KR20130044178A - Polymerizable chiral compound - Google Patents

Abstract

PURPOSE: A polymerization chiral compound is provided to manufacture an optical anisotropic body which has an excellent optical property due to a strong torsional force. CONSTITUTION: A polymerization group of a polymerization chiral compound is hardened by radical polymerization, radical addition polymerization, cationic polymerization, and anion polymerization. The polymerization chiral compound is indicated as a general formula (I). The polymerization chiral compound obtains high HTP by increasing rigidity of a mesogen region due to direct combination of a ring skeleton and a polymeric group. As solubility of the polymerization chiral compound improves, optical anisotropic body obtains an excellent reflection property for a liquid crystal composition.

Description

Polymerizable chiral compound {POLYMERIZABLE CHIRAL COMPOUND}

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

In recent years, the importance of the optically anisotropic body used for the deflection plate, phase difference plate, etc. which is essential for a display display according to the progress of the information society is increasing. Since the optical properties required for the optically anisotropic body are different depending on the purpose, a compound having properties suitable for the purpose is required. In addition, not only the optical properties but also the polymerization rate, solubility, melting point, glass transition point, transparency of the polymer, mechanical strength of the polymer, etc. are important factors.

In recent years, the circularly polarized light separating function element using a polymeric cholesteric liquid crystal is utilized as a brightness improving film. A cholesteric liquid crystal can be normally prepared by adding an optically active compound (henceforth a chiral compound) to a nematic liquid crystal. As an optical compensation film of a liquid crystal device, in order to obtain the circularly polarized light separation function from an ultraviolet region to a visible light region, a spiral structure with a very short pitch p is required. The pitch p of a molecular helix is inversely proportional to the density | concentration c of a chiral compound in a liquid crystal composition according to Formula (a). The proportional integer is the helix torsional force (HTP) of the chiral compound. In order to obtain a short pitch value, it is obtained by increasing the concentration of the chiral compound or by increasing the torsional force.

However, when a large amount of a chiral compound is blended, it is not preferable because of lowering optical properties such as liquid crystallinity, solubility, transparency of the polymer, and high cost of the chiral compound. Therefore, the liquid crystal composition using the chiral compound with strong HTP is preferable. As a compound which shows such a strong HTP, the chiral compound which has the optically active site of ring structure is proposed (refer the citation documents 1 and 2). These citations include strong HTPs based on optically active compounds such as 1,4: 3,6- dianhydro-D-mannitol (isomannide), dianhydro-D-glucinitol (isosorbide), and vinaphthol. A polymerizable chiral compound having is disclosed. However, these optically active compounds had problems such as high melting point, poor solubility, and low compatibility with some liquid crystal compounds (Citation Document 1). In addition, the compound having an asymmetrical structure in order to improve solubility shows some improvement in terms of solubility, but has a problem in that manufacturing cost is high due to complicated manufacturing, which causes a high cost of the optically anisotropic substance ( Citations 2).

Japanese Patent Application Laid-Open No. 9-506088 Japanese Patent Application Laid-Open No. 2003-137887

An object of the present invention is to provide a polymerizable chiral compound excellent in solubility having strong HTP.

MEANS TO SOLVE THE PROBLEM As a result of studying the various substituents in a polymeric compound, this inventor discovered that the polymeric compound which has a specific structure can solve the above-mentioned subject, and came to complete this invention.

This invention is general formula (I)

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

A ¹ , A ² , A ³ and A ⁴ independently of each other represent a 1,4-phenylene group, a naphthalene-2,6-diyl group, a 1,4-cyclohexylene group or a pyridine-2,5-diyl group And hydrogen atoms contained in A ¹ , A ² , A ^3, and A ⁴ may be each independently substituted with an alkyl group, a halogenated alkyl group, an alkoxy group, a halogen, a cyano group, or a nitro group, and B ¹ and B ² may be independent from each other. -O-, -S-, -OCH _2- , -CH ₂ O-, -CO-, -COO-, -OCO-, -OCOO-, -CO-NR ^11- , -NR ¹¹ -CO- , -SCH _2- , -CH ₂ S-, -CH = CH-COO-, -OCO-CH = CH-, -COO-CH = CH-, -CH = CH-OCO-, -CH ₂ CH _2- COO-, -COO-CH ₂ CH _2- , -CH ₂ CH ₂ -OCO-, -OCO-CH ₂ CH _2- , -C≡C- or a single bond (wherein R ¹¹ represents a hydrogen atom or carbon number) 1-4 represents an alkyl group), Z ¹ is, -COO-, -CH = CH-COO- , -CH 2 CH 2 -COO-, -CH 2 O- or -CF represents ^₂ O-, Z ₂ Represents -OCO-, -OCO-CH = CH-, -OCO-CH ₂ CH _2- , -OCH ₂ -or -OCF _2- , Z represents the following general formulas (Z-1) to (Z- 3) as mark It represents any one of divalent substituents,

(In the formulas, each substituent indicates bonding to Z ¹ on one side of the bond represented by a dotted line and Z ² on the other side, and Y ¹ , Y ² , Y ³ , Y ⁴ , Y ^5, and Y ⁶ are each independently. To an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a hydrogen atom, and the divalent substituent represented by general formulas (Z-1) to (Z-3) in the formula represents a single three-dimensional structure) m and n, independently of each other, represent 0, 1 or 2, but when a plurality of A ¹ , A ² , B ¹ or / and B ² are present, they may be the same as or different from each other independently; Provided is a compound, a polymerizable composition comprising the compound as a constituent member, and an optically anisotropic body using the polymerizable composition.

Since the polymerizable chiral compound of the present invention has strong HTP and low melting point, and has a low melting point, it has excellent solubility with other liquid crystal compounds and is useful as a structural member of the polymerizable liquid crystal composition. In addition, there is a merit that can be manufactured at low cost because the production method is simple. Since the polymeric chiral compound of this invention has a strong torsional force, the optically anisotropic body which has the outstanding optical characteristic can be manufactured. The optically anisotropic body of this invention is useful for uses, such as a deflection plate, retardation plate, and a selective reflection plate.

In general formula (I), although R <^1> and R <^2> represent a polymeric group independently from each other, the structure shown below is illustrated as a specific example of a polymeric group.

These polymerizers are cured by radical polymerization, radical addition polymerization, cationic polymerization, and anionic polymerization. In particular, when the ultraviolet polymerization is carried out as the polymerization method, the formula (R-1), formula (R-2), formula (R-4), formula (R-5), formula (R-7), and formula (R- 11), formula (R-13) or formula (R-15) are preferable, and formula (R-1), formula (R-2), formula (R-7), formula (R-11) or formula (R-11) R-13) is more preferable, and a formula (R-1) or a formula (R-2) is more preferable.

