WO2021131856A1 - Procédé de fabrication de composé cristallin liquide - Google Patents

Procédé de fabrication de composé cristallin liquide Download PDF

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WO2021131856A1
WO2021131856A1 PCT/JP2020/046554 JP2020046554W WO2021131856A1 WO 2021131856 A1 WO2021131856 A1 WO 2021131856A1 JP 2020046554 W JP2020046554 W JP 2020046554W WO 2021131856 A1 WO2021131856 A1 WO 2021131856A1
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group
carbon atoms
particles
liquid crystal
methanol
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PCT/JP2020/046554
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Japanese (ja)
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坂本　圭
加奈子 佐貫
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日本ゼオン株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C07D277/82—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters

Definitions

  • the present invention relates to a method for producing a liquid crystal compound.
  • Non-Patent Document 1 in general, in a crystallization method for precipitating a target substance from a solution, it is important to slowly generate a supersaturation degree in order to obtain particles having a large particle size having excellent filterability (for example). , See Non-Patent Document 1).
  • an object of the present invention is to provide a technique for obtaining a liquid crystal compound contained in a solution by precipitating it as particles having a large particle size having excellent filterability.
  • the present inventors have conducted diligent studies to achieve the above object. Then, when the poor solvent is added to the solution containing the liquid crystal compound to precipitate the liquid crystal compound, the present inventors start the precipitation of particles with a predetermined amount of the poor solvent added, and after the start of precipitation of the particles.
  • the present invention has been completed by newly finding that coarse particles of a liquid crystal compound can be obtained by continuing addition and stirring of a poor solvent while maintaining a high hypersaturation state.
  • the present invention aims to advantageously solve the above problems, and according to the present invention, the following method for producing a liquid crystal compound is provided.
  • a method for producing a liquid crystal compound wherein the solution is stirred while adding the poor solvent so that the saturated solubility of the sex compound ⁇ ⁇ 100%) is in the range of 125% or more and 300% or less.
  • the liquid crystal compound has the following formula (I): (I) [In the formula (I), Ar is a group represented by any of the following formulas (II-1) to (II-8) which may have a substituent and is represented by any of the following formulas (II-1) to (II-8). In formulas (II-1) to (II-8), * represents a bond with Z 1 or Z 2.
  • R 11 and R 12 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • D 1 represents an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent.
  • D 2 and D 3 may independently have an aromatic hydrocarbon ring group or a substituent which may have a substituent. Represents a good aromatic heterocyclic group
  • D 4 and D 5 are independently acyclic groups that may have substituents, or D 4 and D 5 together form a ring.
  • R g represents an organic group having 1 to 30 carbon atoms which may have a hydrogen atom or a substituent.
  • R h represents an organic group having one or more aromatic rings selected from the group consisting of an aromatic hydrocarbon ring having 6 to 30 carbon atoms and an aromatic heterocycle having 2 to 30 carbon atoms.
  • R i represents an organic group having one or more aromatic ring selected from the group consisting of aromatic heterocyclic aromatic hydrocarbon ring and 2-30 having 6 to 30 carbon atoms
  • a 1 , A 2 , B 1 and B 2 each independently represent a cyclic aliphatic group which may have a substituent or an aromatic group which may have a substituent.
  • R 22 and R 23 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • G 1 and G 2 are independently one of an aliphatic hydrocarbon group having 1 to 20 carbon atoms and a methylene group (-CH 2- ) contained in the aliphatic hydrocarbon group having 3 to 20 carbon atoms.
  • the liquid crystal compound contained in the solution can be obtained as particles having excellent filterability and a large particle size.
  • alkyl group means a chain (linear or branched) saturated hydrocarbon group, and the “alkyl group” is a cyclic saturated hydrocarbon group, "cyclo”. "Alkyl groups” shall not be included.
  • the liquid crystal compound in the method for producing a liquid crystal compound of the present invention, can be obtained as particles having excellent filterability and a large particle size.
  • the liquid crystal compound produced by using the method for producing a liquid crystal compound of the present invention is not particularly limited and can be used, for example, when preparing a polymer.
  • the polymer can be used, for example, as a constituent material of an optical film and a constituent material of a layer of an optically anisotropic substance without particular limitation.
  • the optically anisotropic substance can be used, for example, as a polarizing plate without particular limitation.
  • the polarizing plate can be used for, for example, a display device and an antireflection film without particular limitation.
  • a step (A) of adding a poor solvent to a solution in which the liquid crystal compound is dissolved to generate particles of the liquid crystal compound, and a step (A) of producing particles of the liquid crystal compound are produced.
  • step (B) of separation by filtration optionally, a step of synthesizing a liquid crystal compound, a step of preparing a solution in which the liquid crystal compound is dissolved, a step of washing the separated particles, a step of drying the obtained particles, and the like. Other steps may be further included.
  • the method for producing a liquid crystal compound of the present invention is characterized in that the addition of the poor solvent in the step (A) is carried out so as to satisfy the following conditions (1) and (2).
  • the addition of the poor solvent in the step (A) is carried out so as to satisfy the following conditions (1) and (2).
  • coarse particles can be obtained without slowly producing a supersaturation degree.
  • -Condition (1) The amount of the poor solvent added when the precipitation of the liquid crystal compound starts is less than 30% of the total amount of the poor solvent added in the step (A).
  • -Condition (2) While the amount of the poor solvent added is 30% or more and 40% or less of the total amount of the poor solvent added in the step (A), the degree of supersaturation should be within the range of 125% or more and 300% or less. Stir the solution while adding a poor solvent to.
  • the liquid crystal compound is not particularly limited, and any liquid crystal compound can be mentioned. Among them, a liquid crystal compound having an inverse wavelength dispersibility is preferable as the liquid crystal compound from the viewpoint of being useful as a material for an optical film or an optically anisotropic substance.
  • the molecular weight of the liquid crystal compound is preferably 800 or more, more preferably 900 or more, further preferably 1000 or more, preferably 3000 or less, and more preferably 2500 or less. It is preferably 2000 or less, and more preferably 2000 or less.
  • the liquid crystal compound is preferably a compound represented by the following formula (I).
  • Ar is a group represented by any of the following formulas (II-1) to (II-8) which may have a substituent.
  • * represents a bond with Z 1 or Z 2.
  • E 1 and E 2 are independently of —S—.
  • D 1 represents an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent, and represents the formula (II-1).
  • D 2 and D 3 are each independently aromatic hydrocarbon ring group which may have a substituent or an aromatic which may have a substituent.
  • D 4 and D 5 are independently acyclic groups that may have substituents, or D 4 and D 5 are combined.
  • R f represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • R g represents an organic group having 1 to 30 carbon atoms which may have a hydrogen atom or a substituent, and R h.
  • R i is carbon number of 6 to Represents an organic group having one or more aromatic rings selected from the group consisting of 30 aromatic hydrocarbon rings and aromatic heterocycles having 2 to 30 carbon atoms.
