanoyl group, a cyano group or a halogen atom. A compound represented by the formula (1) may be substituted. Among the compounds represented by the general formula (II), compounds represented by (II-1) to (II-8) are particularly preferable.

(In the formula, r and s have the same meaning as in general formula (II).)
In general formulas (II-1) to (II-8), r and s are each independently preferably an integer of 3 to 6.
In addition, the general formula (III)

(Wherein W ³ and W ⁴ each independently represents a single bond, —O—, —COO— or —OCO—, Y ⁵ represents —COO— or —OCO—, p, And q each independently represents an integer of 2 to 18, and the hydrogen atoms of the three 1,4-phenylene groups present in the formula are each independently an alkyl group or alkoxy group having 1 to 7 carbon atoms. , An alkanoyl group, a cyano group, or a halogen atom may be substituted one or more). Among the compounds represented by the general formula (III), compounds represented by the general formula (III-1) to the general formula (III-8) are particularly preferable.

(In the formula, p and q have the same meaning as in general formula (III).)
Among these compounds, compounds of general formulas (III-2), (III-5), (III-6), (III-7), and (III-8) are preferable from the viewpoint of heat resistance and durability. The compounds of general formula (III-2) are particularly preferred.
In addition, as the polymerizable liquid crystal compound having two or more polymerizable functional groups in the molecule, compounds represented by general formulas (a-1) to (a-9) can be contained.

(In the formula, u and v each independently represents an integer of 2 to 18)
(In the formula, u and v each independently represents an integer of 2 to 18)
Among these, the use of the compounds of the general formulas (a-2) and (a-3) is preferable. u and v are each independently preferably 3 to 18, preferably 4 to 16, and more preferably 6 to 12.
Furthermore, for the purpose of adjusting the liquid crystal temperature range and birefringence, and reducing viscosity, the general formula (IV)

(In the formula, e represents an integer of 0 to 18, f represents 0 when e is 0 or 1, f represents an integer of 0 or 1 when e is 2 to 18, and i represents 0 to 2 C, D and E are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1 , 3-Dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6-diyl group, pyridine -2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group Phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9,10a-octahydrophenanthrene 2,7-diyl group or fluorene 2 , 7-diyl group, the 1,4-phenylene group, 1,2,3,4-tetrahydrona Talen-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9 , 10a-Octahydrophenanthrene 2,7-diyl group and fluorene 2,7-diyl group are unsubstituted or substituted with one or more F, Cl, CF ₃ , OCF ₃ or CH ₃ as substituents Y ⁶ and Y ⁷ are each independently a single bond, —COO—, —OCO—, —CH═N—, —N═CH—, —C≡C—, —CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ CH _2- , -CH ₂ CH ₂ CH ₂ O-, -OCH ₂ CH ₂ CH _2- , -CH ₂ O-, -OCH _2- , -CF ₂ O-,- OCF _2- , -CH = NN = CH-, -CF = CF-, -CH = CH-, -CH ₂ CH ₂ CH = CH-, -CH = CHCH ₂ CH _2- , -CH ₂ CH = CHCH ₂ -, -CH = CHCOO-, -OCOCH = CH-, -CH ₂ CH ₂ OCO- or -COOCH ₂ CH _2- , Y ⁸ represents a single bond, -O-, -CO-, -COO-,- _{OCO -, - CH 2 -,} - CH 2 O -, - OCH 2 -, - CONH -, - NHCO -, - CH 2 COO- or an -CH ₂ OCO-, Z is from 1 to 18 carbon atoms Alkyl group, carbon source Represents an alkenyl group having 2 to 18 atoms, a halogen atom, CN or NCS, wherein the alkyl group or alkenyl group is unsubstituted or substituted with one or more F, Cl, CN, CH ₃ or may have a CF _3, 1 or two or more CH ₂ groups existing in said alkyl group or alkenyl group include, but are O atoms are not linked directly to one another, O, substituted by CO or COO May be. It is also possible to add a monofunctional polymerizable compound represented by The amount added is preferably 50% by mass or less, more preferably 30% by mass or less, and particularly preferably 15% by mass or less. Among the compounds represented by the general formula (IV), the compounds represented by the general formulas (IV-1) to (IV-11) are particularly preferable.

