Atropisomer of 1,1'-binaphthyl derivative, polymerizable liquid crystal composition, optical film, image display device and eyewear

Abstract

To provide an atropisomer of a 1,1'-binaphthyl derivative that exhibits a high HTP value even in small quantities.SOLUTION: The present invention provides an atropisomer represented by, for example, a following structural formula (2.1), a polymerizable liquid crystal composition comprising the atropisomer and a polymerizable liquid crystal compound, an optical film, an image display device and an eyewear.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an atropisomer of a 1,1'-binaphthyl derivative, and to a polymerizable liquid crystal composition, an optical film, an image display device, and eyewear using the same. [Background technology]

[0002] Cholesteric liquid crystals with circularly polarized light separation function have been widely used in optical films as optical compensation plates used in image display devices such as liquid crystal displays and eyewear such as polarized sunglasses. Liquid crystal molecules in cholesteric liquid crystals have a helically twisted orientation and have the property of selectively reflecting one of the left and right circularly polarized light components, which corresponds to the pitch of the helix. Such cholesteric liquid crystals can be obtained by polymerizing a polymerizable liquid crystal composition containing a liquid crystalline compound, such as a nematic liquid crystal, having a polymerizable functional group and a dopant agent, also having a polymerizable functional group.

[0003] In order for cholesteric liquid crystals to achieve circularly polarized light separation, a short-pitch helical structure is required, and therefore it is desirable to use a liquid crystal composition containing a dopant with a strong helical twisting power in the liquid crystal. The dopant can be used as a dopant that induces or enhances the helical twist in the liquid crystal, and HTP (Helical Twisting Power) is generally used as an index of the helical alignment ability of the dopant.

[0004] A helical structure with a short pitch can be obtained by using a large amount of dopant or by using a dopant with a high HTP value. Conventionally known dopant agents often exhibit low HTP values, so a large amount of dopant must be used to obtain a helical structure with the desired short pitch. However, there is a concern that using a large amount of dopant may adversely affect the properties of the liquid crystal, such as the dielectric anisotropy, viscosity, and driving voltage. Therefore, there is a need to develop a dopant agent that does not adversely affect the properties of the liquid crystal.

[0005] Patent Document 1 discloses that polymerizable chiral compounds having a specific structural formula have a high HTP value. However, the HTP value of polymerizable chiral compounds actually obtained through testing is at most about 65, and no polymerizable chiral compounds with higher HTP values ​​are described. Furthermore, taking into account the adverse effects on the properties of the liquid crystal, it is desirable to keep the concentration of the dopant agent relative to the liquid crystal compound as low as possible. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2013-87109 Summary of the Invention [Problem to be solved by the invention]

[0007] An object of the present invention is to provide an atropisomer of a 1,1'-binaphthyl derivative that has a high HTP value even in small amounts. [Means for solving the problem]

[0008] The atropisomer according to an embodiment of the present invention is represented by the following general formula (1) and / or general formula (2): [ka] [In formula (1) and formula (2), R1 and R2 each independently represent any one of the structures (R-1) to (R-20), and at least one of R1 and R2 is any one of (R-1) to (R-5), provided that, except when the structure is (R-1), R1 and R2 are not the same; [ka] [ka] [ka] [ka] [ka] A is C 1-12 is an alkyl group, R 3 ~R 12 are, independently of each other, -C n H 2n+1 , -OC n H 2n+1 , CN, F, Cl, Br, CF3, Y-((CH2) k1 -O) m -, Y-(CH2) k2 -OC(O)- or Y-(CH2) k3 -COO- Y represents HC=C(Z1)COO-, (H2COCH)-CH2-, HC=CH-CH2-, or HC=CH-O-; Z1 represents H or CH3; k1 to k3 are each independently an integer from 0 to 12, m is 0 or 1; n is an integer from 0 to 12, X 1 ~X 12 represent, independently of one another, -CH=CH-, -C≡C-, -HC=CH-COO-, -(O)CO-CH=CH-, -CH2-, -O-, -C(O)-, -CH2CH2-, -C2O-, -OCH2-, -COO-, -OC(O)-, -C(CH3)2-, -N=N-, -CH=N-, -N=CH-, -NHCO- or -OCNH-, p1 to p12 are each independently 0 or 1; q1 to q20 are each independently 0, 1, or 2, and and s1 to s10 are each independently 0, 1, 2, or 3.

[0009] In one embodiment of the present invention, R1 and R2 each independently represent any one of the structures (R-1) to (R-10), and at least one of R1 and R2 is any one of (R-1) to (R-4).

[0010] The polymerizable liquid crystal composition according to the embodiment of the present invention contains the above-described atropisomer and a polymerizable liquid crystal compound.

[0011] The optical film according to the embodiment of the present invention has a cured film of the polymerizable liquid crystal composition described above.

[0012] In one embodiment of the present invention, the above-mentioned optical film has a selective reflection function.

[0013] An image display device according to an embodiment of the present invention includes the optical film described above.

[0014] Eyewear according to an embodiment of the present invention includes the optical film described above. [Effects of the Invention]

[0015] According to the present invention, it is possible to realize atropisomers of 1,1'-binaphthyl derivatives that have high HTP values ​​even in small amounts. DETAILED DESCRIPTION OF THE INVENTION

[0016] The atropisomer according to this embodiment, and the polymerizable liquid crystal composition, optical film, image display device, and eyewear using the same will be described in detail below.

