Atropiomer of 1, 1 '-binaphthalene derivative, polymerizable liquid crystal composition, optical film, image display device, and glasses

Abstract

The present invention relates to an atropisomer represented by the following general formula (1) and / or general formula (2). [In formula (1) and formula (2), R1 and R2 each independently represent a structure of (R-1) to (R-20), and at least one of R1 and R2 is a structure of (R-1) to (R-5), but R1 and R2 are different except when the structure is (R-1). # imgabs0 #

Description

Technical Field

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

[0002] In the past, cholesterol liquid crystals with circular polarization separation functions have been widely used as optical films used as optical compensation plates in image display devices such as liquid crystal displays and glasses such as polarized sunglasses. The liquid crystal molecules in the cholesterol liquid crystal have a twisted spiral orientation, and have the property of selectively reflecting one of the left circular polarization component or the right circular polarization component corresponding to the pitch of the spiral. Such cholesterol liquid crystals can be obtained by polymerizing a polymerizable liquid crystal composition, and the polymerizable liquid crystal composition contains a liquid crystal compound such as a nematic liquid crystal having a polymerizable functional group and a dopant having the same polymerizable functional group.

[0003] In order to make cholesterol liquid crystal obtain circular polarization separation function, a short-pitch helical structure is required, so it is desirable to use a liquid crystal composition containing a dopant with strong helical torsion in the liquid crystal. The dopant can be used as a dopant that induces or enhances helical torsion in the liquid crystal, and the helical torsion power (HTP) is generally used as an indicator of the helical orientation ability of the dopant.

[0004] A short-pitch spiral structure can be obtained by using a large amount of dopants or by using a dopant with a high HTP value. Dopants known in the past often show low HTP values. In order to obtain a spiral structure with an expected short pitch, a large amount of dopants must be used. However, if a large amount of dopants are used, it may have an adverse effect on the properties of liquid crystals such as dielectric anisotropy, viscosity, and driving voltage. Therefore, it is required to develop a dopant that will not damage the properties of the liquid crystal.

[0005] Patent Document 1 discloses that a polymerizable chiral compound represented by a given structural formula has a high HTP value. However, the maximum HTP value of the polymerizable chiral compound obtained in actual experiments is only about 65, and no polymerizable chiral compound with a higher HTP value is recorded. In addition, if the adverse effect on the properties of liquid crystal is also considered, it is desirable to reduce the concentration of the dopant relative to the liquid crystal compound as much as possible.

[0006] [Prior art literature]

[0007] [Patent Document]

[0008] [Patent Document 1] Japanese Patent Application Publication No. 2013-87109. Summary of the invention

[0009] [Problems to be solved by the invention]

[0010] An object of the present invention is to provide an atropisomer of a 1,1'-binaphthyl derivative having a high HTP value even in a small amount.

[0011] [Methods to solve the problem]

[0012] The atropisomers according to the embodiments of the present invention are compounds represented by the following general formula (1) and / or general formula (2):

[0013]

[0014] [In formula (1) and formula (2),

[0015] R 1 and R 2 Each independently represents any structure from (R-1) to (R-20), and R 1 and R 2 At least one of is any one of (R-1) to (R-5), except when the aforementioned structure is (R-1), R 1 and R 2 Not the same;

[0016]

[0017]

[0018]

[0019]

[0020]

[0021] A is C 1-12 alkyl,

[0022] R 3 To R 12 Independently represent -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 -COO-;

[0023] Y stands for H2 C=C(Z 1 )COO-、(H 2 COCH)-CH 2 -、H 2 C=CH-CH 2 - or H 2 C=CH-O-;

[0024] Z 1 Indicates H or CH 3 ; k1 to k3 independently represent integers from 0 to 12;

[0025] m is 0 or 1;

[0026] n is an integer from 0 to 12;

[0027] X 1 To X 12 represent 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-;

[0028] p1 to p12 independently represent 0 or 1;

[0029] q1 to q20 independently represent 0, 1 or 2; and

[0030] s1 to s10 independently represent 0, 1, 2 or 3].

[0031] In one embodiment of the present invention, R 1 and R 2 Each independently represents any structure from (R-1) to (R-10), and R 1 and R 2 At least one of is any one of (R-1) to (R-4).

[0032] The polymerizable liquid crystal composition according to the embodiment of the present invention contains the above-mentioned atropisomer and a polymerizable liquid crystal compound.

