WO2020059634A1 - Procédé de production d'un intermédiaire - Google Patents

Procédé de production d'un intermédiaire Download PDF

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Publication number
WO2020059634A1
WO2020059634A1 PCT/JP2019/035933 JP2019035933W WO2020059634A1 WO 2020059634 A1 WO2020059634 A1 WO 2020059634A1 JP 2019035933 W JP2019035933 W JP 2019035933W WO 2020059634 A1 WO2020059634 A1 WO 2020059634A1
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group
compound
carbon atoms
solution
substituent
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PCT/JP2019/035933
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English (en)
Japanese (ja)
Inventor
坂本　圭
久美 奥山
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日本ゼオン株式会社
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Priority to CN201980059201.XA priority Critical patent/CN112689622A/zh
Priority to JP2020548438A priority patent/JP7327408B2/ja
Publication of WO2020059634A1 publication Critical patent/WO2020059634A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C69/75—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring of acids with a six-membered ring

Definitions

  • the present invention relates to a method for producing an intermediate.
  • the retardation plate examples include a ⁇ wavelength plate that converts linearly polarized light into circularly polarized light, and a ⁇ wavelength plate that converts the polarization oscillation plane of linearly polarized light by 90 degrees. These retardation plates are capable of accurately converting a specific monochromatic light into a phase difference of ⁇ ⁇ or ⁇ of the light wavelength.
  • the conventional retardation plate has a problem that polarized light output through the retardation plate is converted into colored polarized light. This is because the material constituting the retardation plate has a wavelength dispersion property with respect to the retardation, and distribution occurs in the polarization state for each wavelength with respect to white light, which is a composite wave in which light rays in the visible light region are mixed.
  • Patent Documents 1 to 3 have a problem that the number of steps in the manufacturing method is large and the manufacturing method is complicated.
  • Patent Document 4 an intermediate containing the target compound at a high concentration was not obtained, and the amount of the solvent used in the reaction was large, and there was room for improvement from the viewpoint of production efficiency.
  • the present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a method for producing an intermediate which can efficiently produce an intermediate containing a predetermined compound (I) at a high concentration.
  • the present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, added a protic solvent to a solution (X) containing the compound (I) and the compound (II) to precipitate the compound (II).
  • the inventors have found that removing the precipitated compound (II) makes it possible to efficiently produce an intermediate containing the compound (I) at a high concentration, and has completed the present invention.
  • the present invention there is provided the following method for producing an intermediate.
  • R 21 to R 26 each independently represent a hydrogen atom or a carbon atom.
  • R 31 and R 32 each independently represent a hydrogen atom, a methyl group or a chlorine atom; d1 and d2 each independently represent an integer of 1 to 20, e1 and e2 are each independently 1 or 2.
  • a protic solvent is added to the solution (X) to precipitate the compound (II), and the precipitated compound (II) is removed to obtain an intermediate containing the compound (I).
  • a method for producing an intermediate comprising a step ( ⁇ ), The method for producing an intermediate, wherein the intermediate obtained in the step ( ⁇ ) contains 86% by mass or more of the compound (I).
  • the method for producing an intermediate of the above [1] is a method for producing an intermediate containing the compound (I), (I) a step ( ⁇ ) of obtaining a solution (X) containing the formula compound (I) and the compound (II); (Ii) A protic solvent is added to the solution (X) to precipitate the compound (II), and the precipitated compound (II) is removed to contain the compound (I) at 86% by mass or more. Step ( ⁇ ) of obtaining an intermediate.
  • “may have a substituent” means “unsubstituted or has a substituent”.
  • an organic group such as an alkyl group or an aromatic hydrocarbon ring group included in the general formula has a substituent
  • the carbon number of the organic group having the substituent does not include the carbon number of the substituent.
  • the aromatic hydrocarbon ring group having 6 to 20 carbon atoms has a substituent
  • the carbon number of the aromatic hydrocarbon ring group having 6 to 20 carbon atoms does not include the carbon number of such a substituent.
  • the “alkyl group” means a chain (linear or branched) saturated hydrocarbon group, and the “alkyl group” includes a cyclic saturated hydrocarbon group “cyclo” "Alkyl group” is not included.
  • the “total number of ⁇ electrons contained in the ring structure in Rf” includes the ⁇ electrons of the ring structure contained in the substituent.
  • the “intermediate” includes at least the compound (I), may be the compound (I) alone, or may be a compound other than the compound (I) and the compound (I). And a mixture containing
  • the process for producing an intermediate according to the present invention comprises a step ( ⁇ ) of obtaining a solution (X) containing a compound (I) and a compound (II), and adding a protic solvent to the solution (X) to obtain a compound (II) ), And removing the precipitated compound (II) to obtain an intermediate containing the compound (I) ( ⁇ ), and further including other steps as necessary.
  • Step ( ⁇ ) is a step of obtaining a solution (X) containing compound (I) and compound (II).
  • Solution (X) contains at least compound (I) and compound (II), and further contains an organic solvent and other components as necessary.
  • the concentration of the compound (I) in the solution (X) is preferably 8.0% by mass or more, more preferably 8.5% by mass or more, and particularly preferably 9.0% by mass or more.
  • the content is preferably 40% by mass or less, more preferably 30% by mass or less, and particularly preferably 20% by mass or less.
  • concentration of the compound (I) in the solution (X) is equal to or higher than the lower limit and equal to or lower than the upper limit, the compound represented by the formula (II) can be selectively removed.
  • the concentration of the compound (II) in the solution (X) is preferably at least 3.0% by mass, more preferably at least 3.5% by mass, particularly preferably at least 4.0% by mass. Preferably, it is preferably at most 10% by mass, more preferably at most 9.0% by mass, particularly preferably at most 8.0% by mass.
  • concentration of the compound (II) in the solution (X) is equal to or higher than the lower limit and equal to or lower than the upper limit, the compound represented by the formula (II) can be selectively removed.
  • the ratio of the concentration of compound (II) in solution (X) to the concentration of compound (I) in solution (X) Is preferably 20% or more, more preferably 25% or more, particularly preferably 30% or more, and preferably 60% or less, and 55% or less. More preferably, it is particularly preferably at most 50%.
  • the ratio of the concentration of the compound (II) in the solution (X) is not less than the lower limit, When the content is equal to or less than the above upper limit, the compound represented by the formula (II) can be highly selectively removed.
  • the compound (I) represented by the following formula (I) may be composed of only one kind of compound or may be composed of two kinds of compounds, but is composed of only one kind of compound. Is preferred.
  • the compound (I) is composed of only one compound, the corresponding groups in the compounds (II) is a symmetrical about the A 21.
  • a 2 and B 2 each independently represent a cyclic aliphatic group which may have a substituent, or an aromatic group which may have a substituent.
  • a 2 and B 2 each independently represent a cycloaliphatic group having 5 to 20 carbon atoms which may have a substituent or 2 carbon atoms which may have a substituent. Up to 20 aromatic groups are preferred.
  • cycloaliphatic group examples include cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cycloheptane-1,4-diyl group, cyclooctane-1,5-diyl group and the like.
  • the cycloaliphatic group is preferably an optionally substituted cycloalkanediyl group having 5 to 20 carbon atoms, more preferably a cyclohexanediyl group, and particularly preferably a 1,4-cyclohexylene group (cyclohexane-1,4 -Diyl group), and a trans-1,4-cyclohexylene group is more preferable.
  • aromatic group examples include 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 1,4-naphthylene group, 1,5-naphthylene group and 2,6-naphthylene group
  • Aromatic hydrocarbon ring groups having 6 to 20 carbon atoms such as 4,4'-biphenylene group; furan-2,5-diyl, thiophen-2,5-diyl, pyridine-2,5-diyl, pyrazine-
  • the aromatic group is preferably an aromatic hydrocarbon ring group having 6 to 20 carbon atoms, more preferably a phenylene group, and particularly preferably a 1,4-phenylene group.
  • Examples of the substituent for the cyclic aliphatic group and the aromatic group include a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom; an alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group; An alkoxy group having 1 to 5 carbon atoms such as a propoxy group; a nitro group; a cyano group;
  • the cyclic aliphatic group, the cyclic aliphatic group having 5 to 20 carbon atoms, the aromatic group, and the aromatic group having 2 to 20 carbon atoms may have at least one substituent selected from the above-described substituents. Good. When a compound has a plurality of substituents, the substituents may be the same or different.
  • a 2 is preferably a cyclic aliphatic group which may have a substituent
  • B 2 is preferably an aromatic group which may have a substituent
  • a 2 is a “trans-1,4-cyclohexylene group optionally having a substituent” represented by the formula (a)
  • B 2 is a “trans-1,4-cyclohexylene group” represented by the formula (b).
  • the combination of "1,4-phenylene group which may have a substituent" is more preferable.
  • Ra is an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or a substituent.
  • a halogen atom such as a fluorine atom and a chlorine atom
  • an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group and a propyl group
  • a cyano group such as a nitro group
  • an alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group or a propoxy group
  • p1 represents an integer of 0 to 4, and is preferably 0.
  • alkyl group having 1 to 20 carbon atoms of the alkyl group having 1 to 20 carbon atoms which may have a substituent include a methyl group, an ethyl group, an n-propyl group, an isopropyl group and an n-butyl group.
  • the alkenyl group having 2 to 20 carbon atoms alkenyl group substituents to 2 carbon atoms which may have a 20, a vinyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, pentenyl Group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, nonadecenyl group, and icosenyl group.
  • Examples of the substituent for the alkyl group having 1 to 20 carbon atoms and the alkenyl group having 2 to 20 carbon atoms for Ra include a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; N, N-dialkylamino group; an alkoxy group having 1 to 20 carbon atoms such as methoxy group, ethoxy group, isopropoxy group and butoxy group; an alkoxy group having 1 to 12 carbon atoms such as methoxymethoxy group and methoxyethoxy group Substituted alkoxy group having 1 to 12 carbon atoms; nitro group; aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as phenyl group and naphthyl group; triazolyl group, pyrrolyl group, furanyl group, thiophenyl group, benzothiazole group An aromatic heterocyclic group having 2 to 20 carbon atoms such as a 2-ylthio group; a
  • halogen atoms such as fluorine atom and chlorine atom
  • cyano group methoxy group, ethoxy group
  • An alkoxy group having 1 to 20 carbon atoms such as a propoxy group or a butoxy group; a nitro group
  • an aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as a phenyl group or a naphthyl group
  • An aromatic heterocyclic group having from 20 to 20; a cycloalkyl group having from 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group and a cyclohexyl group; at least one group such as a trifluoromethyl group, a pentafluoroethyl group and -CH 2 CF 3 ;
  • the alkyl group having 1 to 20 carbon atoms and the alkenyl group having 2 to 20 carbon atoms of Ra may have a plurality of substituents selected from the above-described substituents.
  • the alkyl group having 1 to 20 carbon atoms and the alkenyl group having 2 to 20 carbon atoms of Ra have a plurality of substituents, the plurality of substituents may be the same or different.
  • Examples of the cycloalkyl group having 3 to 12 carbon atoms of the cycloalkyl group having 3 to 12 carbon atoms which may have a substituent include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and a cyclooctyl group. And the like. Among these, a cyclopentyl group and a cyclohexyl group are preferred.