[0017] <Atropisomers> The atropisomer according to this embodiment is a compound represented by the following general formula (1) and / or general formula (2). These compounds are atropisomers of 1,1'-binaphthyl derivatives, with the compound represented by general formula (1) being the R-form and the compound represented by general formula (2) being the S-form. The atropisomer may be either the compound represented by general formula (1) or the compound represented by general formula (2), or may contain both.

[0018] [ka]

[0019] In the compounds represented by the general formulas (1) and (2), R1 and R2 each independently represent one of the following structures (R-1) to (R-20), and at least one of R1 and R2 is one of (R-1) to (R-5). However, except when the structure is (R-1), R1 and R2 are not the same. That is, except when both R1 and R2 are (R-1), R1 and R2 have different structures. Furthermore, since at least one of R1 and R2 contains a polymerizable group represented by HC=C(CH)-C(O)O-, the compounds represented by the general formulas (1) and (2) exhibit polymerizability and function as dopants for polymerizable liquid crystal compounds, which are the same liquid crystal components.

[0020] [ka] [ka] [ka] [ka] [ka]

[0021] In the structure of (R-6) above, A is C 1-12 is an alkyl group, C 3-6 It is preferably an alkyl group. 1-12 The alkyl group may be linear or branched. 1-12Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group, and an n-propyl group or a pentyl group is preferred.

[0022] In the structures of (R-11) to (R-20) above, R 3 ~R 12 are, independently of each other, -C n H 2n+1 , -OC n H 2n+1 , CN, F, Cl, Br, CF3, Y-((CH2) k1 -O) m -, Y-(CH2) k2 -OC(O)- or Y-(CH2) k3 -COO- Y represents H2C=C(Z1)COO-, (H2COCH)-CH2-, H2C=CH-CH2-, or H2C=CH-O-, and preferably H2C=C(Z1)COO-; Z1 represents H or CH3, preferably CH3; k1 to k3 are each independently an integer of 0 to 12, preferably 0; m is 0 or 1, preferably 0; n is an integer of 0 to 12, preferably 1, 3, 4, 5, or 6, and in the structures of (R-19) and (R-20), it is particularly preferable that n=1. X 1 ~X 12 represent, independently from one another, -CH=CH-, -C≡C-, -HC=CH-COO-, -(O)CO-CH=CH-, -CH-, -O-, -C(O)-, -CHCH-, -CHO-, -OCH-, -COO-, -OC(O)-, -C(CH)-, -N=N-, -CH=N-, -N=CH-, -NHCO- or -OCNH-, preferably -COO-; p1 to p12 are each independently 0 or 1, and preferably 0; q1 to q20 are each independently 0, 1, or 2, preferably 1, with the proviso that in the structures of (R-15) and (R-16), q7 and q10 are each particularly preferably 0; and s1 to s10 are each independently 0, 1, 2 or 3, preferably 1, with the particular preference that in the structures of (R-19) and (R-20), s9 and s10 are each 0.

[0023] Preferably, R1 and R2 each independently represent any one of the structures (R-1) to (R-10), and at least one of R1 and R2 is any one of the structures (R-1) to (R-4). When one of R1 and R2 represents any one of the structures (R-11) to (R-20), it is preferably (R-11), (R-13), (R-15), (R-17), or (R-19).

[0024] In the atropisomers according to this embodiment, R1 and R2 are asymmetric with each other, and R1 and R2 do not combine to form a single skeletal structure, except when both R1 and R2 are (R-1) in the compounds represented by general formulas (1) and (2). Because the compounds represented by general formulas (1) and (2) have such specific structures, atropisomers exhibiting high HTP values ​​can be obtained even in small amounts. Furthermore, optical films obtained using polymerizable liquid crystal compositions containing atropisomers with such properties as dopants can exhibit a wide range of center reflection wavelengths depending on the content of the atropisomer, and can particularly widen the reflection band in the visible light region.

[0025] <Method for producing atropisomers> The atropisomer according to this embodiment can be produced, for example, by the synthesis method described below.

[0026] <Production Example 1: Production of a compound represented by general formula (2) in which R1 and R2 are symmetrical> (S)-1,1'-Bi-2-naphthol (S-Binol), dimethylaminopyridine (DMAP), and 4-({6-[(2-methylprop-2-enoyl)oxy]naphthalene-2-carbonyl}oxy)benzoic acid (Ma-NP-BA) are added to a reaction vessel and stirred in dichloromethane (DCM). The resulting suspension is added with 1-(3-dimethylaminopropyl) By adding 3-ethylcarbodiimide hydrochloride (EDC) in small amounts at regular intervals, a compound in which S-Binol is diesterified with Ma-NP-BA, i.e., a compound represented by the following general formula (2.1) in which R1 and R2 are each structure (R-1), can be obtained.

[0027] [ka]

[0028] <Production Example 2: Production of a compound represented by general formula (2) in which R1 and R2 are asymmetric> (Process 1) S-Binol, DMAP, and 4-(trans-4-pentylcyclohexyl)benzoic acid (5PCA) are added to a reaction vessel and stirred in DCM. EDC is added in small amounts at regular intervals to the resulting suspension to synthesize the compound in which S-Binol is monoesterified with 5PCA (S-Binol monoester of 5PCA).