(In the formula, e and f are the same as in the general formula (IV), R represents an alkyl group having 1 to 12 carbon atoms and an alkenyl group having 2 to 12 carbon atoms.)
Furthermore, when using for a cholesteric liquid crystal composition etc., the addition amount of a polymeric chiral compound has preferable 0.1-40 mass%. Furthermore, the polymerizable liquid crystal composition of the present invention may be added with a compound having a polymerizable functional group and not exhibiting liquid crystallinity. Such a compound can be used without particular limitation as long as it is generally recognized as a polymer-forming monomer or polymer-forming oligomer in this technical field. It is necessary to adjust to exhibit sex.

  Moreover, 0.1-10 mass% is preferable and, as for the density | concentration of the photoinitiator in the polymeric liquid crystal composition of this invention, 0.2-5 mass% is more preferable. Examples of the photopolymerization initiator include benzoin ethers, benzophenones, acetophenones, benzyl ketals, and acylphosphine oxides.

  In addition, a stabilizer can 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 monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, β-naphthylamines, β-naphthols, and nitroso compounds. . When the stabilizer is used, the addition amount is preferably in the range of 0.005 to 1% by mass, more preferably 0.02 to 0.5% by mass with respect to the liquid crystal composition.

  In addition, when the polymerizable liquid crystal composition of the present invention is used for a raw material of a polarizing film or an alignment film, a printing ink, a paint, a protective film or the like, a metal, a metal complex, a dye, or a pigment depending on the purpose. , Dyes, fluorescent materials, phosphorescent materials, surfactants, leveling agents, thixotropic agents, gelling agents, polysaccharides, ultraviolet absorbers, infrared absorbers, antioxidants, ion exchange resins, metal oxides such as titanium oxide, etc. Can also be added.

Next, the optical anisotropic body of the present invention will be described. The optical anisotropic body produced by polymerizing the polymerizable liquid crystal composition of the present invention can be used for various applications. For example, when the polymerizable liquid crystal composition of the present invention is polymerized without being oriented, it can be used as a light scattering plate, a depolarizing plate, or a moire fringe prevention plate. Moreover, the optically anisotropic body produced by polymerizing the polymerizable liquid crystal composition of the present invention in an aligned state has optical anisotropy in physical properties and is useful. Such an optical anisotropic body 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 a substrate surface on which an organic thin film is formed with a cloth, or SiO _2. Can be produced by polymerizing the liquid crystal of the present invention after it is supported on a substrate having an orientation film deposited obliquely or sandwiched between the substrates.

  Examples of the method for supporting the polymerizable liquid crystal composition on the substrate include spin coating, die coating, extrusion coating, roll coating, wire bar coating, gravure coating, spray coating, dipping, and printing. . Further, an organic solvent may be added to the polymerizable liquid crystal composition during coating. Examples of the organic solvent include ethyl acetate, tetrahydrofuran, toluene, hexane, methanol, ethanol, dimethylformamide, methylene chloride, isopropanol, acetone, methyl ethyl ketone, acetonitrile, and cellosolves. These may be used alone or in combination, and may be appropriately selected in consideration of the vapor pressure and the solubility of the polymerizable liquid crystal composition. As a method for volatilizing the added organic solvent, natural drying, heat drying, reduced pressure drying, or reduced pressure heat drying can be used. In order to further improve the applicability of the polymerizable liquid crystal material, it is also effective to provide an intermediate layer such as a polyimide thin film on the substrate or to add a leveling agent to the polymerizable liquid crystal material. Providing an intermediate layer such as a polyimide thin film on the substrate is also effective as a means for improving the adhesion when the adhesion between the optically anisotropic substance obtained by polymerizing the polymerizable liquid crystal material and the substrate is not good. .

Examples of the alignment treatment other than the rubbing treatment or the oblique deposition of SiO ₂ include the use of fluid orientation of a liquid crystal material and the use of an electric field or a magnetic field. These orientation means may be used alone or in combination. Furthermore, a photo-alignment method can be used as an alignment treatment method instead of rubbing. As a shape of the substrate, in addition to a flat plate, a curved surface may be included as a constituent part. The material which comprises a board | substrate can be used regardless of an organic material and an inorganic material. Examples of the organic material used as the substrate material include polyethylene terephthalate, polycarbonate, polyimide, polyamide, polymethyl methacrylate, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polychlorotrifluoroethylene, polyarylate, polysulfone, and triacetyl. Cellulose, cellulose, polyetheretherketone and the like can be mentioned, and examples of the inorganic material include silicon, glass and calcite.