A ¹ , A ² , A ³ and A ⁴ independently represent a 1,4-phenylene group and a naphthalene-2,6-diyl group, a 1,4-cyclohexylene group or a pyridine-2,5-diyl group, A ¹ , A ² , A ³ and A ⁴ may be independently substituted with an alkyl group, a halogenated alkyl group, an alkoxy group, a halogen, a cyano group or a nitro group, but in terms of strong HTP and solubility, the 1,4-phenylene group , Naphthalene-2,6-diyl group or pyridine-2,5-diyl group is preferable, 1,4-phenylene group or naphthalene-2,6-diyl group is more preferable, As a substituent, it is halogen, C1-C1- The alkyl group and alkoxy group of 4 are preferable.

B ¹ and B ² are each independently of the other -O-, -S-, -OCH _2- , -CH ₂ O-, -CO-, -COO-, -OCO-, -OCOO-, -CO-NR ¹¹ -, -NR ¹¹ -CO-, -SCH _2- , -CH ₂ S-, -CH = CH-COO-, -OCO-CH = CH-, -CH ₂ CH ₂ -COO-, -OOC-CH ₂ CH _2- , -CH ₂ CH ₂ -OCO-, -OCO-CH ₂ CH _2- , -C≡C- or a single bond, but -OCH _2- , -CH ₂ O-, -COO-,- OCO-, -CH = CH-COO-, -OCO-CH = CH-, -CH ₂ CH ₂ -COO-, -OOC-CH ₂ CH _2- , -CH ₂ CH ₂ -OCO-, -OCO-CH ₂ CH _2- , -C≡C- or a single bond is preferred, -OCH _2- , -CH ₂ O-, -COO-, -OCO-, -CH = CH-COO-, -OCO-CH = CH -Or a single bond is more preferable.

Z ¹ represents -COO-, -CH = CH-COO-, -CH ₂ CH ₂ -COO-, -CH ₂ O-, or -CF ₂ O-, and Z ² represents -OCO- or -OCO- _{CH = CH-, -OCO-CH 2} CH 2 -, -OCH 2 - or -OCF ₂ - represents the, in order to increase the rigidity of the molecule, strongly HTP, Z ¹ is -COO- or -CH = CH -COO- are preferred, Z ² is preferably -OCO- or -OCO-CH = CH-. Although Z <^1> and Z <^2> may be same or different, the same one is preferable because the manufacturing process is simple.

Z represents any of the divalent substituents represented by the following General Formulas (Z-1) to (Z-3), but is a divalent substituent represented by General Formula (Z-1) or (Z-3). Is more preferable.

Moreover, the bivalent substituent represented by general formula (Z-3) is a compound which is axial asymmetric. In addition, the divalent substituent represented by general formula (Z-1) or (Z-3) represents a substantially single isomer.

m and n represent 0, 1 or 2, but m and n are preferably 0 or 1.

When ^two or more A <^1> , A <^2> , B <^1> and / or B <^2> exist, they may mutually be same or different independently.

In addition, since the polymerizable chiral compound represented by the general formula (I) of the present invention is directly bonded to the ring skeleton and the polymerizable group, the rigidity of the mesogen moiety increases, and high HTP is obtained. Moreover, solubility is also improved and the optically anisotropic body by the said liquid crystal composition has the outstanding reflection characteristic. This invention provides the compound, the liquid crystal composition used as a structural member, and the optically anisotropic body using the said liquid crystal composition.

As for the compound represented by general formula (I), the compound represented by following formula (I-1)-general formula (I-38) more specifically is preferable.

Formulas (I-21) to (I-24) and (I-37) have R bodies and S bodies, but the torsional forces are the same, so any of them may be used except for specific applications. The compound of this invention can be synthesize | combined by the synthesis method described below.

(Manufacture method 1) Preparation of the compound represented by general formula (I-3)

Dicyclohexylcarbodiimide (DCC) of 4-benzyloxy-3-chlorobenzoic acid and isosorbide ((3s, 3aα, 6aα) -hexahydropro [3,2-b] furan-3α, 6β-diol) The compound represented by the formula (S-1) obtained by esterification using N, N-dimethyl-4-aminopyridine (DMAP) or the like as a dehydrating condensing agent such as a catalyst is subjected to catalytic hydrogen reduction by palladium carbon. To desorb the benzyl group to obtain an isosorbide derivative represented by the formula (S-2). Moreover, the target compound represented by Formula (I-3) can be obtained by esterification with methacrylic acid chloride.

(Manufacture method 2) Preparation of the compound represented by general formula (I-8)

Contact hydrogen by palladium carbon (Pd / C) with the compound represented by Formula (S-3) obtained by esterification using 4'-benzyloxybiphenylcarboxylic acid and dehydrating condensing agent, such as DCC of isosorbide. The benzyl group is released by reduction to obtain an isosorbide derivative represented by the formula (S-4). Moreover, the target compound represented by Formula (I-8) can be obtained by esterification with methacrylic acid chloride.

(Manufacture method 3) Preparation of the compound represented by general formula (I-14)

The compound represented by the formula (S-5) obtained by the esterification reaction using a dehydrating condensing agent such as DCC of 4-benzyloxybenzoic acid and isosorbide is desorbed from the benzyl group by catalytic hydrogen reduction with Pd / C. An isosorbide derivative represented by formula (S-6) is obtained.

Next, an isosorbide derivative is obtained by esterification using a tetrahydropyranyl ether compound of 4-hydroxycinnamic acid and a dehydrating condensing agent such as DCC of the compound represented by formula (S-6). Furthermore, the isosorbide derivative is deprotected with tetrahydrofuran (THF) / hydrochloric acid to obtain an isosorbide derivative represented by the formula (S-7), and the esterification reaction with acrylic acid chloride gives the formula (I-14). The target compound represented by) can be obtained.

(Manufacture method 4) Preparation of the compound represented by general formula (I-17)

After the trimethylsilylacetylene derivative represented by the formula (S-7) was synthesized by the sonogashi reaction of methyl 4-bromobenzoate and trimethylsilylacetylene, the trimethylsilyl group (TMS) was desorbed by tetrabutylammonium fluoride. And the acetylene derivative represented by formula (S-8). Furthermore, a tolan derivative represented by the formula (S-9) was obtained by a sonogashira reaction of 4-bromo-2-fluorophenol with a tetrahydropyranylether compound, followed by hydrolysis with sodium hydroxide. A benzoic acid derivative represented by formula (S-10) having a tolan skeleton is obtained.