[0029] (Process 2) By adding 4'-[(2-methylprop-2-enoyl)oxy][1,1'-biphenyl]-4-carboxylic acid (Ma-BPh-A) and EDC to a solution containing the S-binol monoester of 5PCA, a compound in which S-binol is diesterified with 5PCA and Ma-BPh-A, i.e., a compound represented by general formula (2.2) in which one of R1 and R2 is structure (R-6) and the other is structure (R-4), can be obtained.

[0030] [ka]

[0031] <Polymerizable liquid crystal composition> The polymerizable liquid crystal composition according to this embodiment contains a polymerizable liquid crystal compound and the above-described atropisomer as a dopant. The polymerizable liquid crystal composition also contains a polymerization initiator that polymerizes the compound to promote curing of the polymerizable liquid crystal composition, a solvent for dissolving the compound, and optionally various additives. Such a polymerizable liquid crystal composition can be prepared by dissolving the polymerizable liquid crystal compound and the above-described atropisomer liquid crystal component in a solvent and adding a polymerization initiator and optional additives to the resulting solution. Adding the above-described atropisomer to the polymerizable liquid crystal compound transforms the polymerizable liquid crystal compound into a cholesteric liquid crystal state, causing the liquid crystal molecules to align helically. The helical alignment of the liquid crystal molecules provides optical elements prepared using the polymerizable liquid crystal composition with a selective reflection function that selectively reflects circularly polarized light components of light wavelengths corresponding to the helical pitch.

[0032] Polymerizable liquid crystal compounds exhibit liquid crystallinity within a specific temperature and concentration range, and can be polymerized by ultraviolet light or heat while maintaining their alignment, thereby fixing the alignment. Such polymerizable liquid crystal compounds are preferably polymerizable liquid crystal monomers having a polymerizable group within the molecule. Examples of the polymerizable group include (meth)acryloyl, vinyl, chalcone, cinnamoyl, and epoxy groups. Furthermore, to exhibit liquid crystallinity, it is preferable for the compound to have a mesogenic group within the molecule. The mesogenic group refers to a rod-shaped or plate-shaped substituent, such as a biphenyl group, a terphenyl group, a (poly)benzoic acid phenyl ester group, a (poly)ether group, a benzylideneaniline group, or an acenaphthoquinoxaline group, or a discotic substituent, such as a triphenylene group, a phthalocyanine group, or an azacrown group, i.e., a group capable of inducing liquid crystal phase behavior. Liquid crystal compounds having rod-shaped or plate-shaped substituents are known in the art as calamitic liquid crystals. Specific examples of such polymerizable liquid crystal monomers include the polymerizable liquid crystal compounds described in JP-A Nos. 2003-315556 and 2004-29824 and Japanese Patent No. 5463666, and polymerizable nematic liquid crystal monomers such as the PALIOCOLOR series (manufactured by BASF) and the RMM series (manufactured by Merck).The polymerizable liquid crystal compounds may be used alone or in combination of two or more.

[0033] The atropisomers functioning as dopants can cause the polymerizable liquid crystal compounds to be twisted in a right-handed or left-handed orientation, thereby making it possible to obtain polymerizable liquid crystal compositions exhibiting a cholesteric liquid crystal phase. The polymerization reaction forms a polymer having repeating units derived from the polymerizable liquid crystal compound and repeating units derived from the compound represented by general formula (1) and / or general formula (2). The content of the atropisomer contained in the polymerizable liquid crystal composition is preferably 0.05 parts by mass or more and 15 parts by mass or less, more preferably 0.1 parts by mass or more and 10 parts by mass or less, and even more preferably 1.0 parts by mass or more and 5.0 parts by mass or less, relative to 100 parts by mass of the polymerizable liquid crystal compound used in combination. The lower the content of the polymerizable atropisomer in the liquid crystal composition, the less the effect on liquid crystallinity can be.

