JP2010083781A - Polymerizable liquid crystalline compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymerizable liquid crystalline compound that has a high liquid crystal phase transition temperature, large birefringence, high mechanical strength and excellent compatibility with other liquid crystalline compounds. <P>SOLUTION: The polymerizable liquid crystalline compound is exemplified, for example, by the formula. As the polymerizable liquid crystalline compound has a high liquid crystal phase transition temperature, large birefringence, high adhesion to a supporting base material, high hardness and excellent compatibility with other liquid crystalline compound, it is useful as a constituting member of a liquid crystal composition. The polymerizable liquid crystal composition comprising the polymerizable liquid crystalline compound as a constituting member affords an optically anisotropic body that has the high liquid crystal phase transition temperature, large birefringence, high adhesion to a supporting base material and high hardness and exhibits excellent optical properties, and therefore is serviceable for use for a polarizing plate, a retardation plate and the like. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a polymerizable liquid crystal compound, a polymerizable 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 optical properties, the polymerization rate, solubility, melting point, glass transition point of the compound, transparency of the polymer, birefringence, and the adhesion and hardness of the optical anisotropic body using it, etc. It becomes an important factor.

  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 liquid crystal compound described in the cited document has problems such as low solubility. On the other hand, a polymerizable liquid crystal compound having an asymmetric structure in order to improve solubility (see Patent Document 3) has been reported, but it has been improved in terms of solubility compared to conventional polymerizable liquid crystal compounds. However, the liquid crystal phase transition temperature is low, the birefringence is small, and the optical anisotropic body using the compound has problems such as low adhesion to the support substrate and low hardness.

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

  The problem to be solved by the present invention is to provide a polymerizable liquid crystal compound having a high liquid crystal phase transition temperature, a large birefringence, and an excellent solubility with other liquid crystal compounds. When the polymerizable liquid crystal composition used is applied, no repelling or the like is observed, and an optical anisotropic body using the polymerizable liquid crystal composition is provided with good adhesion to the support substrate and high hardness.

  As a result of studying various structures in the polymerizable compound, the present inventors have found that a polymerizable compound having a specific structure can solve the above-mentioned problems, and have completed the present invention.

  The present invention relates to the general formula (I)

(Wherein R ¹ and R ² are each independently a polymerizable group represented by the following structural formula group:

S ¹ and S ² each independently represents an alkylene group, a substituted alkylene group or a single bond, and the alkylene group is not bonded directly to each other, and the carbon atom is replaced with an oxygen atom. L ¹ , L ² , L ³ , L ⁴ and L ⁵ may be independently of each other -O-, -S-, -OCH _2- , -CH ₂ O-, -CO-, -COO -, - OCO -, - OCOOCH 2 -, - CH 2 OCOO -, - CONR 3 -, - NR 3 CO -, - SCH 2 -, - CH 2 S -, - CH = CHCOO -, - OCOCH = CH- _{, -COOCH 2 CH 2 -, -} CH 2 CH 2 OCO -, - OCOCH 2 CH 2 -, - CH 2 CH 2 COO -, - COOCH 2 -, - CH 2 OCO -, - OCOCH 2 -, - CH 2 _{COO -, - OCOOCH 2 CH 2} -, - CH 2 CH 2 OCOO -, - OCOOCH 2 -, - CH 2 OCOO -, - CH 2 OCOCH 2 -, - CH 2 COOCH 2 -, - CH 2 CH 2 -, —CH═CH—, —CF═CH—, —CH═CF or —C≡C— (wherein R ³ represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom), L ² , L ³ and L ⁴ are at least one of -COOCH ₂ CH _2- , -CH ₂ CH ₂ OCO-, -O COCH ₂ CH ₂ -or -CH ₂ CH ₂ COO- represents, 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-diyl group, tetrahydronaphthalene-2,6-diyl group or 1,3-dioxane-2,5-diyl group, but the carbon atom in the group is Independently of each other, they may be unsubstituted or substituted by alkyl groups, halogenated alkyl groups, alkoxy groups, halogen groups, cyano groups or nitro groups, and X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ⁹ and X ¹⁰ each independently represent a hydrogen atom, alkyl group, halogenated alkyl group, alkoxy group, halogen group, cyano group or nitro group. And a polymerizable liquid crystal composition using the compound.

