Overlapping compounds, mixtures

Abstract

To provide a polymerizable compound that is capable of lowering the crystallization temperature of a polymerizable liquid crystal compound by being mixed with the polymerizable liquid crystal compound.SOLUTION: One example of the present invention is a polymerizable compound represented by the following formula (1-A).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polymerizable compound, a mixed composition containing the polymerizable compound, a phase difference film containing a cured product of the mixed composition, an elliptic polarizer, an optical display, and a flexible image display device. [Background technology]

[0002] Conventionally, one of the required properties of a phase difference film is its ability to perform polarization conversion across the entire wavelength range. For example, it is known that in the wavelength range exhibiting inverse wavelength dispersion of [Re(450) / Re(550)] < 1, uniform polarization conversion is theoretically possible. Various polymerizable liquid crystal compounds capable of constituting such a phase difference film exhibiting inverse wavelength dispersion have been developed (for example, Patent Document 1). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2017-101235 [Overview of the project] [Problems that the invention aims to solve]

[0004] A coating-type optical film can be obtained by dissolving a polymerizable liquid crystal compound, such as that disclosed in Patent Document 1, in a solvent to form a composition, applying the composition to a support substrate or the like to form a coating film, then transferring the polymerizable liquid crystal compound contained in the coating film to a liquid crystal phase state, drying the coating film to evaporate the solvent, and polymerizing it by UV exposure. However, conventional polymerizable liquid crystal compounds often have poor solubility in various solvents due to their molecular structure, and such polymerizable liquid crystal compounds with low solubility may crystallize between the time the solvent evaporates and polymerization occurs. This phenomenon can cause not only a decrease in film-forming ability but also a decrease in the optical properties of the resulting optical film.

[0005] An object of the present invention is to provide a polymerizable compound capable of lowering the crystallization temperature of a polymerizable liquid crystal compound by mixing it with the polymerizable liquid crystal compound.

Means for Solving the Problems

[0006] As a result of intensive studies to solve the above problems, the present inventors have completed the present invention. That is, the present invention provides the following preferred embodiments. [1] A polymerizable compound represented by the following formula (1).

Chemical formula

Chemical formula

[10] P in equation (2) 21 and P 22 The mixed composition according to any one of [5] to [9] above, wherein each of them is an acryloyloxy group.

[11] The mixed composition according to any one of [5] to

[10] , wherein the area percentage value of the polymerizable compound represented by formula (1), measured by liquid chromatography, is 1% or more and less than 50%, based on the sum of the area values ​​of the polymerizable compound represented by formula (1) and the polymerizable liquid crystal compound represented by formula (2) contained in the mixed composition.

[12] The mixed composition according to any one of [4] to

[11] , further comprising a photopolymerization initiator.

[13] A mixed composition according to any one of [4] to

[12] , further comprising an organic solvent.

[14] A phase difference film comprising a liquid crystal cured film which is a cured product of any of the mixed compositions described in [4] to

[13] above.

[15] The liquid crystal curing film is given by formula (ii): 0.75≦Re(450) / Re(550)<1.00 (ii) [In equation (ii), Re(λ) represents the in-plane phase difference value of the liquid crystal cured film at a wavelength of λnm.] A phase difference film according to

[14] above, which satisfies the conditions.

[16] Elliptical polarizer including the phase difference film described in

[14] or

[15] above.

[17] An optical display including the elliptic polarizer described in

[16] above.

[18] A flexible image display device including the elliptical polarizer described in

[16] above. [Effects of the Invention]

[0007] According to the present invention, it is possible to provide a polymerizable compound that, when mixed with a polymerizable liquid crystal compound, can lower the crystallization temperature of the polymerizable liquid crystal compound. [Modes for carrying out the invention]

[0008] The embodiments of the present invention will be described in detail below. However, the scope of the present invention is not limited to the embodiments described herein, and various modifications can be made without departing from the spirit of the invention.

[0009] <Polymerizable compound> The polymerizable compound of the present invention is of formula (1): [ka] It is a compound represented by (hereinafter also referred to as "polymerizable compound (1)").

[0010] In formula (1), L represents a bond or group selected from the group consisting of single bonds and acyclic aliphatic hydrocarbon groups and carbonyl groups having 1 to 13 carbon atoms. The hydrogen atoms contained in the aliphatic hydrocarbon group are halogen atoms, -R 10 , -OR 10 L may be substituted with a cyano group or a nitro group, and if L is an aliphatic hydrocarbon group having 2 to 13 carbon atoms, the -CH2- contained in the aliphatic hydrocarbon group may be substituted with -O-, -S-, -CO-O-, -O-CO-, or -NH-. However, if there are multiple -O- and / or -S- groups, they are not adjacent to each other. 10 This represents an alkyl group having 1 to 4 carbon atoms, and the hydrogen atoms contained in the alkyl group may be substituted with fluorine atoms. Hereinafter, an acyclic aliphatic hydrocarbon group having 1 to 13 carbon atoms that can be substituted by or into which the above group can be inserted will also be referred to as an "acyclic aliphatic hydrocarbon group having 1 to 13 carbon atoms that may have substituents".

[0011] If L in formula (1) is a bond or group selected from the group consisting of a single bond, a cyclic aliphatic hydrocarbon group having 1 to 13 carbon atoms which may have substituents, and a carbonyl group, the solubility of the polymerizable compound (1) in various organic solvents tends to improve. A polymerizable compound (1) having such a structure is excellent at lowering the crystallization temperature of the resulting mixed composition when mixed with a polymerizable liquid crystal compound, in particular, another polymerizable liquid crystal compound having a molecular structure similar to that of polymerizable compound (1), such as the polymerizable liquid crystal compound represented by formula (2) described later. If the crystallization temperature of the mixed composition with the polymerizable liquid crystal compound is high, it is necessary to keep the processing temperature higher than the crystallization temperature to prevent crystallization from occurring between the formation of the coating film of the mixed composition and the removal of the solvent to polymerize the liquid crystal. This can lead to problems such as the heating affecting the resulting liquid crystal cured film, or placing a load on other materials or manufacturing equipment of the optical film. The polymerizable compound (1) of the present invention is excellent at lowering the crystallization temperature of the mixed composition, thus allowing for lower processing temperatures and reducing the impact of heating on the optical properties of the liquid crystal cured film, which is advantageous in terms of manufacturing efficiency. This effect tends to be significantly higher, in particular, compared to cases where L in formula (1) has a cyclic structure such as an alicyclic hydrocarbon group. The reason for this is not limited to, but is the G in formula (1). 1 , G 2 , A 1 and A 2 Because the group L located between the alicyclic hydrocarbon group and aromatic hydrocarbon group represented by the formula does not have a rigid cyclic structure, the molecular flexibility is increased, making it easier to improve solubility in organic solvents, which is presumed to lead to a significant decrease in the crystallization temperature when mixed with polymerizable liquid crystal compounds.

[0012] The C1-C13 aliphatic hydrocarbon group represented by L in formula (1) is an acyclic divalent aliphatic hydrocarbon group. The acyclic aliphatic hydrocarbon group may be linear or branched, and may be saturated or unsaturated hydrocarbons, but it is preferably a saturated hydrocarbon group, and more preferably a linear saturated hydrocarbon group. Specific examples of C1-C13 acyclic aliphatic hydrocarbon groups that may have substituents include C1-C13 alkanediyl groups such as methanediyl, ethanediyl, n-propanediyl, i-propanediyl, n-butanediyl, n-pentanediyl, n-hexanediyl, n-heptanediyl, n-octanediyl, n-nonanediyl, and n-decanediyl groups.

[0013] The acyclic aliphatic hydrocarbon group represented by L in formula (1) is preferably an alkanediyl group having 1 to 13 carbon atoms, which may have substituents; more preferably an unsubstituted alkanediyl group having 1 to 13 carbon atoms; even more preferably an unsubstituted alkanediyl group having 2 to 10 carbon atoms; and particularly preferably an unsubstituted alkanediyl group having 2 to 8 carbon atoms.

[0014] In formula (1), L is preferably an acyclic aliphatic hydrocarbon group or carbonyl group having 1 to 13 carbon atoms, which may have substituents, and more preferably an unsubstituted acyclic aliphatic hydrocarbon group or carbonyl group having 1 to 13 carbon atoms. When L in formula (1) is a group of the above structure, it is easier to further reduce the solubility of polymerizable compound (1) in various organic solvents, and the above effect associated with a decrease in crystallization temperature when mixed with polymerizable liquid crystal compound is more easily obtained.

[0015] In equation (1), m represents a number that is either 0 or 1.

[0016] In formula (1), D 1 and D 2 These are, independently, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, and -CO-NR. 11 -, -NR12 -CO-, or represents a single bond, R 11 and R 12 Each of these independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms. 1 and D 2 These are, respectively, base L and G 1 or G 2 It acts as a linking group that connects the cyclic structure represented by D. 1 and D 2 These are, independently, -O-, -CO-O-, -O-CO-, -C(=S)-O-, -OC(=S)-, and -CO-NR. 11 -or-NR 12 It is preferably -CO-, and more preferably -O-, -CO-O-, or -O-CO-. 11 and R 12 Each of these is preferably independently a hydrogen atom, a methyl group, or an ethyl group. D 1 and D 2 These may be identical or different from each other, but if they are identical, it is advantageous in terms of the ease of industrial production and productivity of polymerizable compound (1).

[0017] In formula (1), E 1 , E 2 B 1 and B 2 Each of these is independently of -CR 11 R 12 -, -CH2-CH2-, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 11 -, -NR 12 -CO-, -O-CH2-, -CH2-O-, -S-CH2-, -CH2-S- or single bond, R 11 and R 12 Each of these independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms. However, if m is 0, E 1 and E 2 -CR 11 R 12-, -CH2-CH2-, -O-CH2-, -CH2-O-, -S-CH2-, and -CH2-S-. 1 and E 2 These are, respectively, base L and or G 1 or G 2 A ring structure represented by A 1 Or A 2 It has the role of a linking group that connects the cyclic structure represented by B. 1 and B 2 These are, A 1 Or A 2 It has the role of a linking group between the cyclic structure represented by E and the polymerizable group. 1 , E 2 B 1 and B 2 These are, independently, -O-, -CO-O-, -O-CO-, -C(=S)-O-, -OC(=S)-, and -CO-NR. 11 -or-NR 12 It is preferably -CO-, and more preferably -O-, -CO-O-, or -O-CO-. 11 and R 12 Each of these is preferably independently a hydrogen atom, a methyl group, or an ethyl group. E 1 and E 2 B 1 and B 2 These may be identical or different from each other, but if they are identical, it is advantageous in terms of the ease of industrial production and productivity of polymerizable compound (1).

[0018] In formula (1), G 1 and G 2 These represent either a 1,4-cyclohexanediyl group or an aromatic hydrocarbon group, respectively. 1 and G 2 Examples of aromatic hydrocarbon groups represented by include divalent aromatic hydrocarbon groups having 6 to 20 carbon atoms. The hydrogen atoms contained in the aromatic hydrocarbon group are halogen atoms, -R 13 , -OR 13 , may be substituted with a cyano group or a nitro group, R 13A represents an alkyl group having 1 to 4 carbon atoms, and the hydrogen atoms in the alkyl group may be substituted with fluorine atoms. Specifically, A in formula (1) 1 and A 2 Examples of divalent aromatic hydrocarbon groups represented by include G 1 and G 2 These are preferably a 1,4-cyclohexanediyl group or a 1,4-phenylene group, and more preferably a 1,4-cyclohexanediyl group. G 1 and G 2 These may be identical or different from each other, but if they are identical, it is advantageous in terms of the ease of industrial production and productivity of polymerizable compound (1).

[0019] In formula (1), A 1 and A 2 Each of these independently represents a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms. The hydrogen atoms contained in the alicyclic hydrocarbon group and the aromatic hydrocarbon group are halogen atoms, -R 13 , -OR 13 , may be substituted with a cyano group or a nitro group, R 13 represents an alkyl group having 1 to 4 carbon atoms, and the hydrogen atoms contained in the alkyl group may be substituted with fluorine atoms.

[0020] A 1 and A 2 Examples of divalent alicyclic hydrocarbon groups having 3 to 16 carbon atoms, represented by formulas (a-1) to (a-4), include alicyclic hydrocarbon groups represented by formulas (a-1) to (a-4), with 5-membered or 6-membered alicyclic hydrocarbon groups being preferred.

[0021] [ka]

[0022] A 1 and A 2Examples of divalent aromatic hydrocarbon groups having 6 to 20 carbon atoms, represented by formulas (a-5) to (a-12), include aromatic hydrocarbon groups having 6 to 20 carbon atoms.

[0023] [ka]

[0024] The hydrogen atoms in the groups represented by formulas (a-1) to (a-12) above may be substituted with C1-C4 alkyl groups such as methyl, ethyl, isopropyl, and tert-butyl groups; C1-C4 alkoxy groups such as methoxy and ethoxy groups; C1-C4 fluoroalkyl groups such as trifluoromethyl groups; cyano groups; nitro groups; or halogen atoms such as fluorine, chlorine, and bromine atoms.

[0025] A 1 and A 2 The preferred group is a 1,4-cyclohexanediyl group or a 1,4-phenylene group, and the 1,4-phenylene group is more preferred. In particular, when m is 1, G 1 and G 2 However, each is a 1,4-cyclohexanediyl group, and A 1 and A 2 However, it is preferable that each of them be a 1,4-phenylene group. A 1 and A 2 These may be identical or different from each other, but if they are identical, it is advantageous in terms of the ease of industrial production and productivity of polymerizable compound (1).

[0026] In formula (1), F 1 and F 2 Each of these independently represents an alkanediyl group having 1 to 12 carbon atoms. The hydrogen atoms contained in the alkanediyl group are -OR 14 Alternatively, it may be substituted with a halogen atom, R 14represents an alkyl group having 1 to 4 carbon atoms, and the hydrogen atoms in the alkyl group may be substituted with fluorine atoms. Furthermore, the -CH2- group in the alkanediyl group may be replaced with -O- or -CO-. F 1 and F 2 Preferably, each of these is an alkanediyl group having 3 to 10 carbon atoms, -(CF2)4-, -(CF2)6-, or -(CF2)8-, and more preferably an alkanediyl group having 4 or 6 carbon atoms [-(CH2)4- or -(CH2)6-]. E 1 and E 2 These may be identical or different from each other, but if they are identical, it is advantageous in terms of the ease of industrial production and productivity of polymerizable compound (1).

[0027] P 1 and P 2 Each of these independently represents a hydrogen atom or a polymerizable group. 1 and P 2 At least one of them is a polymerizable group, P 1 and P 2 It is preferable from the viewpoint of film hardness of the liquid crystal cured film obtained using the polymerizable compound that all of these groups are polymerizable groups.

[0028] The polymerizable group can be any reactive group capable of polymerizing polymerizable compound (1). Specifically, examples include vinyl group, vinyloxy group, styryl group, p-(2-phenylethenyl)phenyl group, acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, carboxyl group, acetyl group, hydroxyl group, carbamoyl group, N-alkylamino group having 1 to 4 carbon atoms, amino group, oxyranyl group, oxetanyl group, formyl group, isocyanate group, isothiocyanate group, etc. In addition, polymerizable groups include the above example groups and F 1 or F 2 It may include an ether bond or ester bond connecting the two. 1 and P 2As for this, a radically polymerizable group or a cationically polymerizable group suitable for photopolymerization is preferable. In particular, an acryloyloxy group or a methacryloyloxy group is preferable because it is easy to handle and easy to manufacture, and an acryloyloxy group is more preferable.

[0029] <000088​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​ [ka]

[0035] [ka]

[0036] [ka]

[0037] [ka]

[0038] [ka]

[0039] [ka]

[0040] [ka]

[0041] Polymerizable compound (1) can be produced by appropriately combining known organic synthesis reactions (e.g., condensation reactions, esterification reactions, Williamson reaction, Ullmann reaction, Wittig reaction, Schiff base formation reaction, benzylation reaction, Sonogashira reaction, Suzuki-Miyaura reaction, Negishi reaction, Kumada reaction, Hiyama reaction, Buchwald-Hartwig reaction, Friedelcraft reaction, Heck reaction, aldol reaction, etc.) described in Methoden der Organischen Chemie, Organic Reactions, Organic Syntheses, Comprehensive Organic Synthesis, New Experimental Chemistry Course, etc., depending on its structure.