  • aromatic ring refers to a cyclic structure having aromaticity in a broad sense according to Huckel's law, that is, a cyclic conjugated structure having (4n + 2) ⁇ electrons, thiophene, furan, benzothiazole and the like. It means a cyclic structure in which isolated electron pairs of heteroatoms such as sulfur, oxygen, and nitrogen are involved in a ⁇ -electron system and exhibit aromaticity.
  • examples of the substituent that the group represented by the above formulas (II-1) to (II-8) can have include a halogen atom, a cyano group, a nitro group, and an alkyl group having 1 to 6 carbon atoms.
  • Examples thereof include an alkylsulfinyl group of 6 and a carboxyl group, a thioalkyl group having 1 to 6 carbon atoms, an N-alkylsulfamoyl group having 1 to 6 carbon atoms, and an N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms. ..
  • an alkyl group having 1 to 6 carbon atoms is preferable, and a tert-butyl group is more preferable.
  • the groups represented by the above formulas (II-1) to (II-8) have a plurality of substituents, they may be the same as each other or may be different from each other.
  • aromatic hydrocarbon ring groups D 1 to D 3 aromatic hydrocarbon ring groups having 6 to 30 carbon atoms such as a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable.
  • the aromatic heterocyclic groups D 1 to D 3 include 1-benzofuranyl group, 2-benzofuranyl group, imidazolyl group, indolinyl group, frazayl group, oxazolyl group, quinolyl group, thiadiazolyl group, thiazolyl group and thiazolopi.
  • the aromatic hydrocarbon ring group and the aromatic heterocyclic group of D 1 to D 3 can have, a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; a methyl group, an ethyl group and a propyl group.
  • a halogen atom such as a fluorine atom and a chlorine atom
  • a cyano group such as a methyl group, an ethyl group and a propyl group.
  • Ra may have an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms as a substituent, and has 6 to 20 carbon atoms.
  • R b may have 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, and a substituent. It represents a good cycloalkyl group having 3 to 12 carbon atoms or an aromatic hydrocarbon ring group having 6 to 12 carbon atoms which may have a substituent.
  • the number of substituents of the aromatic hydrocarbon ring groups and aromatic heterocyclic groups of D 1 to D 3 may be one or a plurality per ring. If a ring has multiple substituents, they may be the same or different from each other.
  • examples of the alkyl group having 1 to 20 carbon atoms of R b include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a 1-methylpentyl group, and a 1-ethyl group.
  • the alkyl group of Rb preferably has 1 to 12 carbon atoms, and more preferably 4 to 10 carbon atoms.
  • substituent that the alkyl group having 1 to 20 carbon atoms of Rb can have include a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; and an N having 2 to 12 carbon atoms such as a dimethylamino group.
  • Cycloalkyloxy group of number 3 to 8 cyclic ether group having 2 to 12 carbon atoms such as tetrahydrofuranyl group, tetrahydropyranyl group, dioxolanyl group and dioxanyl group; aryl having 6 to 14 carbon atoms such as phenoxy group and naphthoxy group.
  • Oxy group fluoroalkyl group having 1 to 12 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms, such as trifluoromethyl group, pentafluoroethyl group, -CH 2 CF 3, etc .; benzofuryl group; benzopyranyl group; Benzodioxolyl groups; and benzodioxanyl groups and the like.
  • the substituents include halogen atoms such as fluorine atom and chlorine atom; cyano group; methoxy group, ethoxy group, isopropoxy group, butoxy group and other alkoxy groups having 1 to 20 carbon atoms; nitro group; phenyl group, Aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as naphthyl group; Aromatic heterocyclic group having 2 to 20 carbon atoms such as furanyl group, thienyl group and thiazolyl group; cyclopropyl group, cyclopentyl group, cyclohexyl group and the like Cycloalkyl group having 3 to 8 carbon atoms; fluoroalkyl group having 1 to 12 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms, such as a trifluoromethyl group, a pentafluoroethyl group, and -CH 2 CF 3. Is preferable.
  • alkenyl groups having 2 to 20 carbon atoms of R b examples include vinyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, decenyl group, undecenyl group, and the like.
  • Examples thereof include a dodecenyl group, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, a hexadecenyl group, a heptadecenyl group, an octadecenyl group, a nonadesenyl group, and an icosenyl group.
  • the carbon number of the alkenyl group having 2 to 20 carbon atoms of R b is preferably 2 to 12.
  • Examples of the substituent alkenyl group having 2 to 20 carbon atoms R b may have may be the same as those mentioned above as substituents may have an alkyl group having 1 to 20 carbon atoms R b.
  • the number of substituents may be one or plural.
  • the alkenyl groups having 2 to 20 carbon atoms of R b have a plurality of substituents, they may be the same as each other or may be different from each other.
  • Examples of the cycloalkyl group having 3 to 12 carbon atoms of R b include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group and the like. Among them, a cyclopentyl group and a cyclohexyl group are preferable as the cycloalkyl group having 3 to 12 carbon atoms of R b.
  • Examples of the substituent that the cycloalkyl group having 3 to 12 carbon atoms of Rb can have include a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; and an N having 2 to 12 carbon atoms such as a dimethylamino group.
  • N-dialkylamino group alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group, propyl group; alkoxy group having 1 to 6 carbon atoms such as methoxy group, ethoxy group, isopropoxy group; nitro group; and , Aromatic hydrocarbon ring groups having 6 to 20 carbon atoms such as phenyl group and naphthyl group.
  • the substituents include halogen atoms such as fluorine atom and chlorine atom; cyano group; alkyl groups having 1 to 6 carbon atoms such as methyl group, ethyl group and propyl group; methoxy group, ethoxy group, isopropoxy group and the like.
  • An alkoxy group having 1 to 6 carbon atoms; a nitro group; and an aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as a phenyl group and a naphthyl group are preferable.
  • the number of substituents may be one or plural.
  • the cycloalkyl group having 3 to 12 carbon atoms of R b has a plurality of substituents, they may be the same as each other or may be different from each other.
  • Examples of the aromatic hydrocarbon ring group having 6 to 12 carbon atoms of R b include a phenyl group, a 1-naphthyl group, a 2-naphthyl group and the like. Among these, a phenyl group is preferable.
  • Examples of the substituent that the aromatic hydrocarbon ring group having 6 to 12 carbon atoms of Rb can have include a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; and a dimethylamino group having 2 to 2 to carbon atoms.
  • alkoxy groups having 1 to 20 carbon atoms such as methoxy group, ethoxy group, isopropoxy group and butoxy group
  • alkoxy groups having 1 to 12 carbon atoms such as methoxymethoxy group and methoxyethoxy group.
  • 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 and a butoxy group; a nitro group; a furanyl group, Aromatic heterocyclic group having 2 to 20 carbon atoms such as thiophenyl group; cycloalkyl group having 3 to 8 carbon atoms such as cyclopropyl group, cyclopentyl group and cyclohexyl group; trifluoromethyl group, pentafluoroethyl group, -CH 2
  • a fluoroalkyl group having 1 to 12 carbon atoms in which one or more hydrogen atoms are substituted with a fluorine atom, such as CF 3 , and one or more substituents selected from ⁇ OCF 3 are preferable.
