CN101792391B - Polymerizable biphenyl compound - Google Patents

Abstract

The problem to be solved by the present invention is to provide a polymerizable compound that has excellent solubility with other liquid crystal compounds when constituting a polymerizable liquid crystal composition and exhibits excellent heat resistance when curing the aforementioned polymerizable liquid crystal composition sex and mechanical strength. The present invention provides a polymerizable compound represented by formula (I), a liquid crystal composition using the compound as a constituent material, and further, an optically anisotropic body or a liquid crystal device using the liquid crystal composition. Since the polymerizable compound of the present invention has excellent solubility with other liquid crystal compounds, it is useful as a constituent material of a polymerizable composition. In addition, the polymerizable composition containing the polymerizable compound of the present invention has a wide liquid crystal phase temperature range; the optically anisotropic body using the polymerizable composition has high heat resistance and is useful for polarizing plates, retardation plates, etc. of.

Description

polymeric biphenyl compound

technical field

The present invention relates to a polymerizable biphenyl compound, a liquid crystal composition containing the compound, and an optically anisotropic body or a liquid crystal device which is a cured product of the liquid crystal composition.

Background technique

In recent years, with the progress of the information society, the importance of optical compensation films used for polarizers, retardation plates, etc. necessary for liquid crystal displays has increased, and high durability and high functional optical compensation films are required For example, an example of polymerizing a polymerizable liquid crystal composition is reported. Optically anisotropic materials used in optical compensation films, etc., not only have optical properties, but also polymerization speed, solubility, melting point, glass transition temperature, light transmittance of polymers, mechanical strength, surface hardness and heat resistance, etc. become an important factor. Furthermore, there are also reports of examples in which a polymerizable compound is added to a liquid crystal medium to improve display characteristics.

As a compound constituting a polymerizable liquid crystal composition, a compound having a structure in which 1,4-phenylene groups are linked via an ester bond (see Patent Document 1) and a compound having a fluorenyl group (see Patent Document 2) have been proposed. However, the polymerizable compound described in this cited document has problems such as low solubility. On the other hand, a polymerizable compound adopting an asymmetric structure for improving solubility is disclosed (Patent Document 3). Compared with the conventional polymerizable compound, although the solubility is improved, it is not sufficient, and there is a resistance Low thermal and mechanical strength issues.

prior art literature

Patent Document 1: Japanese Patent Application Laid-Open No. 10-513457

Patent Document 2: Japanese Patent Laid-Open No. 2005-60373

Patent Document 3: Japanese Tokohei No. 2001-527570

Contents of the invention

The problem to be solved by the invention

The problem to be solved by the present invention is to provide a polymerizable compound that has excellent solubility with other liquid crystal compounds when constituting a polymerizable liquid crystal composition and exhibits excellent heat resistance when curing the aforementioned polymerizable liquid crystal composition and mechanical strength.

means of solving problems

The inventors of the present application have studied various substituents in polymeric compounds, found that a polymeric compound having a specific structure can solve the aforementioned problems, and completed the present invention.

The present invention provides a polymeric compound represented by general formula (I):

[chemical 1]

Wherein, R ¹ and R ² each independently represent any one of the following formulas (R-1) to (R-15),

[Chem 2]

X ¹ and X ² each independently represent a hydrogen atom, an alkyl group, a haloalkyl group, an alkoxy group, a haloalkoxy group, a halogen, a cyano group, or a nitro group; S ¹ and S ² represent each independently, according to the In the way that the carbon atom is not directly connected, the carbon atom is replaced by an oxygen atom, -COO-, -OCO- or -OCOO-, an alkylene group with 2 to 12 carbon atoms, or a single bond; L ¹ means -CH=CH-COO -or -C ₂ H ₄ COO-; L ² and L ³ each independently represent a single bond, -O-, -S-, -OCH ₂ -, -CH ₂ O-, -CO-, -C ₂ H ₄ -, -COO-, -OCO-, -OCOOCH ₂ -, -CH ₂ 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-, -CF _{2 -, -CF 2 O-} , -OCF ₂ -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ - , -CF ₂ CF ₂ -or -C≡C- (wherein, R ¹¹ represents an alkyl group with 1 to 4 carbon atoms); M ¹ represents 1,4-phenylene, 1,4-cyclohexylene, Pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl, tetralin-2,6-diyl or 1,3-dioxane-2,5- Diyl; M ^represents 1,4-phenylene, 1,4-cyclohexylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl, tetra Hydronaphthalene-2,6-diyl, 1,3-dioxane-2,5-diyl, 1,3,5-benzenetriyl, 1,3,4-benzenetriyl, 1,3,4 , 5-benzenetetrayl, 1,3,5-cyclohexanetriyl or 1,3,4-cyclohexanetriyl; M ¹ and M ² can be independently unsubstituted or substituted by alkyl, haloalkyl , alkoxy, halogen, cyano or nitro, p represents 0 or 1, q represents 0, 1, 2 or 3, when q is 0, -(L ³ -S ² -R ² ) ₀ represents hydrogen When atom, q represents 2 or 3, two or three of L ³ , S ² and R ² may be the same or different. The present invention also provides a liquid crystal composition using the compound as a constituent material, and further provides an optically anisotropic body or a liquid crystal device using the liquid crystal composition.

The effect of the invention

The polymerizable compound of the present invention is useful as a constituent material of a 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; the optically anisotropic body using the polymerizable composition has high heat resistance and is useful for applications such as polarizing plates and retardation plates. of.

Detailed ways

In the general formula (I), R ¹ and R ² each independently represent a polymerizable group, and specific examples of the polymerizable group include the following structures:

[Chem 2]

These polymerizable groups are cured by radical polymerization, radical addition polymerization, cationic polymerization and anionic polymerization. Especially in the case of polymerizing with ultraviolet polymerization as the polymerization method, preferred formula (R-1), formula (R-2), formula (R-4), formula (R-5), (R-7), formula ( R-11), formula (R-13) or (R-15), more preferably formula (R-1), formula (R-2), formula (R-7), formula (R-11) or (R -13), more preferably formula (R-1), formula (R-2).