  When appropriate 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 substrate surface according to a known method, and this is rubbed with a cloth or the like. Also good. In the case where the alignment state is controlled 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 aforementioned polyimide thin film on the electrode.

As a method of polymerizing the polymerizable liquid crystal composition of the present invention, since rapid progress of polymerization is desirable, a method of polymerizing by irradiating active energy rays such as ultraviolet rays or electron beams is preferable. When ultraviolet rays are used, a polarized light source or a non-polarized light source may be used. Further, when the polymerization is carried out with the liquid crystal composition sandwiched between two substrates, at least the substrate on the irradiation surface side must be given appropriate transparency to the active energy rays. Moreover, after polymerizing only a specific part using a mask at the time of light irradiation, the orientation state of the unpolymerized part is changed by changing conditions such as an electric field, a magnetic field, or temperature, and further irradiation with active energy rays is performed. Then, it is possible to use a means for polymerization. Moreover, it is preferable that the temperature at the time of irradiation exists in the temperature range by which the liquid crystal state of the polymeric liquid crystal composition of this invention is hold | maintained. In particular, when an optical anisotropic body is to be produced by photopolymerization, the polymerization is carried out at a temperature as close to room temperature as possible from the viewpoint of avoiding unintentional induction of thermal polymerization, that is, typically at a temperature of 25 ° C. It is preferable to make it. The intensity of the active energy ray is preferably 0.1 mW / cm ^{2 to 2} W / cm ² . When the intensity is 0.1 mW / cm ² or less, a great amount of time is required to complete the photopolymerization and the productivity is deteriorated. When the intensity is 2 W / cm ² or more, the polymerizable liquid crystal compound or the polymerizable liquid crystal is used. There is a risk that the composition will deteriorate.

  The optical anisotropic body of the present invention obtained by polymerization can be subjected to heat treatment for the purpose of reducing initial characteristic changes and achieving stable characteristic expression. The heat treatment temperature is preferably in the range of 50 to 250 ° C., and the heat treatment time is preferably in the range of 30 seconds to 12 hours.

  The optical anisotropic body of the present invention produced by such a method may be peeled off from the substrate and used alone or without peeling. Further, the obtained optical anisotropic bodies may be laminated or bonded to another substrate for use.

  EXAMPLES Hereinafter, although an Example is given and this invention is further explained in full detail, this invention is not limited to these Examples. Further, “%” in the compositions of the following examples and comparative examples means “mass%”.

Example 1
A reaction vessel equipped with a stirrer, a reflux condenser, and a thermometer was charged with 30 g (183 mmol) of trans-p-coumaric acid, 3 g of potassium iodide, and 80 ml of ethanol and stirred at room temperature. 80 ml of an aqueous solution in which 16 g of sodium hydroxide was dissolved was slowly added dropwise. After completion of the dropping, the reaction vessel was kept at 80 ° C., and 41.3 g (274 mmol) of 6-chlorohexanol was slowly added dropwise. After completion of the dropwise addition, the reaction vessel was further kept at 80 ° C. and further reacted for 15 hours. After completion of the reaction, the reaction mixture was neutralized with 10% hydrochloric acid and 80 ml of ethyl acetate was added, followed by stirring under ice cooling for 3 hours. After filtration, the obtained crystals were washed successively with water, ethanol and ethyl acetate and then dried to synthesize 42 g of the compound represented by formula (1) (intermediate 1).

Next, 36.7 g (139 mmol) of the above-synthesized (Intermediate 1) and 30.1 g (277 mmol) of 3-chloropropionic acid in a reaction vessel equipped with a stirrer, a reflux condenser and a Dean-Stark water separator. ), 2.5 g of p-toluenesulfonic acid, 150 ml of toluene, and 150 ml of hexane were charged. The reaction vessel was heated to reflux and allowed to react for 5 hours. After completion of the reaction, the reaction solution was washed successively with water and saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After distilling off the solvent, recrystallization was performed with ethanol to obtain 38 g of a compound (intermediate 2) represented by the formula (2).