  • the number of substituents may be one or
  • the acyclic groups of D 4 and D 5 include an alkyl group having 1 to 6 carbon atoms, a cyano group, a carboxyl group, a fluoroalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and ⁇ C.
  • R x is an organic group having 1 to 12 carbon atoms, and specific examples of the organic group having 1 to 12 carbon atoms of R x are substituted with an alkoxy group having 1 to 12 carbon atoms or a hydroxyl group. Examples thereof include an alkyl group having 1 to 12 carbon atoms which may be used.
  • the substituents that the acyclic groups of D 4 and D 5 can have are the same as those described above as the substituents that the aromatic hydrocarbon ring groups and aromatic heterocyclic groups of D 1 to D 3 can have. Things can be mentioned.
  • the number of substituents may be one or plural. If the acyclic groups of D 4 and D 5 have multiple substituents, they may be the same or different from each other.
  • organic group in which D 4 and D 5 form a ring together include the following.
  • * represents the position of the carbon atom to which D 4 and D 5 are bonded (that is, the carbon atom forming a ring together with D 4 and D 5) in the formula (4).
  • R k represents an alkyl group having 1 to 3 carbon atoms
  • R m represents an alkyl group having 1 to 3 carbon atoms or a phenyl group which may have a substituent
  • R n represents a phenyl group having 1 to 3 carbon atoms.
  • R p represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a hydroxyl group or ⁇ COOR ”, and R” represents 1 carbon atoms.
  • R m and R n can have include a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a hydroxyl group, a carboxyl group, an alkoxy group, an aryloxy group and an acyloxy group.
  • Cyan group and amino group preferably a halogen atom, an alkyl group, a cyano group and an alkoxy group.
  • the number of substituents contained in the phenyl group may be one or plural.
  • the phenyl groups of R m and R n have a plurality of substituents, they may be the same or different from each other.
  • examples of the alkyl group having 1 to 6 carbon atoms of R f of D 6 include a methyl group, an ethyl group, a propyl group, an isopropyl group and the like.
  • alkynyl group having 2 to 20 carbon atoms which may have a group a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, and a cycloalkyl group having 6 to 30 carbon atoms which may have a substituent.
  • aromatic hydrocarbon ring group, aromatic heterocyclic group which has 1-2 carbon atoms which may 30 have a substituent, -G x -Y x -F X, -SO 2 R a, -C ( O ) -R b and -CS-NH-R b .
  • At least one of -CH 2- contained in the alkyl group having 1 to 20 carbon atoms and the alkyl group having 1 to 20 carbon atoms which may have a substituent is -O-, -S-, -O-.
  • -CH 2- contained in the alkyl group having 1 to 20 carbon atoms and the alkyl group having 1 to 20 carbon atoms which may have a substituent is -O-, -S-, -O-.
  • G x is a divalent aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent and a divalent aliphatic hydrocarbon group having 3 to 30 carbon atoms which may have a substituent.
  • R 14 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • Examples of the alkyl group having 1 to 20 carbon atoms of R g include the same alkyl groups having 1 to 20 carbon atoms in R b as described above.
  • Examples of the substituent alkyl groups having 1 to 20 carbon atoms R g may have, for example, a fluorine atom, a halogen atom such as a chlorine atom; a cyano group; having 2 to 12 carbon atoms such as a dimethylamino group N, N-dialkylamino group; alkoxy group having 1 to 20 carbon atoms such as methoxy group, ethoxy group, isopropoxy group, butoxy group; substituted with alkoxy group having 1 to 12 carbon atoms such as methoxymethoxy group and methoxyethoxy group.
  • aromatic heterocyclic groups comprising cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl group, cyclopentyl group and cyclohexyl group; cycloalkyloxy groups having 3 to 8 carbon atoms such as cyclopentyloxy group and cyclohexyloxy group; tetrahydrofla Cyclic ether groups having 2 to 12 carbon atoms such as nyl group, tetrahydropyranyl group, dioxolanyl group and dioxanyl group; aryloxy groups having 6 to 14 carbon atoms such as phenoxy group and naphthoxy group; one or more hydrogen atoms are fluorine.
  • Ra and R b are as described above.
  • Examples of the alkenyl group having 2 to 20 carbon atoms of R g include the same alkenyl groups having 2 to 20 carbon atoms in R b as described above. Then, Examples of the substituent alkenyl group having 2 to 20 carbon atoms R g may have may be the same as those mentioned above as substituents for alkyl groups having 1 to 20 carbon atoms R g may have. The number of substituents may be one or plural. When the alkenyl groups having 2 to 20 carbon atoms of R g have a plurality of substituents, they may be the same as each other or may be different from each other.
  • alkynyl groups of R g having 2 to 20 carbon atoms are ethynyl group, propynyl group, 2-propynyl group (propargyl group), butynyl, 2-butynyl, 3-butynyl group, pentynyl group, 2-pentynyl Examples thereof include a group, a hexynyl group, a 5-hexynyl group, a heptynyl group, an octynyl group, a 2-octynyl group, a nonanyl group, a decanyl group, a 7-decanyl group and the like.
  • Examples of the substituent alkynyl group having 2 to 20 carbon atoms R g may have may be the same as those mentioned above as substituents for alkyl groups having 1 to 20 carbon atoms R g may have.
  • the number of substituents may be one or plural.
  • the alkynyl group having 2 to 20 carbon atoms of R g has a plurality of substituents, they may be the same as each other or may be different from each other.
  • Examples of the cycloalkyl group having 3 to 12 carbon atoms of R g include the same cycloalkyl groups having 3 to 12 carbon atoms of R b as described above. Then, Examples of the substituent which the cycloalkyl group having 3 to 12 carbon atoms of R g may have may be the same as those mentioned above as substituents for alkyl groups having 1 to 20 carbon atoms R g may have .. The number of substituents may be one or plural. When the cycloalkyl group having 3 to 12 carbon atoms of R g has a plurality of substituents, they may be the same as each other or may be different from each other.
  • the aromatic hydrocarbon ring group R g C 6 -C 30, identical to those described above as the aromatic hydrocarbon ring group D 1 ⁇ D 3 aromatic hydrocarbon ring can be a group having 6 to 30 carbon atoms Things can be mentioned.
  • the substituent which the aromatic hydrocarbon ring group having 6 to 30 carbon atoms R g may have the same as those described above as substituents may have an aromatic hydrocarbon ring group D 1 ⁇ D 3 Things can be mentioned.
  • the number of substituents may be one or plural.
  • the aromatic hydrocarbon ring group having 6 to 30 carbon atoms of R g has a plurality of substituents, they may be the same as each other or different from each other.