[0042] For example, L in formula (1) is an acyclic aliphatic hydrocarbon group having 1 to 13 carbon atoms, m is 0, and E 1 and E 2 are both -CO-O-, and A 1 and A 2 , B 1 and B 2 , F 1 and F 2 , P 1 and P 2 are each the same, and the polymerizable compound (1) can be produced by subjecting the compound represented by formula (1-1) (hereinafter also referred to as "compound (1-1)") and the compound represented by formula (1-2) (hereinafter also referred to as "compound (1-2)") to an esterification reaction. In formula (1-1), P, F, B, and A are respectively the same as those defined as P 1 and P 2 , F 1 and F 2 , B 1 and B 2 and A 1 and A 2 in formula (1). Also, L in formula (1-2) is the same as that defined as L in formula (1). P, F, B, A, and L are determined corresponding to the desired polymerizable compound (1).

[0043]

Chemical formula

[0044] [[ID=^^^]]<00^00973>

Chemical formula

[0045] The esterification reaction between compound (1-1) and compound (1-2) is preferably carried out in the presence of a condensing agent. By carrying out the esterification reaction in the presence of a condensing agent, the esterification reaction can be carried out efficiently and rapidly.

[0046] The condensing agents include 1-cyclohexyl-3-(2-morpholinoethyl)carbodiimidemetho-p-toluenesulfonate, dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (water-soluble carbodiimide: commercially available as WSC), and bis(2,6-diisopropylphenyl)carbodiimide. Also, carbodiimide compounds such as bis(trimethylsilyl)carbodiimide, 2-methyl-6-nitrobenzoic anhydride, 2,2'-carbonylbis-1H-imidazole, 1,1'-oxalyldiimidazole, diphenylphosphoryl azide, 1(4-nitrobenzenesulfonyl)-1H-1,2,4-triazole, 1H-benzotriazole-1-yloxytripyrrolidinophosphonium hexafluorophosphate, 1H-benzo Triazole-1-yloxytris(dimethylamino)phosphonium hexafluorophosphate, N,N,N',N'-tetramethyl-O-(N-succinimidyl)uronium tetrafluoroborate, N-(1,2,2,2-tetrachloroethoxycarbonyloxy)succinimide, N-carbobenzoxixuccinimide, O-(6-chlorobenzotriazole-1-yl)-N,N,N',N'-tetramethyluronium tetraphosphate Examples include uroborate, O-(6-chlorobenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate, 2-bromo-1-ethylpyridinium tetrafluoroborate, 2-chloro-1,3-dimethylimidazolinium chloride, 2-chloro-1,3-dimethylimidazolinium hexafluorophosphate, 2-chloro-1-methylpyridinium iodide, 2-chloro-1-methylpyridinium para-toluenesulfonate, 2-fluoro-1-methylpyridinium para-toluenesulfonate, and pentachlorophenyl trichloroacetate.

[0047] The condensing agent is preferably a carbodiimide compound, 2,2'-carbonylbis-1H-imidazole, 1H-benzotriazole-1-yloxytripyrrolidinophosphonium hexafluorophosphate, 1H-benzotriazole-1-yloxytris(dimethylamino)phosphonium hexafluorophosphate, N,N,N',N'-tetramethyl-O-(N-succinimidyl)uronium tetrafluoroborate, O-(6-chlorobenzotriazole-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate, 2-chloro-1,3-dimethylimidazolinium chloride, and 2-chloro-1-methylpyridinium iodide, with carbodiimide compounds being more preferred from an economic standpoint.

[0048] Among carbodiimide compounds, dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (water-soluble carbodiimide), and bis(2,6-diisopropylphenyl)carbodiimide are preferred due to their reactivity, cost, and the wide range of solvents that can be used.

[0049] The amount of condensing agent used is typically 0.8 to 1.2 moles per mole of compound (1-1).

[0050] In the esterification reaction, additives such as N-hydroxysuccinimide, benzotriazole, p-nitrophenol, and 3,5-dibutyl-4-hydroxytoluene may be added. The amount of these additives used is preferably 0.01 to 0.1 moles per mole of compound (1-1).

[0051] Furthermore, the esterification reaction may be carried out in the presence of a catalyst. Examples of catalysts include N,N-dimethylaminopyridine, N,N-dimethylaniline, and dimethylammonium pentafluorobenzenesulfonate. Among these, N,N-dimethylaminopyridine and N,N-dimethylaniline are preferred, and N,N-dimethylaminopyridine is more preferred. When a catalyst is used, the amount used is preferably 0.01 to 0.1 moles per mole of compound (1-1).

[0052] Esterification reactions are usually carried out in a solvent. Examples of solvents include ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone, or methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane, or heptane; aromatic hydrocarbon solvents such as toluene, xylene, benzene, or chlorobenzene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran and dimethoxyethane; ester solvents such as ethyl lactate; halogenated hydrocarbon solvents such as chloroform and dichloromethane; and aprotic polar solvents such as dimethyl sulfoxide, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and hexamethylphosphoric triamide. These solvents may be used individually or in combination.

[0053] The solvent is preferably an aromatic hydrocarbon solvent such as toluene, xylene, benzene, or chlorobenzene; an ether solvent such as tetrahydrofuran or dimethoxyethane; or a halogenated hydrocarbon solvent such as chloroform or dichloromethane, and more preferably a halogenated hydrocarbon solvent such as chloroform or dichloromethane.

[0054] The amount of compound (1-2) used in the reaction is preferably 0.25 to 0.6 moles, more preferably 0.3 to 0.5 moles, and even more preferably 0.4 to 0.5 moles, per mole of compound (1-1). When the amount of compound (1-2) used is above the lower limit, the yield of polymerizable compound (1) is good. Furthermore, when the amount of compound (1-2) used is below the upper limit, post-treatment work to remove unreacted compound (1-1) can be easily performed, and production can be carried out with high productivity.

[0055] The amount of solvent used is not particularly limited, but is preferably 0.5 to 50 parts by mass, more preferably 1 to 30 parts by mass, and even more preferably 1 to 20 parts by mass, per 1 part by mass of the total of compound (1-1) and compound (1-2).

[0056] The conditions for the esterification reaction can be determined as appropriate. From the viewpoint of reaction yield and productivity, the temperature of the esterification reaction is preferably -20 to 100°C, more preferably -10 to 50°C, and even more preferably -5 to 30°C. The duration of the esterification reaction is preferably 1 minute to 72 hours, more preferably 1 to 48 hours, and even more preferably 1 to 24 hours. By carrying out the esterification reaction within the above temperature and time ranges, the reaction yield tends to improve.

[0057] Compounds (1-1) and (1-2) used in the above reaction can be produced by appropriately combining the various known organic synthesis reactions described above, depending on their structure.

[0058] Also, for example, in formula (1), L is a carbonyl group, m is 0, and E 1 and E 2 Both are -O-, and A 1 and A 2 B 1 and B 2 F 1 and F 2 , P 1 and P 2A polymerizable compound (1) in which both are identical can be produced by reacting compound (1-1) with, for example, triphosgene, in the presence of a base and a solvent.

[0059] Examples of bases used in the above reaction include amines such as trimethylamine, triethylamine, N,N-diisopropylethylamine, N,N-dimethylaniline, and N,N-diethylaniline, and pyridines such as pyridine and N,N-dimethylaminopyridine. Among these, N,N-diisopropylethylamine, triethylamine, and pyridine are preferred from the viewpoint of easily promoting the reaction.

[0060] The amount of base used in the reaction is preferably 1.0 to 1.5 moles per mole of compound (1-1).

[0061] The amount of triphosgene used in the reaction is preferably 0.1 to 0.5 moles, more preferably 0.1 to 0.4 moles, and even more preferably 0.1 to 0.3 moles per mole of compound (1-1). When the amount of triphosgene used is above the lower limit, the yield of polymerizable compound (1) is good. Furthermore, when the amount of triphosgene used is below the upper limit, post-treatment work to remove unreacted compound (1-1) can be easily performed, and the compound can be manufactured with high productivity.

[0062] The solvent used in the above reaction is the same as that used in the esterification reaction between compound (1-1) and compound (1-2). The amount of solvent used is not particularly limited, but is preferably 1 to 50 parts by mass, more preferably 1 to 20 parts by mass, and even more preferably 1 to 10 parts by mass, per 1 part by mass of the total of compound (1-1) and triphosgene.

[0063] The conditions for the reaction between compound (1-1) and triphosgene can be determined as appropriate. The reaction temperature is, for example, -20 to 60°C, preferably -20 to 40°C, from the viewpoint of reaction yield and productivity. The reaction time is, for example, 1 minute to 72 hours, preferably 1 to 48 hours, more preferably 1 to 24 hours, from the viewpoint of reaction yield and productivity.

[0064] After each reaction by the above method is completed, the desired compound can be isolated by performing any necessary post-treatments such as filtration, neutralization, extraction, and washing with water, or by performing isolation treatments such as distillation and crystallization, which are applicable in organic synthesis chemistry.

[0065] The structure of the obtained compound can be identified by measurements such as NMR spectroscopy, IR spectroscopy, and mass spectroscopy, as well as elemental analysis.

[0066] <Mixed composition> Polymerizable compound (1), when added to a composition containing a polymerizable liquid crystal compound, exhibits excellent effect in lowering the crystallization temperature of the resulting mixed composition. Therefore, the present invention relates to a mixed composition of polymerizable compound (1) and a polymerizable liquid crystal compound different from polymerizable compound (1).

[0067] The effects of polymerizable compound (1) tend to be particularly pronounced when mixed with a polymerizable liquid crystal compound having a molecular structure similar to that of polymerizable compound (1). In the mixed composition of the present invention, polymerizable compound (1) can be used in combination with various polymerizable liquid crystal compounds, but it is preferable to combine it with a polymerizable liquid crystal compound having a structure common to at least a part of the structure of polymerizable compound (1). For example, such a polymerizable liquid crystal compound is formula (2): [ka] Examples include polymerizable liquid crystal compounds represented by (hereinafter also referred to as "polymerizable liquid crystal compound (2)"), and it is preferable that the mixed composition of the present invention contains polymerizable compound (1) and polymerizable liquid crystal compound (2).

[0068] In equation (2), D 21 , D 22 , E 21 , E 22 B 21 and B 22 Each of these is independently of -CR 11 R 12 -, -CH2-CH2-, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR 11 -, -NR 12 -CO-, -O-CH2-, -CH2-O-, -S-CH2-, -CH2-S- or single bond, R 11 and R 12 Each of these independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms. 21 and D 22 These are, respectively, the base Ar and G 1 or G 2 It has the role of a linking group that connects the cyclic structure represented by E. 21 and E 22 These are, G 21 or G 22 A ring structure represented by A 21 Or A 22 It has the role of a linking group that connects the cyclic structure represented by B. 21 and B 22 These are, A 21 Or A 22 It has the role of a linking group between the cyclic structure represented by and the polymerizable group.

[0069] D 21 , D 22 , E 21 , E 22 B 21 and B 22 These are, independently, -O-, -CO-O-, -O-CO-, -C(=S)-O-, -OC(=S)-, and -CO-NR. 11 -or-NR 12 It is preferably -CO-, and more preferably -O-, -CO-O-, or -O-CO-. 11and R 12 Each of these is preferably independently a hydrogen atom, a methyl group, or an ethyl group. D 21 and D 22 , E 21 and E 22 B 21 and B 22 These may be identical or different from each other, but if they are identical, it is advantageous in terms of ease of industrial production and productivity of the polymerizable liquid crystal compound (2).

[0070] In formula (2), G 21 and G 22 These represent either a 1,4-cyclohexanediyl group or an aromatic hydrocarbon group, respectively. 21 and G 22 The aromatic hydrocarbon group represented is G, which constitutes polymerizable compound (1). 1 and G 2 Examples of aromatic hydrocarbon groups represented by are similar to those exemplified. Among them, G 21 and G 22 These are preferably a 1,4-cyclohexanediyl group or a 1,4-phenylene group, and more preferably a 1,4-cyclohexanediyl group from the viewpoint of the optical properties of the resulting liquid crystal cured film. G 21 and G 22 These may be identical or different from each other, but if they are identical, it is advantageous in terms of ease of industrial production and productivity of the polymerizable liquid crystal compound (2).

[0071] In formula (2), A 21 and A 22 Each of these independently represents a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms. The hydrogen atoms contained in the alicyclic hydrocarbon group and the aromatic hydrocarbon group are halogen atoms, -R 13 , -OR 13 , may be substituted with a cyano group or a nitro group, R 13 A represents an alkyl group having 1 to 4 carbon atoms, and the hydrogen atoms contained in the alkyl group may be substituted with fluorine atoms.21 and A 22 As a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, A is a polymerizable compound (1). 1 and A 2 Examples include divalent alicyclic hydrocarbon groups having 3 to 16 carbon atoms or divalent aromatic hydrocarbon groups having 6 to 20 carbon atoms, as exemplified above. Among them, A 21 and A 22 Preferably, the group is either a 1,4-cyclohexanediyl group or a 1,4-phenylene group, and more preferably, the 1,4-phenylene group, from the viewpoint of the optical properties of the resulting liquid crystal cured film. In particular, G 21 and G 22 However, each is a 1,4-cyclohexanediyl group, and A 21 and A 22 However, it is preferable that each of them be a 1,4-phenylene group. A 21 and A 22 These may be identical or different from each other, but if they are identical, it is advantageous in terms of ease of industrial production and productivity of the polymerizable liquid crystal compound (2).

[0072] In formula (2), F 21 and F 22 Each of these independently represents an alkanediyl group having 1 to 12 carbon atoms. The hydrogen atoms contained in the alkanediyl group are -OR 14 Alternatively, it may be substituted with a halogen atom, R 14 represents an alkyl group having 1 to 4 carbon atoms, and the hydrogen atoms in the alkyl group may be substituted with fluorine atoms. Furthermore, the -CH2- group in the alkanediyl group may be replaced with -O- or -CO-. F 21 and F 22 As an alkanediyl group having 1 to 12 carbon atoms represented by , F is a component of polymerizable compound (1). 1 and F 2 Examples of alkanediyl groups with 1 to 12 carbon atoms, as shown above, include those similar to the examples given. Among them, F 21 and F 22Preferably, each of these is an alkanediyl group having 3 to 10 carbon atoms, -(CF2)4-, -(CF2)6-, or -(CF2)8-, and more preferably an alkanediyl group having 4 or 6 carbon atoms [-(CH2)4- or -(CH2)6-]. E 21 and E 22 These may be identical or different from each other, but if they are identical, it is advantageous in terms of ease of industrial production and productivity of the polymerizable liquid crystal compound (2).

[0073] P 21 and P 22 Each of these independently represents a hydrogen atom or a polymerizable group. 21 and P 22 At least one of them is a polymerizable group, P 21 and P 22 It is preferable from the viewpoint of film hardness of the liquid crystal cured film obtained using the polymerizable liquid crystal compound that all of these are polymerizable groups. 21 and P 22 The polymerizable group represented by is P, which constitutes polymerizable compound (1). 1 and P 2 Examples of polymerizable groups represented by the formula are similar to those exemplified. Among these, radical polymerizable groups or cationic polymerizable groups are preferred, and acryloyloxy groups or methacryloyloxy groups are particularly preferred because they are easy to handle and easy to manufacture, with acryloyloxy groups being more preferred.