[0033] The optical film according to the embodiment of the present invention includes a cured film of the polymerizable liquid crystal composition.

[0034] In one embodiment of the present invention, the optical film has a selective reflection function.

[0035] An image display device according to an embodiment of the present invention includes the above-mentioned optical film.

[0036] The glasses according to the embodiment of the present invention include the above-mentioned optical film.

[0037] [Effects of the Invention]

[0038] According to the present invention, an atropisomer of a 1,1'-binaphthyl derivative having a high HTP value can be obtained even in a small amount. DETAILED DESCRIPTION

[0039] The atropisomer according to the present embodiment, and the polymerizable liquid crystal composition, optical film, image display device, and glasses using the atropisomer are described in detail below.

[0040] <Atropisomers>

[0041] The atropisomers of this embodiment are compounds represented by the following general formula (1) and / or general formula (2). These compounds are atropisomers of 1,1'-binaphthyl derivatives, the compound represented by general formula (1) is the R-isomer, and the compound represented by general formula (2) is the S-isomer. The atropisomer may be any one of the compounds represented by general formula (1) and general formula (2), or may include both.

[0042]

[0043] In the compounds represented by the above general formula (1) and general formula (2), R 1 and R 2 Each independently represents any one of the following structures (R-1) to (R-20), and R 1 and R 2 At least one of is any one of (R-1) to (R-5). However, except for the case where the aforementioned structure is (R-1), R 1 and R 2 Different, that is, except for R 1 and R 2 Except when both are (R-1), R 1 and R 2 have different structures from each other. 1 and R 2 At least one of them has H 2 C=C(CH 3 )-, the compounds represented by the general formula (1) and the general formula (2) exhibit polymerizability and function as dopants for polymerizable liquid crystal compounds belonging to the same liquid crystal component.

[0044]

[0045]

[0046]

[0047]

[0048]

[0049] In the structure of (R-6) above, A is C 1-12 Alkyl, preferably C 3-6 Alkyl. C 1-12 The alkyl group may be straight chain or branched. 1-12 Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl, and n-propyl or pentyl is preferred.

[0050] In the structures (R-11) to (R-20) above, R 3 To R 12 Independently represent -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 -COO-;

[0051] Y stands for H 2 C=C(Z 1 )COO-、(H 2 COCH)-CH 2 -、H 2 C=CH-CH 2 - or H 2 C=CH—O—, preferably H 2 C=C(Z 1 )COO-;

[0052] Z 1 Indicates H or CH 3 , preferably CH 3 ;

[0053] k1 to k3 are independently an integer from 0 to 12, preferably 0, m is 0 or 1, preferably 0,

[0054] n is an integer from 0 to 12, preferably 1, 3, 4, 5 or 6. In the structures of (R-19) and (R-20), n=1 is particularly preferred;

[0055] X 1 To X 12 represent 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-, preferably -COO-;

[0056] p1 to p12 independently represent 0 or 1, preferably 0;

[0057] q1 to q20 are independently 0, 1 or 2, preferably 1; however, in the structures of (R-15) and (R-16), it is particularly preferred that q7 and q10 are 0 respectively; and

[0058] s1 to s10 are independently 0, 1, 2 or 3, preferably 1; however, in the structures of (R-19) and (R-20), it is particularly preferred that s9 and s10 are 0, respectively.

[0059] In addition, R 1 and R 2 Each independently represents any structure from (R-1) to (R-10), and R 1 and R 2 At least one of is preferably any one of (R-1) to (R-4). 1 and R 2 When one of represents a structure of (R-11) to (R-20), it is preferably (R-11), (R-13), (R-15), (R-17) or (R-19).

[0060] In the atropisomers of this embodiment, except for the compounds represented by the general formula (1) and the general formula (2), R 1 and R 2 When both are (R-1), R 1 and R 2 are asymmetric to each other. In addition, R1 and R 2 They are not integrated with each other to form a single skeleton structure. Since the compounds represented by the general formula (1) and the general formula (2) have such a specific structure, atropisomers that exhibit a high HTP value even in a small amount can be obtained. In addition, an optical film obtained by using a polymerizable liquid crystal composition containing atropisomers having such characteristics as a dopant can exhibit a central reflection wavelength in a wide band depending on the content of the atropisomer, and can particularly widen the reflection band in the visible light region.

[0061] <Method for producing atropisomers>

[0062] The atropisomer of the present embodiment can be produced, for example, by the synthesis method described below.

