JP2007057609A - Retardation film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To reduce film thickness by disposing at least a specific optically anisotropic layer on a support. <P>SOLUTION: A retardation film has at least one optically anisotropic layer on a support, wherein the optically anisotropic layer is a layer formed of at least one of the compounds represented by formulae (I) and (II), wherein A<SP>1</SP>and A<SP>2</SP>each represent C or N; X<SP>1</SP>represents O, S, C or N; and R<SP>1</SP>and R<SP>2</SP>each represent formula (I-A), wherein A<SP>3</SP>-A<SP>10</SP>each independently represent C or N; M<SP>1</SP>represents a single bond, -O-, -O-CO-, -CO-O-, -O-CO-O-, -S-, -C(=O)-, -SO2-, -CH2-CH2-, -CH2-O-, -O-CH2-, -NH-CO-, -S-CO-, -CH=CH- or -C≡C-; L<SP>1</SP>represents a divalent linking group selected from the group consisting of -O-, -O-CO-, -CO-O-, -O-CO-O-, -S-, -C(=O)-, -SO2-, -NH-, -CH2-, -CH=CH- and -C≡C- and combinations of them, when the linking group is an H-containing group, the H may be substituted by a substituent; Q<SP>1</SP>represents a polymerizable group or H; and n represents 1, 2 or 3. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a retardation plate having an optically anisotropic layer containing a liquid crystal compound and a liquid crystal compound used therein, and more particularly to a retardation plate having an optically anisotropic layer.

  A biaxial film using liquid crystal has an advantage that the film thickness can be reduced as compared with a conventional biaxially stretched film, and thus is a useful means for reducing the thickness and weight of a liquid crystal device. The stretched film often has problems that the dimensional stability is poor and the optical performance is easily changed by wet heat or the like. For this reason, development of (polymerizable) biaxial liquid crystals has been demanded.

For example, it is disclosed that a compound having a heterocyclic skeleton exhibits biaxiality (see Non-Patent Documents 1 and 2).
PHYSICAL REVIEW LETTERS 92, 145505, 2004 PHYSICAL REVIEW LETTERS 92, 145506, 2004

  An object of the present invention is to provide a retardation film having a thin film thickness.

The above problems have been solved by the following means.
(1) A layer having at least one optically anisotropic layer on a support, the optically anisotropic layer being formed of at least one compound represented by the following general formulas (I) and (II) A phase difference plate characterized by the above.

(In the general formula (I) and (II), ^{A 1} and ^{A 2} each independently represents a carbon atom or a nitrogen atom, ^{X 1} is represents an oxygen atom, a sulfur atom, a carbon atom or a nitrogen atom, R ¹ and R ² each independently represents the following general formula (IA).

(In General Formula (IA), A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ⁸ , A ⁹ and A ¹⁰ each independently represents a carbon atom or a nitrogen atom, and M ¹ is , Single bond, —O—, —O—CO—, —CO—O—, —O—CO—O—, —S—, —C (═O) —, —SO ₂ —, —CH ₂ —CH _2- , —CH ₂ —O—, —O—CH ₂ —, —NH—CO—, —S—CO—, —CH═CH—, —C≡C—, and L ¹ represents —O— , —O—CO—, —CO—O—, —O—CO—O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH═. Represents a divalent linking group selected from the group consisting of CH— and —C≡C— and combinations thereof, and when the above group is a group containing a hydrogen atom, the hydrogen atom may be replaced by a substituent. Good. , ^{Q 1} represents a polymerizable group or a hydrogen atom, n represents represents 1, 2 or 3.)

  (2) A compound represented by the above general formula (I) or (II).

  According to the present invention, it is possible to provide a retardation plate having a small film thickness. A compound having a specific substituent can provide a retardation plate having a biaxiality and a thin film thickness.

  Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

  The compound of the present invention is represented by the following general formula (I) or (II).

In the general formulas (I) and (II), A ¹ and A ² each independently represent a carbon atom or a nitrogen atom, X ¹ represents an oxygen atom, a sulfur atom, a carbon atom or a nitrogen atom, and R ¹ , R ² each independently represents the following general formula (IA).