S ¹ and S ² each independently represent a spacer group or a single bond, as a spacer group, preferably an alkylene group or a single bond with 2 to 6 carbon atoms; for the alkylene group, between oxygen atoms On the premise of not being directly connected, the carbon atom may be replaced by an oxygen atom, -COO-, -OCO-, -OCOO-.

L ¹ represents -CH=CH-COO- or -C ₂ H ₄ COO-, and when higher absorbance is required, it is more preferable to have a carbon-carbon double bond conjugated to the biphenyl skeleton and a conjugation that extends π electrons -CH=CH-COO-; for L ² and L ³ , each independently preferably a single bond, -OCH ₂ -, -C ₂ H ₄ -, -CH ₂ O-, -COO-, -OCO- , -OCOOCH ₂ -, -CH ₂ OCOO-, -CH=CH-COO-, -OOC-CH=CH-, -COOC ₂ H ₄ -, -OCOC ₂ H ₄ -, -C ₂ H ₄ OCO-, -C ₂ H ₄ COO-, -CF ₂ O-, more preferably a single bond, -COO-, -OCO-, or -OCH ₂ -, -CH ₂ O- from the viewpoint of inexpensive production and liquid crystal orientation .

^M1 is preferably 1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl; ^M2 is preferably 1,4-phenylene , 1,4-cyclohexylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, 1,3 -Dioxane-2,5-diyl, 1,3,5-benzenetriyl, 1,3,4-benzenetriyl, 1,3,4,5-benzenetetrayl, 1,3,5- Cyclohexanetriyl or 1,3,4-cyclohexanetriyl. p represents 0 or 1, q represents 0, 1, 2 and 3, p=0, q=1 or 2 are particularly preferred.

The compound represented by the general formula (I), more specifically, is preferably a compound represented by the following general formulas (I-1) to (I-24).

[Chem 3]

[chemical 4]

[chemical 5]

The compound of the present invention can be synthesized by the synthesis method described below.

(Preparation method 1) Production of the compound represented by general formula (I-1)

Using 4-bromo-4'-hydroxybiphenyl, tert-butyl acrylate, and a palladium catalyst, a biphenyl derivative (S-1) was obtained by Mirogi-Heck reaction. Further, a biphenyl derivative (S-2) having a methacryloyl group is obtained through an esterification reaction with methacryloyl chloride. Further, trifluoroacetic acid is used to remove the tert-butyl group and transform it into a carboxyl group to obtain a biphenyl derivative (S-3).

[chemical 6]

Then, the target compound (I-1) can be obtained by esterification using a dehydration condensation agent such as 4-(2-acryloyloxy)ethylphenol and dicyclohexylcarbodiimide.

[chemical 7]

(Preparation method 2) Production of the compound represented by the general formula (1-7)

Using 4-bromo-4'-hydroxybiphenyl, tert-butyl acrylate, and a palladium catalyst, a biphenyl derivative (S-1) was obtained by Mirogi-Heck reaction. Further, carry out etherification reaction with 6-chlorohexyl acrylate in the presence of alkali such as potassium carbonate to obtain acryloyl-containing biphenyl derivative (S-4). Further, trifluoroacetic acid is used to remove the tert-butyl group and transform it into a carboxyl group to obtain a biphenyl derivative (S-5).

[chemical 8]

Then, the target compound (I-7) can be obtained by esterification using a dehydration condensation agent such as 4-(2-acryloyloxy)ethylphenol and dicyclohexylcarbodiimide.

[chemical 9]

(Preparation method 3) Production of the compound represented by the general formula (I-16)

Using 4-bromo-4'-hydroxybiphenyl, tert-butyl acrylate, and a palladium catalyst, a biphenyl derivative (S-1) was obtained by Mirogi-Heck reaction. Further, an acryloyl group-containing biphenyl derivative (S-6) is obtained through an esterification reaction with acryloyl chloride. Further, trifluoroacetic acid is used to remove the tert-butyl group and transform it into a carboxyl group to obtain a biphenyl derivative (S-7).

[chemical 10]

Then, 1 mole of phloroglucinol was esterified using 2 moles of acryloyl chloride to obtain a phenol derivative (S-8) having two acryloyl groups. Further, the target compound (I-16) can be obtained by esterification using a dehydration condensation agent such as a biphenyl derivative (S-7) and dicyclohexylcarbodiimide.

[chemical 11]

(Preparation method 4) Production of the compound represented by general formula (I-14)

Using 2-fluoro-4-bromobiphenyl, acetyl chloride and aluminum trichloride to carry out Friedel-Crafts reaction (Friedel-Crafts reaction), further, using performic acid generated from formic acid and hydrogen peroxide, to obtain fluorine Atom-substituted hydroxybiphenyl compound (S-10). Further, utilize tert-butyl acrylate and palladium catalyst to obtain biphenyl derivative (S-11) by Mirōgi-Heck reaction, and further, obtain biphenyl derivative (S-11) by using palladium-carbon contact hydrogen reduction ( S-12). Then, carry out etherification reaction with 6-chlorohexyl acrylate in the presence of alkali such as potassium carbonate to obtain acryloyl-containing biphenyl derivative (S-13). Further, trifluoroacetic acid is used to remove the tert-butyl group and transform it into a carboxyl group to obtain a biphenyl derivative (S-14).

[chemical 12]

Then, a biphenyl derivative (S-15) having an acryloyl group is obtained by esterification using 4'-hydroxybiphenylcarboxylic acid and hydroxyethyl acrylate with a dehydration condensation agent such as dicyclohexylcarbodiimide. Further, the target compound (I-14) can be obtained by esterification using biphenyl derivatives (S-14) and (S-15) with a dehydration condensation agent such as dicyclohexylcarbodiimide.