  • Examples of the substituent of the cycloalkyl group having 3 to 12 carbon atoms of Ra include a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; an N, N-dialkylamino group having 2 to 12 carbon atoms such as a dimethylamino group; C1-C6 alkyl groups such as methyl group, ethyl group and propyl group; C1-C6 alkoxy groups such as methoxy group, ethoxy group and isopropoxy group; nitro group; and phenyl group and naphthyl group And an aromatic hydrocarbon ring group having 6 to 20 carbon atoms.
  • a halogen atom such as a fluorine atom and a chlorine atom
  • a cyano group such as a dimethylamino group
  • C1-C6 alkyl groups such as methyl group, ethyl group and propyl group
  • examples of the substituent of the cycloalkyl group having 3 to 12 carbon atoms of Ra include a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group and a propyl group. Groups; alkoxy groups having 1 to 6 carbon atoms such as methoxy group, ethoxy group and isopropoxy group; nitro groups; and aromatic hydrocarbon ring groups having 6 to 20 carbon atoms such as phenyl group and naphthyl group.
  • the cycloalkyl group having 3 to 12 carbon atoms of Ra may have a plurality of substituents. When the cycloalkyl group having 3 to 12 carbon atoms of Ra has a plurality of substituents, the plurality of substituents may be the same or different.
  • Examples of the aromatic hydrocarbon ring group having 5 to 12 carbon atoms of the optionally substituted aromatic hydrocarbon ring group having 5 to 12 carbon atoms for Ra include a phenyl group, a 1-naphthyl group, -Naphthyl group and the like. Among these, a phenyl group is preferred.
  • Examples of the substituent of the aromatic hydrocarbon ring group having 5 to 12 carbon atoms which may have a substituent include a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; N, N-dialkylamino group; C1-C20 alkoxy group such as methoxy group, ethoxy group, isopropoxy group, butoxy group; C1-C12 alkoxy group such as methoxymethoxy group, methoxyethoxy group A nitro group; an aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as a phenyl group or a naphthyl group; a triazolyl group, a pyrrolyl group, a furanyl group, a thiophenyl group or the like; An aromatic heterocyclic group having 2 to 20 carbon atoms; a cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopent
  • a substituent of an aromatic hydrocarbon ring group having 5 to 12 carbon atoms includes a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; a carbon atom having 1 carbon atom such as a methoxy group, an ethoxy group, an isopropoxy group and a butoxy group.
  • Aromade group aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as phenyl group and naphthyl group; aromatic group having 2 to 20 carbon atoms such as triazolyl group, pyrrolyl group, furanyl group and thiophenyl group A heterocyclic group; a cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group; at least one hydrogen atom such as a trifluoromethyl group, a pentafluoroethyl group, and —CH 2 CF 3 Is preferably a fluoroalkyl group having 1 to 12 carbon atoms substituted with a fluorine atom; and at least one substituent selected from —OCF 3 is preferable.
  • the aromatic hydrocarbon ring group having 5 to 12 carbon atoms may have a plurality of substituents. When the aromatic hydrocarbon ring group having 5 to 12
  • R 21 to R 26 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • Y 2 is preferably -O-
  • R 3 represents a hydrogen atom, a methyl group or a chlorine atom.
  • R 3 is preferably a hydrogen atom from the viewpoint of ease of synthesis and polymerization rate.
  • FG 2 represents a hydroxyl group, a carboxyl group or an amino group.
  • FG 2 is synthesized from the standpoint of ease and desired optical properties expression is preferably a carboxyl group.
  • d represents an integer of 1 to 20.
  • d is preferably an integer of 2 to 12, more preferably an integer of 4 to 12, and more preferably an integer of 4 to 10, from the viewpoints of ease of synthesis and expression of desired optical properties. Is particularly preferred.
  • e is 1 or 2.
  • e is preferably 1.
  • the two B 2 may be the same or different and also, the two L 2 may be different even in the same.
  • the compound (I) include, for example, a compound (I-1) represented by the following formula (I-1).
  • R 3 and d have the same meanings as described above, and preferred examples thereof are also the same as described above.
  • compound (I) (compound (Ia) represented by the following formula (Ia)) includes, for example, compound (A-0) represented by the following formula (A-0) It can be obtained by reacting a compound (B-0) represented by the following formula (B-0), and more specifically, a compound (A-1) represented by the following formula (A-1) , And trans-1,4-cyclohexanedicarboxylic acid dichloride are subjected to an esterification reaction in a reaction solvent containing a base such as triethylamine, followed by hydrolysis.
  • a base such as triethylamine
  • a compound (A-1) represented by the following formula (A-1) and trans-1,4-cyclohexanedicarboxylic acid are reacted in a reaction solvent in the presence of a dehydration condensing agent.
  • a 2 , B 2 , Y 2 , L 2 , R 3 , FG 2 and d are each independently the same as defined above. The meaning is shown, and preferable examples are the same as described above.
  • Z represents a hydroxyl group, a carboxyl group, or an amino group. Among them, Z is preferably a hydroxyl group from the viewpoint of ease of synthesis.
  • R 3 and d have the same meanings as described above, and preferred examples thereof are also the same as described above.
  • the compound (I) (compound (Ib) represented by the following formula (Ib)) is, for example, a compound (A-2) represented by the following formula (A-2) It can be obtained by reacting with a compound (B-0) represented by the following formula (B-0).
  • a 2 , B 2 , Y 2 , L 2 , R 3 , FG 2 and d are each independently the same as defined above. Meaning is shown, and preferable examples are the same as described above.
  • Z represents a hydroxyl group, a carboxyl group, or an amino group.
  • Z is preferably a hydroxyl group from the viewpoint of easy synthesis.
  • FQ has the same meaning as described above, and preferred examples thereof are also the same as described above.
  • Two B 2 in the formula (Ib) may be the same or different, and two L 2 in the formula (Ib) may be the same or different.
  • reaction solvent examples include ethers such as cyclopentyl methyl ether (CPME), tetrahydrofuran, methyl-t-butyl ether, diethyl ether, dibutyl ether, diisopropyl ether, and 1,2-dimethoxyethane; ketones such as 2-butanone and methyl isobutyl ketone Halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; esters such as ethyl acetate and propyl acetate; aromatic hydrocarbons such as benzene, toluene and xylene; alicycles such as cyclopentane and cyclohexane Formula hydrocarbons; amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone; nitriles such as acetonitrile and propionitrile;
  • ethers such as
  • the amount of the reaction solvent used in the above reaction is preferably 10 mL or more, more preferably 20 mL or more, and more preferably 40 mL or more, based on 10 g of the compound (A-0) or the compound (A-2). It is particularly preferable, and the volume is preferably 500 mL or less, more preferably 250 mL or less, and particularly preferably 100 mL or less.
  • the amount of the reaction solvent is at least the lower limit and at most the upper limit, the selectivity of the compound represented by the formula (I) can be improved.
  • Compound represented by the following formula (II) (II) is, around the A 21, even symmetrical, but may be asymmetrical in terms of ease of synthesis, the left and right around the A 21 Symmetric (ie, B 21 and B 22 are the same, Y 21 and Y 22 are the same, L 21 and L 22 are the same, R 31 and R 32 are the same, Preferably, d1 and d2 are the same, and e1 and e2 are the same.
  • a 21 , B 21 , B 22 each independently represent the same meaning as A 2 and B 2, and preferred examples thereof are also the same as A 2 and B 2 .
  • Y 21 , Y 22 each independently represent the same meaning as Y 2, and preferred examples thereof are also the same as Y 2 .
  • L 21 , L 22 each independently represent the same meaning as L 2, and preferred examples thereof are also the same as L 2 .
  • R 31 and R 32 each independently represent the same meaning as R 3, and preferred examples thereof are also the same as R 3 .
  • d1 and d2 each independently represent the same meaning as d, and preferred examples thereof are also the same as d.
  • the compound (II) include, for example, a compound (II-1) represented by the following formula (II-1).
  • R 3 and d represent the same meaning as described above, and preferred examples thereof are also the same as described above.
  • Organic solvent examples include cyclopentyl methyl ether (CPME), tetrahydrofuran, methyl-t-butyl ether, diethyl ether, dibutyl ether, diisopropyl ether, 1,2-dimethoxyethane, 1,4-dioxane, and 1,3-dioxolan.
  • CPME cyclopentyl methyl ether
  • tetrahydrofuran methyl-t-butyl ether
  • diethyl ether diethyl ether
  • dibutyl ether diisopropyl ether
  • 1,2-dimethoxyethane 1,4-dioxane
  • 1,3-dioxolan examples include 1,3-dioxolan.
  • Ketones such as 2-butanone and methyl isobutyl ketone; halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; esters such as ethyl acetate and propyl acetate; aromatics such as benzene, toluene and xylene Hydrocarbons; alicyclic hydrocarbons such as cyclopentane and cyclohexane; amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone; acetonitrile, propionitrile Nitriles such as; Beauty a mixed solvent thereof and the like.
  • halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane
  • esters such as ethyl acetate and propyl acetate
  • aromatics such as benzene, toluene and xylene Hydro
  • water-immiscible organic solvent is an organic solvent having a property of being separated into two phases without being compatible even when mixed with water.
  • the solubility of the water-immiscible organic solvent in water is 40 g (organic solvent) / 100 mL (water) or less, preferably 30 g (organic solvent) / 100 mL (water) or less, more preferably 15 g (organic solvent) / 100 mL (water). Water).
  • the mixed solvent is a “water-immiscible organic solvent”.
  • water-immiscible organic solvent examples include cyclopentyl methyl ether (CPME), 2-methyltetrahydrofuran, 1,4-dioxane, 1,3-dioxolan, tetrahydrofuran, methyl-t-butyl ether, diethyl ether, dibutyl ether, Ethers such as diisopropyl ether and 1,2-dimethoxyethane; ketones such as 2-butanone; halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; esters such as ethyl acetate and propyl acetate; Hydrocarbons such as cyclopentane and cyclohexane; amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone Acetonitrile, pro Nitriles such as Onitoriru; and mixed solvents thereof.
  • Solubility parameter of the water-immiscible organic solvent in Hildebrand is preferably at 14.0 MPa 1/2 or more, more preferably 14.3MPa 1/2 or more, is 14.5 MPa 1/2 or more it is particularly preferred, also, is preferably 22.0MPa 1/2 or less, more preferably 20.0 MPa 1/2 or less, and particularly preferably 19.5MPa 1/2 or less.
  • solubility parameter of Hildebrand of the water-immiscible organic solvent is equal to or higher than the lower limit and equal to or lower than the upper limit, the compound represented by the formula (I) can be obtained with high selectivity.
  • Hildebrand solubility parameter is a value ( ⁇ ) introduced by Hildebrand that provides a numerical prediction of the degree of interaction between materials, as defined by regular solution theory.
  • cyclopentyl methyl ether (Hildebrand solubility parameter ( ⁇ ): 17.2 MPa 1/2 ) , Tetrahydrofuran (( ⁇ ): 18.6 MPa 1/2 ), methyl-t-butyl ether (( ⁇ ): 15.6 MPa 1/2 ), diethyl ether (( ⁇ ): 15.1 MPa 1/2 ), dibutyl ether (( ⁇ ): 14.9 MPa 1/2 ), diisopropyl ether (( ⁇ ): 14.1 MPa 1/2 ), 1,2-dimethoxyethane (( ⁇ ): 19.2 MPa 1/2 ), 2-butanone (( ⁇ ): 19.0MPa 1/2) ethers such as: chloroform (( ⁇ ): 19.0MPa 1/2) halogen, such as Hydrocarbons; ethyl acetate (( ⁇ ): 18.6MPa 1/2) esters such as: tol
  • the content of the organic solvent in the solution (X) is preferably 50% by mass or more, more preferably 60% by mass or more, particularly preferably 70% by mass or more, and 95% by mass. Or less, more preferably 93% by mass or less, particularly preferably 90% by mass or less.