When A ¹ and A ² are carbon atoms, the carbon atoms may have a substituent. Here, “the atom may have a substituent” means that the hydrogen atom part bonded to the atom part of the cyclic structure containing the atom may be substituted with another group (The same applies below). Examples of the substituent that the carbon atom may have include an alkyl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, an alkoxycarbonylamino group, an alkylthio group, an arylthio group, and a halogen atom. And cyano group can be mentioned as preferred examples. Among these substituents, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, a halogen atom and a cyano group are more preferable, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and a carbon number Most preferred are an alkoxycarbonyl group having 2 to 12 carbon atoms, an acyloxy group having 2 to 12 carbon atoms, a halogen atom and a cyano group.
A ¹ and A ² each independently represent a carbon atom or a nitrogen atom. At least one of A ¹ and A ² is preferably a nitrogen atom, and more preferably both are nitrogen atoms.
X ¹ represents an oxygen atom, a sulfur atom, a carbon atom or a nitrogen atom, preferably an oxygen atom. In the case of a carbon atom and a nitrogen atom, they are represented by C (R ⁰¹ R ⁰² ) and NR ⁰³ , respectively, and R ⁰¹ , R ⁰² and R ⁰³ are each independently a hydrogen atom or a substituent (the substituent is A ¹ etc. The same as the substituent on the carbon atom).
R < ¹ >, R < ² > represents the said general formula (IA) each independently.

In the general formula ^{(I-A), A 3} , A 4, A 5, A 6, A 7, A 8, A 9, A 10 represents a carbon atom or a nitrogen atom independently. At least 6 of A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ⁸ , A ⁹ , A ¹⁰ are preferably carbon atoms, and more preferably all are carbon atoms. When A ³ , A ⁴ , A ⁵ , A ⁶ and A ⁷ , A ⁸ , A ⁹ , A ¹⁰ are carbon atoms, the carbon atom may have a substituent. Examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, alkyl group having 1 to 16 carbon atoms, alkenyl group having 2 to 16 carbon atoms, carbon An alkynyl group having 2 to 16 atoms, an alkyl group substituted with a halogen having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, an acyl group having 2 to 16 carbon atoms, and 1 to 16 carbon atoms An alkylthio group having 2 to 16 carbon atoms, an alkoxycarbonyl group having 2 to 16 carbon atoms, a carbamoyl group, an alkyl-substituted carbamoyl group having 2 to 16 carbon atoms, and an acylamino group having 2 to 16 carbon atoms. included. Among these, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkyl group substituted with a halogen having 1 to 6 carbon atoms are preferable, a halogen atom, an alkyl group having 1 to 4 carbon atoms, An alkyl group substituted with a halogen having 1 to 4 carbon atoms is more preferable, and a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a trifluoromethyl group are more preferable. M ¹ is a single bond, —O—, —O—CO—, —CO—O—, —O—CO—O—, —S—, —C (═O) —, —SO ₂ —, —CH _{2. -CH 2 -, - CH 2 -O} -, - O-CH 2 -, - NH-CO -, - S-CO -, - CH = CH -, - C≡C- represents, -O in this -, -O-CO-, and -CO-O- are more preferable. * Represents the position bonded to the 5-membered ring in the above general formula (I) or (II). n represents 1, 2 or 3, and 1 is more preferable.

L ¹ in the general formula (IA) represents —O—, —O—CO—, —CO—O—, —O—CO—O—, —S—, —C (═O) —, — It represents a divalent linking group selected from the group consisting of SO ₂ —, —NH—, —CH ₂ —, —CH═CH—, —C≡C—, and combinations thereof. Here, the hydrogen atoms of —NH—, —CH ₂ —, and —CH═CH— may be substituted with a substituent. Examples of such a substituent include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a halogen having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. , An acyl group having 2 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, an acyloxy group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, a carbamoyl group, and 2 to 2 carbon atoms Preferred examples include a carbamoyl group substituted with 6 alkyls and an acylamino group having 2 to 6 carbon atoms, and a halogen atom and an alkyl group having 1 to 6 carbon atoms are more preferred.

L ¹ represents —O—, —O—CO—, —CO—O—, —O—CO—O—, —S—, —C (═O) —, —SO ₂ —, —NH—, — It is preferably selected from the group consisting of CH ₂ —, —CH═CH— and —C≡C— and combinations thereof, more preferably containing —CH ₂ —, and further comprising only —CH ₂ —. preferable. L ¹ represents ¹ to 2 carbon atoms.
It is preferable to contain 0, more preferably 2 to 14 carbon atoms. Further ^{L 1} is, -CH ₂ - preferably contains 1 to 16 a, -CH ₂ - and more preferably contains 2 to 12 a, -CH ₂ - further may contain 2 to 8 preferable.