[0063] <Production Example 1: R 1 and R 2 Preparation of compounds represented by the symmetrical general formula (2)>

[0064] (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) were added to a reaction vessel and stirred in dichloromethane (DCM). 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC) was added to the resulting suspension in small amounts at regular intervals, thereby obtaining a compound in which S-Binol was diesterified via Ma-NP-BA, namely R 1 and R 2 Each of them is a compound represented by the following general formula (2.1) of structure (R-1).

[0065]

[0066] <Production Example 2: R 1 and R 2 Preparation of asymmetric compounds represented by general formula (2)

[0067] (Step 1)

[0068] S-Binol, DMAP and 4-(trans-4-pentylcyclohexyl)benzoic acid (5PCA) were added to a reaction vessel and stirred in DCM. EDC was added in small amounts to the resulting suspension at regular intervals to synthesize a compound in which S-Binol was monoesterified with 5PCA (S-Binol monoester of 5PCA).

[0069] (Step 2)

[0070] 4'-[(2-methylprop-2-enoyl)oxy][1,1'-biphenyl]-4-carboxylic acid (Ma-BPh-A) and EDC are added to a solution of S-Binol monoester containing 5PCA, thereby obtaining a compound in which S-Binol is diesterified with 5PCA and Ma-BPh-A, namely R 1 and R 2 A compound represented by the general formula (2.2) in which one of them has the structure (R-6) and the other has the structure (R-4).

[0071]

[0072] <Polymerizable Liquid Crystal Composition>

[0073] The polymerizable liquid crystal composition of the present embodiment includes a polymerizable liquid crystal compound and the above-mentioned atropisomer as a dopant. In addition, the polymerizable liquid crystal composition includes a polymerization initiator that polymerizes these components to promote the hardening of the polymerizable liquid crystal composition, a solvent that dissolves these components, and further arbitrarily includes various additives. Such a polymerizable liquid crystal composition can be made by dissolving the liquid crystal components of the polymerizable liquid crystal compound and the above-mentioned atropisomer in a solvent, and adding a polymerization initiator and any additives to the resulting solution. If the above-mentioned atropisomer is added to the polymerizable liquid crystal compound, the polymerizable liquid crystal compound becomes a cholesterol liquid crystal state, and the liquid crystal molecules are oriented in a spiral shape. By orienting the liquid crystal molecules in a spiral shape, in each optical element made using the polymerizable liquid crystal composition, a selective reflection function is given to selectively reflect the circularly polarized component of the wavelength of light corresponding to its spiral pitch.

[0074] The polymerizable liquid crystal compound exhibits liquid crystal properties within a predetermined temperature range and concentration range, and can be polymerized by ultraviolet rays or heat while maintaining the orientation state to fix the orientation state. Such a polymerizable liquid crystal compound is preferably a polymerizable liquid crystal monomer having a polymerizable group in the molecule. As a polymerizable group, for example: (meth) acryloyl, vinyl, chalcone (Chalkonyl), cinnamoyl and epoxy groups can be listed. In addition, in order to show liquid crystal properties, it is preferred to have a mesogen group in the molecule, and the mesogen group is, for example, a rod-shaped or plate-shaped substituent such as a biphenyl, a terphenyl, a (poly) benzoic acid phenyl ester group, a (poly) ether group, a benzylidene aniline group or an acenaphthoquinoxaline (acenaphthoquinoxaline) group, or a disc-shaped substituent such as a terphenylene, a phthalocyanine or an azacrown group, that is, a group having the ability to induce liquid crystal phase behavior. In this technical field, as a rod-shaped (calamitic) liquid crystal, a liquid crystal compound having a rod-shaped or plate-shaped substituent is known. Specific examples of such polymerizable liquid crystal monomers include polymerizable liquid crystal compounds described in Japanese Patent Publication No. 2003-315556, Japanese Patent Publication No. 2004-29824, and Japanese Patent No. 5463666, and polymerizable nematic liquid crystal monomers such as PALIOCOLOR series (manufactured by BASF) and RMM series (manufactured by Merck). The polymerizable liquid crystal compound may be used alone or in combination of two or more.