[chemical 13]

(Preparation method 5) preparation of compound shown in general formula (I-21)

Etherification reaction of 3-ethyl-3-hydroxymethyloxetane (trade name EOXA, manufactured by Toagosei Co., Ltd.) and 1-bromo-3-chloropropane in the presence of a base such as sodium hydroxide , to obtain the oxetane derivative (S-16). Furthermore, a biphenyl derivative (S-12) was obtained. Then, the biphenyl derivative (S-1) and the oxetane derivative (S-16) are subjected to an etherification reaction in the presence of a base such as potassium carbonate, and further passed through trifluoroacetic acid to make tert-butyl The group is removed to obtain a biphenyl derivative (S-18) containing an oxetanyl group and a carboxyl group.

[chemical 14]

Then, hydroquinone monotetrahydropyranyl ether and oxetane derivative (S-16), which are the reaction products of hydroquinone and 3,4-dihydro-2H-pyran, were The etherification reaction is carried out in the presence of a base such as potassium carbonate, and the protecting group of phenol is further removed with hydrochloric acid to obtain a phenol derivative (S-19). Further, the target compound (1-21) can be obtained by subjecting the biphenyl derivatives (S-18) and (S-19) to esterification using a dehydration condensation agent such as dicyclohexylcarbodiimide.

[chemical 15]

(Preparation method 6) Production of the compound represented by the general formula (I-9)

Use 4-benzyloxybenzoic acid, 4-(3-chlorinated propionyloxy) ethylphenol, and dehydration condensation agents such as dicyclohexylcarbodiimide to obtain phenylbenzoate derivatives through esterification (S-20). Then, the phenol derivative (S-21) was obtained by catalytic hydrogen reduction using palladium carbon. Further, an acryloyl-containing phenol derivative (S-22) was obtained by de-HCl reaction using excess triethylamine.

[chemical 16]

Then, the target compound (I-9 ).

[chemical 17]

The compound of the present invention can be used in nematic liquid crystal, smectic liquid crystal, chiral nematic liquid crystal, chiral smectic liquid crystal and cholesteric liquid crystal composition. In the liquid crystal composition of the present invention, in addition to using one or more compounds of the present invention, other polymerizable compounds may be added within an arbitrary range. The polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition of the present invention is particularly preferably a compound containing an acryloyloxy group or a methacryloyloxy group as a polymerizable functional group. Furthermore, the polymerizable liquid crystal compound is preferably a compound having two or more polymerizable functional groups in the molecule. In addition, when the liquid crystal composition of the present invention is a cholesteric liquid crystal, it is preferable to add a chiral compound. Furthermore, a liquid crystal composition having no polymerizable group, especially a material useful for a polymer-stabilized liquid crystal device can also be added.

Specific examples of polymerizable compounds other than the present invention are not particularly limited except for the compound represented by the general formula (I); as a polymerizable liquid crystal compound used in combination, it is preferable that the compound contains an acryloyloxy group (R-1 ) or methacryloyloxy (R-2), more preferably two or more polymerizable functional groups in the molecule.

The polymerizable liquid crystal compound used in combination is specifically a compound represented by the general formula (II).

[chemical 18]

Among them, in the formula, A is H, F, Cl, CN, SCN, OCF ₃ , an alkyl group containing 1 to 12 carbon atoms, and when the oxygen atoms are not directly connected to each other, the carbon atoms can also be replaced by oxygen atoms, sulfur atoms, etc. atom, -CO-, -COO-, -OCO-, -OCOO-, -CH=CH-, -C≡C-, or -L ⁶ -S ⁴ -R ⁴ ; R ³ and R ⁴ are A polymerizable group; S ³ and S ⁴ each independently represent a single bond, or an alkylene group containing 1 to 12 carbon atoms, and for one or more -CH ₂ - here, the oxygen atoms are not directly connected to each other When connected, the carbon atoms can be replaced by oxygen atoms, -COO-, -OCO-, -OCOO-; L ⁴ , L ⁵ and L ⁶ each independently represent a single bond, -O-, -S-, - OCH ₂ -, -CH ₂ O-, -CO-, -COO-, -OCO-, -OCOOCH ₂ -, -CH ₂ 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-, -C ₂ H ₄ -, -CF=CH-, -CH=CF-, -CF ₂ -, -CF ₂ O- , -OCF ₂ -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -CF ₂ CF ₂ -, or -C≡C- (wherein, R ¹¹ represents an alkyl group having 1 to 4 carbon atoms) ; M ³ and M ⁴ independently represent 1,4-phenylene, 1,4-cyclohexylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6- Diyl, tetrahydronaphthalene-2,6-diyl or 1,3-dioxane-2,5-diyl; M ³ and M ⁴ can be independently unsubstituted or replaced by alkyl, haloalkyl, alkane Oxygen, haloalkoxy, halogen, cyano or nitro; n represents 0, 1, 2 or 3. When n represents 2 or 3, the two or three ^L5 and ^M4 present may be the same or different.

As a particularly preferred compound, such a compound is preferred: L ⁴ , L ⁵ and L ⁶ each independently represent a single bond, -O-, -COO- or -OCO-, M ³ and M ⁴ each independently represent 1, 4-phenylene, 1,4-cyclohexylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl.

The compound represented by the general formula (II), specifically, is preferably a compound represented by the general formula (II-1) to general formula (II-22).

[chemical 19]

[chemical 20]

[chem 21]

In the formula, m and 1 represent an integer of 0 to 12, but when it is 0, the oxygen atom bonded to the aromatic ring is removed. In addition, as the polymerizable liquid crystal compound used in the liquid crystal composition of the present invention, in order to adjust the liquid crystal temperature range and birefringence, and to lower the viscosity, it is preferable to mix general formulas (III-1) to (III-11).