  When the above group is a group containing a hydrogen atom, the hydrogen atom may be replaced with a substituent. Examples of such a substituent include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a halogen having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. , An acyl group having 2 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, an acyloxy group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, a carbamoyl group, and 2 to 2 carbon atoms Preferred examples include a carbamoyl group substituted with 6 alkyls and an acylamino group having 2 to 6 carbon atoms, and a halogen atom and an alkyl group having 1 to 6 carbon atoms are more preferred.

Q ¹ in the general formula (IA) represents a polymerizable group or a hydrogen atom. When the compound of the present invention is used for an optical film or the like that preferably has a phase difference that does not change due to heat, such as an optical compensation film, Q ¹ is preferably a polymerizable group. The polymerization reaction is preferably addition polymerization (including ring-opening polymerization) or condensation polymerization. That is, the polymerizable group is preferably a functional group capable of addition polymerization reaction or condensation polymerization reaction. Examples of polymerizable groups are shown below.

  Furthermore, the polymerizable group is particularly preferably a functional group capable of addition polymerization reaction. Such a polymerizable group is preferably a polymerizable ethylenically unsaturated group or a ring-opening polymerizable group.

  Examples of the polymerizable ethylenically unsaturated group include the following formulas (M-1) to (M-6).

In formulas (M-3) and (M-4), R represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group.
Among the above formulas (M-1) to (M-6), (M-1) or (M-2) is preferable, and (M-1) is more preferable.

  The ring-opening polymerizable group is preferably a cyclic ether group, more preferably an epoxy group or oxetanyl group, and most preferably an epoxy group.

  Specific examples of the compounds represented by the general formulas (I) and (II) are shown below, but the present invention is not limited thereto.

  Among the compounds represented by the general formulas (I) and (II), the compound represented by the general formula (I) is more preferable.

  The uniformly oriented state of the present invention refers to a monodomain oriented state that is uniform and free of defects. In order to realize such an alignment state, a liquid crystal phase exhibiting good monodomain properties is desirable. When the monodomain property is poor, the resulting structure becomes a polydomain, an orientation defect occurs at the boundary between domains, and light is scattered. When good monodomain properties are exhibited, for example, when used for a phase difference plate, the phase difference plate tends to have a high light transmittance.

  In order to obtain the thin film of the present invention as a uniformly oriented thin film, other additives are added as required for the liquid crystalline compound to form a liquid crystalline composition, and after the liquid crystal composition is applied, it is uniform in the liquid crystal state. Obtained by orientation. Examples of the additive that can be added to the liquid crystal compound include an air interface alignment controller, a repellency inhibitor, a polymerization initiator, and a polymerizable monomer, which will be described later.

In order to realize a uniformly aligned state, it is preferable to provide an alignment film. However, in the case where the optical axis direction of the liquid crystalline compound coincides with the normal direction of the thin film surface (homeotropic alignment), the alignment film is not necessarily required.
The alignment film is an organic compound (eg, ω-tricosanoic acid) formed by rubbing treatment of an organic compound (preferably polymer), oblique deposition of an inorganic compound, formation of a layer having a microgroove, or Langmuir-Blodgett method (LB film). , Methyl stearylate). Furthermore, an alignment film in which an alignment function is generated by application of an electric field, application of a magnetic field, or light irradiation is also known.
Any layer can be used as the alignment film as long as the liquid crystal composition of the present invention can have a desired alignment. In the present invention, an alignment film formed by rubbing treatment or light irradiation is preferable. An alignment film formed by a polymer rubbing treatment is particularly preferable. The rubbing treatment can be generally carried out by rubbing the surface of the polymer layer several times in a certain direction with paper or cloth. In the present invention, in particular, the method described in the liquid crystal manual (Maruzen Co., Ltd.) is used. Preferably it is done. The thickness of the alignment film is preferably 0.01 to 10 μm, and more preferably 0.05 to 3 μm.

In the present invention, the state in which the orientation state is fixed is a state in which the orientation is maintained, which is the most typical and preferred embodiment, but is not limited thereto, and is 0 ° C. to 50 ° C. under normal conditions. The conditions of −30 ° C. to 70 ° C. are preferable under more severe conditions. In such a temperature range, the fixed liquid crystal composition has no fluidity, and the fixed alignment form can be kept stable without causing a change in the alignment form due to an external field or an external force. It refers to the state. When the alignment state is finally fixed and an optically anisotropic layer is formed, the liquid crystalline composition of the present invention does not need to exhibit liquid crystallinity. For example, since a compound having a polymerizable group is used as the liquid crystal compound, as a result, the polymerization or the cross-linking reaction proceeds by reaction with heat, light, etc., and the liquid crystallinity may be lost by increasing the molecular weight.
Examples of additives that can be added to the liquid crystalline composition of the present invention in forming the optically anisotropic layer include an air interface alignment controller, a repellency inhibitor, a polymerization initiator, and a polymerizable monomer.