  • Examples of the aromatic heterocyclic group having 2 to 30 carbon atoms of R g include the same aromatic heterocyclic groups having 2 to 30 carbon atoms which can be D 1 to D 3 aromatic heterocyclic groups. Be done. And, as the substituent which the aromatic heterocyclic group having 2 to 30 carbon atoms R g may have, the same as those mentioned above as substituents may have the aromatic heterocyclic group D 1 ⁇ D 3 Can be mentioned. The number of substituents may be one or plural. When the aromatic heterocyclic group having 2 to 30 carbon atoms of R g has a plurality of substituents, they may be the same as each other or may be different from each other.
  • the divalent aliphatic hydrocarbon group is preferably a divalent chain aliphatic hydrocarbon group, more preferably an alkylene group.
  • the carbon number of the organic group F X of R g is preferably 2 to 30, more preferably 7 or more, more preferably 8 or more, particularly preferably 10 or more.
  • F X is at least one hydrogen atom is replaced by ring-containing group having at least one aromatic hydrocarbon ring and aromatic heterocyclic ring, and, have a substituent other than the ring-containing group It may be an alkyl group having 1 to 18 carbon atoms, or a cyclic group having 2 to 20 carbon atoms which may have a substituent and has at least one of an aromatic hydrocarbon ring and an aromatic heterocycle. preferable.
  • FX has a plurality of aromatic hydrocarbon rings and / or a plurality of aromatic heterocycles, they may be the same or different.
  • ring-containing group and the aromatic hydrocarbon ring contained in the cyclic group include aromatic hydrocarbons having 6 to 30 carbon atoms such as a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, and a fluorene ring. Ring is mentioned. These aromatic hydrocarbon rings may have a substituent.
  • ring-containing group and the aromatic heterocycle of the cyclic group include 1H-isoindole-1,3 (2H) -dione ring, 1-benzofuran ring, 2-benzofuran ring, aclydin ring, and isoquinoline ring.
  • Imidazole ring Imidazole ring, indole ring, oxaziazole ring, oxazole ring, oxazolopyrazine ring, oxazolopyridine ring, oxazolopyridadyl ring, oxazolopyrimidine ring, quinazoline ring, quinoxalin ring, quinoline ring, cinnoline ring, thiazol Ring, thiazole ring, thiazolopyrazine ring, thiazolopyridine ring, thiazolopyridazine ring, thiazolopyrimidine ring, thiophene ring, triazine ring, triazole ring, naphthylidine ring, pyrazine ring, pyrazole ring, pyranone ring, pyran ring, pyridine Ring, pyridazine ring, pyrimidine ring, pyrrole ring
  • examples of the substituent that the above-mentioned aromatic hydrocarbon ring and aromatic heterocycle can have include a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; a carbon number such as a methyl group, an ethyl group and a propyl group.
  • R b has the same meaning as described above.
  • F X may have a plurality of substituents selected from the above substituents. If F X has plural substituents, the substituents may be the same or different.
  • examples of the alkyl group having 1 to 18 carbon atoms include a methyl group, an ethyl group, a propyl group, and an isopropyl group.
  • aromatic hydrocarbon ring and the aromatic heterocycle may be directly bonded to the carbon atom of the alkyl group having 1 to 18 carbon atoms, or may be directly bonded to the carbon atom of the alkyl group having 1 to 18 carbon atoms, or-S-, -O-,-.
  • R 13 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • a group having at least one of the aromatic hydrocarbon ring and the aromatic heterocycle such as a fluorenyl group and a benzothiazolyl group, is substituted.
  • examples of the aromatic hydrocarbon ring group include aromatic hydrocarbon ring groups having 6 to 30 carbon atoms such as a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, and a fluorenyl group.
  • aromatic hydrocarbon ring groups having 6 to 30 carbon atoms such as a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, and a fluorenyl group.
  • the substituent which may have an aromatic hydrocarbon ring group the same as those of a substituent which the "aromatic hydrocarbon ring and aromatic heterocyclic ring F X has" may have.
  • aromatic heterocyclic group examples include a phthalimide group, a 1-benzofuranyl group, a 2-benzofuranyl group, an acridinyl group, an isoquinolinyl group, an imidazolyl group, an indolinyl group, a frazayl group, an oxazolyl group and an oxazolopyrazinyl group.
  • Examples of the group consisting of an aromatic hydrocarbon ring having a linking group and the group consisting of an aromatic heterocycle having a linking group include a phenylthio group, a naphthylthio group, an anthracenylthio group, a phenanthrenylthio group, a pyrenylthio group and a fluorenylthio group.
  • a cyclic group having 2 to 20 carbon atoms which may have a substituent and having at least one of an aromatic hydrocarbon ring and an aromatic heterocyclic ring for example, 1) at least one carbon number 6 A hydrocarbon ring group having 6 to 20 carbon atoms and optionally having a substituent having an aromatic hydrocarbon ring of 18 to 18 2) an aromatic hydrocarbon ring having 6 to 18 carbon atoms and 2 to 18 carbon atoms. Examples thereof include a heterocyclic group having 2 to 20 carbon atoms which may have a substituent and which has at least one aromatic ring selected from the group consisting of aromatic heterocycles.
  • hydrocarbon ring group of 1) for example, an aromatic hydrocarbon ring group having 6 to 18 carbon atoms (phenyl group (6 carbon atoms), naphthyl group (10 carbon atoms), anthracenyl group (anthracenyl group). 14 carbon atoms), phenanthrenyl group (14 carbon atoms), pyrenyl group (16 carbon atoms), fluorenyl group (13 carbon atoms), etc.), indanyl group (9 carbon atoms), 1,2,3,4-tetrahydronaphthyl group (10 carbon atoms), 1,4-dihydronaphthyl group (10 carbon atoms) and the like.
  • aromatic hydrocarbon ring group having 6 to 18 carbon atoms phenyl group (6 carbon atoms), naphthyl group (10 carbon atoms), anthracenyl group (anthracenyl group). 14 carbon atoms), phenanthrenyl group (14 carbon atoms), pyrenyl group (16 carbon
  • examples of the hydrocarbon ring group of 1) above include groups represented by the following formulas (1-1) to (1-21), which may have a substituent.
  • heterocyclic group of 2) above examples include aromatic heterocyclic groups having 2 to 18 carbon atoms (phthalimide group, 1-benzofuranyl group, 2-benzofuranyl group, acridinyl group, isoquinolinyl group, imidazolyl group, etc.
  • examples of the heterocyclic group of 2) above include groups represented by the following formulas (2-1) to (2-51), which may have a substituent.
  • X represents -CH 2- , -NR c- , oxygen atom, sulfur atom, -SO- or -SO 2-
  • Y and Z are independently of -NR c- , respectively.
  • E represents -NR c- , oxygen atom or sulfur atom (provided that oxygen atom, sulfur atom, -SO-,-in each formula. SO 2- shall not be adjacent to each other).
  • R c in the above-NR 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.
  • F X when Ar is a group represented by formula (II-5), is preferably one of the following formulas (i-1) ⁇ (i -9), Ar has the formula When it is a group represented by (II-6) or (II-7), it is preferably any of the following formulas (i-1) to (i-13).
  • the groups represented by the following formulas (i-1) to (i-13) may have a substituent.