[chem 22]

[chem 23]

In the formula, m and 1 represent an integer of 0 to 12, but when it is 0, the oxygen atom bonded to the aromatic ring is removed. When the liquid crystal composition of the present invention is a cholesteric liquid crystal, a chiral compound is usually added, and specific compounds are represented by general formulas (IV-1) to (IV-7). The compounding amount of the chiral compound is preferably 0.5 to 30% by weight, more preferably 2 to 20% by weight, based on the liquid crystal composition.

[chem 24]

In addition, a liquid crystal composition without a polymerizable group can be added to the liquid crystal composition of the present invention; examples of liquid crystals used in common liquid crystal devices such as STN (super twisted nematic) liquid crystals, TN (twisted nematic) liquid crystals, TFT (thin film Transistors) Nematic liquid crystal compositions, ferroelectric liquid crystal compositions, etc. used in liquid crystals and the like.

In addition, a compound that has a polymerizable functional group and does not exhibit liquid crystallinity may also be added. As such a compound, generally, as long as it is recognized as a polymer-forming monomer or a polymer-forming oligomer in the technical field, it can be used without particular limitation. volume needs to be adjusted.

Since the liquid crystal composition of the present invention has a biphenyl skeleton in which π electrons are extensively conjugated, it can be polymerized by heat and light without adding a polymerization initiator, but it is preferable to add a photopolymerization initiator. The concentration of the photopolymerization initiator to be added is preferably 0.1 to 10% by mass, more preferably 0.2 to 10% by mass, particularly preferably 0.4 to 5% by mass. Examples of the photoinitiator include benzoin ethers, benzophenones, acetophenones, biphenyl ketals, acylphosphine oxides, and the like.

Moreover, in order to improve the storage stability of the liquid crystal composition of this invention, you may add a stabilizer there. Examples of usable stabilizers include hydroquinones, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, β-naphthylamines, β-naphthols, nitroso compounds, etc. The amount added when using a stabilizer is preferably in the range of 0.005 to 1% by mass, more preferably 0.02 to 0.5% by mass, particularly preferably 0.03 to 0.1% by mass, based on the liquid crystal composition.

In addition, when using the liquid crystal composition of the present invention as a raw material for retardation films, polarizing films, and alignment films, or for applications such as printing inks, paints, and protective films, metals, metal complexes, etc. can also be added depending on the purpose. dyes, pigments, pigments, fluorescent materials, phosphorescent materials, surfactants, leveling agents, thixotropic agents, gelling agents, polysaccharides, ultraviolet absorbers, infrared absorbers, antioxidants, ion exchange resins, titanium dioxide and other metal oxides.

Next, the optically anisotropic body of the present invention will be described. The optically anisotropic body produced by polymerizing the liquid crystal composition of the present invention can be used in various applications. For example, when the polymerizable liquid crystal composition of the present invention is polymerized in a non-aligned state, it can be used as a light-scattering plate, a depolarizing plate, or a Moire preventing plate. In addition, an optically anisotropic body produced by polymerizing the polymerizable liquid crystal composition of the present invention in an aligned state has optical anisotropy in terms of physical properties and is useful. Such an optically anisotropic body can be produced, for example, by carrying the surface of the polymerizable liquid crystal composition of the present invention on a substrate subjected to rubbing treatment with cloth or the like, or by covering the surface of a substrate on which an organic thin film has been formed with cloth or the like. The liquid crystal of the present invention is polymerized after being sandwiched between substrates on a rubbing-treated substrate or a substrate having an alignment film on which SiO ₂ is obliquely vapor-deposited.

Examples of methods for supporting the polymerizable liquid crystal composition on a substrate include spin coating, die coating, extrusion coating, roll coating, wire bar coating, gravure coating, and spray coating. , dip coating method, printing coating method, etc. In addition, at the time of coating, the polymerizable liquid crystal composition may be used as it is, or an organic solvent may be added. Examples of organic solvents include ethyl acetate, tetrahydrofuran, toluene, hexane, methanol, ethanol, dimethylformamide, methylene chloride, isopropanol, acetone, methyl ethyl ketone, acetonitrile, cellosolve, cyclohexanone, γ-butyrolactone, acetate-2-ethoxyethane, propylene glycol monomethyl ether acetate, N-methylpyrrolidones. These may be used alone or in combination, and may be appropriately selected according to the vapor pressure and solubility of the polymerizable liquid crystal composition. In addition, the added amount thereof is preferably 90% by weight or less. As a method of volatilizing the added organic solvent, natural drying, heating drying, reduced-pressure drying, and reduced-pressure heating drying can be used. In order to further improve the coatability of the polymerizable liquid crystal material, it is effective to provide an intermediate layer such as a polyimide film on the substrate, or to add a leveling agent to the polymerizable liquid crystal material. Providing an intermediate layer such as a polyimide film on the substrate is also effective as a means for improving the adhesion when the adhesiveness between the optically anisotropic body obtained by polymerizing the polymerizable liquid crystal material and the substrate is poor.

As a method of sandwiching the liquid crystal composition between the substrates, an injection method utilizing a capillary phenomenon is mentioned. It is also effective to depressurize the space formed between the substrates and then inject the liquid crystal material.

Examples of alignment treatments other than rubbing treatment or oblique vapor deposition of SiO ₂ include flow alignment using a liquid crystal material, and using an electric field or a magnetic field. These orientation means may be used alone or in combination. Furthermore, as an alignment treatment method instead of rubbing, a photo-alignment method can also be used. The method is, for example, by irradiating polarized light, preferably polarized ultraviolet rays, on an organic film having a photodimerization functional group in the molecule, an organic film having a photoisotropic functional group, or an organic film such as polyimide, such as polyvinyl cinnamate. On, an alignment film is formed. In this photo-alignment method, since an alignment pattern can be easily realized by selecting a photomask, the molecular alignment inside the optically anisotropic body can also be precisely controlled.