[0034] The polymerizable liquid crystal composition may contain a polymerizable compound that can react with the polymerizable liquid crystal compound but does not have liquid crystallinity. Examples of such a polymerizable compound include an ultraviolet-curable resin. Examples of ultraviolet curable resins include dipentaerythritol hexa(meth)acrylate, a reaction product of dipentaerythritol penta(meth)acrylate and 1,6-hexamethylene-diisocyanate, a reaction product of a triisocyanate having an isocyanuric ring and pentaerythritol tri(meth)acrylate, a reaction product of pentaerythritol tri(meth)acrylate and isophorone-diisocyanate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, tris(acryloxyethyl)isocyanurate, tris(methacryloxyethyl)isocyanurate, tris(acryloxyethyl)isocyanurate, reaction products of glycerol triglycidyl ether and (meth)acrylic acid, caprolactone-modified tris(acryloxyethyl)isocyanurate, reaction products of trimethylolpropane triglycidyl ether and (meth)acrylic acid, triglycerol-di-(meth)acrylate, reaction products of propylene glycol-di-glycidyl ether and (meth)acrylic acid, polypropylene glycol-di-(meth)acrylate, tripropylene glycol-di-(meth)acrylate, polyethylene glycol-di-(meth)acrylate, tetraethylene glycol-di-(meth)acrylate, triethylene glycol-di-(meth)acrylate, pentaerythritol-di-(meth)acrylate, reaction products of 1,6-hexanediol-di-glycidyl ether and (meth)acrylic acid, 1,6-Hexanediol-di-(meth)acrylate, glycerol-di-(meth)acrylate, reaction products of ethylene glycol-di-glycidyl ether and (meth)acrylic acid, reaction products of diethylene glycol-di-glycidyl ether and (meth)acrylic acid, bis(acryloxyethyl)hydroxyethyl isocyanurate, bis(methacryloxyethyl)hydroxyethyl isocyanurate, reaction products of bisphenol A-di-glycidyl ether and (meth)acrylic acid, tetrahydrofurfuryl (meth)acrylate, caprolactone-modified tetrahydrofurfuryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, polypropylene glycol (meth)acrylate, polyethylene glycol (meth)acrylate, phenoxyhydroxy Examples of such a resin include propyl (meth)acrylate, acryloylmorpholine, methoxypolyethylene glycol (meth)acrylate, methoxytetraethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxyethylene glycol (meth)acrylate, methoxyethyl (meth)acrylate, glycidyl (meth)acrylate, glycerol (meth)acrylate, ethyl carbitol (meth)acrylate, 2-ethoxyethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, 2-cyanoethyl (meth)acrylate, a reaction product of butyl glycidyl ether and (meth)acrylic acid, butoxytriethylene glycol (meth)acrylate, and butanediol mono(meth)acrylate. These may be used alone or in combination. These UV-curable resins that do not have liquid crystallinity may be added to the liquid crystal composition to an extent that the polymerizable liquid crystal composition does not lose its liquid crystallinity, and are preferably added in an amount of 0.1 part by mass or more per 100 parts by mass of the polymerizable liquid crystal compound. The amount added is at most 25 parts by mass, more preferably at least 0.5 parts by mass and at most 10 parts by mass.

[0035] The polymerizable liquid crystal composition may contain a polymerization initiator in order to cure the polymerizable liquid crystal composition by a polymerization reaction. Since the curing reaction of the polymerizable liquid crystal composition generally proceeds by irradiation with ultraviolet light, the polymerization initiator used is preferably a photopolymerization initiator that can initiate a polymerization reaction by irradiation with ultraviolet light. The photopolymerization initiator is not particularly limited, and examples thereof include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (manufactured by IGM Resins BV under the trade name "Omnirad 907"), 1-hydroxycyclohexylphenyl ketone (manufactured by IGM Resins BV under the trade name "Omnirad 184"), 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone (manufactured by IGM Resins BV under the trade name "Omnirad 2959"), 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one (manufactured by Merck under the trade name "Darocur 953"), 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one (manufactured by Merck under the trade name "Darocur 1116"), 2-hydroxy-2-methyl-1-phenylpropan-1-one (manufactured by IGM Resins BV under the trade name "Darocur 1116"), and the like. Acetophenone compounds such as "Omnirad 1173" manufactured by BV, diethoxyacetophenone; benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and 2,2-dimethoxy-2-phenylacetophenone ("Omnirad 651" manufactured by IGM Resins BV); benzophenone compounds such as benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and 3,3'-dimethyl-4-methoxybenzophenone ("KAYACURE MBP" manufactured by Nippon Kayaku Co., Ltd.); Phosphine oxide compounds such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (Omnirad TPO manufactured by IGM Resins BV) and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (Omnirad 819 manufactured by IGM Resins BV); and Examples of the photopolymerization initiator include thioxanthone compounds such as thioxanthone, 2-chlorothioxanthone (manufactured by Nippon Kayaku Co., Ltd. under the trademark "KAYACURE CTX"), 2-methylthioxanthone, 2,4-dimethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd. under the trademark "KAYACURE RTX"), isopropylthioxanthone, 2,4-dichlorothioxanthone (manufactured by Nippon Kayaku Co., Ltd. under the trademark "KAYACURE CTX"), 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd. under the trademark "KAYACURE DETX"), and 2,4-diisopropylthioxanthone (manufactured by Nippon Kayaku Co., Ltd. under the trademark "KAYACURE DITX"). These photopolymerization initiators may be used alone or in combination of two or more types.

[0036] When a benzophenone compound or a thioxanthone compound is used as the photopolymerization initiator, it is preferable to use a reaction aid in combination to promote the photopolymerization reaction. The reaction aid is not particularly limited, and examples thereof include amine compounds such as triethanolamine, methyldiethanolamine, triisopropanolamine, n-butylamine, N-methyldiethanolamine, diethylaminoethyl methacrylate, Michler's ketone, 4,4'-diethylaminophenone, ethyl 4-dimethylaminobenzoate, 2-butoxyethyl 4-(dimethylamino)benzoate, and isoamyl 4-(dimethylamino)benzoate.