  The polymerizable liquid crystal compound of the present invention is useful as a constituent member of a liquid crystal composition because it has excellent solubility with other liquid crystal compounds. Therefore, the polymerizable liquid crystal compound of the present invention and the optically anisotropic body of the polymerizable liquid crystal composition comprising the compound as a constituent member are useful for applications such as a deflection plate and a retardation plate.

In the general formula (I), R ¹ and R ² are polymerizable groups and are cured by radical polymerization, radical addition polymerization, cationic polymerization, or 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) is preferred, formula (R-1), formula (R-2), formula (R-7), formula (R-11) or formula ( R-13) is more preferred, and formula (R-1) or formula (R-2) is particularly preferred.

S ¹ and S ² each independently represent an alkylene group, a substituted alkylene group or a single bond, but the carbon atom may be replaced with an oxygen atom as the oxygen atoms in the group are not directly bonded to each other. An alkylene group having 18 carbon atoms is preferable, and an alkylene group having 2 to 8 carbon atoms is more preferable from the viewpoint of liquid crystallinity and compatibility with other liquid crystal compounds.

L ¹ , L ² , L ³ , L ⁴ and L ⁵ are independently of each other -O-, -S-, -OCH _2- , -CH ₂ O-, -CO-, -COO-, -OCO-, _{-OCOOCH 2 -, - CH 2 OCOO} -, - CONR 3 -, - NR 3 CO -, - SCH 2 -, - CH 2 S -, - CH = CHCOO -, - OCOCH = CH -, - COOCH 2 CH 2 _{-, - CH 2 CH 2 OCO} -, - OCOCH 2 CH 2 -, - CH 2 CH 2 COO -, - COOCH 2 -, - CH 2 OCO -, - OCOCH 2 -, - CH 2 COO -, - OCOOCH 2 _{CH 2 -, - CH 2 CH} 2 OCOO -, - OCOOCH 2 -, - CH 2 OCOO -, - CH 2 OCOCH 2 -, - CH 2 COOCH 2 -, - CH 2 CH 2 -, - CH = CH-, -CF = CH-, -CH = CF or -C≡C- (wherein R ³ represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom), L ² , L ³ and L ⁴ At least one of them represents -COOCH ₂ CH _2- , -CH ₂ CH ₂ OCO-, -OCOCH ₂ CH ₂ -or -CH ₂ CH ₂ COO-, but L ³ is -COOCH in terms of solubility. ₂ CH _2- , -CH ₂ CH ₂ OCO-, -OCOCH ₂ CH ₂ -or -CH ₂ CH ₂ COO- are preferred, and L ¹ , L ² , L ⁴ and L ⁵ are independently of each other -O-, -S-, -OCH _2- , -CH ₂ O-, -CO-, -COO-, -OCO-, -CH = CHCOO- or -O It preferably represents COCH = CH-.

M ¹ and M ² are preferably each independently 1,4-phenylene group or 1,4-cyclohexylene group.

X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ⁹ and X ¹⁰ are a hydrogen atom, alkyl group, halogenated alkyl group, alkoxy group, halogen group, cyano group Or a nitro group, preferably a hydrogen atom, or any ^one of X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ⁹ and X ¹⁰ It is also preferred that one is a methoxy group or a fluorine atom.

  Specifically, the compounds represented by the general formula (I) are particularly preferably compounds represented by the following general formulas (I-1) to (I-22).

  In the formula, n represents an integer of 2 to 18, and an integer of 2 to 8 is preferable.

  In the present invention, production examples of the compound represented by the general formula (I) will be given below. Of course, the gist and scope of the present invention are not limited by these production examples.

  The compound (I) of the present invention can be produced, for example, as follows.

  Formula (II)

(In the formula, R ¹ , S ¹ , L ¹ , L ² , M ¹ , X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ represent the same meaning as in general formula (I).) A naphthoic acid derivative represented by an acid catalyst such as p-toluenesulfonic acid or dicyclohexylcarbodiimide (DCC), 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (WSC), diisopropylcarbodiimide (DIC) In the presence of a dehydration condensing agent such as a carbodiimide derivative such as ethyl azodicarboxylate (DEAD) or an azodicarboxylic acid ester such as isopropyl azodicarboxylate (DIAD), the general formula (III)

(Wherein R ² , S ² , L ⁴ , L ⁵ , M ² , X ⁷ , X ⁸ , X ⁹ and X ¹⁰ have the same meaning as in general formula (I)). By acting with a derivative, the general formula (Ia)

(Where R ¹ , R ² , S ¹ , S ² , L ¹ , L ² , L ⁴ , L ⁵ , M ¹ , M ² , X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ⁹ and X ¹⁰ represent the same meaning as in general formula (I)).