As the shape of the substrate, in addition to a flat plate, a curved surface may also be used as a constituent. As the material constituting the substrate, both organic and inorganic materials can be used. Examples of organic materials constituting the substrate material include polyethylene terephthalate, polycarbonate, polyimide, polyamide, polymethyl methacrylate, polystyrene, polyvinyl chloride, poly Tetrafluoroethylene, polychlorotrifluoroethylene, polyarylate, polysulfone, triacetyl cellulose, cellulose, polyether ether ketone, etc., and examples of inorganic materials 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 film such as a polyimide film or a polyvinyl alcohol film may be formed on the surface of the substrate by a known method and then rubbed with a cloth or the like. In addition, a polyimide film for providing a pretilt angle used in a general TN liquid crystal device or an STN liquid crystal device is more preferable because it can further finely control the molecular orientation structure inside the optical anisotropic body.

In addition, when the orientation state is controlled by an electric field, a substrate having an electrode layer is used. In such a 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 liquid crystal composition of the present invention, since rapid polymerization is desired, a method of polymerizing by irradiating active energy rays such as ultraviolet rays or electron beams is preferable. When ultraviolet light is used, either a polarized light source or a non-polarized light source may be used. In addition, when polymerization is performed with the liquid crystal composition sandwiched between two substrates, at least the substrate on the irradiated side must have appropriate translucency with respect to active energy rays. In addition, it is also possible to use a method of polymerizing only a specific portion using a mask during light irradiation, changing the orientation state of the unpolymerized portion by changing conditions such as an electric field, a magnetic field, or temperature, and further irradiating active energy rays to perform polymerization. In addition, the temperature at the time of irradiation is preferably within a temperature range capable of maintaining the liquid crystal composition of the present invention in a liquid crystal state. In particular, when an optically anisotropic body is to be produced by photopolymerization, it is preferable to polymerize at a temperature as close to room temperature as possible, that is, typically, at a temperature of 25° C., from the viewpoint of avoiding undesired thermal polymerization . The intensity of the active energy rays is preferably 0.1 mW/cm ² to 2 W/cm ² . When the intensity is less than 0.1 mW/cm ² , it takes a long time to complete the photopolymerization and the productivity deteriorates, and when it is more than 2 W/cm ² , the polymerizable liquid crystal compound or the polymerizable liquid crystal composition may deteriorate.

The optically anisotropic body of the present invention obtained by polymerization may be subjected to heat treatment in order to reduce initial characteristic changes and exhibit stable characteristics. The temperature of the heat treatment is in the range of 50 to 250° C., and the preferable heat treatment time is in the range of 30 seconds to 12 hours.

The optically anisotropic body of the present invention produced by this method may be peeled off from the substrate and used alone, or may be used without peeling off. In addition, the obtained optically anisotropic body may be laminated or bonded to another substrate for use.

[Example]

Hereinafter, examples are given to further describe the present invention in detail, but the present invention is not limited by these examples. In addition, "%" in the composition of the following Examples and a comparative example means "mass %".

(Example 1)

10 g (40.1 mmol) of 4-bromo-4′-hydroxybiphenyl, 6.2 g (48.2 mmol) of tert-butyl acrylate, and 4.8 g of triethylamine were placed in a reaction vessel equipped with a stirring device, a cooler, and a thermometer. (48 mmol), 530 mg of palladium acetate, and 300 ml of dimethylformamide, and the reaction was carried out by heating the reactor to 100° C. under a nitrogen atmosphere. After completion of the reaction, ethyl acetate and THF were added, and the organic layer was washed with 10% aqueous hydrochloric acid, pure water, and saturated brine. After distilling off the solvent, purification was carried out with a silica gel column in a double amount (weight ratio) to obtain 11 g of the compound represented by the formula (1).

[chem 25]

Then, 3 g (10.1 mmoles) of the compound represented by the above-mentioned formula (1), 1 g (11 mmoles) of acryloyl chloride, and 50 ml of dichloromethane were charged into a reaction vessel equipped with a stirring device, a cooler, and a thermometer. The reactor was cooled to below 5°C. Then, 1.2 g (12 mmol) of triethylamine was slowly added dropwise. After completion of the dropwise addition, the reaction was carried out at below 20° C. for 3 hours. After the reaction was completed, dichloromethane was added, and the organic layer was washed with 10% aqueous hydrochloric acid, pure water, and saturated brine. After distilling off the solvent, purification was carried out with a silica gel column of double the amount (weight ratio) to obtain 3.6 g of the compound represented by the formula (2).

[chem 26]

Then, in a reaction vessel equipped with a stirring device, a cooler and a thermometer, after dissolving 3.6 g of the compound represented by the above-mentioned formula (2) in 10 ml of dichloromethane, 10 ml of trifluoroacetic acid was added dropwise, and stirred at room temperature for 30 point. Then, 200 ml of ethyl acetate was added, and the organic layer was washed with pure water and saturated brine. The solvent was distilled off to obtain 2.4 g of the compound represented by the formula (3).

[chem 27]

Then, 2.4 g (8.1 mmol) of compounds represented by the above-mentioned formula (3) and 1.7 g (4-hydroxyphenyl) ethyl acrylate ( 9 mmol), dimethylaminopyridine 120 mg, dichloromethane 100 ml, and keep the reaction vessel below 5°C in an ice bath. Under a nitrogen atmosphere, 1.2 g (9.7 mmol) of diisopropylcarbodiimide was slowly added dropwise. After the dropwise addition was completed, the reaction vessel was returned to room temperature and reacted for 5 hours. After filtering the reaction liquid, 200 ml of dichloromethane was added to the filtrate, washed with a 10% aqueous hydrochloric acid solution, and further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After distilling off the solvent, purification was carried out with a silica gel column in an amount (weight ratio) doubled, and recrystallized with dichloromethane/methanol to obtain 3 g of the target compound represented by the formula (1). The compound exhibits a liquid crystal phase in a wide temperature range from 113°C to over 200°C.