An isosorbide derivative is obtained by esterification of a benzoic acid derivative represented by formula (S-10) having a tolan skeleton with isosorbide using a dehydrating condensing agent such as DCC, and an isosorbide derivative is converted into THF / hydrochloric acid. Deprotection is performed to obtain an isosorbide derivative represented by formula (S-11).

Next, the target compound represented by Formula (I-17) can be obtained by esterification with methacrylic acid chloride.

(Manufacture method 5) Preparation of the compound represented by general formula (I-23)

Binaphthyl derivative (S-12) was obtained by esterification using a dehydrating condensing agent such as dicyclohexylcarbodiimide of vinaptol and acetoxybenzoic acid, and then acetyl group was removed by butylamine to decompose the hydroxybenzoic acid derivative. Obtain (S-13). Next, the target compound (I-23) can be obtained by esterification using a dehydrating condensing agent such as hydroxybenzoic acid derivative (S-14) and dicyclohexylcarbodiimide of 4-acryloyloxybenzoic acid. .

(Manufacture method 6) Preparation of the compound represented by general formula (I-25)

Target compound (I-25) can be obtained by esterification of ethyl tartrate and 4-acryloyloxybenzoic acid using dehydrating condensing agents such as dicyclohexylcarbodiimide.

(Manufacture method 7) Preparation of the compound represented by general formula (I-38)

A naphthoic acid derivative (S-14) is obtained by esterification using a dehydrating condensing agent such as dicyclohexylcarbodiimide of ethyl tartrate and acetoxynaphthoic acid, and deacetyl group reaction using butylamine. Next, the target compound (I-38) can be obtained by esterification using dehydrating condensing agents such as dicyclohexylcarbodiimide with maleimide acetic acid.

The polymeric compound of this invention can be used suitably for a chiral nematic, a chiral smectic, and a cholesteric liquid crystal composition. In the liquid crystal composition which uses the compound of this invention as a structural member, 0.1-40 mass% is preferable and, as for the addition amount of a polymeric chiral compound, 3-25 mass% is more preferable.

Although the polymeric composition containing the polymeric chiral compound of this invention does not need to show or show liquid crystallinity, it is preferable to show liquid crystallinity, and as a structure, the restriction | limiting other than containing the compound represented by General formula (I) is However, as a polymeric compound used in combination, what has acryloyloxy group (R-1) or a methacryloyloxy group (R-2) in a compound is preferable, and what has two or more polymerizable functional groups in a molecule | numerator More preferred.

Although it is preferable that the polymeric compound used in combination shows liquid crystallinity, Specifically, general formula (II)

(Wherein A is H, F, Cl, CN, SCN, OCF ₃ , an alkyl group having 1 to 12 carbon atoms, and the alkyl group does not directly bond with oxygen atoms, and the carbon atoms are oxygen atoms, sulfur May be substituted with an atom, -CO-, -COO-, -OCO-, -OCOO-, -CH = CH-, -C≡C-, or -L ⁶ -S ⁴ -R ⁴ , R ³ and R ⁴ independently of each other, represent the same meaning as R ¹ in General Formula (I), and S ³ and S ⁴ independently represent a single bond or an alkylene group having 1 to 12 carbon atoms, and here In one or more -CH ₂ -is not directly bonded to the oxygen atoms may be substituted with -O-, -COO-, -OCO-, -OCOO-, L ⁴ , L ⁵ , and L ⁶ are independent of each other 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 CO O-, -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 are independently of each other, 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 M ³ and M ⁴ are independently unsubstituted or substituted with an alkyl group, halogenated alkyl group, alkoxy group, halogenated alkoxy group, halogen group, It may be substituted by the cyano group or the nitro group, and p represents 0, 1, 2 or 3. When p represents 2 or 3, the compound represented by two or three L <^5> and M <^4> which are independent of each other may be same or different) is preferable.

In particular, L ⁴ , L ⁵ and L ⁶ independently of each other, represent a single bond, -O-, -COO- or -OCO-, M ³ and M ⁴ independently of each other, 1,4-phenylene group, 1, The polymeric compound represented by a 4-cyclohexylene group, a pyridine-2, 5- diyl group, a pyrimidine-2, 5- diyl group, or a naphthalene-2, 6- diyl group is preferable.

As for the polymeric compound represented by general formula (II), the compound specifically, represented by general formula (II-1)-general formula (II-22) is preferable.

(In formula, p and q represent the integer of 0-12 independently of each other, but when p and / or q are 0, one oxygen atom is removed, without directly bonding two oxygen atoms.)

Moreover, as a polymeric liquid crystal compound used for the polymeric composition of this invention, general formula (III-1)-general formula (III-11) are used for the purpose of adjustment of a liquid crystal temperature range, birefringence, and a viscosity reduction. It is preferable to mix.

(In formula, p and q represent the integer of 0-12 independently of each other, but when p is 0, one oxygen atom is removed, without directly bonding two oxygen atoms.)

Moreover, as a specific compound which may also add chiral compounds other than the compound of this invention, it is represented by General formula (IV-1)-general formula (IV-7). 0.5-30 mass% is preferable with respect to a liquid crystal composition, and, as for the compounding quantity of a chiral compound, 2-20 mass% is more preferable.

(In formula, p and q represent the integer of 0-12 independently of each other, but when p and / or q are 0, one oxygen atom is removed, without directly bonding two oxygen atoms.)

Moreover, you may add to the liquid crystal composition which does not have a polymeric group by the liquid crystal composition of this invention, and a normal liquid crystal device, for example, STN (super twisted nematic) liquid crystal, TN (twisted nematic) liquid crystal, TFT (Thin Film Transistor) Examples of nematic liquid crystal compositions, ferroelectric liquid crystal compositions, and the like used for liquid crystals are illustrated.

Moreover, as a compound which has a polymeric functional group, the compound which does not show liquid crystallinity can also be added. As such a compound, if it is generally recognized as a polymer-forming monomer or a polymer-forming oligomer in the art, it can be used without particular limitation, but when the composition is required to have a liquid crystal phase, the amount of addition is It is necessary to adjust so that it may be liquid crystalline as a composition.

Although the liquid crystal composition of this invention can superpose | polymerize by heat and light without adding a polymerization initiator, addition of a photoinitiator is preferable. 0.1-10 mass% is preferable, as for the density | concentration of the photoinitiator to add, 0.2-10 mass% is more preferable, and 0.4-5 mass% is especially preferable. Examples of the photoinitiator include benzoin ethers, benzophenones, acetphenones, benzyl ketals, acylphosphine oxides, and the like.