  • the compound represented by the formula (II) can be removed with a high selectivity.
  • Other components include, for example, bases such as triethylamine (Et 3 N), diisopropylethylamine, pyridine, N, N-dimethyl-4-dimethylaminopyridine; dicyclohexylcarbodiimide, N, N-diisopropylcarbodiimide, 1- (3- Dehydration condensing agents such as dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride; and polymerization inhibitors such as 2,6-di-tert-butyl-p-cresol and paramethoxyphenol.
  • bases such as triethylamine (Et 3 N), diisopropylethylamine, pyridine, N, N-dimethyl-4-dimethylaminopyridine
  • dicyclohexylcarbodiimide N, N-diisopropylcarbodiimide
  • 1- 3- Dehydration condensing agents such as dimethylamino
  • Step ( ⁇ )> a step of adding a protic solvent to the solution (X) to precipitate the compound (II) and removing the precipitated compound (II) to obtain an intermediate containing the compound (I) It is.
  • the protic solvent examples include alcohols such as ethanol, methanol, 1-propanol, 2-propanol, 1-butanol, cyclohexanol and cyclopentanol; glycols such as glycerin, ethylene glycol and propylene glycol; formic acid and acetic acid. Carboxylic acids; hydroxy acids such as glycolic acid, 2-hydroxymalonic acid and glyceric acid; and the like. One of these may be used alone, or two or more of them may be used in any ratio. Among these, alcohol is preferable and methanol is more preferable in that the compound (II) can be efficiently precipitated.
  • alcohols such as ethanol, methanol, 1-propanol, 2-propanol, 1-butanol, cyclohexanol and cyclopentanol
  • glycols such as glycerin, ethylene glycol and propylene glycol
  • formic acid and acetic acid formic acid and acetic acid
  • the amount of the protic solvent to be used is preferably at least 0.1 times by mass, more preferably at least 0.2 times by mass, based on the compound (A-0) or the compound (A-2). It is particularly preferably at least 0.3 times by mass, more preferably at most 5 times by mass, even more preferably at most 3 times by mass, particularly preferably at most 2 times by mass. If the amount of the protic solvent used is greater than or equal to the lower limit and less than or equal to the upper limit, the compound represented by the formula (II) is removed with a high selectivity to remove the compound represented by the formula (I) Can be improved in purity.
  • Examples of the removal method for removing the precipitated compound (II) include filtration, centrifugation, and the like, and more specifically, suction filtration, pressure filtration, and the like as filtration. Among these, centrifugal separation and pressure filtration are preferred from the viewpoint of removal efficiency.
  • the intermediate contains at least the compound (I), may be the compound (I) alone, or may contain the compound (I) and components other than the compound (I) (eg, the compound (II)). May be used as a mixture.
  • the content of the compound (I) in the intermediate must be 86% by mass or more, is preferably 88% by mass or more, more preferably 90% by mass or more, and is 92% by mass or more. Is particularly preferred.
  • the content of the compound (I) in the intermediate is not less than the above lower limit, a compound capable of obtaining an optical film capable of performing uniform polarization conversion in a wide wavelength range can be efficiently produced.
  • the cooling temperature is preferably 20 ° C. or lower, more preferably 10 ° C. or lower, particularly preferably 5 ° C. or lower, and most preferably about 0 ° C. When the cooling temperature is equal to or lower than the upper limit, the intermediate can be efficiently precipitated.
  • ⁇ Other steps> Other steps include, for example, a step of preparing the above-mentioned compound (I) such as drying.
  • the polymerizable compound produced from the intermediate produced by the method for producing an intermediate of the present invention will be described.
  • the polymerizable compound is, for example, a compound represented by the following formula (III) (hereinafter, sometimes referred to as “polymerizable compound (III)”), and prepares a polymer, an optical film, and an optically anisotropic material described later. Can be used advantageously.
  • Ar is represented by the following formula (IV-1) or (IV-2), and preferably by the following formula (IV-3) or (IV-4).
  • IV-1) and (IV-2) * represents binding to Y 3 or Y 4.
  • IV-3) and (IV-4) * represents binding to Y 3 or Y 4.
  • R represents an organic group having 1 to 60 carbon atoms which may have a substituent, and is represented by Rf-K-Ga (Ga is bonded to N). It is preferable that it is represented by Gb.
  • the organic group having 1 to 60 carbon atoms of the organic group having 1 to 60 carbon atoms which may have a substituent is not particularly limited, and examples thereof include (i) an alkyl group having 1 to 60 carbon atoms. (Ii) an alkenyl group having 2 to 60 carbon atoms; (iii) an alkynyl group having 2 to 60 carbon atoms;
  • alkyl group having 1 to 60 carbon atoms examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, and an n-hexyl group. , N-heptyl, n-undecyl, n-dodecyl, 1-methylpentyl, 1-ethylpentyl and the like.
  • an alkyl group having 1 to 12 carbon atoms is preferable, an n-butyl group, an n-hexyl group, and an n-octyl group are more preferable, and an n-hexyl group is particularly preferable.
  • alkenyl group having 2 to 60 carbon atoms examples include a vinyl group, an allyl group, an isopropenyl group and a butynyl group, and an alkenyl group having 2 to 12 carbon atoms is preferable.
  • Alkynyl group having 2 to 60 carbon atoms examples include a propynyl group, a propargyl group and a butynyl group, and an alkynyl group having 2 to 12 carbon atoms is preferable.
  • Examples of the substituent of the organic group having 1 to 60 carbon atoms for R include a cyano group; a nitro group; a hydroxyl group; a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom; Alkoxy group having 1 to 6 carbon atoms such as methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, t-butoxy group; methoxymethoxy group, methoxyethoxy group, ethoxyethoxy group C1-C6 alkoxy group substituted by C1-C6 alkoxy group; C3-C8 cycloalkyl group such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group; methyl Substituted amino groups such as an amino group, an ethylamino group, an acetylamino group, and a
  • Rf represents a cyclic group having at least one of an aromatic hydrocarbon ring and an aromatic heterocyclic ring. Among these, an aromatic hydrocarbon ring group having 6 to 30 carbon atoms is more preferable.
  • -Aromatic hydrocarbon ring examples include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, and a fluorene ring.
  • a benzene ring, a naphthalene ring, an anthracene ring and a fluorene ring are preferred, and a benzene ring and a naphthalene ring are more preferred.
  • aromatic heterocycle examples include a 1H-isoindole-1,3 (2H) -dione ring, a 1-benzofuran ring, a 2-benzofuran ring, an acridine ring, an isoquinoline ring, an imidazole ring, an indole ring, and an oxadiazole ring.
  • examples of the aromatic heterocyclic ring include monocyclic aromatic heterocyclic rings such as furan ring, pyran ring, thiophene ring, oxazole ring, oxadiazole ring, thiazole ring, and thiadiazole ring; and benzothiazole ring and benzoxazole Ring, quinoline ring, 1-benzofuran ring, 2-benzofuran ring, benzo [b] thiophene ring, 1H-isoindole-1,3 (2H) -dione ring, benzo [c] thiophene ring, thiazolopyridine ring, thia
  • a condensed aromatic heterocyclic ring such as a zolopyrazine ring, a benzoisoxazole ring, a benzooxadiazole ring, or a benzothiadiazole ring is preferable.
  • the aromatic hydrocarbon ring and the aromatic hetero ring of Rf may have a substituent.
  • a substituent include a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group and a propyl group; An alkenyl group having 1 to 6 carbon atoms, wherein at least one hydrogen atom such as a trifluoromethyl group and a pentafluoroethyl group is substituted with halogen; an N, N-dialkyl having 2 to 12 carbon atoms such as a dimethylamino group amino group; methoxy group, an ethoxy group, an alkoxy group having 1 to 6 carbon atoms such as an isopropoxy group, a nitro group, a phenyl group, an aromatic having 6 to 20 carbon atoms such as phenyl or naphthyl hydrocarbon ring group
  • R x represents “(i) an alkyl group having 1 to 20 carbon atoms which may have a substituent” or “(ii) an alkenyl group having 2 to 20 carbon atoms which may have a substituent. ", (Iii) a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent", or "(iv) an aromatic carbon atom having 5 to 18 carbon atoms which may have a substituent”.
  • a hydrogen ring group ".
  • R b is an alkyl group having 1 to 6 carbon atoms such as a methyl group or an ethyl group; or an alkyl group having 1 to 6 carbon atoms such as a phenyl group, a 4-methylphenyl group or a 4-methoxyphenyl group; Represents an aromatic hydrocarbon ring group having 6 to 20 carbon atoms which may have an alkoxy group having 1 to 6 carbon atoms as a substituent.
  • a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms are preferable as the substituent of the aromatic hydrocarbon ring and the aromatic hetero ring of Rf.
  • Rf may have a plurality of substituents selected from the above-described substituents. When Rf has a plurality of substituents, the substituents may be the same or different.
  • alkenyl group having 2 to 20 carbon atoms which may have a substituent examples include a vinyl group, a propenyl group, an isopropenyl group, Butenyl, isobutenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl And an icosenyl group.
  • alkenyl group having 2 to 20 carbon atoms examples include a vinyl group, a propenyl group, an isopropenyl group, Butenyl, isobutenyl, pentenyl, hexenyl, heptenyl, octeny
  • R x represents “(i) an alkyl group having 1 to 20 carbon atoms which may have a substituent”, “an alkyl group having 1 to 20 carbon atoms”, and “(ii) an alkyl group having a substituent.
  • substituent of the "alkenyl group having 2 to 20 carbon atoms" of the “alkenyl group having 2 to 20 carbon atoms” include a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; An alkoxy group having 1 to 20 carbon atoms such as a methoxy group, an ethoxy group, an isopropoxy group or a butoxy group; an alkoxy group having 1 to 12 carbon atoms such as a methoxymethoxy group or a methoxyethoxy group A nitro group; an aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as a phenyl group or a naphthyl group; a triazolyl group,
  • R x has “(i) an alkyl group having 1 to 20 carbon atoms which may have a substituent”, “an alkyl group having 1 to 20 carbon atoms” and “(ii) a substituent.
  • the substituent of the "alkenyl group having 2 to 20 carbon atoms" of the "alkenyl group having 2 to 20 carbon atoms which may be substituted” includes a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; a methoxy group, an ethoxy group, C1-C20 alkoxy groups such as isopropoxy group and butoxy group; nitro group; C6-C20 aromatic hydrocarbon ring groups such as phenyl group and naphthyl group; furanyl group, thiophenyl group, benzothiazole-2 An aromatic heterocyclic group having 2 to 20 carbon atoms, such as -ylthio group; a cycloalkyl group having 3 to
  • Rx has “(i) an alkyl group having 1 to 20 carbon atoms which may have a substituent”, “an alkyl group having 1 to 20 carbon atoms” and “(ii) a substituent.