[chem 28]

(physical value)

H-NMR (solvent: deuterated chloroform): δ: 2.98(t, 2H), 4.36(t, 2H), 5.82(d, 1H), 6.03-6.18(m, 2H), 6.32-6.44(m, 2H) ), 6.62-6.66 (m, 2H), 7.12 (d, 2H), 7.22-7.33 (m, 4H), 7.65 (m, 6H), 7.88 (d, 1H) C-NMR (solvent: deuterated chloroform) : δ: 34.6, 64.8, 117.0, 121.5, 127.4, 127.9, 128.2, 128.6, 129.7, 130.7, 132.7, 133.0, 135.1, 137.6, 142.3, 145.7, 149.2, 150.2, 165.2

Infrared Absorption Spectrum (IR) (KBr): 2925, 2855, 1760, 1652-1622, 809cm ^-1 Melting point: 113°C

(Example 2)

In the autoclave container equipped with stirring device, the intermediate 4.5g (15.2 mmoles) of embodiment 1 synthesis shown in the charging formula (1), 5% palladium carbon 250mg, tetrahydrofuran 50ml, ethanol 5ml, at 0.3MPa The reduction reaction was carried out in a hydrogen atmosphere (room temperature, 8 hours). After filtering the reaction liquid, the reaction solvent was distilled off to obtain 4.5 g of the compound represented by the formula (5).

[chem 29]

Then, 4.5 g (15.1 mmoles) of the compound represented by the above-mentioned formula (5), 1.6 g (18 mmoles) of acryloyl chloride, and 50 ml of dichloromethane were charged into a reaction vessel equipped with a stirring device, a cooler, and a thermometer. The reactor was cooled to below 5°C under nitrogen atmosphere. Then, 1.8 g (18 mmol) of triethylamine was slowly added dropwise. After completion of the dropwise addition, the reaction was carried out at below 20° C. for 3 hours. After the reaction was completed, dichloromethane was added, and the organic layer was washed with 10% aqueous hydrochloric acid, pure water, and saturated brine. After distilling off the solvent, purification was carried out with a silica gel column in a double amount (weight ratio) to obtain 4.7 g of the compound represented by the formula (6).

[chem 30]

Then, in a reaction vessel equipped with a stirring device, a cooler and a thermometer, after dissolving 4.7 g of the compound represented by the above-mentioned formula (6) in 10 ml of dichloromethane, 10 ml of trifluoroacetic acid was added dropwise, and stirred at room temperature for 30 minute. Then, 200 ml of ethyl acetate was added, and the organic layer was washed with pure water and saturated brine. The solvent was distilled off to obtain 2.7 g of the compound represented by the formula (7).

[chem 31]

Then, 2.7 g (9.1 mmol) of the compound represented by the above-mentioned formula (7) and 1.9 g of 2-(4-hydroxyphenyl) ethyl acrylate were charged into a reaction vessel equipped with a stirring device, a cooler, and a thermometer. (10 mmol), 120 mg of dimethylaminopyridine, and 100 ml of dichloromethane, and keep the reaction vessel below 5°C in an ice bath. Under a nitrogen atmosphere, 1.4 g (11 mmol) of diisopropylcarbodiimide was slowly added dropwise. After the dropwise addition was completed, the reaction vessel was returned to room temperature and reacted for 5 hours. After filtering the reaction liquid, 200 ml of dichloromethane was added to the filtrate, washed with a 10% aqueous hydrochloric acid solution, and further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After the solvent was distilled off, purification was performed with a silica gel column in a double amount (weight ratio), and recrystallization was performed with dichloromethane/methanol to obtain 2.5 g of the target compound represented by the formula (8). This compound exhibits a liquid crystal phase over a wide temperature range from 87°C to 123°C.

[chem 26]

(physical value)

H-NMR (solvent: deuterated chloroform): δ: 2.89-2.98 (m, 4H), 3.11 (t, 2H), 4.33 (t, 2H), 5.80 (dd, 1H), 6.02-6.12 (m, 2H) ), 6.32-6.40(m, 2H), 6.61(dd, 1H), 6.95(d, 2H), 7.20-7.28(m, 4H), 7.32(d, 2H), 7.52(d, 2H), 7.59( d, 2H)

¹³ C-NMR (solvent: deuterated chloroform): δ: 30.6, 34.5, 35.9, 64.8, 121.4, 121.6, 127.1, 127.7, 128.2, 128.7, 129.7, 130.7, 132.5, 135.2, 138.3, 139.1, 149.0, 149.7, 164.3, 165.8, 171.1

Infrared Absorption Spectrum (IR) (KBr): 2925, 2855, 1760, 1652-1622, 809cm ^-1 Melting point: 87°C

(Example 3)

12.8 g (96 mmol) of aluminum trichloride and 100 ml of dichloromethane were added to a reaction vessel equipped with a stirring device, a cooler, and a thermometer, followed by stirring. Then, 8.4 g (110 mmol) of acetyl chloride was slowly added dropwise over 90 minutes, and further, 80 ml of a dichloromethane solution of 20 g (80 mmol) of 4-bromo-2-fluorobiphenyl was slowly added dropwise over 2 hours. After the dropwise addition was completed, stirring was continued for 2 hours to complete the reaction. The reaction solution was slowly poured into 500 ml of ice water, extracted with dichloromethane, and the organic layer was washed with pure water and saturated brine. After distilling off the solvent, drying was performed to obtain 23 g of a compound into which an acetyl group was introduced. Next, 23 g of an acetyl group-introduced compound and 300 ml of formic acid were placed in a reaction vessel equipped with a stirring device, a cooler, and a thermometer, and 20 ml of 34.5% hydrogen peroxide was added, followed by heating to reflux for 6 hours. After the reaction was completed, 450 ml of 10% aqueous sodium bisulfite solution was added to decompose the peroxide, the precipitated solid was filtered, dissolved in ethyl acetate, and the organic layer was washed with water and saturated brine. After the solvent was distilled off, purification was performed with a silica gel column in a double amount (weight ratio) to obtain 18 g of the compound represented by the formula (9).