Moreover, in order to improve the storage stability, you may add a stabilizer to the liquid crystal composition of this invention. Examples of stabilizers that can be used include, for example, hydroquinones, hydroquinone monoalkyl ethers, tertiary butylcatechols, pyrogallols, thiophenols, nitro compounds, β-naphthylamines, β-naphthols and nitrosos. Compounds and the like. The range of 0.005-1 mass% is preferable with respect to a liquid crystal composition, as for the addition amount when using a stabilizer, 0.02-0.5 mass% is more preferable, 0.03-0.1 mass% is especially preferable.

Moreover, when using the liquid crystal composition of this invention for the use of retardation film, the raw material of a polarizing film, an oriented film, or a printing ink, a coating material, a protective film, etc., according to the objective, it is a metal, a metal complex, dye, a pigment, a pigment. , 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 and the like can be added.

Next, the optically anisotropic body of this invention is demonstrated. The optically anisotropic body manufactured by polymerizing the liquid crystal composition of this invention can be used for various uses. For example, when superposing | polymerizing in the state which does not orientate the polymeric liquid crystal composition of this invention, it can use as a light scattering plate, a polarization canceling plate, and a moire pattern prevention plate. Moreover, in the state which orientated the polymerizable liquid crystal composition of this invention, the optically anisotropic body manufactured by superposing | polymerizing has optical anisotropy in physical property, and is useful. Such an optically anisotropic body is, for example, a substrate obtained by rubbing the surface of the polymerizable liquid crystal composition of the present invention with a cloth, or a substrate obtained by rubbing the substrate surface on which the organic thin film is formed with a cloth, or SiO ₂ . It can manufacture by carrying out on a board | substrate which has the oriented film deposited, or pinching between board | substrates, and polymerizing the liquid crystal of this invention.

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, printing, and the like. In addition, you may use a polymeric liquid crystal composition as it is at the time of coating, or may add an organic solvent. As the organic solvent, ethyl acetate, tetrahydrofuran, toluene, hexane, methanol, ethanol, dimethylformamide, dichloromethane, isopropanol, acetone, methyl ethyl ketone, acetonitrile, cellosolve, cyclohexanone, γ-butyllactone, ace Oxy-2-ethoxyethane, propylene glycol monomethyl acetate, and N-methylpyrrolidinones can be illustrated. These may be used individually or in combination, What is necessary is just to select suitably in consideration of the vapor pressure and the solubility of a polymeric liquid crystal composition. Moreover, as for the addition amount, 90 mass% or less is preferable. As a method of volatilizing the added organic solvent, natural drying, heat drying, reduced pressure drying, and reduced pressure heating 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 intermediate | middle layers, such as a polyimide thin film, on a board | substrate is effective also as a means of improving adhesiveness, when adhesiveness of the optically anisotropic body obtained by superposing | polymerizing a polymeric liquid crystal material and a board | substrate is not good.

As a method of clamping a liquid crystal composition between board | substrates, the injection method using a capillary phenomenon is illustrated. The means for depressurizing the space formed between the substrates and then injecting the liquid crystal material is also effective.

Examples of the rubbing treatment or the alignment treatment other than the vapor deposition of SiO ₂ include the use of flow orientation of the liquid crystal material and the use of an electric field or a magnetic field. These orientation means may be used independently, or may be used in combination. Moreover, as an orientation processing method which replaces rubbing, the photo-alignment method can also be used. This method is, for example, an organic thin film having a functional group for photodimerization reaction in a molecule such as polyvinyl cinnamate, an organic thin film having a functional group for isomerizing with light or an organic thin film such as polyimide The alignment film is formed by irradiating polarized light, preferably polarized ultraviolet light. By applying a photomask to this photo-alignment method, the patterning of an orientation can be achieved easily, and it becomes possible to precisely control the molecular orientation inside an optically anisotropic body.

The shape of the substrate may have a curved surface in addition to the flat plate as a constituent portion. The material which comprises a board | substrate can be used regardless of an organic material and an inorganic material. As an organic material used as a material of a board | substrate, for example, polyethylene terephthalate, polycarbonate, polyimide, polyamide, polymethyl methacrylate, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polychlorotrifluoroethylene, Polyarylate, polysulfone, triacetyl cellulose, cellulose, polyether ether ketone and the like are exemplified, and examples of the inorganic material include silicon, glass, calcite and the like.

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 may be formed on the surface of the substrate in accordance with a known method and then rubbed with a cloth or the like. Moreover, the polyimide thin film which gives the pretilt angle used by a normal TN liquid crystal device or STN liquid crystal device is especially preferable at the point which can control the molecular orientation structure inside an optically anisotropic body more precisely.

In addition, when controlling an orientation state by electric field, the board | substrate which has an electrode layer is used. In this case, it is preferable to form organic thin films, such as the above-mentioned polyimide thin film, on an electrode.

As a method of superposing | polymerizing the liquid crystal composition of this invention, since rapid superposition | polymerization is preferable, the method of superposing | polymerizing by irradiating active energy rays, such as an ultraviolet-ray or an electron beam, is preferable. In the case of using ultraviolet rays, a polarized light source may be used or a non-polarized light source may be used. In addition, when superposing | polymerizing in the state which pinched the liquid crystal composition between two board | substrates, at least the board | substrate by the irradiation surface side should be provided with moderate transparency with respect to active energy ray. Moreover, after polymerizing only a specific part using a mask at the time of light irradiation, the orientation state of an unpolymerized part is changed by changing conditions, such as an electric field, a magnetic field, or temperature, and an active energy ray is irradiated further. You may use the means for making it superpose | polymerize. Moreover, it is preferable that the temperature at the time of irradiation is in the temperature range in which the liquid crystal state of the liquid crystal composition of this invention is maintained. In particular, in the case where the 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, even in the sense of avoiding unintentional thermal polymerization. As for the intensity | strength of an active energy ray, 0.1 kW / cm <2> -2W / cm <2> is preferable. When the intensity is 0.1 mW / cm 2 or less, a large amount of time is required to complete the photopolymerization, and the productivity is deteriorated. When the intensity is 2 W / cm 2 or more, the polymerizable liquid crystal compound or the polymerizable liquid crystal composition is deteriorated. There is this.

The optically anisotropic body of this invention obtained by superposition | polymerization can also heat-treat for the purpose of reducing initial characteristic change and aiming at stable characteristic expression. The temperature of heat processing is 50-250 degreeC, and the heat processing time of 30 second-12 hours is preferable.

The optically anisotropic body of this invention manufactured by such a method may be used alone or peeled off from a board | substrate, or may be used without peeling. Moreover, even if the obtained optically anisotropic body is laminated | stacked, you may bond to another board | substrate and use it.

[Example]

Hereinafter, although an Example is given and this invention is further explained, this invention is not limited to these Examples. In addition, "%" in the composition of the following example and a comparative example means "mass%."