[0075] The above-mentioned atropisomer that functions as a dopant can orient the above-mentioned polymerizable liquid crystal compound to right-handed or left-handed twist, so that a polymerizable liquid crystal composition presenting a cholesterol liquid crystal phase can be obtained. Through the polymerization reaction of the above-mentioned polymerizable liquid crystal compound and the above-mentioned atropisomer, a polymer having a repeating unit derived from the polymerizable liquid crystal compound and a repeating unit derived from the compound represented by the general formula (1) and / or the general formula (2) is formed. Relative to 100 parts by mass of the polymerizable liquid crystal compound used in combination, 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, and the lower limit of its content is more preferably 0.1 parts by mass, and more preferably 1.0 parts by mass. In addition, relative to 100 parts by mass of the polymerizable liquid crystal compound, the upper limit of the content of the atropisomer contained in the polymerizable liquid crystal composition is more preferably 10 parts by mass or less, and more preferably 5.0 parts by mass or less. Therefore, the content of the atropisomer contained in the polymerizable liquid crystal composition is more preferably 0.1 to 10 parts by mass, and more preferably 1.0 to 5.0 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal compound. In the liquid crystal composition, the less the content of the polymerizable atropisomer is, the less the effect on the liquid crystallinity can be reduced.

[0076] The polymerizable liquid crystal composition may contain a polymerizable compound that is reactive with the polymerizable liquid crystal compound and does not have liquid crystallinity. Examples of such polymerizable compounds include ultraviolet curable resins and the like.Examples of the ultraviolet curable resin 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 acid 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, di-trimethylolpropane tetra(meth)acrylate, tri(acryloyloxyethyl) isocyanurate, tri(methyl)acrylate acryloyloxyethyl) triisocyanate, reaction product of glycerol triglycidyl ether and (meth) acrylic acid, caprolactone-modified tri(acryloyloxyethyl) triisocyanate, reaction product of trimethylolpropane triglycidyl ether and (meth) acrylic acid, triglycerol-di-(meth)acrylate, reaction product 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, 1,6-hexanediol-di-glycidyl ether and (meth) acrylic acid reaction products of 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(acryloyloxyethyl)hydroxyethyl triisocyanate, bis(methacryloyloxyethyl)hydroxyethyl triisocyanate, 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, (meth) Phenoxyhydroxypropyl acrylate, acryloyl morpholine, 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, etc., can be used alone or in combination of two or more.The ultraviolet curable resin that does not have these liquid crystal properties can be added to the liquid crystal composition to an extent that does not cause the polymerizable liquid crystal composition to lose its liquid crystal properties. The added amount is preferably 0.1 parts by mass to 25 parts by mass, and more preferably 0.5 parts by mass to 10 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal compound.

[0077] In order to cure the polymerizable liquid crystal composition by polymerization reaction, the polymerizable liquid crystal composition may also contain a polymerization initiator. The polymerizable liquid crystal composition is generally cured by ultraviolet irradiation, so the polymerization initiator used is preferably a photopolymerization initiator that can initiate polymerization reaction by ultraviolet irradiation. The photopolymerization initiator is not particularly limited, and examples thereof include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one ("Omnirad 907" manufactured by IGM Resins BV), 1-hydroxycyclohexylphenyl ketone ("Omnirad 184" manufactured by IGM Resins BV), 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone ("Omnirad 2959" manufactured by IGM Resins BV), 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one ("Darocur 953" manufactured by Merck), 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one ("Darocur 1116" manufactured by Merck), 2-hydroxy-2-methyl-1-phenylpropane-1-one ("IGM Resins BV company "Omnirad1173"), diethoxyacetophenone and other acetophenone compounds;

[0078] 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);

[0079] Benzophenone compounds such as benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and 3,3'-dimethyl-4-methoxybenzophenone ("KAYACUREMBP" manufactured by Nippon Kayaku Co., Ltd.);

[0080] Phosphine oxide compounds such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide ("Omnirad TPO" manufactured by IGM Resins BV), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide ("Omnirad 819" manufactured by IGM Resins BV); and

[0081] Thioxanthone compounds such as thioxanthone, 2-chlorothioxanthone ("KAYACURE CTX" manufactured by Nippon Kayaku Co., Ltd.), 2-methylthioxanthone, 2,4-dimethylthioxanthone ("KAYACURE RTX" manufactured by Nippon Kayaku Co., Ltd.), isopropylthioxanthone, 2,4-dichlorothioxanthone ("KAYACURE CTX" manufactured by Nippon Kayaku Co., Ltd.), 2,4-diethylthioxanthone ("KAYACURE DETX" manufactured by Nippon Kayaku Co., Ltd.), and 2,4-diisopropylthioxanthone ("KAYACURE DITX" manufactured by Nippon Kayaku Co., Ltd.) etc. These photopolymerization initiators may be used alone or in combination of two or more.