An autoclave vessel equipped with a stirrer was charged with 38 g (108 mmol) of the above synthesized (intermediate 2), 3.8 g of 5% palladium carbon, 200 ml of ethyl acetate, and 200 ml of ethanol at room temperature under a pressure of 0.5 mPa. Hydrogen reduction reaction (4 hours) was performed. After filtering the reaction solution, the reaction solvent was distilled off to obtain 37.4 g of a compound (intermediate 3) represented by the formula (3).

A reaction vessel equipped with a stirrer, a reflux condenser, and a thermometer was charged with 20 g (56 mmol) of the above synthesized (Intermediate 3), 28.5 g of triethylamine, and 100 ml of tetrahydrofuran, and heated under reflux for 15 hours under a nitrogen atmosphere. did. After completion of the reaction, the reaction mixture was neutralized with 10% hydrochloric acid, extracted with ethyl acetate, washed with saturated brine, dried over anhydrous sodium sulfate, the solvent was evaporated, and the compound represented by formula (4) ( 18 g of intermediate 4) were synthesized.

In a reaction vessel equipped with a stirrer, a reflux condenser, and a thermometer, 15 g (79 mmol) of 4-bromo-2-fluorophenol, 16 g of (p-hydroxyphenyl) boronic acid, tetrakis (triphenylphosphine) palladium complex 1 .8 g, 14 g of potassium carbonate, 100 ml of water and 160 ml of tetrahydrofuran were charged, and the mixture was heated to reflux for 11 hours under a nitrogen atmosphere. After completion of the reaction, the reaction mixture was neutralized with 10% hydrochloric acid and extracted with ethyl acetate. After washing with saturated brine, the solution was dried over anhydrous sodium sulfate, and the solvent was distilled off. Purification by silica gel column chromatography and recrystallization yielded 5 g of the compound represented by formula (5) (intermediate 5).

  Into a reaction vessel equipped with a stirrer, a reflux condenser, and a thermometer, 7.8 g (24 mmol) of intermediate (4) synthesized above, 2.5 g (12 mmol) of intermediate (5), dimethylaminopyridine 360 mg and 50 ml of methylene chloride were charged, the reaction vessel was kept at 5 ° C. or lower with an ice-cooled bath, and 3.7 g (29 mmol) of diisopropylcarbodiimide was slowly added dropwise under a nitrogen atmosphere. After completion of dropping, the reaction vessel was returned to room temperature and allowed to react overnight. After the reaction solution was filtered, the filtrate was washed successively with 10% aqueous hydrochloric acid solution, water and saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After the solvent was distilled off, the residue was purified by silica gel column chromatography and recrystallization to obtain 6.7 g of the desired compound represented by the formula (6).

Cr 110 N 123 I
(Physical property value)
¹ H-NMR (solvent: deuterated chloroform): δ: 7.53 (m, 2H), 7.30 (m, 2H), 7.18 (d, 4H), 7.09 (m, 3H), 6 .85 (d, 4H), 6.40 (dd, 2H), 6.13 (dd, 2H), 5.81 (dd, 2H), 4.17 (t, 4H), 3.95 (t, 4H), 3.03 (m, 4H), 2.89 (m, 4H), 1.80 (m, 4H), 1.71 (m, 4H), 1.48 (m, 8H).
¹³ C-NMR (solvent: deuterated chloroform): δ: 171.2, 170.3, 166.1, 157.5, 150.3, 136.9, 131.8, 130.4, 129.2, 128 5, 128.0, 123.8, 122.8, 121.9, 121.7, 115.3, 115.1, 114.5, 67.8, 64.5, 36.4, 35.9 , 30.2, 30.1, 29.3, 28.6, 25.8.
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1765, 1652-1622, 810
(Melting point) 110 ° C

(Example 2)
In a reaction vessel equipped with a stirrer, a reflux condenser, and a thermometer, 12 g (48 mmol) of 1,4-dibromo-2-fluorobenzene, 20 g of (p-hydroxyphenyl) boronic acid, tetrakis (triphenylphosphine) palladium 1.1 g of complex, 9 g of potassium carbonate, 70 ml of water, and 130 ml of tetrahydrofuran were charged and heated under reflux for 14 hours under a nitrogen atmosphere. After completion of the reaction, the reaction mixture was neutralized with 10% hydrochloric acid and extracted with ethyl acetate. After washing with saturated brine, the solution was dried over anhydrous sodium sulfate, and the solvent was distilled off. Purification by silica gel column chromatography and recrystallization yielded 6 g of the compound represented by formula (7) (intermediate 7).