Hereinafter, although an Example is given and this invention is further explained, this invention is not limited to these Examples. Various analysis was performed by the following method.

Phase transition temperature: measured by polarized light microscope equipped with temperature control stage

Structure of compound: confirmed by nuclear magnetic resonance spectrum (NMR), mass spectrum (MS)

"%" In the composition of the following example and a comparative example means "mass%."

T _{n -i} represents the transition temperature of the nematic phase-isotropic phase.

Measurement method of HTP (torsional force): A composition obtained by adding 2% by weight of a polymerizable chiral compound to a nematic liquid crystal (DON-103, manufactured by DIC Corporation) was injected into a commercially available wedge-shaped cell subjected to uniaxial alignment treatment, and then polarized light microscope The spiral pitch was measured at room temperature using. This value was substituted into said Formula (a), and HTP was calculated | required.

Circularly polarized light characteristics: 450 to 650 nm spectrum was measured with an ultraviolet visible spectrophotometer U-4100 (manufactured by Hitachi Seisakusho)

The following symbol is used for a compound base material.

(Example 1)

33.2 g (240 mmol) of 3- (p-hydroxyphenyl) benzoic acid, 4 g of potassium iodide, 1 g of tetrabutylammonium bromide, and 400 ml of ethanol were added to a reaction vessel equipped with a stirring device, a cooler, and a thermometer, followed by stirring at room temperature. A 25% aqueous solution of 24 g of sodium hydroxide was slowly added dropwise. After completion of the dropwise addition, the reaction vessel was maintained at 50 ° C, and 50 g (288 mmol) of benzyl bromide was slowly added dropwise. After completion of the dropwise addition, the reaction vessel was further warmed to 70 ° C and allowed to react for 3 hours. After completion | finish of reaction, it neutralized with 10% hydrochloric acid, extracted with ethyl acetate, dried with sodium sulfate, concentrated the solvent, and synthesize | combined 38g of compounds represented by Formula (1).

Next, 28 g (123 mmol) of the compound represented by Formula (1) synthesized above, 7.7 g (55 mmol) of isosorbide, 1.8 g of dimethylaminopyridine, dichloro, in a reaction vessel equipped with a stirring device, a cooler, and a thermometer. 500 ml of methane were thrown in, the reaction container was hold | maintained at 5 degrees C or less in an ice-cooling bath, and 19 g (150 mmol) of diisopropyl carbodiimide was slowly dripped under the atmosphere of nitrogen gas. After completion of the dropwise addition, the reaction vessel was returned to room temperature and allowed to react for 5 hours. After the reaction solution was filtered, 200 ml of dichloromethane was added to the filtrate, washed with 10% aqueous hydrochloric acid solution, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After distilling off the solvent, the mixture was purified by a silica gel column of 5 times (weight ratio) to obtain 23 g of the compound represented by the formula (2).

Next, 23 g (40.5 mmol) of the compound represented by Formula (2) synthesized above, 1 g of palladium carbon, and 150 ml of ethanol were added to an autoclave vessel equipped with a stirring device, and the reaction was reduced with 0.1 MPa of hydrogen (reaction). Temperature 50 ° C., 3 hours). After filtering the reaction liquid, the reaction solvent was distilled off and the compound 14g shown by Formula (3) was obtained.

Next, 4 g (10.3 mmol) of the compound represented by the above formula (3), 2.26 g (25 mmol) of acrylic acid chloride, and 50 mL of dichloromethane were added to a reaction vessel equipped with a stirring device, a cooler, and a thermometer, and nitrogen gas. The reactor was cooled to 5 ° C. or less under the atmosphere. Next, triethylamine 2.5g (25 mmol) was dripped slowly. After completion of the dropwise addition, the mixture was reacted at 20 ° C or lower for 3 hours. After the completion of the reaction, dichloromethane was added, and the organic layer was washed with 10% aqueous hydrochloric acid solution, pure water and saturated brine. After distilling off the solvent, the product was purified by a silica gel column having a double amount (weight ratio) to obtain 4.2 g of the target compound represented by Formula (4).

(Property value)

¹ H-NMR (solvent: heavy chloroform): δ: 4.05 to 4.11 (m, 4H), 4.67 (m, 1H), 5.06 (m, 1H), 5.42 (m, 1H), 5.49 (s, 1H), 6.04 (d, 2H), 6.29 (m, 2H), 6.65 (d, 2H), 7.21-7.26 (m, 4H), 8.06 (dd, 4H)

¹³ C-NMR (solvent: heavy chloroform): δ: 70.7, 73.4, 74.5, 78.5, 81.1, 86.1, 121.7, 126.9, 127.0, 127.5, 131.3, 133.3, 154.5, 163.8, 164.7, 165.1

Infrared Absorption Spectrum (IR): 2925, 2855, 1760, 1652 ~ 1622, 809

(Melting point) 125 ℃

When 5.0% of the compounds represented by Formula (4) were added to the nematic liquid crystal composition shown below, and HTP was computed from the pitch calculated | required by an optical microscope, the high value of HTP = 31 was shown.

(Example 2)

4 g (10.3 mmol) of the compound represented by Formula (3) synthesized in Example 1, 4.6 g (24 mmol) of 4-acryloyloxybenzoic acid and 200 mg of dimethylaminopyridine in a reaction vessel equipped with a stirring device, a cooler and a thermometer. , 500 ml of dichloromethane was added, the reaction vessel was kept at 5 ° C. or lower in an ice-cooled bath, and 3.6 g (28 mmol) of diisopropylcarbodiimide was slowly added dropwise under an atmosphere of nitrogen gas. After completion of the dropwise addition, the reaction vessel was returned to room temperature and allowed to react for 5 hours. After the reaction solution was filtered, 200 ml of dichloromethane was added to the filtrate, washed with 10% aqueous hydrochloric acid solution, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After distilling a solvent off, it refine | purified by the silica gel column of 5 times (weight ratio), and obtained the target compound 5.2g shown by Formula (5).

(Property value)

¹ H-NMR (solvent: heavy chloroform): δ: 4.05-4.11 (m, 4H), 4.67 (m, 1H), 5.06 (m, 1H), 5.42 (m, 1H), 5.49 (s, 1H), 6.04 (d, 2H), 6.29 (m, 2H), 6.65 (d, 2H), 7.26-7.37 (m, 8H), 8.10 (d, 2H), 8.17 (d, 2H), 8.24-8.27 (m, 4H)

¹³ C-NMR (solvent: heavy chloroform): δ: 70.7, 73.4, 74.6, 78.5, 81.1, 86.1, 121.8, 121.9, 126.5, 127.0, 127.1, 127.4, 131.4, 131.8, 133.4, 154.5, 163.7, 164.7, 165.1

Infrared Absorption Spectrum (IR): 2925, 2855, 1760, 1652 ~ 1622, 809

(Melting point) 177 ° C

As a result of HTP being calculated in the same manner as in Example 1, a high value of HTP = 42 was shown.