  Alternatively, the general formula (IV)

(In the formula, R ¹ , S ¹ , L ¹ , L ² , M ¹ , X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ represent the same meaning as in general formula (I).) A naphthol derivative represented by the formula: acid catalyst such as p-toluenesulfonic acid or dicyclohexylcarbodiimide (DCC), 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (WSC), diisopropylcarbodiimide (DIC), etc. In the presence of a dehydration condensing agent such as carbodiimide derivatives of azodicarboxylates such as ethyl azodicarboxylate (DEAD) and isopropyl azodicarboxylate (DIAD)

(Wherein R ² , S ² , L ⁴ , L ⁵ , M ² , X ⁷ , X ⁸ , X ⁹ and X ¹⁰ represent the same meaning as in general formula (I)). By reacting with an acid derivative, the general formula (Ib)

(Where R ¹ , R ² , S ¹ , S ² , L ¹ , L ² , L ⁴ , L ⁵ , M ¹ , M ² , X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ⁹ and X ¹⁰ represent the same meaning as in general formula (I)).

  Or the general formula (VI)

(Wherein X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ have the same meaning as in general formula (I)), 6-hydroxy-2-naphthoic acid represented by p -In the presence of an acid catalyst such as toluenesulfonic acid, general formula (VII)

(Wherein, X ⁵ , X ⁶ , X ⁷ and X ⁸ represent the same meaning as in general formula (I)), and 4-hydroxyphenethyl alcohol represented by acid catalyst such as p-toluenesulfonic acid is present. Under dehydration condensation, general formula (VIII)

(Wherein, X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ and X ⁸ represent the same meaning as in general formula (I)). To this, the general formula (IX)

(Wherein R ¹ , S ¹ , L ¹ , and M ¹ have the same meaning as in general formula (I)), a carboxylic acid derivative represented by an acid catalyst such as p-toluenesulfonic acid or dicyclohexyl Carbodiimide derivatives such as carbodiimide (DCC), 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (WSC), diisopropylcarbodiimide (DIC) or ethyl azodicarboxylate (DEAD), isopropyl azodicarboxylate (DIAD) By reacting in the presence of a dehydration condensing agent such as azodicarboxylic acid ester such as general formula (Ic)

(Wherein R ¹ , S ¹ , S ² , L ¹ , M ¹ , X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ and X ⁸ are as in general formula (I) A polymerizable liquid crystal compound represented by the same meaning can also be obtained.

  Or the general formula (X)

(Wherein Z ¹ represents a protecting group such as a benzyl group, and X ¹ , X ² , X ³ and X ⁴ have the same meaning as in general formula (I)), a naphthoic acid derivative represented by General formula (XI) in the presence of an acid catalyst such as p-toluenesulfonic acid

(Wherein Z ² represents a protecting group such as a benzyl group, and X ⁵ , X ⁶ , X ⁷ and X ⁸ have the same meaning as in general formula (I)), By dehydration condensation in the presence of an acid catalyst such as p-toluenesulfonic acid, general formula (XII)

(Wherein Z ¹ represents the same meaning as in general formula (X), Z ² represents the same meaning as in general formula (XI), and X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ and X ⁸ represent the same meaning as in general formula (I)). By deprotecting this, a compound represented by the general formula (VIII) can also be obtained.

  Or the general formula (XIII)

(Wherein Z ³ represents a protecting group such as an alkyl group, and X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ have the same meaning as in general formula (I)). The compound represented by the general formula (VIII) can also be obtained by transesterifying the naphthoic acid derivative with 4-hydroxyphenethyl alcohol (VII) in the presence of a transesterification catalyst such as dialkyltin oxide.