In a reaction vessel equipped with a stirrer, a reflux condenser, and a thermometer, 7.8 g (24 mmol) of intermediate (4) synthesized in Example 1 and 3.4 g (12) of intermediate (7) synthesized above were added. Mmol), 360 mg of dimethylaminopyridine, and 60 ml of methylene chloride were kept in an ice-cooled bath at 5 ° C. or lower, and 3.7 g (29 mmol) of diisopropylcarbodiimide was slowly added dropwise under a nitrogen atmosphere. After completion of dropping, the reaction vessel was returned to room temperature and allowed to react overnight. After the reaction solution was filtered, the filtrate was washed successively with 10% aqueous hydrochloric acid solution, water and saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After distilling off the solvent, the residue was purified by silica gel column chromatography and recrystallization to obtain 7.5 g of the desired compound represented by the formula (6).

Cr 155 N 205 I
(Physical property value)
¹ H-NMR (solvent: deuterated chloroform): δ: 7.59 (m, 4H), 7.48 (t, 1H), 7.37 (m, 2H), 7.19 (d, 4H), 7 .09 (d, 4H), 6.86 (d, 4H), 6.40 (dd, 2H), 6.12 (dd, 2H), 5.81 (dd,
2H), 4.17 (t, 4H), 3.95 (t, 4H), 3.04 (t, 4H), 2.88 (t, 4H), 1.80 (m, 4H), 1. 71 (m, 4H), 1.48 (m, 8H). ¹³ C-NMR (solvent: deuterated chloroform): δ: 171.3, 157.6, 131.9, 130.8, 130.4, 129.9, 129.8, 129.2, 128.5, 127 .9, 122.8, 122.0, 121.5, 114.5, 114.4, 67.8, 64.5, 36.4, 30.2, 29.3, 28.7, 25.9 .
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1765, 1652-1622, 810.
(Melting point) 155 ° C

(Example 3)
A reaction vessel equipped with a stirrer, a reflux condenser, and a thermometer was charged with 30 g (183 mmol) of trans-p-coumaric acid, 3 g of potassium iodide, and 100 ml of ethanol and stirred at room temperature. 100 ml of an aqueous solution in which 16 g of sodium hydroxide was dissolved was slowly added dropwise. After completion of the dropping, the reaction vessel was kept at 80 ° C., and 34 g (274 mmol) of diethylene glycol monochlorohydrin was slowly added dropwise. After completion of the dropwise addition, the reaction vessel was further kept at 80 ° C. and further reacted for 19 hours. After completion of the reaction, the reaction mixture was neutralized with 10% hydrochloric acid and 50 ml of ethyl acetate was added, followed by stirring under ice cooling for 3 hours. After filtration, the obtained crystals were washed successively with water and ethanol and dried to synthesize 10 g of the compound represented by formula (8) (intermediate 8).

In a reaction vessel equipped with a stirrer, a reflux condenser, and a Dean-Stark water separator, 9.5 g (38 mmol) of the above synthesized (intermediate 8), 8.2 g (76 mmol) of 3-chloropropionic acid, 0.7 g of p-toluenesulfonic acid, 40 ml of toluene, and 40 ml of hexane were charged. The reaction vessel was heated to reflux and allowed to react for 5 hours. After completion of the reaction, the reaction solution was washed successively with water and saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After the solvent was distilled off, recrystallization was performed with an ethyl acetate / hexane mixed solvent to obtain 12 g of a compound (intermediate 9) represented by the formula (9).

An autoclave vessel equipped with a stirrer was charged with 12 g (34 mmol) of the above synthesized (intermediate 9), 1.2 g of 5% palladium carbon, 150 ml of ethyl acetate, and 100 ml of ethanol at room temperature under a pressure of 0.5 mPa. Hydrogen reduction reaction (4 hours) was performed. After the reaction solution was filtered, the reaction solvent was distilled off to obtain 12 g of a compound (intermediate 10) represented by the formula (10).