(Example 3)

4 g (10.3 mmol) of the compound represented by Formula (3) synthesized in Example 1 and 7.4 g of 4- (4-methacryloyloxy) phenyl cinnamic acid (24) in a reaction vessel equipped with a stirring device, a cooler, and a thermometer. Mmol), 200 mg of dimethylaminopyridine and 500 ml of dichloromethane were added, the reaction vessel was kept at 5 ° C or lower in an ice-cooled bath, and 3.6 g (28 mmol) of diisopropylcarbodiimide was slowly added dropwise under an atmosphere of nitrogen gas. . After completion of the dropwise addition, the reaction vessel was returned to room temperature and allowed to react for 5 hours. After the reaction solution was filtered, 200 ml of dichloromethane was added to the filtrate, washed with 10% aqueous hydrochloric acid solution, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After distilling off the solvent, the product was purified by a silica gel column of 5 times (weight ratio) to obtain 6.4 g of the target compound represented by the formula (6).

(Property value)

¹ H-NMR (solvent: heavy chloroform): δ: 1.92 (s, 6H), 3.91-3.95 (m, 2H), 4.05-4.15 (m, 2H), 4.63 (m, 1H), 4.98 (m, 1H ), 5.31-5.39 (m, 2H), 5.77 (s, 1H), 6.41 (s, 2H), 6.44-6.65 (m, 4H), 7.22 (d, 2H), 7.40-7.70 (m, 12H), 7.76-7.85 (m, 2H)

¹³ C-NMR (solvent: heavy chloroform): δ: 70.3, 73.6, 74.1, 76.7, 81.0, 86.0, 116.9, 117.0, 122.0, 127.4, 127.1, 128.0, 128.7, 133.0, 133.2, 135.7, 137.6, 142.3, 142.4 , 145.3, 150.8, 165.7, 165.8, 166.2

Infrared Absorption Spectrum (IR): 2925, 2855, 1760, 1652 ~ 1622, 809

(Melting point) 248 ℃

As a result of adding 2.0% of the compound represented by Formula (6) to the nematic liquid crystal composition used in Example 1 and calculating HTP from the pitch calculated | required by an optical microscope, the high value of HTP = 56 was shown.

(Example 4)

4 g (10.3 mmol) of the compound represented by Formula (3) synthesized in Example 1, 5.8 g (24 mmol) of 6-acryloyloxy-2-naphthoic acid, in a reaction vessel equipped with a stirring device, a cooler and a thermometer, 200 mg of dimethylaminopyridine and 500 ml of dichloromethane were added, the reaction vessel was kept at 5 ° C or lower in an ice-cooled bath, and 3.6 g (28 mmol) of diisopropylcarbodiimide was slowly added dropwise under an atmosphere of nitrogen gas. After completion of the dropwise addition, the reaction vessel was returned to room temperature and allowed to react for 5 hours. After the reaction solution was filtered, 200 ml of dichloromethane was added to the filtrate, washed with 10% aqueous hydrochloric acid solution, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After distilling off the solvent, the product was purified by a silica gel column of 5 times (weight ratio) to obtain 5.7 g of the target compound represented by Formula (7).

(Property value)

¹ H-NMR (solvent: heavy chloroform): δ: 4.13 to 4.19 (m, 4H), 4.77 (m, 1H), 5.16 (m, 1H), 5.50 (m, 1H), 5.52 (s, 1H), 6.04 (d, 2H), 6.29 (m, 2H), 6.65 (d, 2H), 7.26-7.37 (m, 8H), 8.10 (d, 2H), 8.17 (d, 2H), 8.24-8.27 (m, 4H)

¹³ C-NMR (solvent: heavy chloroform): δ: 70.7, 73.5, 74.7, 78.5, 81.2, 86.1, 118.5, 122.1, 125.8, 126.5, 127.6, 128.0, 130.3, 130.9, 131.1, 133.1, 136.2, 150.2, 164.3 , 165.5, 165.9

Infrared Absorption Spectrum (IR): 2925, 2855, 1760, 1652 ~ 1622, 809

179 ℃ (melting point)

As a result of HTP being calculated in the same manner as in Example 1, a high value of HTP = 34 was shown.

(Example 5)

Next, 15.7 g (55 mmol) of (R) -1,1'-2-binaftol and 4- (4'-acryloyloxy) biphenylcarboxylic acid were added to the reaction vessel provided with a stirring device, a cooler, and a thermometer. 1.8 g of 35.3 g (130 mmol) dimethylaminopyridine and 500 ml of dichloromethane were added thereto, and the reaction vessel was kept at 5 ° C or lower in an ice-cooled bath, and 19 g (150 mmol) of diisopropylcarbodiimide was slowly added under an atmosphere of nitrogen gas. Dropped. After completion of the dropwise addition, the reaction vessel was returned to room temperature and allowed to react for 5 hours. After the reaction solution was filtered, 200 ml of dichloromethane was added to the filtrate, washed with 10% aqueous hydrochloric acid solution, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After distilling a solvent off, it refine | purified by the silica gel column of 5 times (weight ratio), and obtained the target compound (R body) 35g shown by Formula (8).

(Property value)

¹ H-NMR (solvent: heavy chloroform): δ: 4.05 to 4.11 (m, 4H), 4.67 (m, 1H), 5.06 (m, 1H), 5.42 (m, 1H), 5.49 (s, 1H), 6.04 (d, 2H), 6.29 (m, 2H), 6.65 (d, 2H), 7.26-7.37 (m, 8H), 8.10 (d, 2H), 8.17 (d, 2H), 8.24-8.27 (m, 4H)

¹³ C-NMR (solvent: heavy chloroform): δ: 121.7, 121.9, 123.6, 125.7, 126.1, 126.8, 127.7, 128.0, 128.2, 129.6, 130.4, 131.5, 132.3, 133.3, 137.6, 144.9, 146.9, 150.6, 164.4 , 164.5

Infrared Absorption Spectrum (IR): 1760, 1652-1622, 809

(Melting point) 107 ° C

As a result of HTP being calculated in the same manner as in Example 1, a high value of HTP = 65 was shown.