[0037] The amounts of the photopolymerization initiator and the reaction aid added are preferably within a range that does not affect the liquid crystallinity of the polymerizable liquid crystal composition, and are preferably 0.05 parts by mass or more and 10 parts by mass or less, more preferably 0.1 parts by mass or more and 5 parts by mass or less, relative to 100 parts by mass of the compound curable by ultraviolet light in the polymerizable liquid crystal composition. The amount of the aid added is at least twice as much as the photopolymerization initiator on a mass basis. Preferably, it is above.

[0038] The polymerizable liquid crystal composition further contains a solvent. Such a solvent is not particularly limited as long as it can dissolve the polymerizable liquid crystal compound, dopant, and the like used, and examples thereof include methyl ethyl ketone, toluene, methyl isobutyl ketone, cyclopentanone, acetone, xylene, anisole, and the like. These solvents can be added in any ratio, and one type alone or multiple solvents may be added in combination. These solvents are dried and removed in a drying zone such as an oven or film coater line.

[0039] The polymerizable liquid crystal composition may further contain additives such as a leveling agent, an ultraviolet absorber, a light stabilizer, an antioxidant, a polymerization inhibitor, a crosslinking agent, a plasticizer, and a flow adjuster in any proportion, as necessary. Examples of leveling agents include fluorine-based compounds, silicone-based compounds, and acrylic compounds. Examples of ultraviolet absorbers include benzotriazole-based compounds, benzophenone-based compounds, and triazine-based compounds. Examples of light stabilizers include hindered amine-based compounds and benzoate-based compounds. Examples of antioxidants include phenol-based compounds. Examples of polymerization inhibitors include methoquinone, methylhydroquinone, and hydroquinone. Examples of crosslinking agents include polyisocyanates and melamine compounds. Examples of plasticizers include phthalates such as dimethyl phthalate and diethyl phthalate, trimellitic esters such as tris(2-ethylhexyl) trimellitate, aliphatic dibasic esters such as dimethyl adipate and dibutyl adipate, orthophosphates such as tributyl phosphate and triphenyl phosphate, and acetates such as glyceryl triacetate and 2-ethylhexyl acetate. Examples of flow control agents include "TEGO (registered trademark) Rad 2100" (manufactured by Evonik).

[0040] <Optical film> The polymerizable liquid crystal composition according to this embodiment can be used as a raw material for optical films such as light-reflecting films, retardation films, and polarizing films. Such optical films can be produced by forming a coating film of the polymerizable liquid crystal composition on a predetermined film used as a substrate and then curing the coating film. For example, when producing a light-reflecting film using the polymerizable liquid crystal composition, the polymerizable liquid crystal composition containing the above-described components is applied to a substrate, such as a triacetyl cellulose (TAC) film, an acrylic film, a polycarbonate film, a polyvinyl chloride film, a polyolefin film, or a polyethylene terephthalate (PET) film, so as to have as uniform a thickness as possible. The coating is then left for a certain period of time while heating to remove the solvent, thereby forming a coating film on the substrate. The heating conditions are not particularly limited as long as the polymerizable liquid crystal compound on the substrate is in a cholesteric liquid crystal state and oriented with the desired helical pitch, but are preferably 40 to 90°C. In this case, by subjecting the surface of the substrate to an orientation treatment such as rubbing or stretching before coating the polymerizable liquid crystal composition, the cholesteric liquid crystal alignment can be made more uniform, thereby reducing the haze value of the optical film. Next, while maintaining this orientation, ultraviolet light is irradiated from a high-pressure mercury lamp or the like to fix the orientation of the cholesteric liquid crystal, thereby producing an optical film (light-reflecting film) having a cured film of the polymerizable liquid crystal composition. When an atropisomer exhibiting right-handed helical orientation is used, an optical film that selectively reflects right-handed circularly polarized light is obtained. On the other hand, when an atropisomer exhibiting left-handed helical orientation is used, an optical film that selectively reflects left-handed circularly polarized light is obtained. This phenomenon of selectively reflecting specific circularly polarized light is called selective reflection, and an optical film with selective reflection function can be obtained.

[0041] The optical film according to this embodiment exhibits a selective reflection function, and is therefore capable of reducing the amount of incident light and glare, and reflecting light in a specific wavelength band, and is therefore effective for application to, for example, eyewear such as eyeglasses, sunglasses, and goggles, and image display devices such as liquid crystal display devices and organic EL display devices. [Example]

[0042] Examples of the present invention will be described below, but the present invention is not limited to these examples as long as they do not depart from the spirit of the present invention. Furthermore, unless otherwise specified, the "%" and "parts" below are based on mass, and room temperature is in the range of 20°C ± 5°C.

[0043] Example 1 1.43 g of (S)-1,1'-bi-2-naphthol (5 mmol: S-binol), 61 mg of dimethylaminopyridine (DMAP), and 4.33 g of 4-({6-[(2-methylprop-2-enoyl)oxy]naphthalene-2-carbonyl}oxy)benzoic acid (11.5 mmol: Ma-NP-BA) were added to a reaction vessel containing 50 mL of dichloromethane (DCM) and stirred at room temperature. To the resulting suspension, 2.22 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (11.5 mmol: EDC) was added in two 1.11 g portions at 1 hour intervals and stirred for 20 hours. Analysis by thin layer chromatography (TLC) showed complete conversion of S-binol to the diester. For post-treatment, this solution was washed with 10% sodium chloride solution to remove the EDC-urea by-product and dried over anhydrous magnesium sulfate. The DCM-containing solution was then concentrated to approximately 30% (based on the maximum yield of compound 2.1) and precipitated with 250 ml of methanol. The precipitate was filtered, washed twice with methanol, and dried to give 4.49 g of the compound represented by the following general formula (2.1) (yield: 90%).