[0074] In formula (2), Ar may be a substituted divalent aromatic hydrocarbon group or a divalent aromatic heterocyclic group (hereinafter, these are collectively referred to as "substituted divalent aromatic groups"). In the present invention, a substituted divalent aromatic hydrocarbon group means a divalent linking group containing at least one aromatic hydrocarbon ring, and a substituted divalent aromatic heterocyclic group means a divalent linking group containing at least one aromatic heterocycle. Here, an aromatic hydrocarbon ring and an aromatic heterocycle refer to a ring structure having [4n+2] π electrons according to Hückel's rule (in the case of an aromatic heterocycle, Hückel's rule is satisfied including non-covalent electron pairs on heteroatoms such as -N= and -S-). Ar may contain one aromatic hydrocarbon ring or aromatic heterocycle, or it may contain two or more. If the compound contains one aromatic hydrocarbon ring or aromatic heterocycle, Ar may be a substituted or substituted divalent aromatic hydrocarbon group, or a substituted or substituted divalent aromatic heterocycle group. If the compound contains two or more aromatic hydrocarbon rings or aromatic heterocycles, it may contain multiple aromatic hydrocarbon rings only, or multiple aromatic heterocycles only, or one or more aromatic hydrocarbon rings and one or more aromatic heterocycles. Two or more aromatic hydrocarbon rings and / or aromatic heterocycles may be linked to each other by single bonds, divalent bonding groups such as -CO-O-, and -O-.

[0075] Examples of aromatic hydrocarbon rings that may be contained in Ar include benzene rings, naphthalene rings, and anthracene rings, with benzene rings and naphthalene rings being preferred. Examples of aromatic heterocycles include furan rings, benzofuran rings, pyrrole rings, indole rings, thiophene rings, benzothiophene rings, pyridine rings, pyrazine rings, pyrimidine rings, triazole rings, triazine rings, pyrroline rings, imidazole rings, pyrazole rings, thiazole rings, benzothiazole rings, thienothiazole rings, oxazole rings, benzoxazole rings, and phenantholine rings. If Ar contains a nitrogen atom, it is preferable that the nitrogen atom has π electrons.

[0076] In particular, Ar preferably has an aromatic heterocycle containing at least two heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur atoms, more preferably a thiazole ring, a benzothiazole ring, or a benzofuran ring, and even more preferably a benzothiazole ring. When Ar has an aromatic heterocycle containing at least two heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur atoms, the aromatic heterocycle is D in formula (2). 21 Or D 22 It may also be a divalent linking group that is directly bonded to and constitutes the main chain of polymerizable liquid crystal compound (2), D 21 Or D 22 Although it may be included as a substituent of a divalent linking group that is directly bonded to, it is preferable that the entire Ar group including the aromatic heterocycle is stereoconfigured in a direction substantially orthogonal to the molecular orientation direction.

[0077] In formula (2), the total number of π electrons N contained in the divalent aromatic group which may have substituents represented by Ar. π Each of these values ​​is preferably 8 or more, more preferably 12 or more, particularly preferably 16 or more, and especially preferably 20 or more. Also, it is preferably 36 or less, more preferably 32 or less, even more preferably 30 or less, particularly preferably 26 or less, and especially preferably 24 or less.

[0078] Examples of divalent aromatic groups that may have substituents represented by Ar in formula (2) include the groups represented by formulas (Ar-1) to (Ar-5) below. These groups share the following characteristics in the polymerizable liquid crystal compound represented by formula (2): they give a bulky molecular structure in a direction intersecting the long axis, the absorption wavelength in the short axis direction is a long wavelength, and the phase difference generated by the oriented liquid crystal molecules exhibits inverse wavelength dispersion. [ka]

[0079] In equations (Ar-1) to (Ar-5), * represents D in equation (2). 21 Or D 22This represents the connection point.

[0080] In formula (Ar-1), Q 1 is -S-, -O-, or -NR 15 - represents R 15 Q represents a C1-C6 alkyl group which may have a hydrogen atom or substituents. In formulas (Ar-3) and (Ar-4), Q 2 represents an alkyl group having 1 to 6 carbon atoms, which may have a hydrogen atom or substituents.

[0081] In formula (Ar-2), W 1 and W 2 These are -O-, -S-, -CO-, and -NR, respectively, independently. 15 - represents R 15 represents an alkyl group having 1 to 6 carbon atoms, which may have a hydrogen atom or substituents.

[0082] In formula (Ar-1), Y 1 represents an alkyl group having 1 to 6 carbon atoms, an optionally substituted aromatic hydrocarbon group, or an aromatic heterocyclic group. In formula (Ar-2), Y 2 represents a C1-C12 alkyl group which may have a CN group or substituents. Here, the hydrogen atoms in the alkyl group may be substituted with halogen atoms, and the -CH2- in the alkyl group may be substituted with -O-, -CO-, -O-CO-, or -CO-O-.

[0083] In equations (Ar-1) to (Ar-5), Z 1 , Z 2 and Z 3 These are, independently, a hydrogen atom or an aliphatic hydrocarbon group or alkoxy group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a halogen atom, a cyano group, a nitro group, and -NR. 15 R 16 or -SR 15 Represents Z 1 and Z 2 These may bond to each other to form an aromatic ring or an aromatic heterocycle. 15 and R 16Each of these independently represents either a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0084] In formulas (Ar-3) and (Ar-4), Ax represents an organic group having 2 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles, Ay represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have substituents, or an organic group having 2 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles, and Ax and Ay may be bonded to form a ring.

[0085] In formula (Ar-1), Y 1 Preferably, the aromatic hydrocarbon group or aromatic heterocyclic group may have substituents, and more preferably, an aromatic hydrocarbon group having 6 to 12 carbon atoms or an aromatic heterocyclic group having 3 to 12 carbon atoms may have substituents. The aromatic hydrocarbon group or aromatic heterocyclic group may have substituents is preferably a polycyclic aromatic hydrocarbon group or polycyclic aromatic heterocyclic group that may be substituted. In this specification, "polycyclic aromatic hydrocarbon group" means an aromatic hydrocarbon group having at least two aromatic rings, and includes condensed aromatic hydrocarbon groups formed by the condensation of two or more aromatic rings and aromatic hydrocarbon groups formed by the bonding of two or more aromatic rings. "Polycyclic aromatic heterocyclic groups" refer to aromatic heterocyclic groups having at least one heteroaromatic ring and at least one ring selected from the group consisting of aromatic rings and heteroaromatic rings. Examples include aromatic heterocyclic groups formed by the condensation of one or more aromatic heterocyclic rings with one or more rings selected from the group consisting of aromatic rings and heteroaromatic rings, and aromatic heterocyclic groups formed by the bonding of at least one heteroaromatic ring with at least one ring selected from the group consisting of aromatic rings and heteroaromatic rings.

[0086] Substituents that the aromatic hydrocarbon group or aromatic heterocyclic group may have include halogen atoms, C1-C6 alkyl groups, cyano groups, nitro groups, nitroso groups, C1-C6 alkylsulfinyl groups, C1-C6 alkylsulfonyl groups, carboxyl groups, C1-C6 fluoroalkyl groups, C1-C6 alkoxy groups, C1-C6 alkylsulfanyl groups, C1-C4 N-alkylamino groups, C2-C8 N,N-dialkylamino groups, sulfamoyl groups, C1-C6 N-alkylsulfamoyl groups, and C2-C12 N,N-dialkylsulfamoyl groups.

[0087] Y 1 For example, the following formula (Y 1 -1)~(Y 1 A group represented by -7) is an example. [ka]

[0088] Equation (Y 1 -1) ~ Equation (Y 1 -7) In the middle, the * section represents a connecting part.

[0089] Equation (Y 1 -1) ~ Equation (Y 1 -7) Medium, Z 4 Each of these independently represents a halogen atom or an organic group having 1 to 20 carbon atoms. For example, fluorine, chlorine, bromine, methyl, ethyl, isopropyl, sec-butyl, cyano, nitro, sulfone, nitroxyoxide, carboxyl, trifluoromethyl, methoxy, thiomethyl, N,N-dimethylamino, and N-methylamino groups are preferred; halogen, methyl, ethyl, isopropyl, sec-butyl, cyano, nitro, and trifluoromethyl groups are more preferred; and methyl, ethyl, isopropyl, sec-butyl, pentyl, and hexyl groups are particularly preferred.

[0090] Equation (Y 1 -1) ~ Equation (Y 1 -7) Medium, V 1and V 2 These are -CO-, -S-, and -NR, respectively, independently. 17 -, -O-, -Se- or -SO2- represent -S-, -NR 17 - or -O- is preferable. 17 This represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0091] Equation (Y 1 -1) ~ Equation (Y 1 -7) Medium, W 3 ~W 7 These independently represent -C= or -N=.

[0092] Equation (Y 1 -1) ~ Equation (Y 1 -7) Medium, V 1 , V 2 and W 3 ~W 7 Preferably, at least one of these represents a group containing S, N, or O.

[0093] Equation (Y 1 -1) ~ Equation (Y 1 -7) In this case, a independently represents an integer between 0 and 3, and is preferably 0 or 1. b independently represents an integer between 0 and 2, and is preferably 0.

[0094] Equation (Y 1 -1) ~ Equation (Y 1 Any of the groups represented by -7) are given by the following formula (Y 1 -8) ~ Equation (Y 1 It is preferable that the group is one of the groups represented by formula (Y -13), and formula (Y 1 It is more preferable that the base be represented by -8). Note that the * part represents a connecting part.

[0095] [ka]

[0096] Equation (Y 1 -8) ~ Equation (Y 1 -13) Medium, Z 4a, b, V 1 , V 2 and W 3 is, (Y 1 -1) ~ Equation (Y 1 -7) Z inside 4 a, b, V 1 , V 2 and W 3 It expresses the same meaning.

[0097] Y 1 Specific examples include, for instance, the groups represented by formulas (ar-1) to (ar-840) described in Japanese Patent Publication No. 2019-003177. Among these, the group represented by the following formula is preferred.

[0098] [ka]

[0099] In one embodiment of the present invention, the group represented by formula (Ar-1) is specifically the following formula (Ar 1 -1)~(Ar 1 Examples of the group represented by -126) are given. The * part in the formula is D in formula (2). 21 Or D 22 This represents the connection point.

[0100] [ka]

[0101] [ka]

[0102] [ka]

[0103] [ka]

[0104] [ka]

[0105] [ka]

[0106] In one embodiment of the present invention, the group represented by formula (Ar-2) is specifically the following formula (Ar 2 -1)~(Ar 2 Examples of the group represented by -13) are given by the * part in formula (2) 21 Or D 22 This represents the connection point.

[0107] [ka]

[0108] In one embodiment of the present invention, the group represented by formula (Ar-3) is specifically the following formula (Ar 3 -1)~(Ar 3 Examples of the group represented by -23) are given by the * part in formula (2) 21 Or D 22 This represents the connection point.

[0109] [ka]

[0110] [ka]

[0111] The groups represented by formulas (Ar-1) to (Ar-4) may include, in addition to the groups specifically exemplified above, groups described in, for example, Japanese Patent Publication No. 2011-207765, Japanese Patent Publication No. 2008-107767, WO2014 / 010325, etc.

[0112] In formula (Ar-5), Y 3and Y 4 Each of these independently corresponds to the following equation (Y 3 -1): [ka] It is selected from the base represented by

[0113] Equation (Y 3 -1) Medium, R Y1 X represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The alkyl group has one or more substituents X 3 It may be replaced by this.

[0114] Substituent X 3 This includes fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, pentafluorosulfuranyl groups, nitro groups, cyano groups, isocyano groups, amino groups, hydroxyl groups, mercapto groups, methylamino groups, dimethylamino groups, diethylamino groups, diisopropylamino groups, trimethylsilyl groups, dimethylsilyl groups, thioisocyano groups, or one -CH2- or two or more non-adjacent -CH2- groups, each independently of -O-, -S-, -CO-, - Represents a linear or branched alkyl group having 1 to 20 carbon atoms, which may be replaced by COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or -C≡C-, and any hydrogen atom in the alkyl group may be replaced by a fluorine atom, or -B 31 -F 31 -P 31 The group may also be represented by B 31 F 31 and P 31 These are, respectively, B in formula (2) above. 21 F 21 and P 21 It is defined similarly to B in equation (2), respectively. 21 F 21 and P 21 It may be the same as or different from it.

[0115] Substituent X 3 The preferred elements are fluorine atoms, chlorine atoms, -CF3, -OCF3, or cyano groups. Y1 The element is preferably an unsubstituted C1-C6 alkyl group substituted with a hydrogen atom or one or more fluorine atoms, and more preferably a hydrogen atom.

[0116] Equation (Y 3 -1) Middle, U 1 This represents an organic group having 2 to 30 carbon atoms that has an aromatic hydrocarbon group. Any carbon atom of the aromatic hydrocarbon group may be substituted with a heteroatom. 1 This is an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles. The aromatic hydrocarbon group has one or more substituents X 3 It may be replaced by this.

[0117] U 1 It is preferable that the organic group has an aromatic heterocycle in which one or more carbon atoms are substituted with heteroatoms, as this results in good wavelength dispersion. 1 It is more preferable that the organic group has an aromatic heterocycle which is a fused ring of a 5-membered ring and a 6-membered ring, as this results in good wavelength dispersion and high birefringence.

[0118] Specifically U 1 Preferably, it has a group represented by the following formula. Note that in the following formula, these groups can be any position T 1 It has a connecting bond with.

[0119] [ka]

[0120] Equation (Y 3 -1) Medium, T 1 -O-, -S-, -COO-, -OCO-, -OCO-O-, -NU 2 -, -N=CU 2 -, -CO-NU2 -,-OCO-NU 2 -or O-NU 2 - represents U 2 is a C2-C30 organic group having a hydrogen atom, a C1-C20 alkyl group, a C3-C12 cycloalkyl group, a C3-C12 cycloalkenyl group, an aromatic hydrocarbon group (any carbon atom of the aromatic hydrocarbon group may be substituted with a heteroatom), or (E 31 -A 31 ) q -B 32 -F 32 -P 32 This represents the alkyl group, cycloalkyl group, cycloalkenyl group, and aromatic hydrocarbon group, respectively, being unsubstituted or having one or more substituents X. 3 The alkyl group may be substituted by the cycloalkyl group or cycloalkenyl group. One -CH2- or two or more non-adjacent -CH2- in the alkyl group may be independently replaced by -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -SO2-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or -C≡C-, and one -CH2- or two or more non-adjacent -CH2- in the cycloalkyl group or cycloalkenyl group may be independently replaced by -O-, -CO-, -COO-, -OCO- or O-CO-O-. 31 , A 31 B 32 F 32 and P 32 These are, respectively, E in equation (2). 21 , A 21 B 21 F 21 and P 21 Defined similarly to the above E 21 , A 21 B 21 F 21 and P 21It may be the same as or different from, q represents an integer from 0 to 4, and E 31 and / or A 31 If multiple instances exist, they may be identical or different.

[0121] T 1 Due to its good birefringence and ease of synthesis, -O-, -S-, -N=CU 2 -or-NU 2 - Preferably, -O-, -S-, or -NU, as these easily improve wavelength dispersion and birefringence. 2 - is more preferable.

[0122] U 2 one or more of the substituents X 3 Preferably, the alkyl or alkenyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or a cycloalkenyl group having 3 to 12 carbon atoms, or the alkyl or alkenyl group having 1 to 20 carbon atoms, which may be substituted by such group, and one -CH2- or two or more non-adjacent -CH2- may each be independently replaced with -O-, -CO-, -COO-, -OCO-, or -O-CO-O-.

[0123] Among them, U 2 From the viewpoint of birefringence and solvent solubility, it is more preferable that the alkyl group is a linear alkyl group having 1 to 20 carbon atoms, in which hydrogen atoms may be substituted with fluorine atoms, and one -CH2- or two or more non-adjacent -CH2- may each be independently substituted with -O-, -CO-, -COO-, or -OCO-.

[0124] U 1 and U 2 They may be joined together to form a ring. In that case, for example, -NU 1 U 2 A cyclic group represented by -N=CU 1 U 2 Examples of cyclic groups represented by include:

[0125] Y 3 and Y 4 These are expressed by the following equation (Y 3’ -1) ~ Equation (Y 3’ It is particularly preferable to represent a base selected from -47).