  • R x represents “(i) an alkyl group having 1 to 20 carbon atoms which may have a substituent”, “an alkyl group having 1 to 20 carbon atoms”, and “(ii) an alkyl group having a substituent.
  • the plurality of substituents may be the same or different.
  • cycloalkyl group having 3 to 12 carbon atoms which may have a substituent examples include a cyclopropyl group, a cyclobutyl group, and a cyclopentyl Group, cyclohexyl group, cyclooctyl group and the like. Among these, a cyclopentyl group and a cyclohexyl group are preferred.
  • the substituent of the “cycloalkyl group having 3 to 12 carbon atoms” of the “(iii) cycloalkyl group having 3 to 12 carbon atoms which may have a substituent” for R x is a fluorine atom, a chlorine atom A halogen atom such as a cyano group; an N, N-dialkylamino group having 2 to 12 carbon atoms such as a dimethylamino group; an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group and a propyl group; a methoxy group and an ethoxy group A nitro group; an aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as a phenyl group and a naphthyl group; and the like.
  • the substituent of “(iii) a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent” of “(cycloalkyl group having 3 to 12 carbon atoms)” of R x is fluorine.
  • Halogen atoms such as atoms and chlorine atoms; cyano groups; alkyl groups having 1 to 6 carbon atoms such as methyl group, ethyl group and propyl group; alkoxy groups having 1 to 6 carbon atoms such as methoxy group, ethoxy group and isopropoxy group.
  • the “(3) cycloalkyl group having 3 to 12 carbon atoms which may have a substituent” of the “cycloalkyl group having 3 to 12 carbon atoms” of R x has a plurality of substituents. May be.
  • the substituents may be the same or different.
  • an aromatic hydrocarbon ring group having 5 to 18 carbon atoms which may have a substituent As the "(5) aromatic hydrocarbon ring group having 5 to 18 carbon atoms which may have a substituent (s)" for R x , the "aromatic hydrocarbon ring group having 5 to 18 carbon atoms" is a phenyl group , 1-naphthyl group, 2-naphthyl group and the like. Among these, a phenyl group and a naphthyl group are preferable, and a phenyl group, a 1-naphthyl group and a 2-naphthyl group are more preferable.
  • Examples of the substituent of “(iv) an aromatic hydrocarbon ring group having 5 to 18 carbon atoms which may have a substituent” for R x include a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; An N, N-dialkylamino group having 2 to 12 carbon atoms such as a group; an alkoxy group having 1 to 20 carbon atoms such as a methoxy group, an ethoxy group, an isopropoxy group and a butoxy group; a methoxymethoxy group, a methoxyethoxy group and the like; An alkoxy group having 1 to 12 carbon atoms substituted with an alkoxy group having 1 to 12 carbon atoms; a nitro group; an aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as a phenyl group and a naphthyl group; a triazolyl group, a pyrrolyl group, An aromatic heterocyclic group having 2
  • the “(iv) aromatic hydrocarbon ring group having 5 to 18 carbon atoms which may have a substituent” of R x includes a plurality of “aromatic hydrocarbon ring groups having 5 to 18 carbon atoms”. May have a substituent.
  • Rx is represented by “(iv) an aromatic hydrocarbon ring group having 5 to 18 carbon atoms which may have a substituent”, wherein “an aromatic hydrocarbon ring group having 5 to 18 carbon atoms” has a plurality of substituents; In the case of having, the substituents may be the same or different.
  • the “carbon number” of the cyclic group having at least one of an aromatic hydrocarbon ring and an aromatic heterocyclic ring of Rf is at least one of an aromatic hydrocarbon ring and an aromatic heterocyclic ring not containing a carbon atom of a substituent.
  • Rf is preferably a “cyclic group having at least one of an aromatic hydrocarbon ring having 6 to 30 carbon atoms and an aromatic heterocyclic ring having 2 to 30 carbon atoms”.
  • cyclic group having at least one of an aromatic hydrocarbon ring having 6 to 30 carbon atoms and an aromatic heterocyclic ring having 2 to 30 carbon atoms are shown below. However, it is not limited to the following. In the following formula, "-" represents a bond extending from an arbitrary position of the ring to K.
  • Specific examples of the optionally substituted hydrocarbon ring group having at least one aromatic hydrocarbon ring having 6 to 30 carbon atoms include the following formulas (1-1) to (1-21) And a hydrocarbon ring group having 6 to 18 carbon atoms represented by formulas (1-8) to (1-21) is preferable.
  • the groups represented by the following formulas (1-1) to (1-21) may have a substituent.
  • Specific examples include structures represented by the following formulas (2-1) to (2-51) and the like. Sixteen heterocyclic groups are preferred.
  • the groups represented by the following formulas (2-1) to (2-51) may have a substituent.
  • A represents -CH 2- , -NR c- , an oxygen atom, a sulfur atom, -SO- or -SO 2-
  • B and D each independently represent -NR c- , an oxygen atom, a sulfur atom, -SO- or -SO 2-
  • E represents -NR c- , an oxygen atom or a sulfur atom.
  • R c represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, and a propyl group.
  • Rf is determined by the above formulas (1-8), (1-11), (1-12), (1-13), (1-14), (1-15), Formula (1-20), Formula (2-9) to Formula (2-11), Formula (2-24) to Formula (2-33), Formula (2-35) to Formula (2-43), Formula It is preferably any of groups represented by (2-47) and formulas (2-49) to (2-51).
  • the total number of ⁇ electrons contained in the ring structure in Rf is preferably 4 or more, more preferably 6 or more, still more preferably 8 or more, and particularly preferably 10 or more. , 20 or less, more preferably 18 or less.
  • Rf is any of the following (i-1) to (i-6).
  • the groups represented by the following formulas (i-1) to (i-6) may have a substituent.
  • J represents —CH 2 —, —NR d —, an oxygen atom, a sulfur atom, —SO— or —SO 2 —
  • R d represents a hydrogen atom or a carbon number of 1 to 6; Represents an alkyl group.
  • the “cyclic group having at least one of an aromatic hydrocarbon ring having 6 to 30 carbon atoms and an aromatic heterocyclic ring having 2 to 30 carbon atoms” of Rf may have one or more substituents. . When it has a plurality of substituents, the plurality of substituents may be the same or different from each other.
  • Examples of the substituent of “a cyclic group having at least one of an aromatic hydrocarbon ring having 6 to 30 carbon atoms and an aromatic heterocyclic ring having 2 to 30 carbon atoms” of Rf include, for example, a fluorine atom, a chlorine atom and the like.
  • Rx and Rb represent the same meaning as described above, and preferred examples thereof are also the same as described above.
  • the plurality of substituents may be the same or different.
  • at least one substituent selected from a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms is preferable.
  • R 14 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • Rc and Rb each independently represent a hydrogen atom or a substituent having 6 to 12 carbon atoms. It represents a good aromatic hydrocarbon ring group or an aromatic heterocyclic group which may have a substituent having 3 to 12 carbon atoms.
  • R 14 represents (i) a hydrogen atom or (ii) an alkyl group having 1 to 6 carbon atoms such as a methyl group or an ethyl group, and among them, R 14 is preferably a hydrogen atom.
  • Rc and Rb each independently have a hydrogen atom, an aromatic hydrocarbon ring group which may have a substituent having 6 to 12 carbon atoms, or a substituent having 3 to 12 carbon atoms. Represents an aromatic heterocyclic group.
  • Rc and Rb may be the same or different.
  • An aromatic hydrocarbon ring group of Rb and Rc which may have a substituent having 6 to 12 carbon atoms, or an aromatic heterocyclic group which may have a substituent having 3 to 12 carbon atoms, Specific examples include those having the same defined number of carbon atoms among those similar to Rf described above.
  • the substituents of Rb and Rc the same as the substituents of the above-mentioned Rf can be mentioned, and the preferable ones are also the same.
  • the compound has a plurality of substituents, they may be the same or different.
  • Rc and Rb are each independently preferably a hydrogen atom or an aromatic hydrocarbon ring group which may have a substituent having 6 to 12 carbon atoms, and further each independently is a hydrogen atom, a phenyl group or A naphthyl group is preferred, and a combination in which both Rc and Rb are simultaneously a hydrogen atom, a combination in which a hydrogen atom and a phenyl group, or a combination of a hydrogen atom and a naphthyl group are particularly preferred.
  • Rb and Rc have the same meaning as described above, and T indicates the direction in which Ga is bonded.
  • ⁇ black circle
  • the groups represented by the following formulas (ii-1) to (ii-45) and the groups represented by the following formulas (iii-1) to (iii-46) may have a substituent.
  • J represents —CH 2 —, —NR d —, an oxygen atom, a sulfur atom, Represents —SO— or —SO 2 —, and R d represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • Ga is a divalent organic group having 1 to 20 carbon atoms which may have a substituent, and preferably a divalent organic group having 3 to 20 carbon atoms which may have a substituent. is there. Ga is more preferably —CH 2 contained in (i) a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms and (ii) a divalent aliphatic hydrocarbon group having 3 to 20 carbon atoms.
  • R 15 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • Examples of the substituent of the organic group represented by Ga include an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group and a propyl group; and an alkoxy group having 1 to 5 carbon atoms such as a methoxy group, an ethoxy group and a propoxy group.
  • the substituent for Ga include an alkyl group having 1 to 5 carbon atoms such as a hydroxyl group, a methyl group, an ethyl group and a propyl group; an alkoxy group having 1 to 5 carbon atoms such as a methoxy group, an ethoxy group and an isopropoxy group; Group: a halogen atom such as a fluorine atom and a chlorine atom.
  • the “divalent aliphatic hydrocarbon group” is preferably a divalent chain-like aliphatic hydrocarbon group, and more preferably an alkylene group.
  • the “divalent aliphatic hydrocarbon group” preferably has 3 to 20 carbon atoms, more preferably 3 to 18 carbon atoms.
  • the “divalent aliphatic hydrocarbon group” is preferably a divalent aliphatic hydrocarbon group having 2 to 20 carbon atoms, and is preferably a divalent linear aliphatic hydrocarbon group having 2 to 18 carbon atoms. It is preferably a hydrogen group, more preferably an alkylene group having 2 to 18 carbon atoms.
  • the carbon number of Ga is preferably 4 to 16 carbon atoms, more preferably 5 to 14 carbon atoms, particularly preferably 6 to 12 carbon atoms, and most preferably 6 to 10 carbon atoms.
  • the structure of Ga is preferably an unsubstituted alkylene group having 4 to 16 carbon atoms, more preferably an unsubstituted alkylene group having 5 to 14 carbon atoms, and still more preferably an unsubstituted alkylene group having 6 to 12 carbon atoms.
  • An unsubstituted alkylene group having 6 to 10 carbon atoms is particularly preferred, and an n-hexylene group and an n-octylene group are most preferred.
  • both terminals of Ga be —CH 2 — (both terminals of Ga are not substituted).
  • Gb is an organic group having 1 to 20 carbon atoms which may have a substituent, and preferably an organic group having 3 to 20 carbon atoms which may have a substituent.
  • Gb is more preferably (i) an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and (ii) 3 to 20 carbon atoms optionally having a substituent.
  • R 15 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Among them, a hydrogen atom or a methyl group is preferable.
  • Rg represents a hydrogen atom, a methyl group, or a chlorine atom.