[0044] [ka]

[0045] The compound represented by the general formula (2.1) (compound 2.1) was added without further purification to a polymerizable liquid crystal compound (LC242:RM257 = 1:1) containing 1.9% photopolymerization initiator (Omnirad TPO) and 0.1% flow modifier (TEGO® Rad 2100), adjusting the content of compound 2.1 relative to the polymerizable liquid crystal compound to 3.5%. The resulting mixture of polymerizable liquid crystal compound and compound 2.1 was dissolved in m-xylene (solvent) to prepare a polymerizable liquid crystal composition containing 3.5% compound 2.1 and 35% compound 2.1. This polymerizable liquid crystal composition was applied by spin coating (rotation speed: 750 rpm) onto a PET film (thickness: 100 μm) manufactured by Toyobo Co., Ltd., which had been previously rubbed with nylon cloth. The resulting coating was dried at 80°C for 5 minutes to align the liquid crystals. The coating was then irradiated with an LED (100mW / cm²) emitting light with a wavelength of 365nm while purging with nitrogen gas. The coating was then cured at 80°C for 30 seconds to produce an optical film with a cholesteric liquid crystal layer formed on a PET film. The central reflection wavelength of this optical film was 494nm, and the HTP value of compound 2.1 was 92.5µm. -1 It was. there were.

[0046] <Example 2> (Process 1) 2.86 g of S-binol (10 mmol), 0.12 g of DMAP, and 2.81 g of 4-(trans-4-pentylcyclohexyl)benzoic acid (10.25 mmol:5PCA) were added to a reaction vessel containing 60 mL of DCM and stirred at room temperature. To the resulting suspension, 2.12 g of EDC (11 mmol) was added in two 1.06 g portions, 1 hour apart, and the mixture was stirred for 20 hours. Analysis by thin-layer chromatography (TLC) then showed the formation of the monoester of S-binol, traces of S-binol, and traces of the diester of S-binol ("by-products").

[0047] (Process 2) To the solution containing the S-binol monoester of 5PCA obtained in step 1, 3.17 g of 4'-[(2-methylprop-2-enoyl)oxy][1,1'-biphenyl]-4-carboxylic acid (11.25 mmol: Ma-BPh-A) and 2.30 g of EDC (12 mmol) were added in two 1.15 g portions at 1-hour intervals and stirred for 20 hours. Analysis by thin-layer chromatography (TLC) showed complete conversion to the S-binol diester. For workup, the solution was washed with 10% sodium chloride solution to remove the EDC-urea byproduct and dried over anhydrous magnesium sulfate. The solution containing DCM was then concentrated to approximately 30% (based on the maximum yield of compound 2.2) and precipitated with 300 ml of methanol. The precipitate was filtered, washed twice with methanol, and dried to give 6.68 g of the compound represented by the following general formula (2.2) (83% yield).

[0048] [ka]

[0049] The obtained compound represented by general formula (2.2) (compound 2.2) was not further purified, and the content of compound 2.2 relative to the polymerizable liquid crystal compound was adjusted to 5.0%. An optical film was produced in the same manner as in Example 1. The central reflection wavelength of this film was 416 nm, and the HTP value of compound 2.2 was 76.9 μm -1 It was. there were.

[0050] The compounds prepared in the following Examples 3 to 9 were synthesized by the same two-step process as the method described in Example 2.

[0051] Example 3

[0052] 2.86 g of S-Binol (10 mmol) was used to react with 4-[(4-methoxybenzoyl)oxy]benzoic acid (MBBA) instead of 4-(trans-4-pentylcyclohexyl)benzoic acid in step 1, and 4'-[(2-methylprop-2-enoyl)oxy][1,1'-biphenyl]-4-carboxylic acid (Ma-BPh-A) was used in step 2. After post-treatment, 7.8 g of a compound represented by the following general formula (2.3) was obtained (yield: 97%). An optical film was produced in the same manner as in Example 1, except that the content of compound 2.3 relative to the polymerizable liquid crystal compound was adjusted to 4.0% without further purification of the obtained compound represented by general formula (2.3) (compound 2.3). The central reflection wavelength of this film was 493 nm, and the HTP value of compound 2.3 was 81.1 μm. -1 It was.

[0053] [ka]

[0054] Example 4 2.86 g of S-Binol (10 mmol) was used in step 1, and reacted with benzoic acid (5PCA-BA) corresponding to the compound represented by (R-7) above instead of 4-(trans-4-pentylcyclohexyl)benzoic acid. Similarly, 4'-[(2-methylprop-2-enoyl)oxy][1,1'-biphenyl]-4-carboxylic acid (Ma-BPh-A) was used in step 2. After post-treatment, 4.1 g of a compound represented by the following general formula (2.4) was obtained (yield: 97%). An optical film was produced in the same manner as in Example 1, except that the content of compound 2.4 relative to the polymerizable liquid crystal compound was adjusted to 3.5% without further purification of the obtained compound represented by general formula (2.4) (compound 2.4). The central reflection wavelength of this film was 545 nm, and the HTP value of compound 2.4 was 83.9 μm. -1 It was.