[0126] [ka]

[0127] [ka]

[0128] [ka]

[0129] From the viewpoint of improving the orientation of polymerizable liquid crystal compound (2), making it easier to manufacture industrially and improving productivity, the following groups can be specifically listed as groups represented by formula (Ar-5): See below (Ar 5 -1)~(Ar 5 -20) The * in equation (2) is D 21 Or D 22 This represents the connection point.

[0130] [ka]

[0131] [ka]

[0132] [ka]

[0133] Among the formulas (Ar-1) to (Ar-5), the formulas (Ar-1), (Ar-2), and (Ar-5) are preferred, the formulas (Ar-1) and (Ar-5) are more preferred, and the formula (Ar-1) is even more preferred.

[0134] *-D in formula (2) 21 -G 21 -E 21 -A 21 -B 21 -F 21 -P 21 , and, *-D 22 -G 22 -E 22 -A 22 -B 22 -F 22 -P 22 Specific examples of, and, *-(D 1 -G 1 )m-E 1 -A 1 -B 1 -F 1 -P 1 , and, *-(D 2 -G 2 )m-E 2 -A 2 -B 2 -F 2 -P 2 Structures represented by the formulas (R-46) to (R-106) exemplified as the part and the like can be mentioned.

[0135] In the present invention, examples of the polymerizable liquid crystal compound represented by the formula (2) include compounds as described in JP-A-2019-003177, JP-A-2019-073496, and the like.

[0136] When the mixed composition contains the polymerizable compound (1) and the polymerizable liquid crystal compound (2) having a molecular structure similar to the polymerizable compound (1), the crystallization temperature in the liquid crystal composition tends to decrease. As a combination of the polymerizable compound (1) and the polymerizable liquid crystal compound (2) whose molecular structures are similar or approximate to each other, in one aspect of the present invention, P in the formula (1) 1 , F 1 , B 1 , A 1and E 1 is the same as P in formula (2), respectively 21 F 21 B 21 A 21 and E 21 and is the same as P in formula (1), respectively 2 F 2 B 2 A 2 and E 2 is preferably the same as P in formula (2), respectively 22 F 22 B 22 A 22 and E 22 -(D 1 -G 1 ) m -E 1 -A 1 -B 1 -F 1 -P 1 and P 2 -F 2 -B 2 -A 2 -E 2 -(G 2 -D 2 ) m - represented by the part and -D in formula (2) 21 -G 21 -E 21 -A 21 -B 21 -F 21 -P 21 and P 22 -F 22 -B 22 -A 22 -E 22 -G 22 -D 22It is more preferable to include a polymerizable compound (1) and a polymerizable liquid crystal compound (2) that have a common or identical molecular structure with the part represented by -. In such a mixed composition, the crystallization temperature of the mixed composition is easily lowered, and it is not necessary to raise the processing temperature to prevent crystallization of the polymerizable compound during film formation. For this reason, an optical film can be obtained from the polymerizable liquid crystal compound (2) at a lower processing temperature, which is advantageous in that the effect of heating on the optical properties of the optical film can be reduced and in terms of manufacturing efficiency. The mixed composition may contain only one type of polymerizable compound (1) and a polymerizable liquid crystal compound (2), or multiple types, but it is preferable that at least one of the polymerizable compounds (1) has a structure similar to, approximates, or is identical to at least one of the polymerizable liquid crystal compounds (2).

[0137] The content of polymerizable compound (1) and polymerizable liquid crystal compound (2) in the mixed composition of the present invention may be appropriately determined within a range in which the effects of the present invention can be obtained, depending on the type of polymerizable compound (1) and / or polymerizable liquid crystal compound (2), but it is preferable that the ratio of the peak area of ​​polymerizable compound (1) to the total peak area of ​​polymerizable compound (1) and polymerizable liquid crystal compound (2), as measured by liquid chromatography (hereinafter also referred to as "area percentage value") is 1% or more and less than 50%. More preferably it is 3% by mass or more, even more preferably 5% by mass or more, and particularly preferably 8% by mass or more, and may be, for example, 10% by mass or more. If the content of polymerizable compound (1) is above the above lower limit, the crystallization temperature in the mixed composition tends to decrease sufficiently, and orientation defects are less likely to occur when producing a liquid crystal cured film. Furthermore, the content of polymerizable compound (1) is more preferably 45% by mass or less, and even more preferably 40% by mass or less. When the content of polymerizable compound (1) is below the above upper limit, the orientation state of the liquid crystals during the production of the liquid crystal cured film can be maintained in good condition, thereby enabling the production of an optical film with excellent optical properties. Even when polymerizable compound (1) of the present invention is blended in a relatively large amount with respect to the polymerizable liquid crystal compound, it does not significantly affect the orientation of the liquid crystals, suppressing the occurrence of orientation defects and enabling the production of an optical film with excellent optical properties. If multiple compounds corresponding to polymerizable compound (1) and / or polymerizable liquid crystal compound (2) are present, the area percentage value of polymerizable compound (1) is calculated based on the total peak area of ​​all polymerizable compounds (1) and all polymerizable liquid crystal compounds (2). The area percentage value can be calculated based on the peak area measured by liquid chromatography, and in detail, it can be measured and calculated by the method described in the examples below.

[0138] The mixed composition of the present invention, by combining polymerizable compound (1) and polymerizable liquid crystal compound (2), can significantly lower the crystallization temperature compared to when polymerizable liquid crystal compound (2) is used alone or when a polymerizable compound having a cyclic structure in group L of formula (1) is used. For example, the crystallization temperature of the mixed composition of polymerizable compound (1) and polymerizable liquid crystal compound (2) constituting the mixed composition of the present invention is preferably 91°C or lower, more preferably 90°C or lower, even more preferably 88°C or lower, and particularly preferably 86°C or lower. Furthermore, when polymerizable compound (1) of the present invention is used in combination with polymerizable liquid crystal compound (2), the crystallization temperature can be lowered by preferably 3°C or more, more preferably 5°C or more, even more preferably 7°C or higher, and particularly preferably 8°C or higher, compared to when polymerizable liquid crystal compound (2) is used alone. In this invention, the crystallization temperature of the mixed composition can be measured by the method described in the examples below. The crystallization temperature of a mixed composition containing two or more polymerizable compounds is measured using a mixed composition having the same composition as the polymerizable compounds constituting the mixed composition.

[0139] The mixed composition of the present invention may contain polymerizable liquid crystal compounds other than polymerizable liquid crystal compound (2). Examples of such polymerizable liquid crystal compounds include those described in Chapter 3, Molecular Structure and Liquid Crystallinity, 3.2 Non-chiral rod-shaped liquid crystal molecules, 3.3 Chiral rod-shaped liquid crystal molecules, of the Liquid Crystal Handbook (edited by the Liquid Crystal Handbook Editorial Committee, published by Maruzen Co., Ltd. on October 30, 2000), as well as those described in Japanese Patent Publication No. 2010-31223, Japanese Patent Publication No. 2011-207765, Japanese Patent No. 5962760, etc., which can exhibit inverse wavelength dispersion when formed into a liquid crystal cured film, or polymerizable liquid crystal compounds that can exhibit positive wavelength dispersion.

[0140] The mixed composition of the present invention may use liquid crystal compounds other than polymerizable liquid crystal compound (2) in combination with polymerizable compound (1) as long as the effects of the present invention are obtained, but it is preferable that the polymerizable liquid crystal compound contains at least one polymerizable liquid crystal compound (2). In this case, the content of polymerizable compounds other than polymerizable compound (1) and polymerizable liquid crystal compound (2) is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less, based on 100 parts by mass of the total of polymerizable compound (1) and polymerizable liquid crystal compound (2). In particular, if the content of liquid crystal compounds with molecular structures significantly different from polymerizable compound (1) or polymerizable liquid crystal compound (2) becomes too high, it may cause phase separation and impair the appearance, so it is preferable that the polymerizable compounds constituting the mixed composition of the present invention are substantially composed of polymerizable liquid crystal compounds having a structure similar to polymerizable compound (1). Note that "similar" means, for example, the -(D) of polymerizable compound (1). 1 -G 1 )mE 1 -A 1 -B 1 -F 1 -P 1 ,-(D 2 -G 2 )mE 2 -A 2 -B 2 -F 2 -P 2 The part represented by, and -D in equation (2) 21 -G21 -E 21 -A 21 -B 21 -F 21 -P 21 , -D 22 -G 22 -E 22 -A 22 -B 22 -F 22 -P 22 This refers to a case where the part represented by and the part represented by Ar have a common structure, and the term "substantially constituted" means that the content of polymerizable compound (1) and polymerizable liquid crystal compound (2) is 90% by mass or more of the total mass of polymerizable compounds contained in the mixed composition. In one embodiment of the present invention, the mixed composition does not contain polymerizable compounds other than polymerizable compound (1) and polymerizable liquid crystal compound (2).

[0141] The polymerizable compound content (total amount of all polymerizable compounds) in the mixed composition of the present invention is, for example, 70 to 99.5 parts by mass, preferably 80 to 99 parts by mass, more preferably 85 to 98 parts by mass, and even more preferably 90 to 95 parts by mass, per 100 parts by mass of solid content of the polymerizable composition. Having the total mass of polymerizable compounds within the above range is advantageous from the viewpoint of the orientation of the resulting liquid crystal cured film. In this specification, the term "polymerizable compound" simply refers to polymerizable compound (1) and polymerizable liquid crystal compounds (polymerizable compound (2) and / or other polymerizable liquid crystal compounds different from polymerizable liquid crystal compound (2), if included). Furthermore, the solid content of the mixed composition refers to the amount of all components excluding volatile components such as organic solvents from the mixed composition.

[0142] The mixed composition of the present invention may further contain additives such as organic solvents, photopolymerization initiators, polymerization inhibitors, photosensitizers, and leveling agents, in addition to the polymerizable compound (1) and polymerizable liquid crystal compound. Each of these components may be used individually or in combination of two or more.

[0143] In the present invention, the mixed composition is usually applied to a substrate or the like in a dissolved state in a solvent, so it is preferable that it contains a solvent. The solvent is preferably one that can dissolve polymerizable compounds such as polymerizable compound (1) and polymerizable liquid crystal compound (2), and is also preferably a solvent that is inert to the polymerization reaction of the polymerizable compound. By combining polymerizable compound (1) and polymerizable liquid crystal compound (2) in the mixed composition of the present invention, the solvent solubility of polymerizable liquid crystal compound (2) can be significantly improved compared to the case where polymerizable liquid crystal compound (2) is dissolved alone in a solvent. Therefore, various solvents can be applied. Examples of solvents include alcoholic solvents such as water, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, 2-butoxyethanol, and propylene glycol monomethyl ether; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, and ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane, and heptane; alicyclic hydrocarbon solvents such as ethylcyclohexane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran and dimethoxyethane; chlorine-containing solvents such as chloroform and chlorobenzene; and amide solvents such as dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone (NMP), and 1,3-dimethyl-2-imidazolidinone. These solvents can be used individually or in combination of two or more. Among these, organic solvents are preferred, with alcohol solvents, ester solvents, ketone solvents, chlorine-containing solvents, amide solvents, and aromatic hydrocarbon solvents being more preferred. From the viewpoint of productivity, at least one selected from the group consisting of methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and N-methylpyrrolidone is even more preferred.

[0144] The solvent content in the mixed composition is preferably 50 to 98 parts by mass, more preferably 50 to 95 parts by mass, per 100 parts by mass of the mixed composition. Therefore, the solid content per 100 parts by mass of the mixed composition is preferably 2 to 50 parts by mass, and more preferably 5 to 50 parts by mass. When the solid content is 50 parts by mass or less, the viscosity of the mixed composition becomes low, which tends to result in a substantially uniform film thickness during coating and reduces the likelihood of unevenness. The above solid content can be appropriately determined considering the thickness of the liquid crystal cured film to be manufactured. The mixed composition of the present invention, by containing a combination of polymerizable compound (1) and polymerizable liquid crystal compound (2), has excellent solubility in solvents, which is advantageous in that it can reduce the amount of organic solvent used during coating and storage.

[0145] The mixed composition of the present invention may contain a polymerization initiator. The polymerization initiator is a compound that can initiate a polymerization reaction, such as a polymerizable compound. As a polymerization initiator, a photopolymerization initiator that generates active radicals upon the action of light is preferred, from the viewpoint of not being dependent on the phase state of the thermotropic liquid crystal.

[0146] Any known photopolymerization initiator can be used as the photopolymerization initiator, as long as it is a compound capable of initiating the polymerization reaction of a polymerizable compound. Specifically, photopolymerization initiators that can generate active radicals or acids upon the action of light are recommended, and among these, photopolymerization initiators that generate radicals upon the action of light are preferred. Photopolymerization initiators can be used alone or in combination of two or more.

[0147] As photopolymerization initiators, known photopolymerization initiators can be used. For example, as photopolymerization initiators that generate active radicals, self-cleaving benzoin compounds, acetophenone compounds, hydroxyacetophenone compounds, α-aminoacetophenone compounds, oxime ester compounds, acylphosphine oxide compounds, azo compounds, etc. can be used. Hydrogen abstraction types such as benzophenone compounds, alkylphenone compounds, benzoin ether compounds, benzyl ketal compounds, dibenzosverone compounds, anthraquinone compounds, xanthone compounds, thioxanthone compounds, halogenoacetophenone compounds, dialkoxyacetophenone compounds, halogenobisimidazole compounds, halogenotriazine compounds, triazine compounds, etc. can be used. As photopolymerization initiators that generate acid, iodonium salts and sulfonium salts, etc. can be used. Self-cleaving photopolymerization initiators are preferred from the viewpoint of excellent reaction efficiency at low temperatures, and acetophenone compounds, hydroxyacetophenone compounds, α-aminoacetophenone compounds, and oxime ester compounds are particularly preferred.

[0148] The content of the photopolymerization initiator is usually 0.1 parts by mass to 20 parts by mass, preferably 1 part by mass to 15 parts by mass, and more preferably 1 part by mass to 10 parts by mass, per 100 parts by mass of the total amount of polymerizable compound. Within this range, the reaction of the polymerizable groups proceeds sufficiently and the orientation of the polymerizable liquid crystal compound is not easily disrupted.

[0149] From the viewpoint of ensuring a stable polymerization reaction, the mixed composition may contain a polymerization inhibitor. The polymerization inhibitor allows for control over the degree of polymerization of the polymerizable compound.

[0150] Examples of polymerization inhibitors include hydroquinone, alkoxy group-containing hydroquinone, alkoxy group-containing catechol (e.g., butylcatechol), pyrogallol, radical scavengers such as 2,2,6,6-tetramethyl-1-piperidinyloxy radical; thiophenols; β-naphthylamines and β-naphthols.

[0151] The polymerization inhibitor is typically 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the total amount of polymerizable compound. When the polymerization inhibitor content is within the above range, polymerization can be carried out without disrupting the orientation of the polymerizable liquid crystal compound.

[0152] The mixed composition may contain a sensitizer. Photosensitizers are preferred as sensitizers. Examples of such sensitizers include xanthone compounds such as xanthones and thioxanthones (e.g., 2,4-diethylthioxanthone, 2-isopropylthioxanthone, etc.); anthracene compounds such as anthracene and alkoxy group-containing anthracene (e.g., dibutoxyanthracene, etc.); phenothiazines and rubrene, etc.

[0153] When the mixed composition contains a photosensitizer, the polymerization reaction of the polymerizable compounds contained in the mixed composition can be further promoted. The amount of photosensitizer is usually 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the total amount of polymerizable compounds.

[0154] The mixed composition may contain a leveling agent. A leveling agent is an additive that adjusts the fluidity of the composition and makes the film obtained by applying the composition flatter. Examples include organic modified silicone oil-based, polyacrylate-based, and perfluoroalkyl-based leveling agents. Among these, polyacrylate-based and perfluoroalkyl-based leveling agents are preferred.