(Comparative Example 1)

21.4 g (100 mmol) of 4- (4-hydroxyphenyl) benzoic acid, 2.5 g of potassium iodide, 0.7 g of tetrabutylammonium bromide and 400 ml of ethanol were added to a reaction vessel equipped with a stirring device, a cooler, and a thermometer at room temperature. Stirred. A 25% aqueous solution of 12 g of sodium hydroxide was slowly added dropwise. After completion of the dropwise addition, the reaction vessel was maintained at 50 ° C, and 20 g (150 mmol) of 6-chloropropanol was slowly added dropwise. After completion of the dropwise addition, the reaction vessel was further warmed to 70 ° C and allowed to react for 3 hours. After the completion of the reaction, the mixture was neutralized with 10% hydrochloric acid, extracted with ethyl acetate, dried over sodium sulfate, and the solvent was concentrated to synthesize 22 g of the compound represented by the formula (9).

Next, 22 g (71 mmol) of the compound represented by Formula (9) synthesized above, 10 g (140 mmol) of acrylic acid, 1 g of p-toluenesulfonic acid, and 100 ml of toluene were added to a reaction vessel equipped with a stirring device, a cooler, and Dean Stark. Committed. The reaction vessel was heated to reflux with toluene and reacted as it was for 4 hours. After completion of the reaction, the reaction solution was washed with saturated sodium hydrogen carbonate, neutralized with 10% aqueous hydrochloric acid solution, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. The solvent was distilled off and 19g of compounds represented by Formula (10) were obtained.

In addition, 19 g (51 mmol) of the compound represented by Formula (10) synthesized above, 3.8 g (27 mmol) of isosorbide, 0.9 g of dimethylaminopyridine, 0.9 g of dichloromethane, were added to a reaction vessel equipped with a stirring device, a cooler, and a thermometer. 200 ml was put, the reaction container was hold | maintained at 5 degrees C or less in the ice-cooling bath, and 9 g (6.3 mmol) of diisopropyl carbodiimide was slowly dripped under the atmosphere of nitrogen gas. After completion of the dropwise addition, the reaction vessel was returned to room temperature and allowed to react for 5 hours. After the reaction solution was filtered, 100 mL of dichloromethane was added to the filtrate, washed with 10% aqueous hydrochloric acid solution, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After distilling off the solvent, purification was carried out by silica gel column and recrystallization to obtain 14 g of the target compound represented by the formula (11). Melting | fusing point of this compound was 150 degreeC or more and was not able to be measured.

(Property value)

¹ H-NMR (solvent: heavy chloroform): δ: 1.55 to 1.45 (m, 8H), 1.71 (m, 4H), 1.83 (m, 4H), 2.66 (m, 4H), 2.96 (m, 4H), 3.93 (m, 2H), 3.98 (m, 2H), 4.03 (s, 4H), 4.30 (t, 4H), 4.50 (t, 4H), 5.35 (s, 2H), 5.65 (dd, 2H), 5.85 (d, 2H), 5.85 (d, 2H), 6.15 (q, 2H), 6.55 (d, 2H), 7.10 (d, 4H), 7.50 (m, 4H), 8.12 (d, 4H), 8.13 ( d, 4H)

Infrared Absorption Spectrum (IR): 2925, 2855, 1760, 1652 ~ 1622, 809

(Melting point)> 150 ℃

The compound represented by Formula (11) described in Comparative Example 1 had a high melting point and also had problems with solubility with other compounds. When HTP was calculated by the same liquid crystal composition as in Example 1, the high value of HTP was 33, but since solubility was bad, only 0.5% could be added to the following composition.

(Comparative Example 2)

19.6 g (120 mmol) of p-hydroxyphenyl cinnamic acid, 2 g of potassium iodide, 0.5 g of tetrabutylammonium bromide, and 400 ml of ethanol were added to a reaction vessel provided with a stirring device, a cooler, and a thermometer, and stirred at room temperature. A 25% aqueous solution of 12 g of sodium hydroxide was slowly added dropwise. After completion of the dropwise addition, the reaction vessel was maintained at 50 ° C, and 25 g (144 mmol) of benzyl bromide was slowly added dropwise. After completion of the dropwise addition, the reaction vessel was further warmed to 70 ° C and allowed to react for 3 hours. After the completion of the reaction, the mixture was neutralized with 10% hydrochloric acid, extracted with ethyl acetate, dried over sodium sulfate, and the solvent was concentrated to synthesize 21 g of the compound represented by the formula (12).

Next, 21 g (82 mmol) of the compound represented by Formula (12) synthesized above, isosorbide 6 g (41 mmol), 1 g of dimethylaminopyridine, 1 g of dichloromethane, and the like in a reaction vessel equipped with a stirring device, a cooler, and a thermometer. ML was added, the reaction container was hold | maintained at 5 degrees C or less in the ice-cooling bath, and 12.4 g (100 mmol) of diisopropyl carbodiimide was slowly dripped under the atmosphere of nitrogen gas. After completion of the dropwise addition, the reaction vessel was returned to room temperature and allowed to react for 5 hours. After the reaction solution was filtered, 200 ml of dichloromethane was added to the filtrate, washed with 10% aqueous hydrochloric acid solution, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After distilling off the solvent, the product was purified by a silica gel column of 5 times (weight ratio) to obtain 19 g.

Next, 19 g of the intermediate synthesized above, 1 g of palladium carbon, 150 ml of ethanol, and 100 ml of tetrahydrofuran were added to an autoclave vessel equipped with a stirring device, and the reaction was reduced with 1 atmosphere of hydrogen (reaction temperature 50 ° C, 3 hours). After filtering the reaction liquid, the reaction solvent was distilled off and the compound 11.5g represented by Formula (13) was obtained.

Next, 11.5 g (26 mmol) of the compound represented by Formula (13) synthesized above, and 15.2 g of 4- (4-acryloyloxyhexyloxy) benzoic acid in a reaction vessel equipped with a stirring device, a cooler, and a thermometer were prepared. 52 mmol), 0.8 g of dimethylaminopyridine and 300 ml of dichloromethane were added thereto, and the reaction vessel was kept at 5 ° C or lower in an ice-cooled bath, and 7.8 g (64 mmol) of diisopropylcarbodiimide was slowly added under an atmosphere of nitrogen gas. Dropped. After completion of the dropwise addition, the reaction vessel was returned to room temperature and allowed to react for 5 hours. After the reaction solution was filtered, 100 mL of dichloromethane was added to the filtrate, washed with 10% aqueous hydrochloric acid solution, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After distilling off the solvent, purification was performed by a silica gel column and recrystallization to obtain 18 g of the target compound represented by the formula (14).