[Air interface alignment control agent]
The liquid crystal composition is aligned at the tilt angle of the air interface at the air interface. The tilt angle varies depending on the type of liquid crystal compound contained in the liquid crystal composition, the type of additive, and the like. Therefore, it is necessary to arbitrarily control the tilt angle of the air interface according to the purpose.

  For controlling the tilt angle, for example, an external field such as an electric field or a magnetic field or an additive (air interface alignment control agent) can be used, and an additive is preferably used. Examples of such an additive include a substituted or unsubstituted aliphatic group having 6 to 40 carbon atoms, or a substituted or unsubstituted aliphatic substituted oligosiloxanoxy group having 6 to 40 carbon atoms in the molecule. A compound having one or more is preferable, and a compound having two or more in the molecule is more preferable. For example, a hydrophobic excluded volume effect compound described in JP-A No. 2002-20363 can be used as the air interface alignment control agent.

  The addition amount of the alignment control additive on the air interface side is preferably 0.001% by mass to 20% by mass, and more preferably 0.01% by mass to 10% by mass with respect to the liquid crystalline composition of the present invention. 0.1 mass% to 5 mass% is most preferable.

[Anti-repellent agent]
As a material for adding to the liquid crystal composition of the present invention and preventing repelling at the time of application of the composition, generally, a polymer compound can be suitably used.
There is no restriction | limiting in particular as a polymer to be used unless the inclination-angle change and orientation of the liquid crystalline composition of this invention are inhibited significantly.
Examples of the polymer are described in JP-A-8-95030, and particularly preferred specific polymer examples include cellulose esters. Examples of cellulose esters include cellulose acetate, cellulose acetate propionate, hydroxypropyl cellulose, and cellulose acetate butyrate.
In order not to disturb the alignment of the liquid crystalline composition of the present invention, the amount of the polymer used for the purpose of preventing repellency is generally in the range of 0.1 to 10% by mass with respect to the liquid crystalline composition of the present invention. More preferably, it is in the range of 0.1 to 8% by mass, and further preferably in the range of 0.1 to 5% by mass.

[Polymerization initiator]
In the present invention, the alignment state is fixed, for example, by heating the liquid crystalline composition once to the liquid crystal phase formation temperature and then cooling it while maintaining the alignment state, without impairing the alignment form in the liquid crystal state. It can be formed by immobilization. Moreover, after heating the composition which added the polymerization initiator to the liquid crystalline composition of this invention to liquid crystal phase formation temperature, it superposes | polymerizes and cools and can form by fixing the orientation state of a liquid crystal state. In the present invention, the alignment state is preferably fixed by the latter polymerization reaction. The polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator, a photopolymerization reaction using a photopolymerization initiator, and a polymerization reaction by electron beam irradiation. In order to prevent the support and the like from being deformed or altered by heat. Also, a photopolymerization reaction or a polymerization reaction by electron beam irradiation is preferable.

Examples of the photopolymerization initiator include α-carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ether (described in US Pat. No. 2,448,828), α-hydrocarbon substituted aromatic acyloin. Compound (described in US Pat. No. 2,722,512), polynuclear quinone compound (described in US Pat. Nos. 3,046,127 and 2,951,758), a combination of triarylimidazole dimer and p-aminophenyl ketone (US Pat. No. 3,549,367) Description), acridine and phenazine compounds (JP-A-60-105667, U.S. Pat. No. 4,239,850), oxadiazole compounds (U.S. Pat. No. 4,212,970), and the like.
The amount of the photopolymerization initiator used is preferably 0.01 to 20% by mass, more preferably 0.5 to 5% by mass, based on the solid content of the coating liquid for the optically anisotropic layer.

It is preferable to use ultraviolet rays for light irradiation for polymerization. The irradiation energy is preferably 10mJ~50J / cm ^2, further preferably 50mJ~800mJ / cm ^2. In order to accelerate the photopolymerization reaction, light irradiation may be performed under heating conditions. Further, since the oxygen concentration in the atmosphere is related to the degree of polymerization, when the desired degree of polymerization is not reached in the air, it is preferable to reduce the oxygen concentration by a method such as nitrogen substitution. A preferable oxygen concentration is preferably 10% or less, more preferably 7% or less, and most preferably 3% or less.