[0155] The leveling agent content in the mixed composition is preferably 0.01 to 5 parts by mass, and more preferably 0.05 to 3 parts by mass, per 100 parts by mass of the total amount of polymerizable compound. When the leveling agent content is within the above range, it is easy to horizontally orient the polymerizable liquid crystal compound, and the resulting optical anisotropic layer tends to be smoother. If the leveling agent content relative to the polymerizable liquid crystal compound exceeds the above range, the resulting optical anisotropic layer tends to be uneven. The composition for forming the optical anisotropic layer may contain two or more types of leveling agents.

[0156] The mixed composition of the present invention can be prepared by adding additives such as a solvent, a photopolymerization initiator, a polymerization inhibitor, a photosensitizer, or a leveling agent to a polymerizable compound (1) and a polymerizable liquid crystal compound (preferably polymerizable liquid crystal compound (2)) prepared separately, as needed, and stirring and mixing them at a predetermined temperature.

[0157] In the present invention, the mixed composition is of formula (i): Re1(450) / Re1(550)≧Re0(450) / Re0(550) (i) [In formula (i), Re0(λ) represents the in-plane phase difference value at wavelength λnm of the cured film formed from the polymerizable liquid crystal compound, and Re1(λ) represents the in-plane phase difference value at wavelength λnm of the cured film formed from the mixed composition.] It is preferable that the following conditions are met. When the mixed composition satisfies the relationship of formula (i), the polymerizable compound (1) can be mixed with the polymerizable liquid crystal compound (2) to adjust to any desired phase difference value.

[0158] The value of Re1(450) / Re1(550) in the above formula (i) is obtained by measuring the front phase difference value at each wavelength using the mixed composition to be measured as the measurement sample. On the other hand, the value of Re0(450) / Re0(550) is obtained by measuring the front phase difference value at each wavelength using a composition that differs from the mixed composition to be measured only in that it does not contain a compound corresponding to polymerizable compound (1) as the measurement sample. The measurement conditions for Re1(450) / Re1(550) are the same as the measurement conditions for Re0(450) / Re0(550). The specific measurement method will be described in the examples below.

[0159] <Phase difference film> The polymerizable compound (1) of the present invention has high solubility in various solvents and is excellent at lowering the crystallization temperature of the mixed composition when mixed with a polymerizable liquid crystal compound, thus enabling film formation at a lower processing temperature while suppressing crystallization. This suppresses damage caused by heating at high temperatures and the occurrence of orientation defects caused by crystallized products, making it possible to form a film without reducing the optical properties that the polymerizable liquid crystal compound used can inherently exhibit, and thus obtaining a liquid crystal cured film with excellent optical properties. Therefore, the present invention also relates to a phase difference film including a cured product of the mixed composition of the present invention, in particular a liquid crystal cured film in which the polymerizable liquid crystal compound in the composition has been cured in an oriented state. The phase difference film composed of the liquid crystal cured film can fully exhibit the optical properties that the polymerizable liquid crystal compound used can inherently exhibit, and can become a phase difference film with high optical performance.

[0160] The liquid crystal cured film constituting the phase difference film of the present invention is preferably composed of a copolymer of polymerizable compound (1) and polymerizable liquid crystal compound, particularly a copolymer of polymerizable compound (1) and polymerizable liquid crystal compound (2) in an oriented state, because the polymerization reaction is easy and a uniform liquid crystal cured film can be easily obtained.

[0161] In one embodiment of the present invention, the phase difference film of the present invention is formed from the mixed composition of the present invention and preferably includes a liquid crystal cured film satisfying the following formula (ii), and more preferably includes a liquid crystal cured film having optical properties represented by formulas (ii), (iii), and (iv). Such a liquid crystal cured film is usually a cured product obtained by curing a polymerizable liquid crystal compound in a state where it is oriented horizontally with respect to the plane of the liquid crystal cured film (hereinafter also referred to as a "horizontally oriented liquid crystal cured film"). 0.75≦Re1(450) / Re1(550)<1.00 (ii) 1.00≦Re1(650) / Re1(550) (iii) 100nm ≤ Re1(550) ≤ 180nm (iv) [In the formula, Re1(λ) represents the in-plane phase difference value of the liquid crystal curing film at a wavelength of λnm, and Re = (nx(λ) - ny(λ)) × d (where d represents the thickness of the liquid crystal curing film, nx represents the principal refractive index at a wavelength of λnm in the refractive index ellipsoid formed by the liquid crystal curing film in a direction parallel to the plane of the liquid crystal curing film, and ny represents the refractive index at a wavelength of λnm in the refractive index ellipsoid formed by the liquid crystal curing film in a direction parallel to the plane of the liquid crystal curing film and perpendicular to the direction of nx).]

[0162] When a horizontally aligned liquid crystal cured film satisfies formulas (ii) and (iii), the horizontally aligned liquid crystal cured film exhibits so-called inverse wavelength dispersion, where the in-plane phase difference value at short wavelengths is smaller than the in-plane phase difference value at long wavelengths. As the inverse wavelength dispersion improves and the optical properties of the phase difference film are further improved, Re1(450) / Re1(550) is preferably 0.78 or higher, more preferably 0.80 or higher, and also preferably 0.96 or lower, more preferably 0.94 or lower, and even more preferably 0.92 or lower. Furthermore, Re(650) / Re(550) is preferably 1.01 or higher, more preferably 1.02 or higher.

[0163] The above in-plane phase difference value can be adjusted by the thickness d of the horizontally aligned liquid crystal cured film. Since the in-plane phase difference value is determined by the above formula Re(λ)=(nx(λ)-ny(λ))×d, to obtain the desired in-plane phase difference value (Re(λ): in-plane phase difference value of the horizontally aligned liquid crystal cured film at wavelength λ (nm)), the three-dimensional refractive index and the film thickness d should be adjusted.

[0164] Furthermore, when the horizontally aligned liquid crystal cured film satisfies formula (iii), the effect of improving the front reflection hue (effect of suppressing coloration) is excellent when an elliptical polarizing plate equipped with a phase difference film containing the horizontally aligned liquid crystal cured film is applied to an organic EL display device. A more preferred range for the in-plane phase difference value is 120 nm ≤ Re(550) ≤ 170 nm, and an even more preferred range is 130 nm ≤ Re(550) ≤ 150 nm.

[0165] The phase difference film of the present invention is, for example, The present invention comprises the steps of forming a coating film of the mixed composition, drying the coating film, and aligning the polymerizable liquid crystal compound in the mixed composition, A process to polymerize polymerizable compound (1) and polymerizable liquid crystal compound by light irradiation while maintaining their orientation, thereby forming a liquid crystal cured film. It can be manufactured by a method that includes [a specific component].

[0166] A coating film of the mixed composition can be formed by applying the mixed composition to a substrate or to an orientation film, as described later. Examples of substrates include glass substrates and film substrates, with film substrates being preferred, and long roll-shaped films being more preferred because they can be manufactured continuously. Examples of resins constituting the film substrate include polyolefins such as polyethylene, polypropylene, and norbornene polymers; cyclic olefin resins; polyvinyl alcohol; polyethylene terephthalate; polymethacrylate esters; polyacrylic acid esters; cellulose esters such as triacetylcellulose, diacetylcellulose, and cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polysulfone; polyethersulfone; polyetherketone; polyphenylene sulfide and polyphenylene oxide; and other plastics. Among these, film substrates selected from triacetylcellulose, cyclic olefin resins, polymethacrylate esters, and polyethylene terephthalate are more preferred from the viewpoint of transparency when used in optical film applications.

[0167] Commercially available products may be used as the base material. Examples of commercially available cellulose ester base materials include cellulose ester base materials manufactured by Fuji Photo Film Co., Ltd., such as Fujitac Film; and cellulose ester base materials manufactured by Konica Minolta Opto, Inc., such as "KC8UX2M," "KC8UY," and "KC4UY." Examples of commercially available cyclic olefin resins include cyclic olefin resins manufactured by Ticona GmbH (Germany), such as "Topas®"; cyclic olefin resins manufactured by JSR Corporation, such as "Arton®"; cyclic olefin resins manufactured by Nippon Zeon Co., Ltd., such as "ZEONOR®" and "ZEONEX®"; and cyclic olefin resins manufactured by Mitsui Chemicals, Inc., such as "APPEL®." Commercially available cyclic olefin resin base materials can also be used. Examples of commercially available cyclic olefin resin substrates include cyclic olefin resin substrates manufactured by Sekisui Chemical Co., Ltd., such as "S-Cina®" and "SCA40®"; cyclic olefin resin substrates manufactured by Optes Co., Ltd., such as "Zeonor Film®"; and cyclic olefin resin substrates manufactured by JSR Corporation, such as "Arton Film®".

[0168] From the viewpoint of thinning the phase difference film, ease of peeling the substrate, and handling of the substrate, the thickness of the substrate is usually 5 to 300 μm, preferably 10 to 200 μm, and more preferably 10 to 50 μm.

[0169] Methods for applying the mixed composition to a substrate include extrusion coating, direct gravure coating, reverse gravure coating, CAP coating, slit coating, microgravure, die coating, and inkjet coating. Other methods include coating using coaters such as dip coaters, bar coaters, and spin coaters. Among these, when applying continuously in a roll-to-roll format, microgravure, inkjet, slit coating, and die coating methods are preferred, and when applying to a single-wafer substrate such as glass, the highly uniform spin coating method is preferred. When applying in a roll-to-roll format, an alignment film-forming composition can be applied to the substrate to form an alignment film, and then the optical anisotropy layer-forming composition can be continuously applied on the obtained alignment film.

[0170] Next, a dried coating film is formed by removing the solvent by drying or other means. Drying methods include natural drying, forced-air drying, heat drying, and reduced-pressure drying. Among these, natural drying or heat drying is preferred. In this case, heating the coating film obtained from the mixed composition allows the solvent to be dried off from the coating film and the polymerizable liquid crystal compound to be oriented in a desired direction relative to the coating film plane. The heating temperature of the coating film can be appropriately determined considering the polymerizable compound (1) used, the polymerizable liquid crystal compound, and the materials of the substrate forming the coating film, but it is usually necessary to heat the coating film to a temperature above the liquid crystal phase transition temperature in order to cause the polymerizable liquid crystal compound to undergo a phase transition to the liquid crystal phase state. In order to remove the solvent contained in the mixed composition and bring the polymerizable liquid crystal compound to a desired orientation state, for example, the coating film can be heated to a temperature above the liquid crystal phase transition temperature (smectic phase transition temperature or nematic phase transition temperature) of the polymerizable liquid crystal compound contained in the mixed composition.

[0171] In one embodiment of the present invention, the solid-liquid crystal phase transition temperature of the polymerizable liquid crystal compound constituting the mixed composition of the present invention is preferably 25°C to 200°C. A phase transition temperature to the liquid crystal phase within the above range is preferable from the viewpoint of ease of industrial production and improved productivity. In the present invention, the solid-liquid crystal phase transition temperature of the polymerizable liquid crystal compound is usually 40°C or higher, more preferably 50°C or higher, and even more preferably 60°C or higher, when the resulting liquid crystal cured film is a compound capable of exhibiting inverse wavelength dispersion characteristics, and is more preferably 180°C or lower, and even more preferably 160°C or lower from the viewpoint of productivity. In the mixed composition of the present invention, the inclusion of polymerizable compound (1) makes it easier to lower the liquid crystal phase transition temperature compared to the case in which the polymerizable liquid crystal compound is contained alone. Lowering the crystallization temperature of the mixed composition and also lowering the phase transition temperature makes it possible to form a film without exposure to high-temperature conditions, and it is expected that the resulting optical film will have even higher optical properties. The liquid crystal phase transition temperature can be measured using, for example, a polarizing microscope equipped with a temperature control stage, a differential scanning calorimeter (DSC), or a thermogravimetric differential thermal analyzer (TG-DTA). When multiple polymerizable liquid crystal compounds are included, the above phase transition temperature refers to the temperature measured using a mixture of polymerizable liquid crystal compounds obtained by mixing all the polymerizable liquid crystal compounds constituting the mixed composition in the same proportions as the composition in the mixed composition.

[0172] The mixed composition of the present invention contains a polymerizable compound (1), and is generally superior in lowering the crystallization temperature compared to cases where a polymerizable liquid crystal compound is contained alone. Therefore, in the production of phase difference films using the mixed composition of the present invention, excessive consumption of thermal energy can be suppressed, and production efficiency can be improved. In addition, since the film can be formed by heating at a relatively low temperature, there is also the advantage of expanding the range of support substrates to which the mixed composition is coated.

[0173] The heating time can be appropriately determined depending on the heating temperature, the type of polymerizable compound used, the type of solvent, its boiling point, and its amount, but it is usually 10 seconds to 10 minutes, preferably 0.5 to 5 minutes.

[0174] The removal of the solvent from the coating film may be performed simultaneously with heating the polymerizable liquid crystal compound to above its liquid crystal phase transition temperature, or separately, but it is preferable to perform it simultaneously from the viewpoint of improving productivity. Before heating the polymerizable liquid crystal compound to above its liquid crystal phase transition temperature, a pre-drying step may be provided to appropriately remove the solvent in the coating film under conditions in which the polymerizable compound (1) and / or polymerizable liquid crystal compound contained in the coating film obtained from the mixed composition do not polymerize. Examples of drying methods in such a pre-drying step include natural drying, forced-air drying, heat drying, and reduced-pressure drying, and the drying temperature (heating temperature) in the drying step can be appropriately determined according to the type of polymerizable compound used, the type and boiling point and amount of solvent, etc.

[0175] Next, in the obtained dried coating film, the polymerizable compound (1) and the polymerizable liquid crystal compound are polymerized by light irradiation while maintaining the orientation state of the polymerizable liquid crystal compound, thereby forming a liquid crystal cured film, which is a polymer as a mixture of the polymerizable compound (1) and the polymerizable liquid crystal compound that exist in a desired orientation state. The mixed composition of the present invention can be highly polymerized by light irradiation such as high-intensity ultraviolet light while suppressing damage to the polymerizable compound, so photopolymerization is usually used as the polymerization method. In photopolymerization, the light irradiated onto the dried coating film is appropriately selected according to the type of polymerization initiator, the type and amount of polymerizable compound contained in the dried coating film. Specific examples include one or more types of light selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, alpha rays, beta rays, and gamma rays, or active electron beams. Among these, ultraviolet light is preferred because it is easy to control the progress of the polymerization reaction and because photopolymerization equipment widely used in this field can be used. It is preferable to select the types of polymerizable compound and polymerization initiator contained in the mixed composition so that photopolymerization is possible by ultraviolet light. Furthermore, the polymerization temperature can be controlled by irradiating light while cooling the dried coating film with an appropriate cooling method during polymerization. By employing such cooling methods, polymerization of polymerizable compounds can be carried out at lower temperatures, allowing for the proper formation of liquid crystal cured films even when using substrates with relatively low heat resistance. It is also possible to accelerate the polymerization reaction by increasing the polymerization temperature within a range that does not cause problems due to heat during light irradiation (such as deformation of the substrate due to heat). Patterned cured films can also be obtained by performing masking or development during photopolymerization.

[0176] Examples of the light sources for the activated energy rays include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, halogen lamps, carbon arc lamps, tungsten lamps, gallium lamps, excimer lasers, LED light sources emitting light in the wavelength range of 380-440 nm, chemical lamps, black light lamps, microwave-excited mercury lamps, metal halide lamps, and the like.

[0177] The UV irradiation intensity is typically 10 mW / cm². 2 ~3,000 mW / cm² 2 The ultraviolet irradiation intensity is preferably in the wavelength range effective for activating the cationic polymerization initiator or radical polymerization initiator. The irradiation time is usually 0.1 seconds to 10 minutes, preferably 1 second to 5 minutes, more preferably 5 seconds to 3 minutes, and even more preferably 10 seconds to 1 minute. When irradiation is performed once or multiple times at such ultraviolet irradiation intensity, the integrated light amount is usually 10 mJ / cm². 2 ~3,000 mJ / cm 2 Preferably 50 mJ / cm² 2 ~2,000 mJ / cm 2 More preferably 100 mJ / cm² 2 ~1,000 mJ / cm 2 If the integrated light intensity is below this range, the polymerizable liquid crystal compound may not cure sufficiently, and good transferability may not be obtained. Conversely, if the integrated light intensity is above this range, the phase difference film containing the liquid crystal curing film may become discolored.