  • Y is as described above.
  • F X when Ar is a group represented by formula (II-5), particularly preferably at any one of the following formulas (ii-1) ⁇ (ii -20), Ar has the formula ( When it is a group represented by II-6) or (II-7), it is preferably any of the following formulas (ii-1) to (ii-26).
  • the groups represented by the following formulas (ii-1) to (ii-26) may have a substituent.
  • Y is as described above.
  • the total number of ⁇ electrons contained in the ring structure in the F X is preferably 8 or more, more preferably 10 or more , 20 or less, more preferably 18 or less.
  • the total number of ⁇ electrons contained in the ring structure in the F X is preferably 4 or more, 6 or more Is more preferable, 20 or less is preferable, and 18 or less is more preferable.
  • an organic group having one or more aromatic rings selected from the group consisting of an aromatic hydrocarbon ring having 6 to 30 carbon atoms and an aromatic heterocycle having 2 to 30 carbon atoms in Rh of D 6, for example.
  • Any of the following groups 1) to 5) which may have a substituent can be mentioned.
  • the number of substituents may be one or plural.
  • An aromatic hydrocarbon ring having 1 or more 6 to 30 carbon atoms and having 6 to 40 carbon atoms 2) An aromatic hydrocarbon ring having 6 to 30 carbon atoms and an aromatic hydrocarbon ring having 2 to 30 carbon atoms.
  • Examples of the substituent that the hydrocarbon ring group having 6 to 40 carbon atoms in 1) above can have include a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; a methyl group, an ethyl group and a propyl group.
  • Ra and R b have the same meanings as described above.
  • substituents one or more substituents selected from the group consisting of 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.
  • Rq represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and when there are a plurality of Rqs, they may be the same or different from each other.
  • the substituents that the heterocyclic group having 2 to 40 carbon atoms in 2) can have are the same as those exemplified as the substituents that the hydrocarbon ring group having 6 to 40 carbon atoms in 1) can have. Things can be mentioned.
  • aromatic hydrocarbon ring group having 6 to 30 carbon atoms in the above 3) to 5 for example, an aromatic hydrocarbon having 6 to 30 carbon atoms which can be an aromatic hydrocarbon ring group having D 1 to D 3 is used.
  • the ring group include the same ones as described above.
  • aromatic heterocyclic group having 2 to 30 carbon atoms in the above 3) to 5) is described above as an aromatic heterocyclic group having 2 to 30 carbon atoms which can be an aromatic heterocyclic group having D 1 to D 3.
  • alkyl group having 1 to 12 carbon atoms in 3) above include a methyl group, an ethyl group, a propyl group, an isopropyl group and the like.
  • Examples of the alkenyl group having 2 to 12 carbon atoms in 4) above include a vinyl group and an allyl group. Further, examples of the alkynyl group having 2 to 12 carbon atoms in 5) above include an ethynyl group and a propynyl group. In addition, examples of the substituents that the groups 3) to 5) can have include the same as those exemplified as the substituents that the hydrocarbon ring group having 6 to 40 carbon atoms in 1) can have.
  • R h a group represented by the following formula is preferable.
  • the group represented by the following formula is more preferable.
  • a group represented by the following formula is particularly preferable.
  • the substituents include a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and 1 to 6 carbon atoms.
  • One or more substituents selected from the six alkoxy groups are preferred.
  • Ra and R b have the same meanings as described above.
  • An organic group having one or more aromatic rings selected from the group consisting of an aromatic hydrocarbon ring having 6 to 30 carbon atoms and an aromatic heterocycle having 2 to 30 carbon atoms in Ri of D 6 is, for example, , Any of the following groups 6) to 7) which may have a substituent can be mentioned. 6) A hydrocarbon ring group having 6 to 40 carbon atoms and having 1 or more aromatic hydrocarbon rings having 6 to 30 carbon atoms 7) An aromatic hydrocarbon ring having 6 to 30 carbon atoms and an aromatic hydrocarbon ring having 2 to 30 carbon atoms. family complex having one or more aromatic rings which rings are selected from the group consisting of heterocyclic group having 2 to 40 carbon atoms among them, R i is preferably one of the following formulas. [In the formula, Rt represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ]
  • Xa may be an alkylene group having 1 to 18 carbon atoms which may have a substituent, or an aromatic hydrocarbon ring group having 6 to 18 carbon atoms which may have a substituent. It is preferable that it is any of the following (Xa-1) to (Xa-29).
  • a group represented by any of the following formulas (1-1) to (8-2), which may have a substituent, is preferable, and an alkyl group having 1 to 6 carbon atoms is preferable. It is more preferable that the group is represented by any of the following formulas (1-1) to (8-2), which may be used as a substituent.
  • a 1 and A 2 and B 1 and B 2 may independently have a cyclic aliphatic group which may have a substituent, or may have a substituent. Represents a good aromatic group. Then, A 1 and A 2 and B 1 and B 2 may independently have a substituent or may have a cyclic aliphatic group having 5 to 20 carbon atoms or a substituent. It is preferably an aromatic group having a good carbon number of 2 to 20.
  • cyclic aliphatic groups of A 1 and A 2 and B 1 and B 2 include cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, and 1,4-cycloheptan.
  • Cycloalkanediyl group having 5 to 20 carbon atoms such as -1,4-diyl group, cyclooctane-1,5-diyl group; decahydronaphthalene-1,5-diyl group, decahydronaphthalene-2,6-diyl
  • Examples thereof include a bicycloalkandyl group having 5 to 20 carbon atoms such as a group.
  • a cycloalkandyl group having 5 to 20 carbon atoms which may be substituted is preferable, a cyclohexanediyl group is more preferable, and a cyclohexane-1,4-diyl group is further preferable.
  • the cyclic aliphatic group may be a trans form, a cis form, or a mixture of a cis form and a trans form, but a trans form is more preferable.
  • aromatic groups of A 1 and A 2 and B 1 and B 2 include 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group and 1,4-naphthylene group. , 1,5-naphthylene group, 2,6-naphthylene group, 4,4'-biphenylene group, and other aromatic hydrocarbon ring groups with 6 to 20 carbon atoms; furan-2,5-diyl group, thiophene-2. , 5-Diyl group, pyridine-2,5-Diyl group, pyrazine-2,5-Diyl group and other aromatic heterocyclic groups having 2 to 20 carbon atoms; and the like.
  • aromatic group an aromatic hydrocarbon ring group having 6 to 20 carbon atoms is preferable, a phenylene group is more preferable, and a 1,4-phenylene group is further preferable.
  • Examples of the substituents of the cyclic aliphatic group and the aromatic group of A 1 and A 2 and B 1 and B 2 include a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a nitro group. Groups, cyano groups and the like can be mentioned.
  • the cyclic aliphatic group and aromatic group may have at least one substituent selected from the above-mentioned substituents. When the cyclic aliphatic group and the aromatic group have a plurality of substituents, the respective substituents may be the same or different from each other.