[chem 27]

4-bromo-3-fluorobiphenyl 10g (37.4 mmol), tert-butyl acrylate 5.7g (44.8 mmol), triethylamine 5.6g ( 56 mmol), palladium acetate 410 mg, dimethylformamide 300 ml, and the reactor was heated to 100° C. under a nitrogen atmosphere to carry out the reaction. After completion of the reaction, ethyl acetate and THF were added, and the organic layer was washed with 10% aqueous hydrochloric acid, pure water, and saturated brine. After distilling off the solvent, purification was carried out with a silica gel column having a double amount (weight ratio) to obtain 10.5 g of the compound represented by the formula (10).

[chem 28]

Then, 10.5 g (33.4 mmoles) of the compound represented by the above-mentioned formula (10), 3.6 g (40 mmoles) of acryloyl chloride, and 100 ml of dichloromethane were charged into a reaction vessel equipped with a stirring device, a cooler, and a thermometer, The reactor was cooled to below 5°C under nitrogen atmosphere. Then, 4 g (40 mmol) of triethylamine was slowly added dropwise. After completion of the dropwise addition, the reaction was carried out at below 20° C. for 3 hours. After the reaction was completed, dichloromethane was added, and the organic layer was washed with 10% aqueous hydrochloric acid, pure water, and saturated brine. After the solvent was distilled off, purification was performed with a silica gel column having a double amount (weight ratio) to obtain 10.5 g of a compound having an acryloyl group.

Next, 10.5 g of the compound having an acryloyl group was dissolved in 20 ml of methylene chloride in a reaction vessel equipped with a stirring device, a cooler, and a thermometer, and then 30 ml of trifluoroacetic acid was added dropwise, followed by stirring at room temperature for 30 minutes. Then, 200 ml of ethyl acetate was added, and the organic layer was washed with pure water and saturated brine. The solvent was distilled off to obtain 8.9 g of the compound represented by the formula (11).

[chem 29]

Then, 8 g (25.6 mmoles) of the compound represented by the above-mentioned formula (11), 4.36 g (25.6 mmoles) of 4-hydroxybiphenyl, dimethyl Aminopyridine 300mg, dichloromethane 150ml, keep the reaction vessel below 5°C in an ice bath. Under a nitrogen atmosphere, 3.8 g (30 mmol) of diisopropylcarbodiimide was slowly added dropwise. After the dropwise addition was completed, the reaction vessel was returned to room temperature and reacted for 5 hours. After filtering the reaction solution, 200 ml of dichloromethane was added to the filtrate, washed with a 10% aqueous hydrochloric acid solution, and further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After distilling off the solvent, purification was carried out with a silica gel column of twice the amount (weight ratio), and recrystallized with dichloromethane/methanol to obtain 9.5 g of the target compound represented by the formula (12). This compound exhibits a liquid crystal phase in a wide temperature range from 164°C to 200°C or higher.

[chem 32]

(physical value)

H-NMR (solvent: deuterated chloroform): δ: 6.04 (d, 1H), 6.32-6.44 (m, 1H), 6.62-6.67 (m, 2H), 7.25-7.28 (m, 4H), 7.34-7.49 (m, 6H), 7.61-7.65 (m, 6H), 7.88 (d, 1H)

¹³ C-NMR (solvent: deuterated chloroform): δ: 115.2, 118.2, 121.4, 121.5, 126.8, 127.0, 127.4, 127.8, 128.4, 129.7, 132.5, 132.0, 135.1, 142.3, 145.7, 149.2, 150.2, 165.2

Infrared absorption spectrum (IR) (KBr): 1760, 1652-1622 ^{, 809cm -1}

Melting point: 164°C

(Example 4)

A polymerizable liquid crystal composition (Composition 1) having the composition shown below was prepared.

[chem 33]

The polymerizable liquid crystal composition has good compatibility stability and shows a nematic liquid crystal phase. 3% of photopolymerization initiator Irgacure 907 (manufactured by Ciba Specialty Chemicals Co., Ltd.) was added to this composition to prepare a polymerizable liquid crystal composition (composition 2). The cyclohexanone solution of this composition 2 was spin-coated on the glass with polyimide, and the result of 120 seconds of ultraviolet radiation of 4mW/cm ² was irradiated on it with a high-pressure mercury lamp, and the composition 2 maintained a uniform Polymerization was carried out in an aligned state to obtain an optically anisotropic body. The surface hardness (according to JIS-SK-5400) of this optically anisotropic body was H. When the phase difference before heating of the obtained optically anisotropic body was 100%, the phase difference after heating at 240° C. for 1 hour was 85%, and the phase difference reduction rate was 15%.

(comparative example 1)

A polymerizable liquid crystal composition (Composition 3) having the composition shown below was prepared.

[chem 34]

Although the polymerizable liquid crystal composition exhibits a nematic liquid crystal phase, its solubility is poor, and crystals are precipitated within 1 hour at room temperature.

(comparative example 2)

A polymerizable liquid crystal composition (Composition 4) having the composition shown below was prepared.