[0178] The thickness of the liquid crystal cured film can be appropriately selected depending on the applicable display device, and is preferably 0.2 to 3 μm, more preferably 0.2 to 2 μm.

[0179] The coating film of the mixed composition may be formed on an alignment film. The alignment film has an alignment-regulating force that causes the polymerizable liquid crystal compound to liquid crystal orientation in a desired direction. The alignment film facilitates the liquid crystal orientation of the polymerizable liquid crystal compound. The state of liquid crystal orientation, such as horizontal orientation, vertical orientation, hybrid orientation, and tilted orientation, changes depending on the properties of the alignment film and the polymerizable liquid crystal compound, and any combination can be arbitrarily selected. For example, if the alignment film is a material that exhibits horizontal orientation as an alignment-regulating force, the polymerizable liquid crystal compound can form horizontal orientation or hybrid orientation, and if it is a material that exhibits vertical orientation, the polymerizable liquid crystal compound can form vertical orientation or tilted orientation. Expressions such as horizontal and vertical refer to the direction of the long axis of the oriented polymerizable liquid crystal compound with respect to the optical anisotropy layer plane. For example, vertical orientation means that the long axis of the oriented polymerizable liquid crystal compound is in a direction perpendicular to the optical anisotropy layer plane. Here, perpendicular means 90° ± 20° with respect to the optical anisotropy layer plane.

[0180] The orientation-regulating force can be arbitrarily adjusted by surface conditions and rubbing conditions if the orientation film is formed from an orientation-oriented polymer, and by polarization irradiation conditions, etc., if it is formed from a photo-oriented polymer. Furthermore, liquid crystal orientation can also be controlled by selecting physical properties such as surface tension and liquid crystalline properties of the polymerizable liquid crystal compound.

[0181] The alignment film formed between the substrate and the liquid crystal curing film is preferably insoluble in the solvent used to form the liquid crystal curing film on the alignment film, and also has heat resistance for solvent removal and heat treatment for liquid crystal alignment. Examples of alignment films include alignment films made of oriented polymers, photoalignment films, groove alignment films, and stretched films stretched in the orientation direction. When applied to long roll-shaped films, photoalignment films are preferred because the orientation direction can be easily controlled.

[0182] The thickness of the orientation film is typically in the range of 10 nm to 5000 nm, preferably in the range of 10 nm to 1000 nm, and more preferably in the range of 30 nm to 300 nm.

[0183] Examples of oriented polymers used in rubbing orientation films include polyamides and gelatins having amide bonds in their molecules, polyimides having imide bonds in their molecules and their hydrolysates such as polyamic acid, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, polyoxazole, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid, and polyacrylic acid esters. Among these, polyvinyl alcohol is preferred. These oriented polymers may be used individually or in combination of two or more.

[0184] One method of rubbing involves wrapping a rubbing cloth around a rotating rubbing roll and bringing the film of the oriented polymer, formed on the surface of the substrate by applying an oriented polymer composition to the substrate and annealing it, into contact with the roll.

[0185] Photo-alignment films consist of polymers, oligomers, or monomers having photoreactive groups. An orientation-regulating force can be obtained by irradiating the photo-alignment film with polarized light. Photo-alignment films are preferable because the direction of the orientation-regulating force can be arbitrarily controlled by selecting the polarization direction of the irradiated polarized light.

[0186] A photoreactive group is a group that generates liquid crystal alignment ability upon irradiation with light. Specifically, it is a group that generates a photoreaction that is the origin of liquid crystal alignment ability, such as molecular orientation induction or isomerization, dimerization, photocrosslinking, or photodegradation, upon irradiation with light. Among these photoreactive groups, those that cause dimerization or photocrosslinking are preferred in terms of their excellent orientation properties. As photoreactive groups that can generate such reactions, those having unsaturated bonds, especially double bonds, are preferred, and more preferably groups having at least one selected from the group consisting of carbon-carbon double bonds (C=C bonds), carbon-nitrogen double bonds (C=N bonds), nitrogen-nitrogen double bonds (N=N bonds), and carbon-oxygen double bonds (C=O bonds).

[0187] Examples of photoreactive groups having a C=C bond include vinyl groups, polyene groups, stilbene groups, stilbazole groups, stilbazolium groups, chalcone groups, and cinnamoyl groups. Chalcone groups and cinnamoyl groups are preferred from the viewpoint of ease of controlling reactivity and the expression of orientation-regulating power during photo-orientation. Examples of photoreactive groups having a C=N bond include groups having structures such as aromatic Schiff bases and aromatic hydrazones. Examples of photoreactive groups having an N=N bond include azobenzene groups, azonaphthalene groups, aromatic heterocyclic azo groups, bisazo groups, and formazan groups, as well as those with azoxybenzene as their basic structure. Examples of photoreactive groups having a C=O bond include benzophenone groups, coumarin groups, anthraquinone groups, and maleimide groups. These groups may have substituents such as alkyl groups, alkoxy groups, aryl groups, allyloxy groups, cyano groups, alkoxycarbonyl groups, hydroxyl groups, sulfonic acid groups, and halogenated alkyl groups.

[0188] Polarized light can be irradiated either by directly irradiating the film surface with polarized light, or by irradiating the substrate with polarized light and allowing it to pass through. Furthermore, it is particularly preferable that the polarized light be substantially parallel. The wavelength of the irradiated polarized light should be in a wavelength range in which the photoreactive groups of the polymer or monomer having photoreactive groups can absorb light energy. Specifically, UV (ultraviolet light) in the wavelength range of 250 to 400 nm is particularly preferred. Examples of light sources used for this polarized light irradiation include xenon lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, and ultraviolet lasers such as KrF and ArF, with high-pressure mercury lamps, ultra-high-pressure mercury lamps, and metal halide lamps being more preferred. These lamps are preferred because they have a high emission intensity of ultraviolet light at a wavelength of 313 nm. Polarized light can be irradiated by passing the light from the light source through a suitable polarizer. Such polarizers can include polarizing filters, polarizing prisms such as Grant-Thomson and Grant-Taylor, and wire grid type polarizers.

[0189] <Elliptic polarizer> The present invention includes an elliptical polarizer comprising the phase difference film of the present invention. The elliptical polarizer comprises a polarizing film together with the phase difference film. The polarizing film is a film in which a dichroic dye is uniaxially oriented. To uniaxially orient the dichroic dye, it can be produced from a film (hereinafter also called a "polarizer") that is uniaxially stretched while impregnated with iodine or an organic dichroic dye in a polymer such as polyvinyl alcohol, or from an optically anisotropic layer (hereinafter also called a "polarizing film") made of a polymer of a polymerizable liquid crystal compound containing a dichroic dye, which is formed by orienting the dichroic dye and the polymerizable liquid crystal compound from a composition containing a polymerizable liquid crystal compound and a dichroic dye (hereinafter also called a "polarizing film forming composition"). In other words, the polarizing function is exhibited by the anisotropic absorption of light by the dichroic dye encapsulated in the stretched polymer or polymer of the polymerizable liquid crystal compound.

[0190] Polarizers can typically be manufactured by a process that involves uniaxial stretching of a polyvinyl alcohol-based resin film, a process of staining the polyvinyl alcohol-based resin film with a dichroic dye such as iodine to adsorb the dichroic dye, a process of treating the polyvinyl alcohol-based resin film with the adsorbed dichroic dye with an aqueous boric acid solution, and a process of washing with water after treatment with the aqueous boric acid solution.

[0191] The thickness of the polarizer is usually 30 μm or less, preferably 18 μm or less, more preferably 15 μm or less, and even more preferably 10 μm or less. The thickness is usually 1 μm or more, for example, 5 μm or more is acceptable.

[0192] Uniaxial stretching of polyvinyl alcohol-based films can be performed before, simultaneously with, or after dyeing with dichroic dyes. If uniaxial stretching is performed after dyeing, it may be performed before or during boric acid treatment. Of course, uniaxial stretching can also be performed in multiple stages as described here. Uniaxial stretching methods include stretching uniaxially in the film transport direction between rolls with different peripheral speeds, stretching uniaxially in the film transport direction using a heated roll, or stretching in the width direction using a tenter. Uniaxial stretching may also be performed by dry stretching in the atmosphere, or by wet stretching using a solvent such as water to swell the polyvinyl alcohol-based film before stretching. The stretching ratio is usually around 3 to 8 times. Alternatively, an aqueous solution containing polyvinyl alcohol may be applied to a thermoplastic resin film, followed by a drying treatment, and then stretched together with the thermoplastic resin film using the above method.

[0193] Dyeing of polyvinyl alcohol-based films with dichroic dyes can be carried out, for example, by immersing the polyvinyl alcohol-based film in an aqueous solution containing a dichroic dye. Specifically, iodine or dichroic organic dyes can be used as dichroic dyes.

[0194] A protective film may be included on one or both sides of the polarizer. A thermoplastic resin film can be used as the protective film. The linear polarizer and the protective film can be laminated together via an adhesive or the like. The film formed from the thermoplastic resin may be surface-treated (e.g., corona treatment) to improve adhesion to the polarizer, and a thin layer such as a primer layer (also called an undercoat layer) may be formed on it.

[0195] The thermoplastic resin constituting the thermoplastic resin film is preferably a transparent film, and examples include cellulose resins such as triacetylcellulose; polyester resins such as polyethylene terephthalate and polyethylene naphthalate; polyethersulfone resins; polysulfone resins; polycarbonate resins; polyamide resins such as nylon and aromatic polyamides; polyimide resins; polyolefin resins such as polyethylene, polypropylene, and ethylene-propylene copolymers; cyclic polyolefin resins having cyclo and norbornene structures (also called norbornene resins); (meth)acrylic resins; polyarylate resins; polystyrene resins; and polyvinyl alcohol resins. Among these, the thermoplastic resin film is preferably a cyclic polyolefin resin film, a cellulose ester resin film, a polyester resin film, or a (meth)acrylic resin film.

[0196] A hard coat layer may be formed on the thermoplastic resin film. The hard coat layer may be formed on one side of the thermoplastic resin film or on both sides. By providing a hard coat layer, a thermoplastic resin film with improved hardness and scratch resistance can be obtained. The hard coat layer is, for example, a cured layer of an active energy ray curable resin, preferably an ultraviolet curable resin. Examples of ultraviolet curable resins include (meth)acrylic resins, silicone resins, polyester resins, urethane resins, amide resins, epoxy resins, and the like. The hard coat layer may contain additives to improve its strength. The additives are not particularly limited and include inorganic fine particles, organic fine particles, or mixtures thereof.

[0197] A polarizing film, or an optically anisotropic layer made of a polymerizable liquid crystal compound containing a dichroic dye, is suitable for flexible display applications, for example, because its hue can be arbitrarily controlled, it can be made significantly thinner, and it is non-shrinkable due to the absence of thermal stretching relaxation.

[0198] A polarizing film is formed by applying a polarizing film-forming composition to an alignment film formed on a substrate as needed, and then orienting the dichroic dye contained in the polarizing film-forming composition. The polarizing film is a film with a thickness of 0.1 μm to 5 μm, more preferably 0.3 μm to 4 μm, and even more preferably 0.5 μm to 3 μm. When the film thickness is within this range, it is easy to obtain the necessary light absorption, and the occurrence of alignment defects due to a decrease in the alignment restricting force by the alignment film is less likely to occur.

[0199] To obtain polarization characteristics in the XY plane, the dichroic dye and polymerizable liquid crystal compound should be oriented horizontally with respect to the substrate surface. To obtain polarization characteristics in the Z direction (the direction of the film thickness of the polarizing film), the dichroic dye and polymerizable liquid crystal compound should be oriented perpendicularly with respect to the substrate surface.

[0200] In an optically anisotropic layer in which a dichroic dye and a polymerizable liquid crystal compound are horizontally oriented with respect to the substrate surface, the ratio (dichroic ratio) of the absorbance A1(λ) in the orientation direction to the absorbance A2(λ) in the direction perpendicular to the orientation plane with respect to light of wavelength λnm is preferably 7 or higher, more preferably 20 or higher, and even more preferably 40 or higher. The higher this value, the better the absorption selectivity of the polarizer. Depending on the type of dichroic dye, in the case of a liquid crystal cured film cured in the nematic liquid crystal phase state, the dichroic ratio is about 5 to 10.

[0201] By mixing two or more dichroic dyes with different absorption wavelengths, polarizing films of various hues can be created, resulting in polarizing films that absorb across the entire visible light spectrum. Such polarizing films with specific absorption characteristics can be applied to a wide range of uses.

[0202] The polymerizable liquid crystal compound in the polarizing film-forming composition is a compound having polymerizable groups and liquid crystalline properties (hereinafter also referred to as polymerizable liquid crystal compound (3)). A polymerizable group is a group that participates in the polymerization reaction, and is preferably a photopolymerizable group. Here, a photopolymerizable group is a group that can participate in the polymerization reaction by active radicals or acids generated from a photopolymerization initiator, which will be described later. Examples of polymerizable groups include vinyl groups, vinyloxy groups, 1-chlorovinyl groups, isopropenyl groups, 4-vinylphenyl groups, acryloyloxy groups, methacryloyloxy groups, oxyranyl groups, and oxetanyl groups. Among these, acryloyloxy groups, methacryloyloxy groups, vinyloxy groups, oxyranyl groups, and oxetanyl groups are preferred, and methacryloyloxy groups or acryloyloxy groups are more preferred. The liquid crystalline properties may be thermotropic liquid crystal or lyotropic liquid crystal, but when mixed with a dichroic dye, which will be described later, thermotropic liquid crystal is preferred.

[0203] If the polymerizable liquid crystal compound (3) is a thermotropic liquid crystal, it may be a thermotropic liquid crystal compound exhibiting a nematic liquid crystal phase, or a thermotropic liquid crystal compound exhibiting a smectic liquid crystal phase. When the polymerizable liquid crystal compound (3) exhibits a polarizing function as a cured film through a polymerization reaction, the liquid crystal state exhibited by the polymerizable liquid crystal compound (3) is preferably a smectic phase, and a higher-order smectic phase is even more preferable from the viewpoint of performance improvement. Among these, higher-order smectic liquid crystal compounds that form smectic B phase, smectic D phase, smectic E phase, smectic F phase, smectic G phase, smectic H phase, smectic I phase, smectic J phase, smectic K phase, or smectic L phase are more preferred, and higher-order smectic liquid crystal compounds that form smectic B phase, smectic F phase, or smectic I phase are even more preferred. When the liquid crystal phase formed by the polymerizable liquid crystal compound (3) is one of these higher-order smectic phases, a polarizing film with higher polarization performance can be manufactured. Furthermore, such a polarizing film with high polarization performance yields Bragg peaks originating from higher-order structures such as the hexatic phase and crystal phase in X-ray diffraction measurements. These Bragg peaks are peaks originating from the periodic structure of molecular orientation, and a film with a periodic interval of 3 to 6 Å can be obtained. In the present invention, it is preferable that the polarizing film contains a polymerizable liquid crystal in which the polymerizable liquid crystal compound (3) is oriented in the smectic phase state, from the viewpoint of obtaining higher polarization characteristics.

[0204] The polymerizable liquid crystal compound (3) may be used alone or in combination of two or more types. The polarizing film forming composition may contain other polymerizable liquid crystal compounds besides polymerizable liquid crystal compound (3), but from the viewpoint of obtaining a polarizing film with a high degree of orientation order, the ratio of polymerizable liquid crystal compound (3) to the total mass of all polymerizable liquid crystal compounds contained in the polarizing film forming composition is preferably 51% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more.

[0205] The content of polymerizable liquid crystal compound (3) in the polarizing film-forming composition is preferably 40 to 99.9% by mass, more preferably 60 to 99% by mass, and even more preferably 70 to 99% by mass, relative to the solid content of the polarizing film-forming composition. When the content of polymerizable liquid crystal compound (3) is within the above range, the orientation of polymerizable liquid crystal compound (3) tends to be high. In this specification, solid content refers to the total amount of components excluding the solvent from the polarizing film-forming composition.