  • R 22 and R 23 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • G 1 and G 2 are independently each of an aliphatic hydrocarbon group having 1 to 20 carbon atoms and a methylene group contained in an aliphatic hydrocarbon group having 3 to 20 carbon atoms.
  • the hydrogen atom contained in the organic group of G 1 and G 2 may be substituted with an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom.
  • aliphatic hydrocarbon group having 1 to 20 carbon atoms include an alkylene group having 1 to 20 carbon atoms, and specific examples of the aliphatic hydrocarbon group having 3 to 20 carbon atoms include carbon atoms. Included are 3 to 20 alkylene groups.
  • P 1 and P 2 each independently represent a polymerizable group.
  • R c is hydrogen.
  • Examples thereof include a group, an amino group, an epoxy group, an oxetanyl group, an aldehyde group, an isocyanate group or a thioisocyanate group.
  • the above-mentioned polymerizable liquid crystal compound can be synthesized by combining known synthetic reactions. That is, in various documents (for example, International Publication No. 2014/10325, International Publication No. 2012/147904, Japanese Patent Application Laid-Open No. 2010-31223, Japanese Patent Application Laid-Open No. 2008-273925, Japanese Patent Application Laid-Open No. 2009-179563) and the like. It can be synthesized by referring to the described method.
  • Step (A)> a poor solvent is added to the solution in which the liquid crystal compound is dissolved so as to satisfy the above-mentioned conditions (1) and (2) to generate particles of the liquid crystal compound to generate the liquid crystal compound particles. Obtain the containing liquid.
  • the solution in which the liquid crystal compound is dissolved contains the liquid crystal compound and the solvent, and optionally further contains other compounds.
  • examples of the liquid crystal compound include the above-mentioned liquid crystal compound.
  • the liquid crystal compound described above may be contained in the solution of only one type or two or more types.
  • the concentration of the liquid crystal compound in the solution is not particularly limited, and is, for example, preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 15% by mass or more. It is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less.
  • the solvent is not particularly limited as long as it does not correspond to the poor solvent described later and can dissolve the liquid crystal compound, and any solvent can be used.
  • a chlorine-based solvent such as chloroform and methylene chloride
  • an ether-based solvent such as 1,4-dioxane, cyclopentylmethyl ether, tetrahydrofuran, tetrahydropyran, and 1,3-dioxolane
  • a nitrile-based solvent such as acetonitrile.
  • Ester solvents such as ethyl acetate, butyl acetate, propyl acetate; aromatic hydrocarbon solvents such as toluene and xylene; N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, hexamethylphosphate
  • amide-based solvents such as triamide
  • mixed solvents composed of two or more of these solvents Among these, as the solvent, a chlorine-based solvent and an ether-based solvent are preferable, and chloroform, tetrahydrofuran, and a mixed solvent thereof are particularly preferable.
  • the saturated solubility of the liquid crystal compound in the solvent is preferably 5% by mass or more.
  • the saturated solubility can be measured at a predetermined temperature (the temperature at which the liquid crystal compound is actually precipitated) according to the method described in Examples.
  • the other compounds are not particularly limited, and examples thereof include raw materials used for synthesizing liquid crystal compounds and reaction by-products produced by side reactions.
  • the solution in which the liquid crystal compound is dissolved is not particularly limited, and for example, a solution obtained by redissolving a solid liquid liquid compound obtained through solid-liquid separation after synthesis in a solvent, or a liquid liquid property.
  • examples thereof include a solution obtained by dissolving a liquid liquid compound in a reaction solvent obtained when the compound is synthesized.
  • the solution obtained by dissolving the liquid crystal compound in the reaction solvent contains an organic layer obtained when the reaction product obtained during the synthesis of the liquid crystal compound is washed with water or the like, and a concentrate of the organic layer. It shall be.
  • the poor solvent is not particularly limited as long as it has a lower solubility of the liquid crystal compound than the above-mentioned solvent and can precipitate the liquid crystal compound by adding it to the above solution, and any solvent can be used. it can.
  • Specific examples of the poor solvent include ether solvents such as methyl tert-butyl ether and dibutyl ether; aliphatic hydrocarbon solvents such as normal hexane; and alcohol solvents such as methanol.
  • ether solvents such as methyl tert-butyl ether and dibutyl ether
  • aliphatic hydrocarbon solvents such as normal hexane
  • alcohol solvents such as methanol.
  • an aliphatic hydrocarbon solvent and an alcohol solvent are preferable, normal hexane, 60% hexane and methanol are more preferable, and methanol is most preferable.
  • the saturated solubility of the liquid crystal compound in the poor solvent is preferably less than 5% by mass, more preferably 1% by mass or less. Further, the ratio of the saturated solubility of the liquid crystal compound to the solvent described above and the saturated solubility of the liquid crystal compound to the poor solvent (saturated solubility in the solvent / saturated solubility in the poor solvent) is preferably 2 times or more. More preferably, it is more preferably 50 times or more.
  • the saturated solubility can be measured at a predetermined temperature (the temperature at which the liquid crystal compound is actually precipitated) according to the method described in Examples.
  • the addition of the poor solvent to the solution in which the liquid crystal compound is dissolved is not particularly limited as long as the conditions (1) and (2) are satisfied, and can be carried out by any method.
  • the poor solvent may be added continuously to the solution or intermittently to the solution.
  • the addition rate of the poor solvent may be constant or may be changed in the step (A).
  • the poor solvent is preferably added continuously to the solution at a constant rate.
  • the amount of the poor solvent added M 1 at the start of precipitation of the liquid crystal compound is less than 30% of the total amount of the poor solvent M added in the step (A) (0.30 ⁇ M> M 1). ) Is required.
  • the liquid crystal compound may be precipitated before the poor solvent is added, but it is preferable that the liquid crystal compound is not precipitated before the poor solvent is added, and the amount of the poor solvent added M 1 is the total amount of the poor solvent. It is more preferably 5%% or more (0.05 ⁇ M ⁇ M 1 ) of M, and further preferably 10% or more (0.1 ⁇ M ⁇ M 1) of the total amount of poor solvent M.
  • start of precipitation of liquid crystal compound is performed visually or by using an in-line particle size distribution measuring device such as a particle track manufactured by METTLER TOLEDO or an in-line microscope such as a particle view manufactured by METTLER TOLEDO. It can be judged by the fact.
  • the particle track manufactured by METTLER TOLEDO include ParticleTrack G400.
  • examples of the particle view manufactured by METTLER TOLEDO include ParticleViewV19.
  • the amount of the poor solvent added M 2 is 30% or more and 40% or less (0.30 ⁇ M ⁇ M 2 ⁇ 0.40 ⁇ M) of the total amount of the poor solvent M added in the step (A). ), It is necessary to stir the solution while adding a poor solvent so that the supersaturation degree is in the range of 125% or more and 300%, and the addition amount M 2 is 30% or more of the total poor solvent amount M.
  • the degree of supersaturation while it is 40% or less is preferably 130% or more, and preferably 260% or less.