  • the “aliphatic hydrocarbon group” is preferably a chain-like aliphatic hydrocarbon group, and more preferably an alkyl group, an alkynyl group, or an alkenyl group.
  • the “aliphatic hydrocarbon group” is preferably an aliphatic hydrocarbon group having 2 to 20 carbon atoms, and is preferably a linear aliphatic hydrocarbon group having 2 to 18 carbon atoms. More preferably, it is an alkyl group (eg, an n-hexyl group), an alkynyl group (eg, a 2-butynyl group), or an alkenyl group (eg, a 1-butenyl group) of Formulas 2 to 18.
  • the carbon number of Gb is preferably 4 to 16 carbon atoms, more preferably 4 to 14 carbon atoms, particularly preferably 4 to 12 carbon atoms, and most preferably 4 to 10 carbon atoms.
  • the structure of Gb is preferably an unsubstituted alkyl group, alkynyl group or alkenyl group having 4 to 16 carbon atoms, more preferably an unsubstituted alkyl group, alkynyl group or alkenyl group having 4 to 14 carbon atoms. And more preferably an unsubstituted alkyl group, alkynyl group or alkenyl group having 4 to 12 carbon atoms, particularly preferably an unsubstituted alkyl group, alkynyl group or alkenyl group having 4 to 10 carbon atoms. More particularly preferred are up to 10 unsubstituted alkyl groups, most preferably n-hexyl groups.
  • Gb has 3 or more carbon atoms
  • one terminal of Gb is —CH 2 — (one terminal of Gb is not substituted).
  • -O- and -S- do not substitute a continuous -CH 2 -in the aliphatic hydrocarbon group (that is, -OO- and -S- It is preferable that the compound does not form an S- structure (that is, it is preferable to exclude the case where
  • (Ii) "It is preferably a linear aliphatic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent", and (iii) "It may have a substituent.
  • (Vi) Unsubstituted alkyl, alkynyl or alkenyl groups having 4 to 14 carbon atoms are even more preferable, and (vi) unsubstituted alkyl, alkynyl or alkenyl groups having 4 to 14 carbon atoms are more preferable; Even more preferred are "unsubstituted alkyl, alkynyl or alkenyl groups having 4 to 12 carbon atoms", and (vii) "unsubstituted alkyl, alkynyl or alkenyl groups having 4 to 10 carbon atoms” Is particularly preferable, and an unsubstituted al
  • Q represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.
  • alkyl group having 1 to 6 carbon atoms of the alkyl group having 1 to 6 carbon atoms which may have a substituent include a methyl group, an ethyl group, a propyl group, and an isopropyl group.
  • aromatic hydrocarbon groups having 6 to 12 carbon atoms such as phenyl and naphthalene groups.
  • R I to R IV each independently represent a hydrogen atom; a halogen atom such as a fluorine atom and a chlorine atom; a carbon atom such as a methyl group, an ethyl group and a propyl group.
  • R I to R IV are hydrogen atoms, or (ii) at least one of R I to R IV has 1 to 1 carbon atoms which may have a substituent.
  • it is an alkoxy group of No. 6 and the remainder is a hydrogen atom.
  • R I to R IV may be the same or different, and at least one of C R I to C R IV constituting the ring may be replaced by a nitrogen atom. Specific examples of the group in which at least one of CR I to CR IV is replaced by a nitrogen atom are shown below. However, the group in which at least one of CR I to CR IV is replaced by a nitrogen atom is not limited to these. [In each formula, R I to R IV represent the same meaning as described above, and preferred examples thereof are also the same as described above. ]
  • a halogen atom such as a fluorine atom and a chlorine atom
  • an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group and a propyl group
  • a cyano group such as a nitro group
  • an alkyl group having 1 to 6 carbon atoms in which at least one hydrogen atom is substituted with a halogen atom, such as a pentafluoroethyl group or a pentafluoroethyl group, or an alkoxy group having 1 to 6 carbon atoms, such as a methoxy group, an ethoxy group, or a propoxy group.
  • R 0 is plural, a plurality of R 0 is may be the same or different from each other.
  • p represents an integer of 0 to 3
  • p1 represents an integer of 0 to 4
  • p2 represents 0 or 1
  • p, p1 and p2 represent Both are preferably 0.
  • R 13 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • a 23 and A 24 each independently and independently represent the same meaning as A 2, and preferred examples thereof are also the same as A 2 .
  • B 21, B 22, Y 21, Y 22, L 21, L 22, R 31, R 32, d1, d2, e1, e2
  • B 21 , B 22 , Y 21 , Y 22 , L 21 , L 22 , R 31 , R 32 , d 1, d 2, e 1 and e 2 have the same meanings as described above, and preferred examples thereof are also included. Same as above.
  • the polymerizable compound (III) has a symmetrical structure around Ar, although not particularly limited (that is, Y 3 and Y 4 , A 23 and A 24 , B 21 and B 22 , Y It is preferable that 21 and Y 22 , L 21 and L 22 , R 31 and R 32 , d 1 and d 2, e 1 and e 2 are the same (symmetric with respect to Ar).
  • the polymerizable compound (III) is preferably a polymerizable compound represented by any of the following formulas (V-1) and (V-2), and is preferably the following formula (V-1) More preferred.
  • R, Q, R I to R IV , R 0 , Y 3 , Y 4 , A 23 , A 24 , B 21 , B 22 , Y 21 , Y 22 , L 21 , L 22 , R 31 , R 32 , d1, d2, e1, e2, p, p1 and p2 have the same meaning as described above, and preferred examples thereof are also the same as described above.
  • the polymerizable compound represented by the formula (V-1) is preferably a polymerizable compound (iii-1) represented by the following formula (iii-1), and is preferably a compound represented by the following formula (iii-2): And more preferably a polymerizable compound (iii-2) represented by the following formula (1) or (2).
  • R, Q, R I to R IV , R 0 , Y 3 , Y 4 , A 23 , A 24 , B 21 , B 22 , Y 21 , Y 22 , L 21 , L 22 , R 31 , R 32 , d 1, d 2, e 1, e 2 and p have the same meaning as described above, and preferred examples thereof are also the same as described above.
  • R I to R IV , Q and R have the same meanings as described above, and preferred examples thereof are also the same as described above.
  • K and l are each independently 1 to 18 Represents an integer.
  • the above-mentioned polymerizable compound (III) can be synthesized by combining known synthesis reactions. That is, various documents (for example, WO2012 / 141245, WO2012 / 147904, WO2014 / 010325, WO2013 / 0466781, WO2014 / 061709, WO WO 2014/126113, WO 2015/064698, WO 2015-140302, WO 2015/129654, WO 2015/141784, WO 2016/159193, WO 2012 / 169424, WO2012 / 176679, WO2015 / 122385, JP-A-2016-190818, WO2017 / 150622, and the like.
  • various documents for example, WO2012 / 141245, WO2012 / 147904, WO2014 / 010325, WO2013 / 0466781, WO2014 / 061709, WO WO 2014/126113, WO 2015/064698, WO 2015-140302, WO
  • R 3 Y 2 , B 2 , L 2 , A 2 , FG 2 , d, e, Y 3 , Y 4 , A 23 , A 24 , B 21 , B 22 , Y 21 , Y 22 , L 21 , L 22 , R 31 , R 32 , d 1, d 2, e 1, e 2, R, and R I to R IV are as described above. And the preferred examples are also the same as above.
  • the polymerizable composition contains at least a polymerizable compound (III) and a polymerization initiator.
  • the polymerizable composition is useful as a raw material for producing a polymer, an optical film, and an optically anisotropic material, as described later. According to the polymerizable composition, an optical film or the like having excellent in-plane uniformity of film thickness and improved in-plane uniformity of optical characteristics can be favorably produced.
  • the polymerization initiator is blended from the viewpoint of more efficiently performing the polymerization reaction of the polymerizable compound (III) contained in the polymerizable composition.
  • the polymerization initiator used include a radical polymerization initiator, an anionic polymerization initiator, and a cationic polymerization initiator.
  • radical polymerization initiator examples include a thermal radical generator, which is a compound that generates an active species capable of initiating polymerization of a polymerizable compound when heated;
  • a photo-radical generator which is a compound that generates an active species capable of initiating polymerization of a polymerizable compound by exposure to exposure light such as X-rays and X-rays; Is preferred.
  • Examples of the photo-radical generator include acetophenone compounds, biimidazole compounds, triazine compounds, O-acyl oxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, ⁇ -diketone compounds, and polynuclear quinone compounds. , A xanthone-based compound, a diazo-based compound, and an imidosulfonate-based compound. These compounds are components that generate active radicals or active acids or both active radicals and active acids upon exposure.
  • the photoradical generator can be used alone or in combination of two or more.
  • acetophenone-based compound examples include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1- [4- (phenylthio) phenyl] -octane-1,2-dione 2- (O-benzoyloxime) and the like.
  • biimidazole compound examples include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, , 2'-Bis (2-bromophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-Tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenyl-1 , 2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimi
  • hydrogen donor means a compound capable of donating a hydrogen atom to a radical generated from a biimidazole-based compound upon exposure.
  • hydrogen donor a mercaptan compound, an amine compound and the like defined below are preferable.
  • mercaptan-based compound examples include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-2,5-dimethyl Aminopyridine and the like can be mentioned.
  • Examples of the amine compound include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, ethyl-4-dimethylaminobenzoate, Examples thereof include 4-dimethylaminobenzoic acid and 4-dimethylaminobenzonitrile.
  • triazine-based compound examples include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5 -Methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl)- s-Triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl)
  • O-acyl oxime compound examples include 1- [4- (phenylthio) phenyl] -heptane-1,2-dione 2- (O-benzoyloxime) and 1- [4- (phenylthio) phenyl]- Octane-1,2-dione 2- (O-benzoyloxime), 1- [4- (benzoyl) phenyl] -octane-1,2-dione 2- (O-benzoyloxime), 1- [9-ethyl- 6- (2-Methylbenzoyl) -9H-carbazol-3-yl] -ethanone 1- (O-acetyloxime), 1- [9-ethyl-6- (3-methylbenzoyl) -9H-carbazole-3- Yl] -ethanone 1- (O-acetyloxime), 1- (9-ethyl-6-benzoyl-9H-carbazol-3-yl) -ethanone 1- (O-acety
  • ⁇ ⁇ As the photoradical generator, a commercially available product can be used as it is.
  • anionic polymerization initiator examples include alkyl lithium compounds; monolithium salts or monosodium salts such as biphenyl, naphthalene and pyrene; and polyfunctional initiators such as dilithium salts and trilithium salts.
  • Examples of the cationic polymerization initiator include protonic acids such as sulfuric acid, phosphoric acid, perchloric acid, and trifluoromethanesulfonic acid; Lewis acids such as boron trifluoride, aluminum chloride, titanium tetrachloride, and tin tetrachloride; A combination system of an aromatic onium salt or an aromatic onium salt and a reducing agent.
  • These polymerization initiators can be used alone or in combination of two or more.
  • the mixing ratio of the polymerization initiator is usually 0.1 to 30 parts by mass, preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the polymerizable compound contained in the polymerizable composition. Parts by weight.
  • the surfactant is not particularly limited, but is preferably a nonionic surfactant.
  • a nonionic surfactant a commercially available product may be used.
  • a nonionic surfactant which is an oligomer containing a fluorine-containing group, a hydrophilic group, and a lipophilic group, such as Surflon manufactured by AGC Seimi Chemical Co., Ltd.