[0082] When a benzophenone compound or a thioxanthone compound is used as a photopolymerization initiator, it is preferred to use a reaction aid in order 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'sketone, 4,4'-diethylaminobenzophenone, ethyl 4-dimethylaminobenzoate, 2-butoxyethyl 4-(dimethylamino)benzoate, and isopentyl 4-(dimethylamino)benzoate.

[0083] The amount of the photopolymerization initiator and the reaction aid added is preferably within the range that does not affect the liquid crystal properties of the polymerizable liquid crystal composition, and is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the compound cured by ultraviolet light in the polymerizable liquid crystal composition. In addition, the amount of the aid added is preferably more than 2 times the amount of the photopolymerization initiator, based on the mass basis.

[0084] The polymerizable liquid crystal composition further includes a solvent. Such a solvent is not particularly limited as long as it can dissolve the polymerizable liquid crystal compound, dopant, etc. used, and examples thereof include methyl ethyl ketone, toluene, methyl isobutyl ketone, cyclopentanone, acetone, xylene, anisole, etc. In addition, these solvents can be added in any proportion, and only one can be added, or multiple solvents can be used in combination. These solvents can be removed by drying in a drying area such as an oven or a film coating production line.

[0085] The polymerizable liquid crystal composition may also include additives such as leveling agents, ultraviolet absorbers, light stabilizers, antioxidants, polymerization inhibitors, crosslinking agents, plasticizers, and flow regulators in any proportion according to demand. As leveling agents, fluorine compounds, silicone compounds, acrylic compounds, etc. can be listed. Ultraviolet absorbers can be listed as benzotriazole compounds, benzophenone compounds, triazine compounds, etc., and light stabilizers can be listed as hindered amine compounds, benzoate compounds, etc., and antioxidants can be listed as phenol compounds, etc. Inhibitors can be listed as hydroquinone monomethyl ether (methoquinone), methyl hydroquinone, hydroquinone, etc., and crosslinking agents can be listed as polyisocyanates, melamine compounds, etc. Examples of plasticizers include phthalates such as dimethyl phthalate and diethyl phthalate, trimellitates such as tri(2-ethylhexyl) trimellitate, aliphatic dibasic acid esters such as dimethyl adipate and dibutyl adipate, orthophosphates such as tributyl phosphate and triphenyl phosphate, acetates such as triacetin and 2-ethylhexyl acetate. Examples of flow regulators include silicon-modified acrylates such as "TEGO (registered trademark) Rad 2100" (manufactured by EVONIK Co., Ltd.).

[0086] <Optical Film>

[0087] The polymerizable liquid crystal composition of this embodiment can be used as a raw material for optical films such as light reflective films, phase difference films, polarizing films, etc. This optical film can be made by forming a coating film of the polymerizable liquid crystal composition on a predetermined film used as a substrate and hardening the coating film. For example, when a light reflective film is made using a polymerizable liquid crystal composition, the polymerizable liquid crystal composition containing the above-mentioned components is applied to a substrate (plastic film) such as triacetyl cellulose (TAC) film, acrylic film, polycarbonate film, polyvinyl chloride film, polyolefin film, polyethylene terephthalate (PET) film in a manner as uniform as possible in thickness, and the solvent is removed by heating and placed for a certain period of time, thereby forming a coating film on the substrate. The heating temperature is not particularly limited as long as it is a temperature at which the polymerizable liquid crystal compound on the substrate becomes a cholesterol liquid crystal state and is oriented with the expected spiral pitch, and is preferably 40 to 90°C. At this time, the surface of the substrate is rubbed before applying the polymerizable liquid crystal composition, and an orientation treatment such as stretching is performed in advance, thereby making the orientation of the cholesterol liquid crystal more uniform, and the haze value as an optical film can be reduced. Next, while maintaining the orientation, ultraviolet rays are irradiated with a high-pressure mercury lamp or the like to fix the orientation of the cholesterol liquid crystal, thereby preparing an optical film (light-reflecting film) having a cured film of a polymerizable liquid crystal composition. Here, when an atropisomer exhibiting a rightward helical orientation is used, an optical film that selectively reflects right circularly polarized light can be obtained. On the other hand, when an atropisomer exhibiting a leftward helical orientation is used, an optical film that selectively reflects left circularly polarized light can be obtained. This phenomenon of selectively reflecting specific circularly polarized light is called selective reflection, and an optical film having a selective reflection function can be obtained.