[chem 35]

The polymerizable liquid crystal composition has good compatibility stability and shows a nematic liquid crystal phase. 3% of photopolymerization initiator Irgacure 907 (manufactured by Ciba Specialty Chemicals Co., Ltd.) was added to this composition to prepare a polymerizable liquid crystal composition (composition 5). The cyclohexanone solution of this composition 5 was spin-coated on the glass with polyimide, and the result of 120 seconds of ultraviolet radiation of 4mW/cm ² was irradiated on it with a high-pressure mercury lamp, and the composition 5 maintained a uniform An optically anisotropic body was obtained by polymerization in an aligned state. The surface hardness (according to JIS-SK-5400) of this optically anisotropic body was 2B. When the phase difference before heating of the obtained optically anisotropic body was 100%, the phase difference after heating at 240° C. for 1 hour was 75%, and the phase difference reduction rate was 25%.

It can be seen that Composition 5 of Comparative Example 2 can produce an optically anisotropic body with a higher retardation reduction rate and inferior heat resistance than Composition 2 of the present invention. Furthermore, the surface hardness was 2B, which was insufficient.

Claims (9)

1. a polymerizable compound, as shown in general formula (I):

Wherein, R ¹and R ²represent any one in following formula (R-1) ~ (R-15) independently of one another,

X ¹and X ²represent hydrogen atom, alkyl, haloalkyl, alkoxyl group, halogenated alkoxy, halogen, cyano group or nitro independently of one another; S ¹represent the alkylidene group of the carbonatoms 2 ~ 12 replaced by-COO-,-OCO-or-OCOO-according to the mode carbon atom directly do not combined between Sauerstoffatom, or singly-bound; S ²represent the alkylidene group of the carbonatoms 2 ~ 12 replaced by Sauerstoffatom ,-COO-,-OCO-or-OCOO-according to the mode carbon atom directly do not combined between Sauerstoffatom; L ¹expression-CH=CH-COO-; L ², L ³represent singly-bound ,-O-,-S-,-OCH independently of one another ₂-,-CH ₂o-,-CO-,-C ₂h ₄-,-COO-,-OCO-,-OCOOCH ₂-,-CH ₂oCOO-,-CO-NR ¹¹-,-NR ¹¹-CO-,-SCH ₂-,-CH ₂s-,-CH=CH-COO-,-OOC-CH=CH-,-COOC ₂h ₄-,-OCOC ₂h ₄-,-C ₂h ₄oCO-,-C ₂h ₄cOO-,-OCOCH ₂-,-CH ₂cOO-,-CH=CH-,-CF=CH-,-CH=CF-,-CF ₂-,-CF ₂o-,-OCF ₂-,-CF ₂cH ₂-,-CH ₂cF ₂-,-CF ₂cF ₂-or-C ≡ C-, in formula, R ¹¹represent the alkyl of carbonatoms 1 ~ 4; M ¹represent Isosorbide-5-Nitrae-phenylene, Isosorbide-5-Nitrae-cyclohexylidene, pyridine-2,5-bis-base, pyrimidine-2,5-bis-base, naphthalene-2,6-bis-base, naphthane-2,6-bis-base or 1,3-diox-2,5-bis-base; M ²represent Isosorbide-5-Nitrae-phenylene, Isosorbide-5-Nitrae-cyclohexylidene, pyridine-2,5-bis-base, pyrimidine-2,5-bis-base, naphthalene-2,6-bis-base, naphthane-2,6-bis-base, 1,3-diox-2,5-bis-base, 1,3,5-benzene three base, 1,3,4-benzene three base, 1,3,4,5-benzene four base, 1,3,5-hexanaphthene three base or 1,3,4-hexanaphthene three base; M ¹and M ²can not be substituted independently of one another or by alkyl, haloalkyl, alkoxyl group, halogen, cyano group or nitro replace, p represent 0 or 1, q represent 1,2 or 3; When q represents 2 or 3,2 of existence or 3 L ³, S ²and R ²can be the same or different.

2. polymerizable compound according to claim 1, wherein, in general formula (I), L ²and L ³represent-O-,-OCH independently of one another ₂-,-CH ₂o-,-COO-,-OCO-,-C ₂h ₄-,-C ≡ C-or singly-bound; M ¹represent Isosorbide-5-Nitrae-cyclohexylidene, Isosorbide-5-Nitrae-phenylene, naphthalene-2,6-bis-base or naphthane-2,6-bis-base; M ²represent Isosorbide-5-Nitrae-phenylene, Isosorbide-5-Nitrae-cyclohexylidene, naphthalene-2,6-bis-base, naphthane-2,6-bis-base, 1,3-diox-2,5-bis-base, 1,3,5-benzene three base, 1,3,4-benzene three base, 1,3,4,5-benzene four base, 1,3,5-hexanaphthene three base or 1,3,4-hexanaphthene three base; M ¹and M ²can be replaced by alkyl, haloalkyl, alkoxyl group, halogenated alkoxy, halogen, cyano group or nitro independently of one another; Q represents 1 or 2.

3. according to the polymerizable compound that claims 1 or 2 is recorded, wherein, in general formula (I), M2 represent be not substituted or by alkyl, haloalkyl, alkoxyl group, halogenated alkoxy, halogen, cyano group or nitro replace 1,4-phenylene, 1,3,5-benzene three base, 1,3,4-benzene three base or 1,3,4,5-benzene four base.

4. according to the polymerizable compound that claims 1 or 2 is recorded, wherein, in general formula (I), R ¹and R ²expression (R-1) or formula (R-2) independently of one another.

5., according to the polymerizable compound that claims 1 or 2 is recorded, wherein, p represents 0.

6. according to the polymerizable compound that claims 1 or 2 is recorded, wherein, S ¹represent singly-bound.

7. a liquid-crystal composition, containing the polymerizable compound that any one in claim 1 ~ 6 is recorded.

8. an optically anisotropic body, the polymkeric substance of the liquid-crystal composition containing polymerizable compound recorded by claim 7 is formed.

9. a liquid crystal display device, is characterized in that, uses the optically anisotropic body that claim 8 is recorded.