  Next, the polymerizable liquid crystal composition of the present invention will be described. The polymerizable liquid crystal composition of the present invention is preferably prepared so as to exhibit a smectic A phase or a nematic phase at room temperature. Specifically, it is preferable that the smectic A phase or the nematic phase is maintained even at 35 ° C. or lower, preferably 30 ° C. or lower, more preferably 25 ° C. or lower. 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. As such a bifunctional or higher compound, the general formula (A)

(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 hydrogen atoms of the three 1,4-phenylene groups present in the formula are each independently an alkyl group having 1 to 7 carbon atoms, An alkoxy group, an alkanoyl group, a cyano group, or a halogen atom may be substituted by one or two or more). Among the compounds represented by the general formula (A), compounds represented by the general formula (A-1) to the general formula (A-8) are particularly preferable.

(Wherein, r and s have the same meaning as in general formula (A).)
r and s are each independently preferably an integer of 3 to 6.

  In addition, the general formula (B)

(W ³ and W ⁴ are each independently a single bond, —O—, —COO— or —OCO—, Y ⁵ is —COO— or —OCO—, and p and q are each independently Each of the three kinds of 1,4-phenylene groups present in the formula is independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group, an alkanoyl group, or a cyano group. Alternatively, one or two or more halogen atoms may be substituted.) Is also preferred. Among the compounds represented by the general formula (B), compounds represented by the general formula (B-1) to the general formula (B-8) are particularly preferable.

(Wherein p and q represent the same meaning as in general formula (B).)
Among these compounds, from the viewpoint of heat resistance and durability, general formula (B-2), general formula (B-5), general formula (B-6), general formula (B-9) or general formula ( The compound of B-10) is preferable, and the compound of the general formula (B-2) is particularly preferable.

  In addition to the above, as the polymerizable liquid crystal compound having two or more polymerizable functional groups in the molecule, compounds of general formula (C-1) to general formula (C-10) can be contained.

(In the formula, u and v independently represent an integer of 2 to 18.)
Among these, compounds of general formula (C-2) and general formula (C-3) are preferable. u and v are preferably an integer of 3 to 18, more preferably an integer of 3 to 8, and particularly preferably 3 to 6.

  Furthermore, for the purpose of adjusting the liquid crystal temperature range and birefringence, and reducing viscosity, the general formula (D)

(In the formula, e represents an integer of 0 to 18, but when e is 0 or 1, f represents 0, or when e represents an integer of 2 to 18, f represents 0 or 1, i represents Represents an integer of 0 to 2, and each of rings C, D and E independently represents 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, Represents a fluorene 2,7-diyl group, the 1,4-phenylene group, Trahydronaphthalene-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 as one or more F, Cl, CF ₃ , OCF ₃ or CH ₃ and 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 1 to 18 carbon atoms An alkyl group of Represents an alkenyl group having 2 to 18 carbon 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 CF ₃ , wherein one or more CH ₂ groups present in the alkyl or alkenyl group are substituted with O, CO or COO as O atoms are not directly bonded to each other May be. It is also possible to add a monofunctional polymerizable liquid crystal compound represented by The addition amount is preferably 50% or less, more preferably 30% or less, and particularly preferably 15% or less. Among the compounds represented by the general formula (D), compounds represented by the general formula (D-1) to the general formula (D-11) are particularly preferable.

(Wherein e and f represent the same meaning as in general formula (D), and R represents an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 2 to 12 carbon atoms.)
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.

  The concentration of the photopolymerization initiator in the polymerizable liquid crystal composition of the present invention is preferably 0.1 to 10%, more preferably 0.2 to 5%. 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, nitroso compounds, and the like. . When the stabilizer is used, the addition amount is preferably 0.005 to 1%, more preferably 0.02 to 0.5% 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 element, for example, a substrate a polymerizable liquid crystal composition surface, substrate was rubbed with a cloth or the like, or the formed surface of the substrate and the organic thin film was rubbed with a cloth or the like of the present invention 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, isopropyl alcohol, 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 orientation 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.

  If proper orientation cannot be obtained by rubbing these substrates with a cloth or the like, an organic thin film such as a polyimide thin film or a polyvinyl alcohol thin film is formed on the 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. In addition, when polymerization is performed 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 to 2.0 mW / cm ² . If the intensity is 0.1 mW / cm ² or less, it takes a long time to complete the photopolymerization and the productivity deteriorates. If it is 2.0 W / cm ² or more, the polymerizable liquid crystal compound or the polymerizable liquid crystal 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.