[0088] The optical film of this embodiment exhibits a selective reflection function, so it can reduce the amount of incident light and the degree of glare, and reflect light in a specific wavelength band. It can be effectively used in eyeglasses such as glasses, sunglasses, goggles, liquid crystal display devices, organic EL display devices and other image display devices.

[0089] [Example]

[0090] The following describes the embodiments of the present invention, but the present invention is not limited to these examples unless it exceeds the gist thereof. In addition, unless otherwise specified, the following "%" and "part" are based on mass, and the room temperature is within the range of 20°C ± 5°C.

[0091] <Example 1>

[0092] 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 twice at intervals of 1 hour, each time 1.11 g, and stirred for 20 hours. After that, analysis by thin layer chromatography (TLC) showed complete conversion to the diester of S-Binol. As a post-treatment, the solution was washed with a 10% sodium chloride solution to remove EDC-urea by-products, and dried over anhydrous magnesium sulfate. Next, the DCM-containing solution was concentrated to about 30% (based on the maximum yield of compound 2.1) and precipitated in 250 ml of methanol. The precipitate was filtered, washed twice with methanol, and dried to obtain 4.49 g of the compound represented by the following general formula (2.1) (yield 90%).

[0093]

[0094] 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% of a photopolymerization initiator (Omnirad TPO) and 0.1% of a flow regulator (TEGO (registered trademark) Rad 2100), and the content of Compound 2.1 relative to the polymerizable liquid crystal compound was adjusted to 3.5%. The resulting mixture of the polymerizable liquid crystal compound and Compound 2.1 was dissolved in m-xylene (solvent) to prepare a polymerizable liquid crystal composition containing 3.5% of Compound 2.1 at 35%. The polymerizable liquid crystal composition was applied to a PET film (thickness 100 μm) manufactured by Toyobo Co., Ltd. that had been rubbed with nylon cloth in advance by spin coating (rotation number: 750 rpm). The resulting coating was dried at 80°C for 5 minutes to orient the liquid crystal, and then, while nitrogen was purged, an LED (100 mW / cm 2 ), and the coating was cured at 80°C for 30 seconds to produce an optical film having a cholesterol 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 .

[0095] <Example 2>

[0096] (Step 1)

[0097] 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. 2.12 g of EDC (11 mmol) was added to the resulting suspension in two portions of 1.06 g each at 1 hour intervals and stirred for 20 hours. Afterwards, analysis by thin layer chromatography (TLC) showed the formation of monoesters of S-Binol, trace amounts of S-Binol and trace amounts of diesters of S-Binol ("by-products").

[0098] (Step 2)

[0099] 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 to the solution of the S-Binol monoester containing 5PCA obtained in step 1 in two portions of 1.15 g at intervals of 1 hour, and stirred for 20 hours. After that, analysis by thin layer chromatography (TLC) showed complete conversion to the diester of S-Binol. As a post-treatment, the solution was washed with 10% sodium chloride solution to remove the EDC-urea by-product and dried over anhydrous magnesium sulfate. Next, the solution containing DCM was concentrated to about 30% (based on the maximum yield of compound 2.2) and precipitated in 300 ml of methanol. The precipitate was filtered, washed twice with methanol and dried to obtain 6.68 g of a compound represented by the following general formula (2.2) (yield 83%).

[0100]

[0101] The obtained compound represented by the 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 prepared 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 .

[0102] The compounds prepared in the following Examples 3 to 9 were synthesized by the same two-step process as the preparation method described in Example 2.

[0103] <Example 3>

[0104] 2.86 g of S-Binol (10 mmol) was used, and in step 1, 4-(trans-4-pentylcyclohexyl)benzoic acid was replaced with 4-[(4-methoxybenzoyl)oxy]benzoic acid (MBBA) to react, and in step 2, 4'-[(2-methylprop-2-enoyl)oxy][1,1'-biphenyl]-4-carboxylic acid (Ma-BPh-A) was used in the same manner. After post-treatment, 7.8 g of a compound represented by the following general formula (2.3) was obtained (yield 97%). The obtained compound represented by the general formula (2.3) (compound 2.3) was not further purified, and the content of compound 2.3 relative to the polymerizable liquid crystal compound was adjusted to 4.0%. Except for this, an optical film was prepared in the same manner as in Example 1. The central reflection wavelength of this film is 493 nm, and the HTP value of compound 2.3 is 81.1 μm -1 .