[0055] [ka]

[0056] <Example 5> Using 2.86 g of S-binol (10 mmol), in step 1, benzoic acid (5PCA-BA) corresponding to the compound represented by (R-7) above was used instead of 4-(trans-4-pentylcyclohexyl)benzoic acid, and in step 2, benzoic acid (Ma-BPh-BA) corresponding to the compound represented by (R-3) above was used instead of 4'-[(2-methylprop-2-enoyl)oxy][1,1'-biphenyl]-4-carboxylic acid. After post-treatment, 10.1 g of a compound represented by the following general formula (2.5) was obtained (yield 97%). An optical film was produced in the same manner as in Example 1, except that the content of compound 2.5 relative to the polymerizable liquid crystal compound was adjusted to 3.0% without further purification of the obtained compound represented by general formula (2.5) (compound 2.5). The central reflection wavelength of this film was 548 nm, and the HTP value of compound 2.5 was 97.3 μm. -1 It was.

[0057] [ka]

[0058] Example 6 In step 1, 2.86 g of S-binol (10 mmol) was reacted with 4-(trans-4-pentylcyclohexyl)benzoic acid (5PCA), and in step 2, benzoic acid (Ma-BPh-BA), corresponding to the compound represented by (R-3) above, was used instead of 4'-[(2-methylprop-2-enoyl)oxy][1,1'-biphenyl]-4-carboxylic acid. After post-treatment, 7.3 g of a compound represented by the following general formula (2.6) was obtained (yield: 78%). An optical film was produced in the same manner as in Example 1, except that the content of compound 2.6 relative to the polymerizable liquid crystal compound was adjusted to 3.5% without further purification of the obtained compound represented by general formula (2.6) (compound 2.6). The central reflection wavelength of this film was 546 nm, and the HTP value of compound 2.6 was 83.7 μm. -1 It was.

[0059] [ka]

[0060] Example 7 Using 2.86 g of S-binol (10 mmol) and 61 mg of DMAP, 4-(trans-4-propylcyclohexyl)benzoic acid (3PCA) was used instead of 4-(trans-4-pentylcyclohexyl)benzoic acid in step 1, and 4-({6-[(2-methylprop-2-enoyl)oxy]naphthalene-2-carbonyl}oxy)benzoic acid (Ma-NP-BA) was used instead of 4'-[(2-methylprop-2-enoyl)oxy][1,1'-biphenyl]-4-carboxylic acid in step 2. After post-treatment, 7.4 g of a compound represented by the following general formula (2.7) was obtained (yield 85%). An optical film was produced in the same manner as in Example 1, except that the content of compound 2.7 relative to the polymerizable liquid crystal compound was adjusted to 3.5% without further purification of the obtained compound represented by general formula (2.7) (compound 2.7). The central reflection wavelength of this film is 572 nm, and the HTP value of compound 2.7 is 79.9 μm -1 It was.

[0061] [ka]

[0062] Example 8 2.86 g of (R)-1,1'-bi-2-naphthol (10 mmol: R-Binol) was used, and in step 1, 4-(trans-4-pentylcyclohexyl)benzoic acid was replaced with benzoic acid (5PCA-BA) corresponding to the compound represented by (R-7) above, and in step 2, 4-({6-[(2-methylprop-2-enoyl)oxy]naphthalene-2-carbonyl}oxy)benzoic acid (Ma-NP-BA) was used instead of 4'-[(2-methylprop-2-enoyl)oxy][1,1'-biphenyl]-4-carboxylic acid. After post-treatment, 10.0 g of a compound represented by the following general formula (2.8) was obtained (yield 98%). An optical film was produced in the same manner as in Example 1, except that the content of compound 2.8 relative to the polymerizable liquid crystal compound was adjusted to 3.5% without further purification of the obtained compound represented by general formula (2.8) (compound 2.8). The central reflection wavelength of this film is 495 nm, and the HTP value of compound 2.8 is 92.4 μm -1 It was.

[0063] [ka]

[0064] Example 9 Using 21.45 g of S-binol (75 mmol) and 0.46 g of DMAP, 4-(trans-4-propylcyclohexyl)benzoic acid (3PCA) was reacted in place of 4-(trans-4-pentylcyclohexyl)benzoic acid in step 1, and 4'-[(2-methylprop-2-enoyl)oxy][1,1'-biphenyl]-4-carboxylic acid was used in step 2. After post-treatment, 53.1 g of a compound represented by the following general formula (2.9) was obtained (yield: 91%). An optical film was produced in the same manner as in Example 1, except that the content of compound 2.9 relative to the polymerizable liquid crystal compound was adjusted to 3.5% without further purification of the obtained compound represented by general formula (2.9) (compound 2.9). The central reflection wavelength of this film was 570 nm, and the HTP value of compound 2.9 was 80.2 μm. -1 It was.