The phase transition temperature was measured using a polarizing microscope equipped with a temperature control stage and a differential scanning calorimeter (DSC). The structure of the compound was confirmed by nuclear magnetic resonance spectrum (NMR), infrared resonance spectrum (IR), gel permeation chromatography (GPC) and the like.
Example 1 6- [4- [2- (acryloyloxy) ethoxy] benzoyloxy] -2-naphthoic acid 2- [4- [4- [2- (acryloyloxy) ethoxy] benzoyloxy] phenyl] ethyl Manufacturing of (IA)

(1-1) Production of methyl 6-hydroxy-2-naphthoate
A mixture of 6-hydroxy-2-naphthoic acid (50.0 g, 0.270 mol), ethanol (300 ml), and concentrated sulfuric acid (20 ml) was heated to reflux for 7 hours. The mixture was allowed to cool to room temperature, poured into water to stop the reaction, and allowed to stand at 5 ° C. overnight. The precipitated solid was collected by filtration and washed with water to give a yellow solid (56.3 g). The obtained solid was purified by recrystallization (dichloromethane + hexane) to obtain a pale yellow solid (51.5 g). (Yield 90%)
(1-2) Production of 2- (4-hydroxyphenyl) ethyl 6-hydroxy-2-naphthoate
Ethylene 6-hydroxy-2-naphthoate (30.0 g, 0.093 mol), 2- (4-hydroxyphenyl) ethanol (14.1 g, 0.100 mol), di-n-butyltin oxide (0.7 g, 0.003 mol) in xylene (200 ml) The mixture was heated to reflux for 21 hours while removing the water from which the mixture was distilled off, and then allowed to stand at 5 ° C. overnight. The precipitated solid was collected by filtration, and the obtained solid was washed with cold methanol to obtain slightly yellow crystals (21.2 g). (Yield 74%)
(1-3) 6- [4- [2- (acryloyloxy) ethoxy] benzoyloxy] -2-naphthoic acid 2- [4- [4- [2- (acryloyloxy) ethoxy] benzoyloxy] phenyl] ethyl Manufacturing of (IA)
4- [2- (acryloyloxy) ethoxy] benzoic acid (17.0 g, 0.072 mol), 2- (4-hydroxyphenyl) ethyl 6-hydroxy-2-naphthoate (10.0 g, 0.032 mol), N, N ′ -A suspension of diisopropylcarbodiimide (DIC, 16.5 g, 0.130 mol) and 4-dimethylaminopyridine (DMAP, 1.0 g, 0.008 mol) in dichloromethane (150 ml) was vigorously stirred at room temperature for 4 hours. The reaction solution was filtered, and then washed with 3M hydrochloric acid, water, 5% aqueous sodium hydrogen carbonate solution and saturated brine in this order. The solvent was distilled off, and the resulting solid was purified using a column (silica gel + alumina / dichloromethane) and further purified by recrystallization (dichloromethane + acetone) to obtain colorless crystals (17.0 g). (Yield 70.0%)
¹ H-NMR (400MHz, CDCl ₃ ) δ (ppm) 3.16 (t, 2H, ArCH ₂ ), 4.29-4.34 (m, 4H, OCH ₂ ), 4.54-4.63 (m, 6H, OCH ₂ ), 5.88 ( ddd, 2H, J ₁ = 10.5Hz, J ₂ = 3.9Hz, J ₃ = 1.5Hz, acryl), 6.18 (ddd, 2H, J ₁ = 17.3Hz, J ₂ = 10.5Hz, J ₃ = 3.7Hz, acryl ), 6.47 (ddd, 2H, J ₁ = 17.3Hz, J ₂ = 3.9Hz, J ₃ = 1.5Hz, acryl), 6.98-7.05 (m, 4H, ArH), 7.16-7.20 (m, 2H, ArH) , 7.36-7.74 (m, 3H, ArH), 7.73 (d, 1H, J = 2.2Hz, ArH), 7.86 (d, 1H, J = 8.5Hz, ArH), 8.00-8.08 (m, 2H, ArH) , 8.14-8.22 (m, 4H, ArH), 8.61 (s, 1H, ArH), phase transition temperature (° C) Cr 142 N 204 Iso
(Example 2)
Polymeric liquid crystal composition showing a nematic phase with low viscosity and wide temperature range (M-1)

The nematic phase upper limit temperature (Tni) was 73.0 ° C.