[0206] Dichroic dyes are dyes that have different absorbances along the long axis and short axis of the molecule. Dichroic dyes preferably have the property of absorbing visible light, and more preferably have an absorption maximum wavelength (λMAX) in the range of 380 to 680 nm. Examples of such dichroic dyes include acridine dyes, oxazine dyes, cyanine dyes, naphthalene dyes, azo dyes, and anthraquinone dyes, with azo dyes being preferred. Examples of azo dyes include monoazo dyes, bisazo dyes, trisazo dyes, tetrakisazo dyes, and stilbenazo dyes, with bisazo dyes and trisazo dyes being preferred. Dichroic dyes may be used individually or in combination, but to obtain absorption across the entire visible light range, it is preferable to combine two or more dichroic dyes, and more preferably to combine three or more dichroic dyes.

[0207] Examples of azo dyes include the compound represented by formula (I) (hereinafter sometimes referred to as "compound (I)"). T1-A1(-N=N-A2)pN=N-A3-T2(I) [In formula (I), A1, A2, and A3 independently represent an optionally substituted 1,4-phenylene group, an optionally substituted naphthalene-1,4-diyl group, an optionally substituted phenyl benzoate group, an optionally substituted 4,4'-stilbenylene group, or an optionally substituted divalent heterocyclic group, where T1 and T2 are electron-withdrawing or electron-emitting groups located substantially 180° to the azo bond plane. p represents an integer from 0 to 4. When p is 2 or greater, each A2 may be identical or different from the others. The -N=N- bond may be replaced by -C=C-, -COO-, -NHCO-, or -N=CH- bond in the range showing absorption in the visible region.]

[0208] The content of the dichroic dye (total amount if multiple types are included) is usually 1 to 60 parts by mass, preferably 1 to 40 parts by mass, and more preferably 1 to 20 parts by mass, per 100 parts by mass of the polymerizable liquid crystal compound, from the viewpoint of obtaining good light absorption characteristics. When the content of the dichroic dye is within this range, the necessary light absorption can be secured and sufficient polarization performance can be obtained, and a polarizing film with excellent polarization performance can be obtained without hindering the orientation of liquid crystal molecules.

[0209] A protective film or the like may be laminated on at least one surface of the polarizing film obtained in this way, similar to the configuration in the polarizer described above.

[0210] The elliptic polarizer of the present invention is composed of a phase difference film and a polarizing film of the present invention. For example, the elliptic polarizer of the present invention can be obtained by laminating the phase difference film and the polarizing film of the present invention via an adhesive layer or the like.

[0211] In one embodiment of the present invention, when a phase difference film of the present invention, which includes a horizontally oriented liquid crystal cured film, and a polarizing film are laminated, it is preferable to laminate them such that the angle between the slow axis (optical axis) of the horizontally oriented liquid crystal cured film constituting the phase difference film and the absorption axis of the polarizing film is 45 ± 5°.

[0212] The elliptical polarizer of the present invention may have a configuration similar to that of a conventional elliptical polarizer, or a polarizing film and a phase difference film. Examples of such configurations include an adhesive layer (sheet) for bonding the elliptical polarizer to a display element such as an organic EL, and a protective film used to protect the surface of the polarizing film and the phase difference film from scratches and dirt.

[0213] The elliptical polarizing plate of the present invention can be used in various display devices, particularly optical displays. A display device is a device having a display element, and includes a light-emitting element or a light-emitting device as a light source. Examples of display devices include liquid crystal displays, organic electroluminescent (EL) displays, inorganic electroluminescent (EL) displays, touch panel displays, electron emission displays (e.g., electric field emission displays (FEDs), surface field emission displays (SEDs)), electronic paper (display devices using electronic ink or electrophoretic elements), plasma displays, projection displays (e.g., grating light bulb (GLV) displays, displays having digital micromirror devices (DMDs)), and piezoelectric ceramic displays. Liquid crystal displays include transmissive liquid crystal displays, semi-transmissive liquid crystal displays, reflective liquid crystal displays, direct-view liquid crystal displays, and projection liquid crystal displays. These display devices may display two-dimensional images or three-dimensional images. In particular, the elliptic polarizer of the present invention can be suitably used in organic electroluminescent (EL) displays and inorganic electroluminescent (EL) displays. These display devices (optical displays) can exhibit good image display characteristics by incorporating the elliptic polarizer of the present invention, which has excellent optical properties.

[0214] Furthermore, the elliptic polarizer of the present invention can also be suitably incorporated into a flexible image display device. The flexible image display device consists of, for example, a laminate for flexible image display devices and an organic EL display panel, with the laminate for flexible image display devices positioned on the viewing side relative to the organic EL display panel and configured to be bendable. In addition to the elliptic polarizer of the present invention described above, the laminate for flexible image display devices may include a window, a touch panel touch sensor, etc. The stacking order is arbitrary, but it is preferable that the stacking order from the viewing side is window, elliptic polarizer, touch panel touch sensor, or window, touch panel touch sensor, elliptic polarizer.

[0215] The presence of an elliptical polarizing plate on the viewing side of the touch panel touch sensor is preferable because it makes the pattern of the touch panel touch sensor harder to see, thus improving the visibility of the displayed image. Each component can be laminated using an adhesive, tack, or the like. Furthermore, the laminate for the flexible image display device may have a light-shielding pattern formed on at least one surface of any of the layers of the window, elliptical polarizing plate, or touch panel touch sensor.

[0216] The window is positioned on the viewing side of a flexible image display device and serves to protect other components from external impacts or environmental changes such as temperature and humidity. Conventionally, glass has been used as such a protective layer, but the window in a flexible image display device is not rigid and hard like glass, but has flexible properties. The window is made of a flexible transparent substrate and may include a hard coat layer on at least one surface.

[0217] The windows, touch panels, touch sensors, etc. that constitute the laminate for the flexible image display device are not particularly limited, and conventionally known ones can be used. [Examples]

[0218] The present invention will be described in more detail below with reference to examples. In the examples, "%" and "parts" refer to mass percent and parts by mass, respectively, unless otherwise specified.

[0219] The HPLC measurements used for the analysis of each compound may be performed under any conditions that allow for the separation of peaks originating from each polymerizable compound and polymerizable liquid crystal compound. An example of HPLC measurement conditions is shown below. (Measurement conditions) Measurement device: HPLC LC-10AT (manufactured by Shimadzu Corporation) Column: L-Column ODS (inner diameter 3.0 mm, length 150 mm, particle size 3 μm) Temperature: 40℃ Mobile phase A: 0.1%(v / v)-TFA / water Mobile phase B: 0.1% (v / v)-TFA / acetonitrile Gradient: 0 min 70%-B 30 min 100%-B 60 min 100%-B 60.01 min 70%-B 75 min 70%-B Flow rate: 0.5mL / min Injection volume: 5μL Detection wavelength: 254nm

[0220] 1. Preparation of polymerizable compounds Polymerizable compound (1) and polymerizable liquid crystal compound (2) were prepared according to the following methods.

[0221] (1) Preparation of polymerizable compound (1) (i) Synthesis example 1 According to the following scheme, a polymerizable compound represented by formula (1-A) (hereinafter referred to as "polymerizable compound (1-A)") was synthesized from the compound represented by formula (1-1a) (hereinafter referred to as "compound (1-1a)") and the compound represented by formula (1-2a) (hereinafter referred to as "compound (1-2a)").

[0222] [ka]

[0223] A 100 mL four-necked flask equipped with a Liebig condenser and thermometer was subjected to a nitrogen atmosphere. 14.41 g of compound (1-1a), synthesized according to patent document (JP 2010-1284), 5.00 g of compound (1-2a) (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.18 g of DMAP (N,N-dimethylaminopyridine, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 0.44 g of BHT (dibutylhydroxytoluene, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 75 g of chloroform (manufactured by Kanto Chemical Co., Ltd.) were added and mixed. Next, 9.06 g of IPC (diisopropylcarbodiimide, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added using a dropping funnel, and these were reacted overnight at 0°C. After the reaction was complete, insoluble components were removed by filtration. The obtained chloroform solution was added dropwise to methanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) in an amount three times the mass of chloroform contained in the solution, and a solid was precipitated. Subsequently, the precipitated solid was removed by filtration, washed three times with 10 g of methanol, and then dried under reduced pressure at 30°C to obtain 4.56 g of polymerizable compound (1-A). Analysis of the obtained polymerizable compound (1-A) by HPLC showed that the purity of polymerizable compound (1-A) was 97.7% by area percentage. The yield of polymerizable compound (1-A) was 23.8% based on compound (1-2a).

[0224] (ii) Synthesis Examples 2-4 Polymerizable compounds (1-B) to (1-D) were prepared in the same manner as in Synthesis Example 1, except that compounds (1-2b) to (1-2d) shown in Table 1 were used instead of compound (1-2a). The results of the HPLC analysis are shown in Table 1.

[0225] (iii) Synthesis example 5 A 50 mL four-necked flask equipped with a Liebig condenser and thermometer was subjected to a nitrogen atmosphere. 6.00 g of compound (1-1b), synthesized according to patent document (JP 2010-1284), 0.82 g of hexanediol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 0.04 g of DMAP (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 0.16 g of BHT (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 25 g of chloroform (manufactured by Kanto Chemical Co., Ltd.) were added and mixed. Then, 1.90 g of IPC (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added using a dropping funnel, and the mixture was reacted overnight at 0°C. After the reaction was complete, insoluble components were removed by filtration. The resulting chloroform solution was added dropwise to methanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) in an amount three times the mass of chloroform contained in the solution, and a solid was precipitated. Next, the precipitated solid was removed by filtration, washed three times with 20 g of methanol, and then dried under reduced pressure at 30°C to obtain 4.82 g of polymerizable compound (1-E). Analysis of the obtained polymerizable compound (1-E) by HPLC showed that the purity of compound (1-6) was 97.8% by area percentage. The yield of polymerizable compound (1-E) was 74.8% based on hexanediol.

[0226] [ka]

[0227] (iv) Synthesis example 6 Polymerizable compound (1-E) was synthesized from compound (1-1a) and triphosgene according to the following scheme.

[0228] [ka]

[0229] A 100 mL four-necked flask equipped with a Liebig condenser and thermometer was subjected to a nitrogen atmosphere. 10.00 g of compound (1-1a), 1.87 g of triphosgene (manufactured by Tokyo Chemical Industry Co., Ltd.), and 100 g of chloroform (manufactured by Kanto Chemical Co., Ltd.) were added and mixed. Then, 4.89 g of diisopropylethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added using a dropping funnel and the mixture was allowed to react overnight. After the reaction was complete, 9.4 g of 0.5 M hydrochloric acid was added and stirred, and the aqueous layer was removed by standing and separation twice. Subsequently, 9.4 g of water was added and stirred, and then the mixture was allowed to stand and separated. The recovered organic layer was evaporated to remove the chloroform and obtain a viscous liquid. The obtained liquid was cooled to below 5°C to solidify, and scraped out of the container to obtain 8.6 g of polymerizable compound (1-F). Analysis of the obtained polymerizable compound (1-F) by HPLC revealed that its purity was 97.8% by area percentage. The yield of polymerizable compound (1-F) was 82.0% based on compound (1-1a).

[0230] [Table 1]

[0231] Structures of compounds (1-1) and (1-2) used. ·Compound (1-1a): [ka]

[0232] ·Compound (1-1b): [ka]

[0233] ·Compound (1-2a): [ka]

[0234] ·Compound (1-2b): [ka]

[0235] ·Compound (1-2c): [ka]

[0236] ·Compound (1-2d): [ka]

[0237] (2) Preparation of polymerizable liquid crystal compound (2) (i) Synthesis example 7 According to the following scheme, a polymerizable liquid crystal compound represented by formula (2-A) (hereinafter referred to as "polymerizable liquid crystal compound (2-A)") was synthesized from the compound represented by formula (2-1a) (hereinafter referred to as "compound (2-1a)") and the compound represented by formula (2-2a) (hereinafter referred to as "compound (2-2a)").

[0238] [ka]

[0239] A 100 mL four-necked flask equipped with a Liebig condenser and thermometer was subjected to a nitrogen atmosphere. 11.02 g of compound (2-1a) synthesized in reference to Patent Document (JP 2010-31223), 4.22 g of compound (2-2a) synthesized in reference to Patent Document (JP 2011-207765), 0.02 g of DMAP (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 0.20 g of BHT (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 58 g of chloroform (manufactured by Kanto Chemical Co., Ltd.) were added and mixed. Then, 4.05 g of IPC (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added using a dropping funnel, and the mixture was reacted overnight at 0°C. After the reaction was complete, insoluble components were removed by filtration. The resulting chloroform solution was added dropwise to acetonitrile (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) in an amount three times the mass of chloroform contained in the solution, and a solid was precipitated. Next, the precipitated solid was removed by filtration, washed three times with 20 g of acetonitrile, and then dried under reduced pressure at 30°C to obtain 11.75 g of polymerizable liquid crystal compound (2-A). The yield of polymerizable liquid crystal compound (2-A) was 81% based on compound (2-2a).

[0240] 2. Solubility evaluation At 25°C, 1.00 g of N-methylpyrrolidone (NMP) and a stirring bar were placed in a vial, and while stirring with a magnetic stirrer (HS-30DN, AS ONE), each of the above synthetic compounds was added until undissolved particles were visually confirmed. Once undissolved particles were confirmed, the solubility of each polymerizable compound in NMP was calculated as a weight percentage concentration using the formula (weight of each polymerizable compound) / (weight of each polymerizable compound + weight of NMP). The results were evaluated according to the following criteria. A: 20-30 wt% B: 10-20 wt% C: 5~10 wt% D: 0~5wt% In addition to the above, similar solubility evaluations were performed using cyclopentanone or methyl ethyl ketone as solvents. The results are shown in Table 2.

[0241] 3. Measurement of thermal properties Each of the polymerizable compounds was weighed out at a dose of 1.00 g into a vial, and then dissolved in 2.00 g of chloroform. The resulting solution was applied to a glass substrate with a rubbing-treated PVA alignment film and dried. This substrate was placed on a cooling and heating device (Japan High-Tech Co., Ltd. "LNP94-2") and heated from room temperature to 150°C, then cooled back to room temperature. The behavior during temperature change was observed using a polarizing microscope (LEXT, Olympus Corporation), and the phase transition temperature was measured. The results are shown in Table 2.

[0242] [Table 2]

[0243] In the thermophysical properties shown in Table 2, "Cr" represents the crystalline phase, "I" represents the liquid phase, "Sm" represents the smectic liquid crystal phase, and "N" represents the nematic liquid crystal phase. The temperature (°C) between each sign indicates a change in the phase state. For example, Synthesis Example 1 shows a change from the crystalline phase to the liquid phase at 65°C, while Synthesis Example 6 shows a phase transition from the crystalline phase to the smectic liquid crystal phase at 111°C, from the smectic liquid crystal phase to the nematic liquid crystal phase at 128°C, and from the nematic liquid crystal phase to the liquid phase at 132°C.

[0244] 4. Preparation of the mixed composition (1) Example 1 The polymerizable liquid crystal compound (2-A) obtained in Synthesis Example 7 and the polymerizable compound (1-A) obtained in Synthesis Example 1 were mixed in a vial under the HPLC measurement conditions described above, such that the peak area of ​​polymerizable compound (1-A) was 30% of the total peak area of ​​polymerizable compound (1-A) and polymerizable liquid crystal compound (2-A), thereby obtaining a polymerizable compound mixture (1). To 100 parts by mass of mixture (1), a photopolymerization initiator, leveling agent, polymerization inhibitor, and solvent were charged according to the composition described in Table 3, and the mixture was stirred at 80°C for 30 minutes using a carousel to obtain mixed composition (1). The amount of solvent was set so that the mass% of the liquid crystal mixture was 13% of the total volume of the mixed composition (solution).