  • the mixing ratio of the surfactant is usually 0.01 to 10 parts by mass, preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the polymerizable compound contained in the polymerizable composition. 2 parts by mass.
  • the polymerizable composition may further contain other components in addition to the polymerizable compound, the polymerization initiator, and the surfactant.
  • Other components include metals, metal complexes, dyes, pigments, fluorescent materials, phosphorescent materials, leveling agents, thixotropic agents, gelling agents, polysaccharides, ultraviolet absorbers, infrared absorbers, antioxidants, ion exchange resins, Metal oxides such as titanium oxide are exemplified.
  • Other components include other copolymerizable monomers.
  • the polymerizable composition can be usually prepared by mixing and dissolving a predetermined amount of a polymerizable compound, a polymerization initiator, and other components to be added as required in a suitable organic solvent. .
  • Examples of the organic solvent used for preparing the polymerizable composition include ketones such as cyclopentanone, cyclohexanone, and methyl ethyl ketone; acetates such as butyl acetate and amyl acetate; halogenated hydrocarbons such as chloroform, dichloromethane, and dichloroethane; , 4-dioxane, cyclopentyl methyl ether, tetrahydrofuran, tetrahydropyran, 1,3-dioxolan and the like; and the like.
  • ketones such as cyclopentanone, cyclohexanone, and methyl ethyl ketone
  • acetates such as butyl acetate and amyl acetate
  • halogenated hydrocarbons such as chloroform, dichloromethane, and dichloroethane
  • 4-dioxane 4-dioxane, cyclopentyl
  • the polymer is obtained by polymerizing the above-mentioned polymerizable compound (III) or the above-mentioned polymerizable composition.
  • polymerization means a chemical reaction in a broad sense including a cross-linking reaction in addition to a normal polymerization reaction.
  • the polymer usually has a monomer unit derived from the polymerizable compound (III).
  • the polymer is prepared using the above-mentioned polymerizable compound (III) or the above-mentioned polymerizable composition, it can be used favorably as a constituent material of an optical film or the like.
  • the polymer is not particularly limited, and can be used in an arbitrary shape according to the use such as a film, a powder, and a layer in which the powder is aggregated.
  • a polymer film can be favorably used as a constituent material of an optical film and an optically anisotropic material described later, and a polymer powder is used for a paint, an anti-counterfeit article, a security article, and the like.
  • the layer made of the polymer powder can be favorably used as a constituent material of the optically anisotropic body.
  • the polymer is specifically ( ⁇ ) subjected to the polymerization reaction of the above-mentioned polymerizable compound (III) or the above-mentioned polymerizable composition in the presence of an appropriate organic solvent, and Isolating the polymer, dissolving the obtained polymer in a suitable organic solvent to prepare a solution, applying the solution on a suitable substrate, drying the obtained coating film, and optionally heating.
  • the organic solvent used in the polymerization reaction in the method ( ⁇ ) is not particularly limited as long as it is inert.
  • aromatic hydrocarbons such as toluene, xylene and mesitylene
  • ketones such as cyclohexanone, cyclopentanone and methyl ethyl ketone
  • acetates such as butyl acetate and amyl acetate
  • halogenated hydrocarbons such as chloroform, dichloromethane and dichloroethane
  • Ethers such as cyclopentyl methyl ether, tetrahydrofuran, and tetrahydropyran; and the like.
  • those having a boiling point of 60 to 250 ° C are preferable, and those having a boiling point of 60 to 150 ° C are more preferable from the viewpoint of excellent handling properties.
  • the organic solvent for dissolving the isolated polymer and the organic solvent used in the method ( ⁇ ) include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, Ketone solvents such as cyclohexanone; ester solvents such as butyl acetate and amyl acetate; halogenated hydrocarbon solvents such as dichloromethane, chloroform and dichloroethane; tetrahydrofuran, tetrahydropyran, 1,2-dimethoxyethane, 1,4-dioxane, Ether solvents such as cyclopentyl methyl ether and 1,3-dioxolane; N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, ⁇ -butyrolactone, N-methylpyrrolidone (N-methyl-2-pyrrolidone) and the like
  • a substrate of a known and commonly used material can be used irrespective of organic or inorganic.
  • organic material polycycloolefin [for example, ZEONEX, ZEONOR (registered trademark; manufactured by Nippon Zeon), ARTON (registered trademark; manufactured by JSR), and Apel (registered trademark; manufactured by Mitsui Chemicals, Inc.)], Polyethylene terephthalate, polycarbonate, polyimide, polyamide, polymethyl methacrylate, polystyrene, polyvinyl chloride, polytetrafluoroethylene, cellulose, cellulose triacetate, polyether sulfone, etc., and inorganic materials such as silicon, glass, calcite, etc.
  • the substrate to be used may be a single layer or a laminate.
  • a substrate made of an organic material is preferable, and a resin film in which the organic material is formed into a film is more preferable.
  • examples of the substrate include a substrate used for producing an optically anisotropic body described later.
  • the drying temperature is not particularly limited as long as the solvent can be removed, but the lower limit temperature is preferably 50 ° C or higher, and more preferably 70 ° C or higher, from the viewpoint that a constant temperature can be stably obtained. More preferably, there is.
  • the upper limit of the drying temperature is preferably 200 ° C. or lower, more preferably 195 ° C. or lower, from the viewpoint of not adversely affecting the substrate.
  • Examples of the method of polymerizing the above-mentioned polymerizable compound (III) or the above-mentioned polymerizable composition include a method of irradiating with active energy rays and a thermal polymerization method.
  • the method of irradiating with an active energy ray is preferable because of the progress of the process.
  • a method of irradiating light such as ultraviolet light is preferable because of easy operation.
  • the temperature at which light such as ultraviolet light is irradiated is not particularly limited as long as the liquid crystal phase can be maintained.
  • the temperature is 20 ° C. or higher.
  • the upper limit of the temperature at which light such as ultraviolet rays is irradiated is preferably 200 ° C. or lower, more preferably 195 ° C. or lower, from the viewpoint of not adversely affecting the substrate.
  • the temperature at the time of light irradiation is preferably 100 ° C. or less.
  • the light irradiation intensity is usually in the range of 1 W / m 2 to 10 kW / m 2 , preferably in the range of 5 W / m 2 to 2 kW / m 2 .
  • the dose of ultraviolet rays is preferably 0.1 mJ / cm 2 or more, more preferably 0.5 mJ / cm 2 or more, preferably 5000 mJ / cm 2 or less, more preferably 4000 mJ / cm 2 or less.
  • the polymer obtained as described above can be transferred from the substrate and used, or can be peeled off from the substrate and used alone, or can be used as it is as a constituent material of an optical film without peeling off the substrate You can also. Further, the polymer peeled from the substrate can be used after being pulverized by a known method into powder.
  • the number average molecular weight of the polymer obtained as described above is preferably 500 to 500,000, more preferably 5,000 to 300,000. When the number average molecular weight is in such a range, high hardness is obtained and handleability is excellent, which is desirable.
  • the number average molecular weight of the polymer can be measured by gel permeation chromatography (GPC) using monodispersed polystyrene as a standard sample and tetrahydrofuran as an eluent.
  • an optical film having excellent in-plane uniformity of film thickness and improved in-plane uniformity of optical characteristics can be obtained.
  • the optical film is formed using a polymer and / or a polymerizable compound, and includes a layer having an optical function.
  • the optical function simply means transmission, reflection, refraction, birefringence, and the like.
  • the optical film may be an optical film using a polymer as a main constituent material of the layer having an optical function, or an optical film in which the layer having an optical function contains a polymerizable compound.
  • the occupation ratio of the polymer is more than 50% by mass when all components of the layer having an optical function are 100% by mass.
  • the optical film containing the polymerizable compound contains the polymerizable compound in an amount of 0.01% by mass or more when all the components of the layer having an optical function are 100% by mass.
  • the optical film is in the form as it is formed on the alignment substrate (orientation substrate / (alignment film) / optical film) which may have an alignment film, and is formed on a transparent substrate film different from the alignment substrate. It may be in the form of a transferred film (transparent substrate film / optical film) or, if the optical film has self-supporting properties, in the form of an optical film single layer (optical film).
  • the alignment film and the alignment substrate the same substrate and alignment film as an optical anisotropic body described later can be used as the alignment film and the alignment substrate.
  • the optical film is obtained by applying a solution containing a polymerizable compound (A) or a solution of the polymerizable composition on an alignment substrate, drying the obtained coating film, and performing heat treatment (alignment of liquid crystal), and A method of performing light irradiation and / or heat treatment (polymerization), or (B) a solution of a liquid crystalline polymer obtained by polymerizing a polymerizable compound or a polymerizable composition is applied on an alignment substrate, and optionally obtained. It can be produced by a method of drying the obtained coating film, or a method of applying a solution containing the polymerizable compound and the resin (C) on an alignment substrate and drying the obtained coating film.
  • the optical film can be used for an optical anisotropic body, an alignment film for a liquid crystal display element, a color filter, a low-pass filter, a light polarizing prism, various optical filters, and the like.
  • the optical film is determined from the phase difference at a wavelength of 400 nm to 800 nm measured with a Mueller Matrix Polarimeter Axoscan. It is preferable that the following ⁇ value and ⁇ value are within a predetermined range. Specifically, the ⁇ value is preferably from 0.70 to 0.99, more preferably from 0.75 to 0.90. Further, the ⁇ value is preferably from 1.00 to 1.25, and more preferably from 1.01 to 1.20.
  • the optically anisotropic body has a layer containing a polymer as a constituent material.
  • the optically anisotropic body can be obtained, for example, by forming an alignment film on a substrate and further forming a polymer layer (liquid crystal layer) on the alignment film.
  • the optically anisotropic body may be a layer in which a polymer layer (liquid crystal layer) is directly formed on a substrate, or may be a layer only of a polymer layer (liquid crystal layer).
  • the polymer layer may be a film-like polymer or may be a powdery polymer aggregate.
  • the alignment film is formed on the surface of the substrate in order to regulate the alignment of the polymerizable compound in one direction within the plane.
  • a solution composition for alignment film
  • a polymer such as polyimide, polyvinyl alcohol, polyester, polyarylate, polyamide imide, or polyether imide is applied on a substrate in a film form, dried, and dried in one direction. Rubbing treatment or the like.
  • the thickness of the alignment film is preferably from 0.001 to 5 ⁇ m, more preferably from 0.001 to 1.0 ⁇ m.
  • the method of the rubbing treatment is not particularly limited, and examples thereof include a method of rubbing the alignment film in a certain direction with a roll made of synthetic fiber such as nylon or natural fiber such as cotton, or a roll around which felt is wound.
  • the alignment film is preferably washed with isopropyl alcohol or the like in order to remove the fine powder (foreign matter) generated during the rubbing treatment and to keep the surface of the alignment film clean.
  • a method of irradiating polarized ultraviolet light to the surface of the alignment film can also have a function of regulating the alignment in one direction in the plane.
  • the substrate on which the alignment film is formed examples include a glass substrate and a substrate made of a synthetic resin film.
  • synthetic resin acrylic resin, polycarbonate resin, polyether sulfone resin, polyethylene terephthalate resin, polyimide resin, polymethyl methacrylate resin, polysulfone resin, polyarylate resin, polyethylene resin, polystyrene resin, polyvinyl chloride resin, cellulose diacetate , Cellulose triacetate, and thermoplastic resins such as alicyclic olefin polymers.