A reaction vessel equipped with a stirrer, a reflux condenser, and a thermometer was charged with 12 g (35 mmol) of the above synthesized (intermediate 10), 18 g of triethylamine, and 90 ml of tetrahydrofuran, and heated under reflux for 6.5 hours under a nitrogen atmosphere. did. After completion of the reaction, the mixture was neutralized with 10% hydrochloric acid, extracted with ethyl acetate, washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated. Recrystallization was performed with an acetone / hexane mixed solvent to synthesize 8.7 g of the compound represented by formula (11) (intermediate 11).

In a reaction vessel equipped with a stirrer, a reflux condenser, and a thermometer, 4.7 g (15 mmol) of the intermediate (11) synthesized above, 2.1 g (7) of the intermediate (7) synthesized in Example 1 (7 Mmol), 200 mg of dimethylaminopyridine, and 40 ml of methylene chloride were kept in an ice-cooled bath at 5 ° C. or lower, and 2.3 g (18 mmol) of diisopropylcarbodiimide was slowly added dropwise under a nitrogen atmosphere. After completion of dropping, the reaction vessel was returned to room temperature and allowed to react overnight. After the reaction solution was filtered, the filtrate was washed successively with 10% aqueous hydrochloric acid solution and saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After the solvent was distilled off, the residue was purified by silica gel column chromatography and recrystallization to obtain 4.2 g of the objective compound represented by the formula (12).

Cr 133 N 190 I
（物性値）
¹Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：７．５９（ｍ，４Ｈ），７．４８（ｔ，１Ｈ），７．３７（ｍ，２Ｈ），７．１９（ｄ，４Ｈ），７．１１（ｄ，４Ｈ），６．８９（ｄ，４Ｈ），６．４３（ｄｄ，２Ｈ），６．１５（ｄｄ，２Ｈ），５．８３（ｄ，２Ｈ），４．３５（ｔ，４Ｈ），４．１３（ｔ，４Ｈ），３．８７（ｔ，４Ｈ），３．８２（ｔ，４Ｈ），３．０４（ｔ，４Ｈ），２．８８（ｔ，４Ｈ）．
^１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：１７１．４，１６６．１，１５７．４，１５０．５，１５０．２，１３２．４，１３１．０，１３０．９，１３０．０，１２９．４，１２８．２，１２８．０，１２２．９，１２２．０，１２１．６，１１４．８，１１４．５，６９．７，６９．３，６７．５，６３．６，３６．３，３０．１．
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：２９２５，２８５５，１７６５，１６５２−１６２２，８１０．
（融点）１３３℃
（実施例４）
以下に示す組成の重合性液晶組成物（組成物１）を調製した。

Cr 133 N 190 I
(Physical property value)
¹ H-NMR (solvent: deuterated chloroform): δ: 7.59 (m, 4H), 7.48 (t, 1H), 7.37 (m, 2H), 7.19 (d, 4H), 7 .11 (d, 4H), 6.89 (d, 4H), 6.43 (dd, 2H), 6.15 (dd, 2H), 5.83 (d, 2H), 4.35 (t, 4H), 4.13 (t, 4H), 3.87 (t, 4H), 3.82 (t, 4H), 3.04 (t, 4H), 2.88 (t, 4H).
¹³ C-NMR (solvent: deuterated chloroform): δ: 171.4, 166.1, 157.4, 150.5, 150.2, 132.4, 131.0, 130.9, 130.0, 129 4,128.2,128.0,122.9,122.0,121.6,114.8,114.5,69.7,69.3,67.5,63.6,36.3 30.1.
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1765, 1652-1622, 810.
(Melting point) 133 ° C
Example 4
A polymerizable liquid crystal composition (Composition 1) having the following composition was prepared.

The polymerizable liquid crystal composition had good compatibility stability and exhibited a nematic liquid crystal phase. A photopolymerization initiator Irgacure 907 (manufactured by Ciba Specialty Chemicals) was added to this composition at 2% to prepare a polymerizable liquid crystal composition (Composition 2). When the cyclohexanone solution of composition 2 was spin-coated on polyimide-coated glass and irradiated with 4 mW / cm ² of ultraviolet light for 120 seconds using a high-pressure mercury lamp, composition 2 remained in a uniform alignment state. Polymerization yielded an optically anisotropic body. The surface hardness (according to JIS-SK-5400) of this optical anisotropic body was H. Assuming that the phase difference before heating of the obtained optical anisotropic body was 100%, the phase difference after heating at 240 ° C. for 1 hour was 81%, and the phase difference reduction rate was 19%.
(Comparative Example 1)
A polymerizable liquid crystal composition (Composition 3) having the following composition was prepared.