[Polymerizable monomer]
A polymerizable monomer may be added to the liquid crystal composition of the present invention. The polymerizable monomer that can be used in the present invention is not particularly limited as long as it is compatible with the compound of the present invention and does not cause significant alignment inhibition of the liquid crystal composition. Among these, compounds having a polymerization active ethylenically unsaturated group such as a vinyl group, a vinyloxy group, an acryloyl group, and a methacryloyl group are preferably used. The addition amount of the polymerizable monomer is generally in the range of 0.5 to 50% by mass and preferably in the range of 1 to 30% by mass with respect to the liquid crystal compound. In addition, it is particularly preferable to use a monomer having two or more reactive functional groups because an effect of improving the adhesion between the alignment film and the optically anisotropic layer can be expected.

[Coating solvent]
As the solvent used for the preparation of the liquid crystalline composition of the present invention, an organic solvent is preferably used. Examples of organic solvents include amides (eg, N, N-dimethylformamide), sulfoxides (eg, dimethyl sulfoxide), heterocyclic compounds (eg, pyridine), hydrocarbons (eg, toluene, hexane), alkyl halides (eg, , Chloroform, dichloromethane), esters (eg, methyl acetate, butyl acetate), ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ethers (eg, tetrahydrofuran, 1,2-dimethoxyethane). Alkyl halides, esters and ketones are preferred. Two or more organic solvents may be used in combination.

[Application method]
The thin film of the present invention can be formed by preparing a coating liquid of the liquid crystalline composition of the present invention using the above solvent, coating the alignment liquid on the alignment film, and subjecting the liquid crystalline composition of the present invention to an alignment treatment. The coating liquid can be applied by a known method (for example, a wire bar coating method, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, or a die coating method).

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

[Synthesis Example: Synthesis of A-10]
Synthesized according to the following scheme.

(Synthesis of Compound 2)
To a three-necked flask, 10 g of 4-hexyloxybenzoic acid and 60 ml of thionyl chloride (SOCl ₂ ) were added, 1 ml of dimethylformamide (DMF) was added dropwise, and the mixture was stirred at 80 ° C. for 3 hours. The obtained solution was evaporated to obtain 10.8 g of Compound 2. (Yield 100%)

(Synthesis of Compound 3)
Into a three-necked flask, 10.8 g of Compound 2 and 100 ml of tetrahydrofuran (THF) were added and cooled to 0 ° C., then 2.3 g of hydrazine monohydrate was added dropwise and stirred at 40 ° C. or lower for 1 hour. Water was added to the obtained solution to precipitate crystals, followed by filtration. Thereafter, it was washed with acetonitrile (AR) to obtain 9.0 g of Compound 3. (Yield 85%)

(Synthesis of Compound 4)
In a three-necked flask, 9.0 g of Compound 3, 100 ml of DMF, and 33 ml of phosphorus oxychloride (POCl ₃ ) were added and stirred at 120 ° C. for 3 hours. Water was added to the obtained solution for crystallization, and then filtered. Furthermore, it was dissolved in methylene chloride (CH ₂ Cl ₂ ), water was added, the organic layer was extracted, and dried over magnesium sulfate. After filtration, the filtrate was concentrated with a rotary evaporator and purified by column chromatography to obtain 12.9 g of Compound 4 as crystals. (Yield 80%)

(Synthesis of Compound 5)
In a three-necked flask, 12.9 g of Compound 4, 120 ml of CH ₂ Cl _{2 and} 120 ml of BBr ₃ (1.0 M in CH ₂ Cl ₂ ) were placed and stirred at 50 ° C. for 1 hour. Water was added to the obtained solution to precipitate crystals, and filtration yielded 7.2 g of compound 5 as crystals.

(Synthesis of Compound 7)
Into a three-necked flask, 20 g of 4-chlorobutanol, 200 ml of ethyl acetate (EtOAc) and 15.6 ml of mesyl chloride (MsCl) were added and cooled to 0 ° C. Then, 28.2 ml of Et ₃ N was added dropwise and stirred at room temperature for 1 hour. did. To the resulting solution was poured 1N aqueous hydrochloric acid, extracted with EtOAc, washed with brine, and dried over magnesium sulfate. After filtration, the filtrate was concentrated with a rotary evaporator to obtain 34.4 g of Compound 7. (Yield 100%)