  • the degree of supersaturation can be measured by the method described in Examples.
  • step (A) from the start of precipitation of the liquid crystal compound until the amount of the poor solvent added reaches 30% of the total amount of the poor solvent added in the step (A), and the amount of the poor solvent added.
  • the addition of the poor solvent while the total amount of the poor solvent added in the step (A) is more than 40% can be carried out under any conditions.
  • the particles of the liquid crystal compound produced in the step (A) may be crystalline particles, but are usually amorphous particles.
  • the particle size of the liquid crystal compound is preferably 40 ⁇ m or more, and more preferably 50 ⁇ m or more in order to perform rapid filtration. Further, the particle size of the liquid crystal compound is preferably 3000 ⁇ m or less, more preferably 2000 ⁇ m or less, in order to facilitate transfer in the manufacturing process.
  • the proportion of particles having a particle size of 50 ⁇ m or more and 2000 ⁇ m or less in the total particles produced in the step (A) is preferably 80% or more based on the number of particles.
  • the number average particle size of the particles of the liquid crystal compound and the ratio of the particles having a particle size of 50 ⁇ m or more and 2000 ⁇ m or less can be obtained by measuring the particle size distribution by the method described in the examples.
  • the liquid crystal compound particle-containing liquid obtained in the step (A) includes particles of the liquid crystal compound and a mixed solution of a solvent in which the liquid crystal compound that did not precipitate is dissolved and a poor solvent, and optionally other compounds. Further contained.
  • Step (B) the particles produced in the step (A) are separated by filtration. Specifically, in the step (B), the liquid crystal compound particle-containing liquid obtained in the step (A) is filtered to separate the particles of the liquid crystal compound.
  • the method for filtering the liquid containing liquid crystal compound particles is not particularly limited, and examples thereof include centrifugal filtration, pressure filtration and vacuum filtration, and among them, the liquid crystal compound is efficiently produced on an industrial scale. From the viewpoint, centrifugal filtration is preferable as the filtration method.
  • the concentration, solubility (saturated solubility) and supersaturation of the liquid crystal compound, and the particle size distribution (number basis) of the particles were measured by using the following methods.
  • the filterability of the liquid crystal compound particle-containing liquid was evaluated using the following method. (1) Concentration of liquid crystal compound, saturation solubility and supersaturation degree The concentration of the liquid crystal compound in the liquid can be determined by sequentially carrying out the following 1) to 4). 1) Take a sample while stirring the solution. 2) Using a disk-type filter with a pore size of 0.45 ⁇ m (ADVANTEC, DISMIC, etc.) and a disposable syringe, the collected sample is filtered to remove the precipitated liquid crystal compound particles. , Get the filtrate.
  • the obtained filtrate is diluted with tetrahydrofuran and analyzed by a high performance liquid chromatograph (manufactured by Agilent) to determine the area value of the liquid crystal compound.
  • a high performance liquid chromatograph manufactured by Agilent
  • the liquid crystal compound in the sample Calculate the concentration.
  • the saturated solubility of the liquid crystal compound can be determined as follows. I) Synthesize liquid crystal compounds to prepare a standard.
  • Step 1 Synthesis of Intermediate A> ... Intermediate A Intermediate A was synthesized by the method described in WO 17/150622.
  • ⁇ Step 2 Synthesis of mixture A> ... Mixture A
  • a three-port reactor equipped with a thermometer 83.05 g (0.397 mol) of trans-1,4-cyclohexanedicarboxylic acid dichloride and 830 g of cyclopentyl methyl ether (CPME) were added in a nitrogen stream.
  • CPME cyclopentyl methyl ether
  • the solution was separated to extract the aqueous layer, and then 416 g of a buffer solution (pH 5.5) consisting of acetic acid and sodium acetate having a concentration of 1 mol / liter was newly added, and the mixture was stirred at 40 ° C. for 30 minutes. This operation was performed a total of 5 times. Further, 250 g of water was added to the obtained organic layer, and the mixture was stirred at 40 ° C. for 30 minutes. After the liquid was separated and the aqueous layer was extracted, 250 g of water was newly added and the mixture was stirred at 40 ° C. for 30 minutes.
  • a buffer solution pH 5.5
  • reaction solution When the reaction solution was allowed to stand, it was separated into three layers, so the lower two layers were extracted.
  • To the obtained toluene layer 430 g of a 10 mass% sodium chloride aqueous solution was added, the temperature was maintained at 60 ° C., and the mixture was stirred for 15 minutes. After separating the aqueous layer, the obtained organic layer was concentrated under reduced pressure to extract 560 g of toluene. The temperature of the concentrated organic layer was raised to 60 ° C., 500 g of water was added, and the mixture was gradually cooled with strong stirring. After reaching 0 ° C., the mixture was stirred at the same temperature for 1 hour. This slurry solution was filtered.
  • Step 4 Synthesis of polymerizable compound 1> Mixture A: 32.4 g (intermediate B net 30 g (71.7 mmol)) and chloroform 300 g, N, N-dimethylformamide synthesized in step 2 in a nitrogen stream in a three-port reactor equipped with a thermometer.
  • the particles having a particle size of 50 to 2000 ⁇ m were 80% of the total number of particles. Then, a pale yellow solid was obtained by centrifugal filtration. The obtained pale yellow solid was dissolved in 120 g of tetrahydrofuran at 25 ° C., 1.5 g of Rocahelp # 479 was added, and the mixture was stirred for 30 minutes. Then, filtration was performed with a Kiriyama funnel on which 1 g of Rocahelp # 479 was laid, and Rocahelp # 479 was removed. To the obtained organic layer, 165 g of methanol was added dropwise at 15 ° C.
  • step (B) When the particle size distribution of the particles precipitated immediately before filtration was measured, the number of particles having a particle size of 50 to 2000 ⁇ m was 92% of the total number of particles. Then, a pale yellow solid was obtained by centrifugal filtration (step (B)). The obtained solid was dried in a vacuum dryer to obtain 34.13 g of the polymerizable compound 1 as a pale yellow solid. The yield was 89.5 mol% (based on 2,5-dihydroxybenzaldehyde).
  • the organic layer 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 at 40 ° C. for 30 minutes, and then the buffer solution was withdrawn. After washing at 40 ° C. for 30 minutes with 416 g of a new buffer solution (pH: 5.5) consisting of acetic acid and sodium acetate having a concentration of 1 mol / liter, the buffer solution was withdrawn. This operation was performed a total of 5 times. Further, 250 g of distilled water was added to the obtained organic layer, and the mixture was washed at 40 ° C. for 30 minutes, and then the aqueous layer was extracted.
  • a buffer solution pH: 5.5
  • a new buffer solution consisting of acetic acid and sodium acetate having a concentration of 1 mol / liter
  • Step 2 Synthesis of polymerizable compound 1>
  • the mixture A 32.4 g (intermediate B net 30 g (71.7 mmol)) was synthesized in step 1 of the mixture B: 43.8 g (intermediate B net 30 g (71)).
  • the same operation was performed except that it was changed to .7 mmol)).