(Property value)

¹ H-NMR (solvent: heavy chloroform): δ: 1.55 to 1.45 (m, 8H), 1.71 (m, 4H), 1.83 (m, 4H), 2.66 (m, 4H), 2.96 (m, 4H), 3.76 (m, 2H), 3.90 (s, 4H), 4.03 (t, 4H), 4.17 (t, 4H), 4.29 (t, 1H), 4.76 (t, 1H), 5.18 (d, 2H), 5.78 (d, 2H), 6.15 (q, 2H), 6.37 (d, 2H), 6.96 (d, 4H) 7.23 (d, 4H), 7.25 (m, 4H), 8.12 (d, 4H)

¹³ C-NMR (solvent: heavy chloroform): δ: 25.6, 28.4, 28.8, 30.1, 30.2, 35.3, 35.5, 64.3, 67.9, 73.0, 73.8, 80.6, 85.7, 114.0, 121.3, 121.5, 128.3, 129.0, 130.2 , 131.9, 137.1, 137.4, 149.2, 163.0, 164.5, 165.9, 171.3, 171.6

Infrared Absorption Spectrum (IR): 2925, 2855, 1760, 1652 ~ 1622, 809

(Melting point) 79 ℃

The compound represented by the formula (14) had a low melting point of 79 ° C. and excellent solubility with other liquid crystal compounds, but the HTP was calculated in the same manner as in Example 1, and the low value was HTP = 12.

Example 6 Preparation of Polymerizable Liquid Crystal Composition

The polymeric liquid crystal composition (composition 1) of the composition shown below was prepared.

The polymerizable liquid crystal composition had good commercial stability and exhibited a cholesteric liquid crystal phase. 1 g of a photoinitiator benzyl dimethyl ketal (brand name Irgacure 651 Chiba Specialty Chemical Co., Ltd.) was added to this composition with respect to 100 g of composition 1, and the polymeric liquid crystal composition (composition 2) was prepared. This composition 2 was injected into the cell with a polyimide of 5 cm in length, 5 cm in width, and 5 micrometers of gaps by the vacuum injection method. When this was irradiated with ultraviolet light of 4 mA / cm <2> for 120 second using the high pressure mercury lamp, the composition 2 superposed | polymerized while maintaining a uniform orientation state, and the optically anisotropic body was obtained. This optically anisotropic body had favorable circularly polarized light characteristic.

Comparative Example 3 Preparation of Polymerizable Liquid Crystal Composition

The polymeric liquid crystal composition (composition 5) of the composition shown below was prepared.

Although the polymeric liquid crystal composition showed the cholesteric liquid crystal phase, the orientation was bad and it was nonuniform. 1 g of a photoinitiator benzyl dimethyl ketal (brand name Irgacure 651 Chiba Specialty Chemical Co., Ltd.) was added to this composition with respect to 100 g of composition 5, and the polymeric liquid crystal composition (composition 6) was prepared. This composition 6 was injected into the cell with a polyimide of 5 cm in length, 5 cm in width, and 5 micrometers of gaps by the vacuum injection method. When this was irradiated with ultraviolet rays of 4 kW / cm 2 for 120 seconds using a high-pressure mercury lamp, the optically anisotropic body had a circularly polarized light characteristic, but was a cloudy and uneven optically anisotropic body.

Claims (9)

The compound of formula (I)

(However, R ¹ and R ² independently of each other represent any one of the following formula (R-1) to formula (R-15),

A ¹ , A ² , A ³ and A ⁴ independently of each other represent a 1,4-phenylene group, a naphthalene-2,6-diyl group, a 1,4-cyclohexylene group or a pyridine-2,5-diyl group And hydrogen atoms contained in A ¹ , A ² , A ^3, and A ⁴ may be each independently substituted with an alkyl group, a halogenated alkyl group, an alkoxy group, a halogen, a cyano group, or a nitro group, and B ¹ and B ² may be independent from each other. -O-, -S-, -OCH _2- , -CH ₂ O-, -CO-, -COO-, -OCO-, -OCOO-, -CO-NR ^11- , -NR ¹¹ -CO- , -SCH _2- , -CH ₂ S-, -CH = CH-COO-, -OCO-CH = CH-, -COO-CH = CH-, -CH = CH-OCO-, -CH ₂ CH _2- COO-, -COO-CH ₂ CH _2- , -CH ₂ CH ₂ -OCO-, -OCO-CH ₂ CH _2- , -C≡C- or a single bond (wherein R ¹¹ represents a hydrogen atom or carbon number) 1-4 represents an alkyl group), Z ¹ is, -COO-, -CH = CH-COO- , -CH 2 CH 2 -COO-, -CH 2 O- or -CF represents a ^₂ O-, Z ₂ Represents -OCO-, -OCO-CH = CH-, -OCO-CH ₂ CH _2- , -OCH ₂ -or -OCF _2- , Z represents the following general formulas (Z-1) to (Z- 3) as mark It represents any one of divalent substituents,

(In the formulas, each substituent indicates bonding to Z ¹ on one side of the bond represented by a dotted line and Z ² on the other side, and Y ¹ , Y ² , Y ³ , Y ⁴ , Y ^5, and Y ⁶ are each independently. To an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a hydrogen atom, and the divalent substituent represented by general formulas (Z-1) to (Z-3) in the formula represents a single three-dimensional structure) m and n, independently of each other, represent 0, 1 or 2, but when a plurality of A ¹ , A ² , B ¹ or / and B ² are present, they may be the same as or different from each other independently; compound. The method of claim 1,
A ¹ , A ² , A ³ and A ⁴ independently of each other represent a 1,4-phenylene group and a naphthalene-2,6-diyl group (A ² and A ³ independently of each other are an alkyl group, a halogenated alkyl group, an alkoxy group) , Halogen, cyano group or nitro group may be substituted). The method of claim 1,
B ¹ and B ² independently of one another are -OCH _2- , -CH ₂ O-, -CO-, -COO-, -OCO-, -CH = CH-COO-, -OCO-CH = CH-, -CH ₂ CH ₂ -COO-, -OOC-CH ₂ CH _2- , -CH ₂ CH ₂ -OCO-, -OCO-CH ₂ CH _2- , -C≡C- or a polymerizable chiral compound exhibiting a single bond. The method of claim 1,
A polymeric chiral compound in which Z ¹ represents -COO- or -CH = CH-COO- and Z ² represents -OCO- or -OCO-CH = CH-. The method of claim 1,
Polymeric chiral compound in which Z represents a bivalent substituent represented by general formula (Z-1) or (Z-3). The method of claim 1,
A polymeric chiral compound in which m and n represent 0 and 1 independently of each other. The method of claim 1,
A polymeric chiral compound in which Z represents a bivalent substituent represented by general formula (Z-1). The polymerizable composition containing the polymerizable chiral compound according to any one of claims 1 to 7. The optically anisotropic body using the polymeric composition of Claim 8.