  Next, 90% of this polymerizable liquid crystal composition (M-1) compound (I-A) obtained in Example 1

When a polymerizable liquid crystal composition (M-2) was prepared by adding 10% of the above compound, it exhibited a nematic phase at room temperature and Tni was 90.0 ° C. When this composition (M-2) was allowed to stand overnight at room temperature, no precipitation was observed, and it was confirmed that its solubility with other compounds was high. Moreover, the Tni was measured and showed a high value without any decrease from the Tni of M-1.
(Comparative Example 1)
Compound (IA) -similar compound (JA) to 90% of the polymerizable liquid crystal composition (M-1) obtained in Example 4

When a polymerizable liquid crystal composition (M-3) was prepared by adding 10% of the above compound, it exhibited a nematic phase at room temperature, Tni was 85.5 ° C., and was 4.5 ° C. lower than the composition (M-2). It was.

As described above, the compound represented by the general formula (I) has good solubility in the polymerizable liquid crystal composition, is stable at room temperature, and is very useful in preparing a liquid crystal composition having a high Tni. I understand.
(Example 3)
Using the compound (IA) obtained in Example 1, a polymerizable liquid crystal composition (M-4) showing a nematic phase having a low viscosity and a wide temperature range

Was prepared. Tni was 135.3 ° C. When this composition (M-4) was allowed to stand at room temperature overnight, no precipitation was observed, and its Tni was measured, but hardly changed. The birefringence (Δn) was 0.191.
(Comparative Example 2)
A polymerizable liquid crystal composition (M-5) showing a nematic phase having a low viscosity and a wide temperature range using the compound (JA) similar to the compound (IA) obtained in Example 1

Was prepared. Tni was 125.9 ° C., which was 9.4 ° C. lower than the liquid crystal composition (M-4). When this composition (M-5) was allowed to stand at room temperature overnight, no precipitation was observed, and its Tni was measured, but hardly changed. Δn was 0.183, 0.008 smaller than (M-4).

As described above, the compound represented by the general formula (I) has a good solubility in the polymerizable liquid crystal composition, is stable at room temperature, has a high Tni, and has a large Δn. It turns out that it is useful.
Example 4
Photopolymerization initiator Irgacure-907 (manufactured by Ciba Specialty Chemicals) 5.0% was added to the polymerizable liquid crystal composition (M-4) obtained in Example 3 to prepare a polymerizable liquid crystal composition (M-6). did. Next, a 2- (1-methoxy) propyl acetate solution (PGMEA solution) containing 20% of this polymerizable liquid crystal composition (M-6) was prepared, and this PGMEA solution was spin coated on a glass substrate with a polyimide alignment film ( 1,300 rpm) for 15 seconds. At this time, no repelling was observed. The polymerizable liquid crystal composition (M-6) was cured by irradiating the spin-coated substrate with ultraviolet rays (30 mW / cm ² , 60 seconds) in a nitrogen atmosphere. When the solid thus obtained was observed under a polarizing microscope, an optical anisotropic body having no alignment defect was obtained. Assuming that the phase difference before heating of the obtained optical anisotropic body was 100%, the phase difference after heating at 240 ° C. for 2 hours was 86%, and the phase difference reduction rate was 14%. Further, the pencil hardness of the obtained solid material (JIS-K-5400 8.4 by pencil scratch test) is 3H, and the cellophane tape peel test (JIS-5400 8.5 adhesion (8.5.2 cross-cut tape method)) is 100. / 100.
(Comparative Example 3)
Immediately after preparing the polymerizable liquid crystal composition (M-5) obtained in Comparative Example 2, 5.0% of photopolymerization initiator Irgacure-907 was added to prepare a polymerizable liquid crystal composition (M-7). Next, a PGMEA solution containing 20% of this polymerizable liquid crystal composition (M-7) was prepared, and this PGMEA solution was spin coated (1,300 rpm / min, 15 seconds) on a glass substrate with a polyimide alignment film. The polymerizable liquid crystal composition (M-7) was cured by irradiating the spin-coated substrate with ultraviolet rays (30 mW / cm ² , 60 seconds) in a nitrogen atmosphere. At this time, no repelling was observed. When the solid thus obtained was observed under a polarizing microscope, an optical anisotropic body having no alignment defect was obtained. Assuming that the phase difference before heating of the obtained optical anisotropic body was 100%, the phase difference after heating at 240 ° C. for 2 hours was 89%, and the phase difference reduction rate was 11%. Further, the obtained solid had a pencil hardness of 2H and a cellophane tape peel test of 100/100. Although it was 3% smaller than the retardation reduction rate of the solid material obtained in Example 4, the pencil hardness was 1H smaller.