[0245] [Table 3]

[0246] Polymerization initiator: 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one (Irgacure 369; manufactured by BASF Japan) Leveling agent: Polyacrylate compound (BYK-361N; manufactured by BIC Chemie Japan) Polymerization inhibitor: BHT (manufactured by Wako Pure Chemical Industries, Ltd.) Solvent: N-methylpyrrolidone (NMP; manufactured by Kanto Chemical Co., Ltd.)

[0247] The thermophysical properties of the mixed composition (1) were confirmed using the same procedure as that used to measure the thermophysical properties of polymerizable compounds, and the nematic phase transition temperature was found to be 150°C.

[0248] (2) Example 2 Mixed composition (2) was prepared in the same manner as in Example 1, except that polymerizable compound (1-E) was used instead of polymerizable compound (1-A). The nematic phase transition temperature of mixed composition (2) was 137°C.

[0249] (3) Example 3 A mixed composition (3) was prepared in the same manner as in Example 1, except that polymerizable compound (1-A) and polymerizable liquid crystal compound (2-A) were mixed under the above HPLC measurement conditions so that the peak area of ​​polymerizable compound (1-A) was 3% of the total peak area of ​​polymerizable compound (1-A) and polymerizable liquid crystal compound (2-A).

[0250] (4) Example 4 A mixed composition (4) was prepared in the same manner as in Example 1, except that polymerizable compound (1-A) and polymerizable liquid crystal compound (2-A) were mixed under the above HPLC measurement conditions so that the peak area of ​​polymerizable compound (1-A) was 50% of the total peak area of ​​polymerizable liquid crystal compound (1-A) and polymerizable liquid crystal compound (2-A).

[0251] (5) Comparative Example 1 Polymerizable liquid crystal compound (2-A) was placed in a vial, and polymerization initiators, leveling agents, polymerization inhibitors, and solvents were added according to the composition shown in Table 3. The mixture was stirred at 80°C for 30 minutes using a carousel to obtain mixed composition (5). The nematic phase transition temperature of mixed composition (5) was 154°C.

[0252] (6) Comparative Example 2 A mixed composition (6) was obtained in the same manner as in Example 1, except that polymerizable compound (1-D) was used instead of polymerizable compound (1-A).

[0253] 5. Creation of optical film (1) Preparation of composition for photoalignment film formation A composition for photo-alignment film formation was obtained by mixing the following components and stirring the resulting mixture at 80°C for 1 hour. Photo-oriented material represented by the following formula (5 parts): [ka] (Number average molecular weight: approx. 28000) Solvent (95 parts): Cyclopentanone

[0254] (2) Manufacturing of optical films (phase difference films) The optical film was manufactured as follows: A cycloolefin polymer film (COP) (ZF-14, manufactured by Zeon Corporation) was treated once using a corona treatment device (AGF-B10, manufactured by Kasuga Electric Co., Ltd.) at an output of 0.3 kW and a processing speed of 3 m / min. The photo-alignment film-forming composition was applied to the corona-treated surface using a bar coater, dried at 80°C for 1 minute, and then treated with a polarizing UV irradiation device (SPOT CURE SP-7; manufactured by Ushio Inc.) at a concentration of 100 mJ / cm². 2 Polarized UV exposure was performed with the integrated light intensity. The thickness of the resulting alignment film was measured using a laser microscope (LEXT, manufactured by Olympus Corporation) and found to be 100 nm.

[0255] Mixed compositions (1) to (6) were each applied to the alignment film using a bar coater, dried at 120°C for 1 minute, and then irradiated with ultraviolet light using a high-pressure mercury lamp (UniCure VB-15201BY-A, manufactured by Ushio Inc.) (under a nitrogen atmosphere, wavelength: 365 nm, integrated light intensity at wavelength 365 nm: 1000 mJ / cm²). 2 An optical film was fabricated by ).

[0256] The optical film prepared as described above was used as the measurement sample, and the front phase difference values ​​for light at wavelengths of 450 nm and 550 nm were measured using a measuring instrument (KOBRA-WR, manufactured by Oji Instruments Co., Ltd.), and the α value = Re1(450) / Re1(550) was calculated. The value of Re0(450) / Re0(550) was measured using a mixed composition (4) containing only polymerizable liquid crystal compound (2-A) as the measurement sample.

[0257] 6. Evaluation of crystallization temperature Mixed compositions (1) to (6) were each coated onto an alignment film using a bar coater. The substrate was then placed on a cooling and heating device and dried at 120°C for 1 minute, after which it was cooled to room temperature. The behavior during temperature changes was observed with a polarizing microscope, and the temperature at which crystals formed was measured. The results are shown in Table 4.

[0258] [Table 4]

[0259] As shown in Table 4, the crystallization temperature can be lowered according to the mixed composition of the present invention.

[0260] 7. Evaluation of Orientation Defects The optical films prepared as described above were cut into 10 cm squares, and the number of orientation defects on the screen was visually inspected and evaluated using a polarizing microscope (LEXT, manufactured by Olympus). No orientation defects were found in the mixed compositions of Examples 1 to 3, but orientation defects occurred in the mixed composition of Example 4, where the area percentage value of polymerizable compound (1) was 50%. This indicates that if the amount of polymerizable compound (1) is too high, it can affect the optical properties of the resulting optical film.

Claims

1. A polymerizable compound represented by the following formula (1). 【Chemistry 1】 [In formula (1), L is an acyclic aliphatic hydrocarbon group having 1 to 13 carbon atoms, and the hydrogen atoms contained in the aliphatic hydrocarbon group are halogen atoms, -R １０ , -OR １０ , may be substituted with a cyano group or a nitro group, R １０ This represents an alkyl group having 1 to 4 carbon atoms, and the hydrogen atoms contained in the alkyl group may be substituted with fluorine atoms. m represents 0 or 1, D １ and D ２ each independently represents -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -O-C(=S)-, -O-C(=S)-O-, -CO-NR １１ -, or -NR １２ -CO-, R １１ and R １２ each independently represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms, E １ , E ２ , B １ and B ２ Each of these is independently -CR １１ R １２ -ien-CH ２ -CH ２ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -O-C(=S)-, -O-C(=S)-O-, -CO-NR １１ -, -NR １２ -CO-, -O-CH ２ -ien-CH ２ -O-, -S-CH ２ -ien-CH ２ -S- represents a single bond, R １１ and R １２ Each of these independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms (however, if m is 0, E １ and E ２ is, -CR １１ R １２ -ien-CH ２ -CH ２ -, -O-CH ２ -ien-CH ２ -O-, -S-CH ２ - and -CH ２ (Not S-) G １ and G ２ These represent either a 1,4-cyclohexanediyl group or an aromatic hydrocarbon group, A １ and A ２ Each of these independently represents a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and the hydrogen atoms contained in the alicyclic hydrocarbon group and the aromatic hydrocarbon group are halogen atoms, -R １３ , -OR １３ , may be substituted with a cyano group or a nitro group, R １３ represents an alkyl group having 1 to 4 carbon atoms, and the hydrogen atoms contained in the alkyl group may be substituted with fluorine atoms. F １ and F ２ Each of these independently represents an alkanediyl group having 1 to 12 carbon atoms, and the hydrogen atoms contained in the alkanediyl group are -OR １４ Alternatively, it may be substituted with a halogen atom, R １４ represents an alkyl group having 1 to 4 carbon atoms, and the hydrogen atoms contained in the alkyl group may be substituted with fluorine atoms. P １ and P ２ Each of these independently represents a hydrogen atom or a polymerizable group (however, P １ and P ２ (At least one of them is a polymerizable group.)

2. The polymerizable compound according to claim 1, which is non-liquid crystallinity.

3. The polymerizable compound according to claim 1, wherein L in formula (1) is an unsubstituted acyclic aliphatic hydrocarbon group having 1 to 13 carbon atoms.

4. A mixed composition comprising a polymerizable compound according to claim 1 and a polymerizable liquid crystal compound different from the polymerizable compound.

5. The mixed composition according to claim 4, wherein the polymerizable liquid crystal compound is a polymerizable liquid crystal compound represented by formula (2). 【Chemistry 2】 [In formula (2), Ar represents a divalent aromatic hydrocarbon group or a divalent aromatic heterocyclic group which may have substituents. D ２１ , D ２２ , E ２１ , E ２２ , B ２１ and B ２２ Each of these is independently -CR １１ R １２ -ien-CH ２ -CH ２ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -O-C(=S)-, -O-C(=S)-O-, -CO-NR １１ -, -NR １２ -CO-, -O-CH ２ -ien-CH ２ -O-, -S-CH ２ -ien-CH ２ -S- represents a single bond, R １１ and R １２ Each of these independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms. G ２１ and G ２２ These represent either a 1,4-cyclohexanediyl group or an aromatic hydrocarbon group, A ２１ and A ２２ Each of these independently represents a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and the hydrogen atoms contained in the alicyclic hydrocarbon group and the aromatic hydrocarbon group are halogen atoms, -R １３ , -OR １３ , may be substituted with a cyano group or a nitro group, R １３ represents an alkyl group having 1 to 4 carbon atoms, and the hydrogen atoms contained in the alkyl group may be substituted with fluorine atoms. F ２１ and F ２２ Each of these independently represents an alkanediyl group having 1 to 12 carbon atoms, and the hydrogen atoms contained in the alkanediyl group are -OR １４ Alternatively, it may be substituted with a halogen atom, R １４ represents an alkyl group having 1 to 4 carbon atoms, and the hydrogen atoms contained in the alkyl group may be substituted with fluorine atoms, and the alkanediyl group contains -CH ２ The dash may be replaced by -O- or -CO-. P ２１ and P ２２ Each of these independently represents a hydrogen atom or a polymerizable group (however, P ２１ and P ２２ (At least one of them is a polymerizable group.)

6. The mixed composition is of formula (i): Re1(450) / Re1(550)≧Re0(450) / Re0(550) (i) [In formula (i), Re0(λ) represents the in-plane phase difference value at wavelength λnm of the cured film formed from the polymerizable liquid crystal compound, and Re1(λ) represents the in-plane phase difference value at wavelength λnm of the cured film formed from the mixed composition.] A mixed composition according to claim 4 that satisfies the requirements.

7. P in formula (1) １ , F １ , B １ , A １ and E １ are the same as P ２１ , F ２１ , B ２１ , A ２１ and E ２１ in formula (2) respectively, and P ２ , F ２ , B ２ , A ２ and E ２ in formula (1) are the same as P ２２ , F ２２ , B ２２ , A ２２ and E ２２ in formula (2) respectively. The mixed composition according to claim 5

8. The mixed composition according to claim 5, wherein Ar in formula (2) is a group represented by any of formulas (Ar-1) to (Ar-5). 【Transformation 3】 [In equations (Ar-1) to (Ar-5), * indicates a joint; Q １ is -S-, -O-, or -NR １５ - represents R １５ This represents an alkyl group having 1 to 6 carbon atoms, which may have a hydrogen atom or substituents. Q ２ represents an alkyl group having 1 to 6 carbon atoms, which may have a hydrogen atom or a substituent; W １ and W ２ These are independently -O-, -S-, -CO-, and -NR １５ - represents R １５ represents an alkyl group having 1 to 6 carbon atoms, which may have a hydrogen atom or a substituent; Y １ This represents an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group which may have substituents, or an aromatic heterocyclic group. Y ２ represents a CN group or an alkyl group having 1 to 12 carbon atoms which may have substituents, and the hydrogen atoms contained in the alkyl group may be substituted with halogen atoms, and the alkyl group contains -CH ２ The dash may be replaced by -O-, -CO-, -O-CO-, or -CO-O-; Z １ Z ２ and Z ３ Each of these independently comprises a hydrogen atom or an aliphatic hydrocarbon group or alkoxy group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a halogen atom, a cyano group, a nitro group, and -NR １５ R １６ or -SR １５ Represents Z １ and Z ２ These may bond to each other to form an aromatic ring or an aromatic heterocycle, R １５ and R １６ Each of these independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Ax represents an organic group having 2 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles, Ay represents an organic group having 2 to 30 carbon atoms having a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have substituents, or at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles, and Ax and Ay may be bonded to form a ring; Y ３ and Y ４ Each of these independently gives the following equation (Y ３ -1): 【Chemistry 4】 [Formula (Y ３ -1) Middle R Ｙ１ X represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and the alkyl group has one or more substituents X ３ The substituent X may be substituted by ３ This may be a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or one -CH ２ - or two or more non-adjacent -CH ２ Each of the hyphens may independently represent a linear or branched alkyl group having 1 to 20 carbon atoms, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom, or -B ３１ -F ３１ -P ３１ It may also be a group represented by B ３１ F ３１ and P ３１ These are, respectively, B in formula (2) above. ２１ F ２１ and P ２１ It is defined similarly, and in equation (2), B ２１ F ２１ and P ２１ It may be the same as or different from; U １ X represents an organic group having 2 to 30 carbon atoms having an aromatic hydrocarbon group, and any carbon atom of the aromatic hydrocarbon group may be substituted with a heteroatom, and the aromatic hydrocarbon group has one or more substituents X ３ It may be replaced by; T １ -O-, -S-, -COO-, -OCO-, -OCO-O-, -NU ２ -, -N=CU ２ -, -CO-NU ２ -, -OCO-NU ２ - or O-NU ２ - represents U ２ is a C2-C30 organic group having a hydrogen atom, a C1-C20 alkyl group, a C3-C12 cycloalkyl group, a C3-C12 cycloalkenyl group, an aromatic hydrocarbon group (any carbon atom of the aromatic hydrocarbon group may be substituted with a heteroatom), or (E ３１ -A ３１ ) ｑ -B ３２ -F ３２ -P ３２ The alkyl group, cycloalkyl group, cycloalkenyl group, and aromatic hydrocarbon group are each unsubstituted or have one or more substituents X. ３ The alkyl group may be substituted by the cycloalkyl group or cycloalkenyl group, and one of the alkyl groups may be -CH ２ - or two or more non-adjacent -CH ２ The hyphens are, independently of each other, -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, and -SO ２ -, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or -C≡C- may be replaced with -CH in the cycloalkyl group or cycloalkenyl group ２ - or two or more non-adjacent -CH ２ The dashes can be independently replaced with -O-, -CO-, -COO-, -OCO-, or O-CO-O-, and E ３１ A ３１ , B ３２ F ３２ and P ３２ These are, respectively, E in equation (2). ２１ A ２１ , B ２１ F ２１ and P ２１ Defined similarly to the above E ２１ A ２１ , B ２１ F ２１ and P ２１ It may be the same as or different from, q represents an integer from 0 to 4, and E ３１ and / or A ３１ If there are multiple instances, they may be the same or different, U １ and U ２ [They may be joined together to form a ring.] [Represents the base selected from.]

9. A in equation (2) ２１ and A ２２ The mixed composition according to claim 5, wherein each is independently a 1,4-cyclohexanediyl group or a 1,4-phenylenediyl group.

10. P in equation (2) ２１ and P ２２ The mixed composition according to claim 5, wherein each of them is an acryloyloxy group.

11. The mixed composition according to claim 5, wherein the area percentage value of the polymerizable compound represented by formula (1), measured by liquid chromatography, is 1% or more and less than 50%, based on the sum of the area values ​​of the polymerizable compound represented by formula (1) and the polymerizable liquid crystal compound represented by formula (2) contained in the mixed composition.

12. The mixed composition according to claim 4, further comprising a photopolymerization initiator.

13. The mixed composition according to claim 4, further comprising an organic solvent.

14. A phase difference film comprising a liquid crystal cured film which is a cured product of the mixed composition described in claim 4.

15. The liquid crystal curing film is given by formula (ii): 0.75≦Re(450) / Re(550)<1.00 (ii) [In equation (ii), Re(λ) represents the in-plane phase difference value at a wavelength of λnm of the liquid crystal cured film.] A phase difference film according to claim 14, satisfying the requirements.

16. An elliptic polarizer including the phase difference film according to claim 14.

17. An optical display including an elliptical polarizer as described in claim 16.

18. A flexible image display device including an elliptical polarizing plate as described in claim 16.

Images