[0105]

[0106] <Example 4>

[0107] 2.86 g of S-Binol (10 mmol) 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 the above-mentioned (R-7), and in step 2, 4'-[(2-methylprop-2-enoyl)oxy][1,1'-biphenyl]-4-carboxylic acid (Ma-BPh-A) was used in the same manner. After post-treatment, 4.1 g of a compound represented by the following general formula (2.4) was obtained (yield 97%). The obtained compound represented by the general formula (2.4) (compound 2.4) was not further purified, and the content of compound 2.4 relative to the polymerizable liquid crystal compound was adjusted to 3.5%. Except for this, an optical film was prepared in the same manner as in Example 1. The central reflection wavelength of this film is 545 nm, and the HTP value of compound 2.4 is 83.9 μm -1 .

[0108]

[0109] <Example 5>

[0110] 2.86 g of S-Binol (10 mmol) 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, 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%). The obtained compound represented by the general formula (2.5) (compound 2.5) was not further purified, and the content of compound 2.5 relative to the polymerizable liquid crystal compound was adjusted to 3.0%. Except for this, an optical film was prepared in the same manner as in Example 1. The central reflection wavelength of this film is 548 nm, and the HTP value of compound 2.5 is 97.3 μm -1 .

[0111]

[0112] <Example 6>

[0113] 2.86 g of S-Binol (10 mmol) was used to react with 4-(trans-4-pentylcyclohexyl)benzoic acid (5PCA) in step 1, and in step 2, benzoic acid (Ma-BPh-BA) equivalent 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%). The obtained compound represented by the general formula (2.6) (compound 2.6) was not further purified, and the content of compound 2.6 relative to the polymerizable liquid crystal compound was adjusted to 3.5%. Otherwise, an optical film was prepared in the same manner as in Example 1. The central reflection wavelength of this film is 546 nm, and the HTP value of compound 2.6 is 83.7 μm -1 .

[0114]

[0115] <Example 7>

[0116] 2.86 g of S-Binol (10 mmol) and 61 mg of DMAP were used. In step 1, 4-(trans-4-pentylcyclohexyl)benzoic acid was replaced with 4-(trans-4-propylcyclohexyl)benzoic acid (3PCA) 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, 7.4 g of the compound represented by the following general formula (2.7) was obtained (yield 85%). The obtained compound represented by the general formula (2.7) (compound 2.7) was not further purified, and the content of compound 2.7 relative to the polymerizable liquid crystal compound was adjusted to 3.5%. Except for this, an optical film was prepared in the same manner as in Example 1. The central reflection wavelength of this film is 572 nm, and the HTP value of compound 2.7 is 79.9 μm -1 .

[0117]

[0118] <Example 8>

[0119] 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 the above (R-7), 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 the compound represented by the following general formula (2.8) was obtained (yield 98%). The obtained compound represented by the general formula (2.8) (compound 2.8) was not further purified, and the content of compound 2.8 relative to the polymerizable liquid crystal compound was adjusted to 3.5%. Except for this, an optical film was prepared in the same manner as in Example 1. The central reflection wavelength of this film is 495 nm, and the HTP value of compound 2.8 is 92.4 μm -1 .

[0120]

[0121] <Example 9>

[0122] Using 21.45 g of S-Binol (75 mmol) and 0.46 g of DMAP, in Step 1, instead of 4-(trans-4-pentylcyclohexyl)benzoic acid, it was reacted with 4-(trans-4-propylcyclohexyl)benzoic acid (3PCA), and in Step 2, 4'-[(2-methylprop-2-enoyl)oxy][1,1'-biphenyl]-4-carboxylic acid was used. After post-treatment, 53.1 g of the compound represented by the following general formula (2.9) was obtained (yield 91%). The obtained compound represented by the general formula (2.9) (Compound 2.9) was not further purified, and the content of Compound 2.9 relative to the polymeric liquid crystal compound was adjusted to 3.5%. Otherwise, an optical film was produced in the same manner as in Example 1. The central reflection wavelength of this film was 570 nm, and the HTP value of Compound 2.9 was 80.2 μm -1 。