  • Examples of the alicyclic olefin polymer include cyclic olefin random multi-component copolymers described in JP-A-05-310845 and US Pat. No. 5,179,171, JP-A 05-97978, and US Pat. No. 5,202,388.
  • a hydrogenated polymer described in JP-A-11-124429 International Publication No. WO 99/20676
  • a hydrogenated product of the thermoplastic dicyclopentadiene-based ring-opened polymer described in JP-A-11-124429. .
  • the same method (the above ( ⁇ ) and ( ⁇ )) as described in the section of the polymer can be used.
  • the thickness of the obtained liquid crystal layer is not particularly limited, but is usually 1 to 10 ⁇ m.
  • optical anisotropic body there is no particular limitation, and a retardation plate, a viewing angle widening plate, and the like can be given.
  • the optically anisotropic body is obtained from a phase difference at a wavelength of 400 nm to 800 nm measured by a Mueller Matrix Polarimeter Axoscan. It is preferable that the following ⁇ value and ⁇ value are within a predetermined range. Specifically, the ⁇ value is preferably from 0.70 to 0.99, more preferably from 0.75 to 0.90. Further, the ⁇ value is preferably from 1.00 to 1.25, and more preferably from 1.01 to 1.25.
  • ⁇ (Phase difference at 450 nm) / (Phase difference at 550 nm)
  • ⁇ (phase difference at 650 nm) / (phase difference at 550 nm)
  • the polarizing plate includes an optically anisotropic body and a polarizing film.
  • Specific examples of the polarizing plate include those obtained by laminating an optically anisotropic body on a polarizing film directly or via another layer (such as a glass plate).
  • the method for producing the polarizing film is not particularly limited.
  • a method of producing a PVA-based polarizing film a method of uniaxially stretching after adsorbing iodine ions to the PVA-based film, a method of adsorbing iodine ions after uniaxially stretching the PVA-based film, A method of simultaneously performing iodine ion adsorption and uniaxial stretching, a method of uniaxially stretching a PVA-based film after dyeing it with a dichroic dye, a method of uniaxially stretching a PVA-based film and then dyeing it with a dichroic dye, PVA-based A method of simultaneously dyeing a film with a dichroic dye and uniaxially stretching the film is exemplified.
  • a method for producing a polyene-based polarizing film a method in which a PVA-based film is uniaxially stretched and then heated and dehydrated in the presence of a dehydration catalyst, and a method in which a polyvinyl chloride-based film is uniaxially stretched and then subjected to a dehydrochlorination catalyst And a known method such as a method of heating and dewatering.
  • the polarizing film and the optically anisotropic body may be in contact with each other via an adhesive layer made of an adhesive (including an adhesive).
  • the average thickness of the adhesive layer is usually 0.01 ⁇ m to 30 ⁇ m, preferably 0.1 ⁇ m to 15 ⁇ m.
  • the adhesive layer is preferably a layer having a tensile breaking strength of 40 MPa or less according to JIS K7113.
  • Examples of the adhesive constituting the adhesive layer include an acrylic adhesive, a urethane adhesive, a polyester adhesive, a polyvinyl alcohol adhesive, a polyolefin adhesive, a modified polyolefin adhesive, a polyvinyl alkyl ether adhesive, a rubber adhesive, and vinyl chloride.
  • Ethylene adhesives, and acrylate ester adhesives such as ethylene-methyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl methacrylate copolymer and ethylene-ethyl acrylate copolymer, etc. Is mentioned.
  • the polarizing plate uses an optically anisotropic body, it has excellent in-plane uniformity of optical characteristics while having reverse wavelength dispersion.
  • a display device having a panel and an antireflection film can be suitably manufactured.
  • the panel include a liquid crystal panel and an organic electroluminescence panel.
  • the display device include a flat panel display device including a polarizing plate and a liquid crystal panel, and an organic electroluminescence display device including a liquid crystal panel and an organic electroluminescence panel.
  • Step 1 Synthesis of compound A> First, a compound A represented by the following structural formula was synthesized by the method described in WO 2017/150622 (Step 1).
  • ⁇ Step 2 Synthesis of compound 1>
  • 83.05 g (0.397 mol) of trans-1,4-cyclohexanedicarboxylic acid dichloride and 830 g of cyclopentyl methyl ether (CPME) were added to a three-necked reactor equipped with a thermometer.
  • 100 g (0.378 mol) of the compound A synthesized in the previous step 1 was added, and the reactor was immersed in an ice bath to adjust the internal temperature of the reaction solution to 0 ° C.
  • 40.2 g (0.397 mol) of triethylamine (Et 3 N) was slowly dropped over 20 minutes while maintaining the reaction solution internal temperature at 10 ° C. or lower.
  • Example 2 Synthesis of compound 1
  • CPME cyclopentyl methyl ether
  • the mixture was further stirred at 10 ° C. or lower for 1 hour.
  • 250 g of water was added to the obtained reaction solution, and the mixture was stirred at 50 ° C. for 2 hours.
  • 250 g of water was newly added, and the mixture was stirred at 50 ° C. for 2 hours. This operation was performed three times in total.
  • the organic layer was further washed by stirring at 40 ° C. for 30 minutes using 416 g of a buffer solution (pH 5.5) composed of acetic acid and sodium acetate at a concentration of 1 mol / liter. After washing, liquid separation was performed, and the aqueous layer was extracted.
  • Example 3 Synthesis of compound 1
  • CPME cyclopentyl methyl ether
  • the mixture was further stirred at 10 ° C. or lower for 1 hour.
  • 250 g of water was added to the obtained reaction solution, and the mixture was stirred at 50 ° C. for 2 hours.
  • 250 g of water was newly added, and the mixture was stirred at 50 ° C. for 2 hours. This operation was performed three times in total.
  • the concentration of Compound 1 in the organic layer (solution (X)) at this stage was determined by high performance liquid chromatography to be 10.59% by mass.
  • the organic layer at this stage contained 45.0 g of the compound X represented by the above structural formula.
  • the filtrate was washed with normal hexane and then dried under vacuum to obtain 99.22 g of a white solid (mixture Y of compound 1 and compound X) as an intermediate.
  • a white solid mixture Y of compound 1 and compound X
  • the content of compound 1 relative to the white solid was 92.5 mass%. %Met.
  • the yield of Compound 1 was 57.97 mol% based on Compound A.
  • Example 4 Synthesis of compound 1
  • CPME cyclopentyl methyl ether
  • the mixture was further stirred at 10 ° C. or lower for 1 hour.
  • 250 g of water was added to the obtained reaction solution, and the mixture was stirred at 50 ° C. for 2 hours.
  • 250 g of water was newly added, and the mixture was stirred at 50 ° C. for 2 hours. This operation was performed three times in total.
  • the organic layer was further washed by stirring at 40 ° C. for 30 minutes using 416 g of a buffer solution (pH 5.5) composed of acetic acid and sodium acetate at a concentration of 1 mol / liter. After washing, liquid separation was performed, and the aqueous layer was extracted.
  • Example 5 Synthesis of compound 1
  • CPME cyclopentyl methyl ether
  • Example 6 Synthesis of compound 1
  • CPME cyclopentyl methyl ether
  • the mixture was further stirred at 10 ° C. or lower for 1 hour.
  • 250 g of water was added to the obtained reaction solution, and the mixture was stirred at 50 ° C. for 2 hours.
  • 250 g of water was newly added, and the mixture was stirred at 50 ° C. for 2 hours. This operation was performed three times in total.
  • the organic layer was further washed by stirring at 40 ° C. for 30 minutes using 416 g of a buffer solution (pH 5.5) composed of acetic acid and sodium acetate at a concentration of 1 mol / liter. After washing, liquid separation was performed, and the aqueous layer was extracted.
  • the obtained organic layer was gradually cooled, and slowly stirred at 0 ° C. for 1 hour to precipitate a solid.
  • the precipitated solid was removed by filtration to obtain a filtrate.
  • the filtrate in the filter was washed with 100 g of separately prepared CPME cooled to 0 ° C., and the washing solution obtained by this washing and the previous filtrate were combined.
  • the filtrate combined with this washing solution was further washed with 416 g of a buffer solution (pH 5.5) consisting of acetic acid and sodium acetate having a concentration of 1 mol / liter by stirring at 40 ° C. for 30 minutes. After washing, liquid separation was carried out, and the aqueous layer was extracted.
  • the mixture was further stirred at 10 ° C. or lower for 1 hour.
  • 250 g of water was added to the obtained reaction solution, and the mixture was stirred at 50 ° C. for 2 hours.
  • 250 g of water was newly added, and the mixture was stirred at 50 ° C. for 2 hours. This operation was performed three times in total.
  • the organic layer was further washed by stirring at 40 ° C. for 30 minutes using 416 g of a buffer solution (pH 5.5) composed of acetic acid and sodium acetate at a concentration of 1 mol / liter. After washing, liquid separation was performed, and the aqueous layer was extracted.
  • the obtained organic layer was gradually cooled, and slowly stirred at 0 ° C. for 1 hour to precipitate a solid.
  • the precipitated solid was removed by filtration to obtain a filtrate.
  • the filtrate in the filter was washed with 100 g of separately prepared CPME cooled to 0 ° C., and the washing solution obtained by this washing was combined with the previous filtrate.
  • the filtrate combined with the washing liquid was separated, and the organic layer (oil layer) obtained by extracting the aqueous layer was added with 1200 g of normal hexane and gradually cooled to 0 ° C. to precipitate a solid.
  • the solid was collected by filtration.
  • the mixture was further stirred at 10 ° C. or lower for 1 hour.
  • 250 g of water was added to the obtained reaction solution, and the mixture was stirred at 50 ° C. for 2 hours.
  • 250 g of water was newly added, and the mixture was stirred at 50 ° C. for 2 hours. This operation was performed three times in total.
  • the concentration of Compound 1 in the organic layer (solution (X)) at this stage was determined by high performance liquid chromatography to be 10.55% by mass. Note that the organic layer at this stage contained 44.6 g of the compound X represented by the above structural formula.
  • the precipitate was mixed with toluene, and the insoluble matter was removed by filtration.
  • the filtrate was concentrated under reduced pressure, and heptane was added to the obtained concentrate.
  • the precipitate was taken out by filtration and dried under vacuum to obtain 7.8 g of a powder (intermediate) containing the compound represented by the above formula (6-a) (compound (I)).
  • the yield of the compound represented by the above formula (6-a) was 40.00 mol% based on the compound represented by the above formula (A-IV).
  • the content (purity) of the compound represented by the above formula (6-a) with respect to the obtained powder was 70.0% by mass.
  • Step 1 Synthesis of compound B>
  • 100 g (0.605 mol) of 2-hydrazinobenzothiazole was added to 750 g of N, N-dimethylformamide in a nitrogen stream, and then 119.9 g (0.1 g) of 1-bromohexane. 726 mol).
  • 192.72 g (0.908 mol) of tripotassium phosphate was added, and the whole volume was stirred at 100 ° C. for 3 hours.
  • reaction solution was cooled to 60 ° C., and 750 g of toluene and 750 g of water were added to the cooled reaction solution, and the mixture was stirred at 60 ° C. for 15 minutes.