[0065] [Chemical formula]

[0066] <Comparative Example 1> Instead of the atropisomer of the present invention, "Lumogen (registered trademark) S750" (manufactured by BASF), a commercially available product, was used as a comparative compound. An optical film was produced in the same manner as in Example 1, except that the content of the comparative compound with respect to the polymerizable liquid crystal compound was adjusted to 5.0%. The central reflection wavelength of this film was 509 nm, and the HTP value of the comparative compound was 62.9 μm. -1 It was.

[0067] Regarding the atropisomers produced in Examples 1 to 9, the comparative compound used in Comparative Example 1, and each optical film, while changing the content of the atropisomer with respect to the polymerizable liquid crystal compound (hereinafter also referred to as "concentration"), the HTP value and the central reflection wavelength were measured as follows. The results are shown in Table 1.

[0068] <HTP Value and Central Reflection Wavelength> Compounds 2.1 to 2.9 and a comparative compound (dopant agent) were respectively added to a polymerizable liquid crystal compound (LC242:RM257 = 1:1), the concentration of the dopant agent with respect to the polymerizable liquid crystal compound was adjusted, and the absolute value of the HTP value was calculated based on the following formula (A). In formula (A), P represents the helical pitch length (μm), and C represents the concentration (%) of the dopant agent with respect to the polymerizable liquid crystal compound. Also, P was measured as the central reflection wavelength (λ r ) in the reflection band of the optical film and calculated based on the following formula (B). Here, the average refractive index (n) of the polymerizable liquid crystal compound was assumed to be 1.6 for calculation. Also, the central reflection wavelength (λ r ) was measured by using a spectrophotometer to measure the reflection spectrum of the optical film, and the wavelengths (λ min and λ max ) corresponding to half of the maximum height of the reflection spectrum were determined, and (λ min +λ max ) / 2 was calculated to identify it.

[0069]

number

[0070]

number

[0071] [Table 1]

[0072] As shown in Table 1, the atropisomers prepared in Examples 1 to 9 were added in the range of 3 to 5%. Even when the amount was changed, the HTP values ​​exceeded 75 in all cases, showing high HTP values ​​even with small amounts. In particular, the atropisomers prepared in Examples 1 and 5 showed extremely high HTP values ​​exceeding 90 even with an addition amount as small as 3%. Furthermore, the optical films prepared in Examples 1 to 6 were able to change the central reflection wavelength depending on the addition amount even with small amounts, so optical films with an expanded reflection band in the visible light region could be obtained without affecting the properties of the liquid crystal.

[0073] On the other hand, the comparative compound used in Comparative Example 1 had a lower HTP value than the atropisomers prepared in Examples 1 to 9. Furthermore, the central reflection wavelengths of the optical film prepared in Comparative Example 1 were 509 nm and 630 nm at addition amounts of 5.0% and 4.0%, respectively, and therefore the reflection band in the visible light region was limited at lower concentrations. [Industrial Applicability]

[0074] The present invention can provide an atropisomer that has a high HTP value even in small amounts, and a polymerizable liquid crystal composition, optical film, image display device, and eyewear using the atropisomer.

Claims

1. General formula (1) and / or general formula (2): 【Chemistry 1】 [In formula (1) and formula (2), R １ and R ２ each independently represents any one of the structures (R-1) to (R-20), and R １ and R ２ is any one of (R-1) to (R-5), provided that, except when the structure is (R-1), R １ and R ２ are not the same, 【Chemistry 2】 【Transformation 3】 【Chemistry 4】 【Transformation 5】 【Transformation 6】 A is C １－１２ is an alkyl group, R ３ ~R １２ are, independently of each other, -C ｎ H ２ｎ＋１ , -OC ｎ H ２ｎ＋１ , CN, F, Cl, Br, CF ３ , Y-((CH ２ ) ｋ１ -O) ｍ -, Y-(CH ２ ) ｋ２ -OC(O)-, or Y-(CH ２ ) ｋ３ represents —COO—, Y is H ２ C=C(Z １ ) COO-, (H ２ COCH)-CH ２ -, H ２ C=CH-CH ２ - or H ２ represents C=CH-O-, Z １ is H or CH ３ represents k1 to k3 are each independently an integer from 0 to 12, m is 0 or 1; n is an integer from 0 to 12, X １ ~X １２ are each independently —CH═CH—, —C≡C—, —HC═CH—COO—, —(O)CO—CH═CH—, —CH ２ -, -O-, -C(O)-, -CH ２ CH ２ -, -CH ２ O-, -OCH ２ -, -COO-, -OC(O)-, -C(CH ３ ) ２ -, -N=N-, -CH=N-, -N=CH-, -NHCO- or -OCNH-; p1 to p12 are each independently 0 or 1; q1 to q20 are each independently 0, 1 or 2, and and s1 to s10 are independently 0, 1, 2 or 3.

2. R １ and R ２ each independently represents any one of the structures (R-1) to (R-10), and R １ and R ２ 2. The atropisomer according to claim 1, wherein at least one of the following is any one of (R-1) to (R-4):

3. A polymerizable liquid crystal composition comprising the atropisomer according to claim 1 or 2 and a polymerizable liquid crystal compound.

4. An optical film having a cured film of the polymerizable liquid crystal composition according to claim 3 .

5. The optical film according to claim 4, which has a selective reflection function.

6. An image display device comprising the optical film according to claim 4 .

7. Eyewear comprising the optical film according to claim 4.

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