[0123]

[0124] <Comparative Example 1>

[0125] As a comparative compound, "Lumogen (registered trademark) S750" (manufactured by BASF), which is a commercially available product, was used instead of the atropisomer of the present invention. In addition, the content of the comparative compound relative to the polymeric liquid crystal compound was adjusted to 5.0%. Otherwise, an optical film was produced in the same manner as in Example 1. The central reflection wavelength of this film was 509 nm, and the HTP value of the comparative compound was 62.9 μm -1 。

[0126] 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 relative to the polymeric liquid crystal compound (hereinafter also referred to as "concentration"), the HTP value and the central reflection wavelength were measured in the following manner. The results are shown in Table 1

[0127] <HTP Value and Central Reflection Wavelength>

[0128] Compounds 2.1 to 2.9 and the comparative compound (dopant) were respectively added to the polymeric liquid crystal compound (LC242:RM257 = 1:1), the concentration of the dopant relative to the polymeric liquid crystal compound was adjusted, and the absolute value of the HTP value was calculated according to the following formula (A). In formula (A), P represents the helical pitch length (μm), and C represents the concentration of the dopant relative to the polymeric liquid crystal compound (%). In addition, P is the central reflection wavelength (λ measured in the reflection band of the optical film r) and calculated according to the following formula (B). Here, the average refractive index (n) of the polymerizable liquid crystal compound is assumed to be 1.6 for calculation. In addition, the central reflection wavelength (λr) is the wavelength (λ corresponding to half the maximum height of the reflection spectrum measured by a spectrophotometer. min With λ max ), and calculate (λ min +λ max ) / 2 and is specific accordingly.

[0129]

[0130] P=λr / n…(B)

[0131] [Table 1]

[0132]

[0133] As shown in Table 1, the atropisomers prepared in Examples 1 to 9 all had HTP values ​​exceeding 75 even when the addition amount was changed within the range of 3 to 5%, and showed high HTP values ​​even in a small amount. In particular, the atropisomers prepared in Examples 1 and 5 showed extremely high HTP values ​​exceeding 90 even when the addition amount was as small as 3%. In addition, the optical films prepared in Examples 1 to 6 could change the central reflection wavelength according to the addition amount even when the addition amount was small, so that the properties of the liquid crystal were not affected, and an optical film with an enlarged reflection band in the visible light region could be obtained.

[0134] On the other hand, the HTP value of the comparative compound used in Comparative Example 1 is lower than the HTP value of the atropisomer prepared in Examples 1 to 9. In addition, the central reflection wavelength of the optical film prepared in Comparative Example 1 is 509nm and 630nm at the addition amounts of 5.0% and 4.0%, respectively. Therefore, at a relatively small concentration, the reflection band in the visible light region is limited.

[0135] [Industrial Applicability]

[0136] The present invention can provide an atropisomer having a high HTP value even in a small amount, and a polymerizable liquid crystal composition, an optical film, an image display device, and glasses using the atropisomer.

Claims

1. An atropisomer, which is a compound represented by the general formula (1) and / or the general formula (2), In formula (1) and formula (2), R1 and R2 each independently represent any structure of (R-1) to (R-20), and at least one of R1 and R2 is any structure of (R-1) to (R-5), but except for the case where the structure is (R-1), R1 and R2 are different; A is C 1-12 alkyl; R3 to R 12 Independently represent -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-; Z1 represents H or CH3; k1 to k3 independently represent an integer from 0 to 12; m is 0 or 1; n is an integer from 0 to 12; X 1 To X 12 independently represent -CH=CH-, -C≡C-, -HC=CH-COO-, -(O)CO-CH=CH-, -CH2-, -O-, -C(O)-, -CH2CH2-, -CH2O-, -OCH2-, -COO-, -OC(O)-, -C(CH3)2-, -N=N-, -CH=N-, -N=CH-, -NHCO- or -OCNH-; p1 to p12 independently represent 0 or 1; q1 to q20 independently represent 0, 1 or 2; and s1 to s10 represent 0, 1, 2 or 3 independently of each other.

2. The atropisomer according to claim 1, wherein R1 and R2 each independently represent any one of structures (R-1) to (R-10), and at least one of R1 and R2 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 comprising a cured film of the polymerizable liquid crystal composition according to claim 3 . The optical film according to claim 4 , having a selective reflection function. 6 . An image display device comprising the optical film according to claim 4 .

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

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