  As described above, since the solid containing the compound represented by the general formula (I) is thermally stable, has high adhesion to the support substrate, and has high hardness, the general formula (I) It can be seen that the solid containing the compound represented is very useful in preparing an optically anisotropic body that is thermally stable, has high adhesion to the support substrate, and has high hardness.

Claims (8)

Formula (I)

(Wherein R ¹ and R ² are each independently a polymerizable group represented by the following structural formula group:

S ¹ and S ² each independently represents an alkylene group, a substituted alkylene group or a single bond, and the alkylene group is not bonded directly to each other, and the carbon atom is replaced with an oxygen atom. L ¹ , L ² , L ³ , L ⁴ and L ⁵ may be independently of each other -O-, -S-, -OCH _2- , -CH ₂ O-, -CO-, -COO -, - OCO -, - OCOOCH 2 -, - CH 2 OCOO -, - CONR 3 -, - NR 3 CO -, - SCH 2 -, - CH 2 S -, - CH = CHCOO -, - OCOCH = CH- _{, -COOCH 2 CH 2 -, -} CH 2 CH 2 OCO -, - OCOCH 2 CH 2 -, - CH 2 CH 2 COO -, - COOCH 2 -, - CH 2 OCO -, - OCOCH 2 -, - CH 2 _{COO -, - OCOOCH 2 CH 2} -, - CH 2 CH 2 OCOO -, - OCOOCH 2 -, - CH 2 OCOO -, - CH 2 OCOCH 2 -, - CH 2 COOCH 2 -, - CH 2 CH 2 -, —CH═CH—, —CF═CH—, —CH═CF or —C≡C— (wherein R ³ represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom), L ² , L ³ and L ⁴ are at least one of -COOCH ₂ CH _2- , -CH ₂ CH ₂ OCO-, -O COCH ₂ CH ₂ -or -CH ₂ CH ₂ COO- represents, 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-diyl group, tetrahydronaphthalene-2,6-diyl group or 1,3-dioxane-2,5-diyl group, but the hydrogen atom in the group is Independently of each other, it may be substituted with an alkyl group, a halogenated alkyl group, an alkoxy group, a halogen group, a cyano group or a nitro group, and X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ⁹ and X ¹⁰ each independently represent a hydrogen atom, an alkyl group, a halogenated alkyl group, an alkoxy group, a halogen group, a cyano group or a nitro group. A polymerizable liquid crystal compound represented by The polymerization according to claim 1, wherein S ¹ and S ² are independently of each other and represent an alkylene group having 2 to 10 carbon atoms in which a carbon atom may be replaced with an oxygen atom as oxygen atoms in the group are not directly bonded to each other. Liquid crystal compound. ^2. The polymerizable liquid crystal compound according to claim 1, wherein M ¹ and M ² each independently represent a 1,4-phenylene group or a 1,4-cyclohexylene group. _2. The polymerizable liquid crystal compound according to claim 1, wherein L ³ represents —COOCH ₂ CH ₂ —, —CH ₂ CH ₂ OCO—, —OCOCH ₂ CH ₂ — or —CH ₂ CH ₂ COO—. L ¹ , L ² , L ⁴ and L ⁵ are independently of each other -O-, -S-, -OCH _2- , -CH ₂ O-, -CO-, -COO-, -OCO-, -CH = 2. The polymerizable liquid crystal compound according to claim 1, which represents CHCOO— or —OCOCH═CH—. 6. A polymerizable liquid crystal composition comprising the polymerizable liquid crystal compound according to claim 1. 7. A polymer obtained by polymerizing the polymerizable liquid crystal composition according to claim 6. 8. An optical anisotropic body using the polymer according to claim 7.