  • reaction solution was allowed to stand, it was separated into three layers. Two lower layers were extracted.
  • 430 g of a 10% by mass aqueous sodium chloride solution was added, and the mixture was stirred at 60 ° C. for 15 minutes.
  • the liquid layer was separated, the aqueous layer was extracted, and the toluene layer (organic layer) obtained was concentrated under reduced pressure to extract 560 g of toluene.
  • the structure of Compound B was identified by 1 H-NMR. The 1 H-NMR spectrum data is shown below.
  • Step 2 Synthesis of polymerizable compound 1>
  • a white solid mixture Y of compound 1 and compound X
  • a pure amount of compound 1 10.00 g (23.90 mmol)
  • 100 g of chloroform and 3.49 g of dimethylformamide (DMF) were added, and the mixture was cooled to 10 ° C or lower.
  • 3.27 g (27.48 mmol) of thionyl chloride was added dropwise while controlling the reaction temperature to 10 ° C. or lower.
  • reaction solution was returned to 25 ° C and stirred for 1 hour. After the completion of the reaction, the reaction solution was concentrated by an evaporator until the amount of the reaction solution became 1/4. Thereafter, 25 g of chloroform was added to obtain a chloroform solution of the acid chloride of Compound 1.
  • a three-necked reactor equipped with a thermometer 1.50 g (10.86 mmol) of 2,5-dihydroxybenzaldehyde and 6.98 g (65.17 mmol) of 2,6-lutidine as a base were placed in a nitrogen stream. And 50 g of chloroform, and the resulting solution was cooled to 10 ° C. or lower.
  • Example 8 Synthesis of polymerizable compound 1
  • a white solid (mixture Y of compound 1 and compound X) as an intermediate synthesized in Example 1 was 10.80 g (10.00 g (23% in pure amount of compound 1). .90 mmol)) instead of using: 10.89 g of a white solid (mixture Y of compound 1 and compound X) as an intermediate synthesized in Example 2 (10.00 g (23.
  • a polymerizable compound 1 was synthesized in the same manner as in Example 7, except that 90 mmol)) was used. As a result, 11.6 g of the polymerizable compound 1 was obtained.
  • the isolation yield of the polymerizable compound 1 was 91.3 mol% based on 2,5-dihydroxybenzaldehyde.
  • Example 9 Synthesis of polymerizable compound 1
  • a white solid (mixture Y of compound 1 and compound X) as an intermediate synthesized in Example 1 was 10.80 g (10.00 g (23% in pure amount of compound 1). .90 mmol)) instead of using: 10.81 g of a white solid (mixture Y of compound 1 and compound X) as an intermediate synthesized in Example 3 (10.00 g (23.
  • a polymerizable compound 1 was synthesized in the same manner as in Example 7, except that 90 mmol)) was used. As a result, 11.7 g of polymerizable compound 1 was obtained.
  • the isolation yield of the polymerizable compound 1 was 92.0 mol% based on 2,5-dihydroxybenzaldehyde.
  • Example 10 Synthesis of polymerizable compound 1
  • a white solid (mixture Y of compound 1 and compound X) as an intermediate synthesized in Example 1 was 10.80 g (10.00 g (23% in pure amount of compound 1).
  • a white solid (mixture Y of compound 1 and compound X) as an intermediate synthesized in Example 4 10.81 g (10.00 g (23.
  • a polymerizable compound 1 was synthesized in the same manner as in Example 7, except that 90 mmol)) was used. As a result, 11.8 g of the polymerizable compound 1 was obtained.
  • the isolation yield of the polymerizable compound 1 was 92.8 mol% based on 2,5-dihydroxybenzaldehyde.
  • Example 11 Synthesis of polymerizable compound 1
  • a white solid (mixture Y of compound 1 and compound X) as an intermediate synthesized in Example 1 was 10.80 g (10.00 g (23% in pure amount of compound 1). .90 mmol)
  • 10.89 g of a white solid (mixture Y of compound 1 and compound X) as an intermediate synthesized in Example 5 (10.00 g (23.
  • a polymerizable compound 1 was synthesized in the same manner as in Example 7, except that 90 mmol)) was used.
  • the isolation yield of the polymerizable compound 1 was 90.5 mol% based on 2,5-dihydroxybenzaldehyde.
  • Example 12 Synthesis of polymerizable compound 1
  • a white solid (mixture Y of compound 1 and compound X) as an intermediate synthesized in Example 1 was 10.80 g (10.00 g (23% in pure amount of compound 1). .90 mmol)), 11.14 g of a white solid (mixture Y of compound 1 and compound X) as an intermediate synthesized in Example 6 (10.00 g of pure compound 1 (23.90 mmol)).
  • a polymerizable compound 1 was synthesized in the same manner as in Example 7, except that 90 mmol)) was used. As a result, 11.6 g of the polymerizable compound 1 was obtained.
  • the isolation yield of the polymerizable compound 1 was 91.3 mol% based on 2,5-dihydroxybenzaldehyde.
  • Step 1 Synthesis of compound C>
  • 500.5 g (2.69 mol) of 1-naphthylacetic acid and 1049 g of toluene were charged into a three-necked reactor equipped with a thermometer.
  • 349.5 g (2.56 mol) of 6-chloro-1-hexanol and 48.6 g (0.26 mol) of paratoluenesulfonic acid monohydrate were added to prepare a solution.
  • the prepared solution was heated, and azeotropic dehydration (internal temperature: about 95 ° C.) was performed for 2 hours while discharging generated water out of the reaction system.
  • Step 2 Synthesis of compound D>
  • 59.52 g (55.35 g (0.182 mol) as a net amount of compound C) of the light brown oil containing compound C synthesized in the above step 1 and N 235 g of -methyl-2-pyrrolidone was charged to obtain a uniform solution.
  • 25.0 g (0.151 mol) of 2-hydrazinobenzothiazole was added to the homogeneous solution.
  • 48.18 g (0.227 mol) of tripotassium phosphate was added, and the whole volume was stirred at 100 ° C. for 3 hours.
  • the reaction solution was cooled to 60 ° C., and after adding 312.5 g of ethyl acetate to the cooled reaction solution, filtration was performed while maintaining the temperature at 60 ° C.
  • the organic layer which was the filtrate, was slowly dropped into 250 g of a 0.5 N aqueous citric acid solution, stirred at an internal temperature of 60 ° C. for 30 minutes, and then the aqueous layer was extracted. Further, 275 g of a 9.1 mass% aqueous sodium chloride solution was added to the organic layer, and the mixture was stirred at an internal temperature of 60 ° C. for 30 minutes, and then allowed to stand for 30 minutes to extract an aqueous layer.
  • Step 3 Synthesis of polymerizable compound 2>
  • a white solid as an intermediate synthesized in Example 3 32.43 g (as a pure amount of compound 1) 30.00 g (71.7 mmol)
  • 300 g of chloroform and 10.5 g (143.4 mmol) of N, N-dimethylformamide (DMF) were added, and the mixture was cooled to 10 ° C. or lower.
  • 9.81 g (82.44 mmol) of thionyl chloride was added dropwise while controlling the reaction temperature to 10 ° C. or lower.
  • the whole amount of the chloroform solution of the acid chloride of Compound 1 synthesized previously was slowly added dropwise while maintaining the reaction solution internal temperature at 10 ° C. or lower. After completion of the dropwise addition, the whole volume was further stirred at 5 to 10 ° C. for 1 hour to carry out a reaction. After completion of the reaction, while maintaining the temperature at 10 ° C. or lower, 120 g of a 1.0 N aqueous hydrochloric acid solution was added to the reaction solution, and the reaction was stirred at 10 ° C. or lower for 30 minutes.
  • the organic layer obtained by extracting the aqueous layer was cooled to 25 ° C., 1.5 g of LocaHelp # 479 was added, and the mixture was stirred for 30 minutes. Thereafter, filtration was performed with a Kiriyama funnel covered with 1 g of LocaHelp # 479 to remove LocaHelp # 479. 180 g of chloroform was extracted with a rotary evaporator from the organic layer obtained by removing LocaHelp # 479, and concentrated. 210 g of hexane was added to the organic layer obtained by concentration over 1 hour to precipitate a solid, and a pale yellow solid was obtained by filtration.
  • the obtained pale yellow solid was dissolved in 120 g of tetrahydrofuran at 25 ° C., 1.5 g of LocaHelp # 479 was added, and the mixture was stirred for 30 minutes. Thereafter, filtration was performed with a Kiriyama funnel covered with 1 g of LocaHelp # 479 to remove LocaHelp # 479. 165 g of methanol was slowly dropped at 15 ° C. to the organic layer obtained by removing LocaHelp # 479 to precipitate a solid, which was filtered to obtain a solid. The obtained solid was dried with a vacuum drier to obtain 40.2 g of the polymerizable compound 2 as a pale yellow solid. The yield of the polymerizable compound 2 was 91.0 mol% based on 2,5-dihydroxybenzaldehyde. The structure of the polymerizable compound 2 was identified by 1 H-NMR. The 1 H-NMR spectrum data is shown below.
  • Example 14 Synthesis of polymerizable compound 2
  • polymerizable compound 2 was synthesized in the same manner as in Example 13.
  • 40.6 g of polymerizable compound 2 was obtained.
  • a method for producing an intermediate which can efficiently produce an intermediate containing compound (I) at a high concentration.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Le but de la présente invention est de fournir un procédé de production d'un intermédiaire capable de produire de manière efficace un intermédiaire contenant un composé (I) à une concentration élevée. La présente invention concerne un procédé de production d'un intermédiaire qui comprend : (i) une étape (α) qui consiste à obtenir une solution (X) contenant un composé (I) représenté par la formule (I) et un composé (II) représenté par la formule (II) ; et (ii) une étape (β) qui consiste à obtenir un intermédiaire contenant 86 % en masse ou plus du composé (I) par ajout d'un solvant protique à la solution (X) pour précipiter le composé (II) et par élimination du composé précipité (II).
PCT/JP2019/035933 2018-09-19 2019-09-12 Procédé de production d'un intermédiaire WO2020059634A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009116657A1 (fr) * 2008-03-18 2009-09-24 住友化学株式会社 Procédé de fabrication d'un monoester d'acide cycloalcanedicarboxylique
WO2011068138A1 (fr) * 2009-12-01 2011-06-09 住友化学株式会社 Procédé de préparation de monoesters d'acides cycloalcanedicarboxyliques
WO2016159193A1 (fr) * 2015-03-31 2016-10-06 日本ゼオン株式会社 Mélange de composé polymérisable et son procédé de production
JP2016183132A (ja) * 2015-03-26 2016-10-20 日本ゼオン株式会社 シクロヘキサンジカルボン酸モノエステル化合物の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009116657A1 (fr) * 2008-03-18 2009-09-24 住友化学株式会社 Procédé de fabrication d'un monoester d'acide cycloalcanedicarboxylique
WO2011068138A1 (fr) * 2009-12-01 2011-06-09 住友化学株式会社 Procédé de préparation de monoesters d'acides cycloalcanedicarboxyliques
JP2016183132A (ja) * 2015-03-26 2016-10-20 日本ゼオン株式会社 シクロヘキサンジカルボン酸モノエステル化合物の製造方法
WO2016159193A1 (fr) * 2015-03-31 2016-10-06 日本ゼオン株式会社 Mélange de composé polymérisable et son procédé de production

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