(Synthesis of Compound 8)
Three-necked flask, the compound 7 34.4 g, was stirred for 3 hours methyl 4-hydroxybenzoate 25.4 g, dimethylacetamide (DMAc) 1L, potassium carbonate _{(K 2} CO 3) 46g at 100 ° C. put. Crystals were precipitated by adding water to the obtained solution, and filtered to obtain 36.5 g of Compound 8. (Yield 90%)

(Synthesis of Compound 9)
In a three-necked flask, 36.5 g of compound 8, 300 ml of methyl alcohol (MeOH), and 30 ml of 1M NaOH aq. Were added and stirred at 60 ° C. for 1 hour. A 1N aqueous hydrochloric acid solution was added to the obtained solution to precipitate crystals, followed by filtration. Thereafter, the residue was purified by column chromatography to obtain 30.9 g of Compound 9 as crystals. (Yield 81%)

(Synthesis of Compound 11)
Three-necked flask, Compound 9 placed 10 g, 100 ml of THF, mesyl chloride (MsCl) 3.7 ml, was cooled to 0 ° _C., and stirred for 1 hour at room temperature was added dropwise Et 3 N6.2ml. 3.7 g of compound 5 dissolved in 30 ml of THF was added dropwise to the obtained solution at 0 ° C. Further, 6.1 ml of Et ₃ N was added dropwise, 500 mg of dimethylaminopyridine (DMAP) was added, and the mixture was stirred at room temperature for 5 hours. MeOH was added to the resulting solution to precipitate crystals and filtered. Thereafter, the residue was purified by column chromatography to obtain 7.4 g of Compound 11 as crystals. (Yield 75%)

(Synthesis of Compound A-10)
In a three-necked flask, 7.4 g of compound 11, 70 ml of DMAc, 7.4 ml of acrylic acid, 23 g of K ₂ CO ₃ and 9.8 g of NaI were added and stirred at 90 ° C. for 3 hours. MeOH was added to the resulting solution to precipitate crystals and filtered. Thereafter, the residue was purified by column chromatography to obtain 5.1 g of Compound A-10 as crystals. (Yield 63%)

[Example: Production of retardation plate in which compound A-10 is uniformly oriented]
An aqueous solution of PVA-203 (manufactured by Kuraray Co., Ltd.) was applied on a glass substrate and dried at 100 ° C. for 3 minutes. The thickness of PVA-203 was 0.5 μm. The following coating solution was spin-coated on the substrate provided with the thin film of PVA-203, put in a thermostatic bath at 200 ° C., and irradiated with 600 mJ / cm ² ultraviolet rays after 5 minutes to fix the alignment state. When the alignment state was observed with a polarizing microscope after cooling to room temperature, it was found that the discotic liquid crystalline compound was tilted or hybrid aligned without defects. The thickness of the liquid crystal compound layer was 1.0 μm.

(Coating solution)
-100 parts by mass of the liquid crystalline compound A-10-0.5 mass parts of the following air interface alignment controller V- (1)-3.0 parts by mass of Irgacure 907 (Nagase Sangyo Co., Ltd.)-1.0 mass of diethylthioxanthone / Methyl ethyl ketone 400 parts by mass

  The Re angle dependency of the thin film obtained in the above example was measured using KOBRA (manufactured by Oji Scientific Instruments). As a result, it was found that biaxiality was exhibited.

Claims (1)

The support has at least one optically anisotropic layer, and the optically anisotropic layer is a layer formed from at least one of the compounds represented by the following general formulas (I) and (II). A retardation film characterized by the following.

(In the general formulas (I) and (II), A ¹ and A ² each independently represent a carbon atom or a nitrogen atom, X ¹ represents an oxygen atom, a sulfur atom, a carbon atom or a nitrogen atom; ¹ and R ² each independently represents the following general formula (IA).

(In General Formula (IA), A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ⁸ , A ⁹ and A ¹⁰ each independently represents a carbon atom or a nitrogen atom, and M ¹ is , Single bond, —O—, —O—CO—, —CO—O—, —O—CO—O—, —S—, —C (═O) —, —SO ₂ —, —CH ₂ —CH _2- , —CH ₂ —O—, —O—CH ₂ —, —NH—CO—, —S—CO—, —CH═CH—, —C≡C—, and L ¹ represents —O— , —O—CO—, —CO—O—, —O—CO—O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH═. Represents a divalent linking group selected from the group consisting of CH— and —C≡C— and combinations thereof, and when the above group is a group containing a hydrogen atom, the hydrogen atom may be replaced by a substituent. Good Q ¹ represents a polymerizable group or a hydrogen atom, and n represents 1, 2 or 3.)