The polymerizable liquid crystal composition showed a nematic liquid crystal phase, but the solubility was poor and crystals were precipitated at room temperature for 1 hour.
(Comparative Example 2)
A polymerizable liquid crystal composition (Composition 4) having the following composition was prepared.

The polymerizable liquid crystal composition had good compatibility stability and exhibited a nematic liquid crystal phase. A photopolymerization initiator Irgacure 907 (manufactured by Ciba Specialty Chemicals) was added to this composition at 2% to prepare a polymerizable liquid crystal composition (Composition 5). The cyclohexanone solution of composition 4 was spin-coated on a glass with polyimide, and irradiated with 4 mW / cm ² ultraviolet rays for 120 seconds using a high-pressure mercury lamp. As a result, composition 4 remained in a uniform alignment state. Polymerization yielded an optically anisotropic body. The surface hardness (according to JIS-S-K-5400) of this optical anisotropic body was 4B. Assuming that the phase difference before heating of the obtained optical anisotropic body was 100%, the phase difference after heating at 240 ° C. for 1 hour was 72%, and the phase difference reduction rate was 28%.

  Thus, it is clear that the composition 4 of Comparative Example 2 has a larger retardation reduction rate of the optically anisotropic body that can be produced and is inferior in heat resistance than the composition 1 of the present invention. Further, the surface hardness was 4B, which was insufficient.

Claims (6)

General formula (1)

(In the formula, R ¹ and R ² are each independently a polymerizable group represented by the following formulas (R-1) to (R-15):

And S ¹ and S ² are each independently an alkylene group having 2 to 10 carbon atoms in which a carbon atom may be replaced with an oxygen atom, or a single atom. Represents a bond, and L ¹ , L ² , L ³ , and L ⁴ each independently represent —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO. _{^{-, - OCOO -, - CO}} -NR 11 -, - NR 11 -CO -, - SCH 2 -, - CH 2 S -, - CH = CH-COO -, - OOC-CH = CH -, - COOC 2 H ₄ —, —OCOC ₂ H ₄ —, —C ₂ H ₄ OCO—, —C ₂ H ₄ COO—, —OCOCH ₂ —, —CH ₂ COO—, —CH═CH—, —CF═CH—, represents a -CH = CF- or -C≡C- ^{(wherein, R 11} is TansoHara . Representing 1-4 alkyl group), ^{L 2,} and at least one of ^{L 3} is _{-COOC 2 H 4 -, - OCOC} 2 H 4 -, - C 2 H 4 OCO- or _-C 2 _H 4 COO M ¹ and M ² each independently represent 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene- 2,6-diyl group, tetrahydronaphthalene-2,6-diyl group or 1,3-dioxane-2,5-diyl group, wherein M ¹ and M ² are each independently unsubstituted or alkyl Group, a halogenated alkyl group, an alkoxy group, a halogen group, a cyano group, or a nitro group, X ^{1 to} X ⁸ may be a hydrogen atom or an alkyl group, a halogenated alkyl group, an alkoxy group, a halogen, Represents a group, a cyano group, or a nitro group, and p represents 1 or 2. ) A polymerizable compound represented. M ¹ and M ² each independently represent a 1,4-cyclohexylene group, a 1,4-phenylene group or a naphthalene-2,6-diyl group, and any one of X ^{1 to} X ⁸ is an alkyl group The polymerizable compound according to claim 1, which represents a halogenated alkyl group, an alkoxy group, or a halogen group. L ² and L ³ each independently represent —COOC ₂ H ₄ —, —OCOC ₂ H ₄ —, —C ₂ H ₄ OCO— or —C ₂ H ₄ COO—, wherein L ¹ and L ⁴ are The polymerizable liquid crystal compound according to claim 1 or 2, which represents -O-, -S-, -COO- or -OCO- independently of each other. The polymerizable compound according to claim 1, wherein S ¹ and S ² represent an alkylene group having 2 to 10 carbon atoms. A polymerizable liquid crystal composition comprising the polymerizable compound according to claim 1. An optical anisotropic body using the polymerizable liquid crystal composition according to claim 5.