  • the amount of dropped methanol became 28% of the total amount of methanol, particles were generated and rapidly increased (condition (1)).
  • sampling is performed, and the mixture is filtered through a disk-type filter having a pore size of 0.45 ⁇ m in the filtrate.
  • the concentration of the polymerizable compound 1 was quantified, it was 160%, 177%, and 230% with respect to the saturated solubility in each solvent composition (condition (2)). Then, after dropping the entire amount of methanol, the mixture was aged by stirring at 15 ° C. for 30 minutes as it was. When the particle size distribution of the precipitated particles was measured immediately before filtration, the particles having a particle size of 50 to 2000 ⁇ m were 91% of the total number of particles. Then, a pale yellow solid was obtained by centrifugal filtration (step (B)). The obtained solid was dried in a vacuum dryer to obtain 34.43 g of the polymerizable compound 1 as a pale yellow solid. The yield was 90.3 mol% (based on 2,5-dihydroxybenzaldehyde).
  • the obtained crystals were analyzed by HPLC and the intermediate B was quantified by a calibration curve. As a result, it was found that the intermediate B was contained in an amount of 99.5% by mass or more.
  • the structure of the object was identified by 1 1 H-NMR.
  • Step 2 Synthesis of polymerizable compound 1>
  • 32.4 g of mixture A (30 g (71.7 mmol) as net of intermediate B) was changed to 30.0 g (71.7 mmol) of intermediate B synthesized in step 1.
  • the same operation was performed.
  • the amount of dropped methanol became 26% of the total amount of methanol, particles were generated and rapidly increased (condition (1)).
  • sampling is performed, and the mixture is filtered through a disk-type filter having a pore size of 0.45 ⁇ m and contained in the filtrate.
  • the concentration of the polymerizable compound 1 was quantified, it was 141%, 168%, and 222% with respect to the saturated solubility in each solvent composition (condition (2)). Then, after dropping the entire amount of methanol, the mixture was aged by stirring at 15 ° C. for 30 minutes as it was. When the particle size distribution of the precipitated particles was measured immediately before filtration, the particles having a particle size of 50 to 2000 ⁇ m were 94% of the total number of particles. Then, a pale yellow solid was obtained by centrifugal filtration (step (B)). The obtained solid was dried in a vacuum dryer to obtain 34.90 g of the polymerizable compound 1 as a pale yellow solid. The yield was 91.5 mol% (based on 2,5-dihydroxybenzaldehyde).
  • Example 4 Production of polymerizable compound 1 ⁇ Step 1: Synthesis of polymerizable compound 1>
  • step 4 of Example 1 the same operation was performed except that the dropping of methanol was changed from 1.5 hours to 3 hours.
  • the amount of dropped methanol became 28% of the total amount of methanol, particles were generated and rapidly increased (condition (1)).
  • sampling is performed, and the mixture is filtered through a disk-type filter having a pore size of 0.45 ⁇ m and contained in the filtrate.
  • the concentration of the polymerizable compound 1 was quantified, it was 141%, 151%, and 155% with respect to the saturated solubility in each solvent composition (condition (2)). Then, after dropping the entire amount of methanol, the mixture was aged by stirring at 15 ° C. for 30 minutes as it was. When the particle size distribution of the precipitated particles was measured immediately before filtration, 90% of the total number of particles was 50 to 2000 ⁇ m. Then, a pale yellow solid was obtained by centrifugal filtration (step (B)). The obtained solid was dried in a vacuum dryer to obtain 33.86 g of the polymerizable compound 1 as a pale yellow solid. The yield was 88.8 mol% (based on 2,5-dihydroxybenzaldehyde).
  • step 4 of Example 1 the mixture A: 32.4 g (intermediate B net 30 g (71.7 mmol)) is changed to the mixture B: 43.8 g (intermediate B net 30 g (71.7 mmol)).
  • step 4 of Example 1 the mixture A: 32.4 g (intermediate B net 30 g (71.7 mmol)) is changed to the mixture B: 43.8 g (intermediate B net 30 g (71.7 mmol)).
  • the dropping of methanol was changed from 1.5 hours to 3 hours.
  • the amount of dropped methanol became 29% of the total amount of methanol, particles were generated and rapidly increased (condition (1)).
  • step (B) a pale yellow solid was obtained by centrifugal filtration (step (B)).
  • the obtained solid was dried in a vacuum dryer to obtain 34.01 g of the polymerizable compound 1 as a pale yellow solid.
  • the yield was 89.2 mol% (based on 2,5-dihydroxybenzaldehyde).
  • step 4 of Example 1 the mixture A: 32.4 g (intermediate B net 30 g (71.7 mmol)) was changed to intermediate B: 30.0 g (71.7 mmol), and methanol was added dropwise. The same operation was performed except that the change was made from 5 hours to 3 hours. As a result, when the amount of dropped methanol became 27% of the total amount of methanol, particles were generated and rapidly increased (condition (1)).
  • step (B) a pale yellow solid was obtained by centrifugal filtration.
  • the obtained solid was dried in a vacuum dryer to obtain 34.13 g of the polymerizable compound 1 as a pale yellow solid.
  • the yield was 89.5 mol% (based on 2,5-dihydroxybenzaldehyde).
  • the temperature of the reaction solution was raised to 40 ° C., and the reaction was carried out for 4 hours. After completion of the reaction, the aqueous layer was extracted. Further, 105 g of distilled water was added to the organic layer, and the organic layer was washed by stirring at 40 ° C. for 30 minutes. After extracting the aqueous layer, the organic layer was cooled to 25 ° C., 1.5 g of Rocahelp # 479 was added, and the mixture was stirred for 30 minutes. Then, filtration was performed with a Kiriyama funnel on which 1 g of Rocahelp # 479 was laid, and Rocahelp # 479 was removed.
  • the concentration of the polymerizable compound 1 was quantified, it was 103%, 105%, and 106% with respect to the saturated solubility in each solvent composition.
  • the mixture was aged by stirring at 15 ° C. for 30 minutes.
  • the particle size distribution of the precipitated particles was measured immediately before filtration, the particles having a particle size of 50 to 2000 ⁇ m were 80% of the total number of particles.
  • a pale yellow solid was obtained by centrifugal filtration. The obtained pale yellow solid was dissolved in 120 g of tetrahydrofuran at 25 ° C., 1.5 g of Rocahelp # 479 was added, and the mixture was stirred for 30 minutes.
  • step (B) When the particle size distribution of the precipitated particles was measured immediately before filtration, the particles having a particle size of 50 to 2000 ⁇ m were 87% of the total number of particles. Then, a pale yellow solid was obtained by centrifugal filtration (step (B)). The obtained solid was dried in a vacuum dryer to obtain 33.59 g of the polymerizable compound 1 as a pale yellow solid. The yield was 88.1 mol% (based on 2,5-dihydroxybenzaldehyde).
  • step 1 of Example 7 the mixture A: 32.4 g (intermediate B net 30 g (71.7 mmol)) is changed to the mixture B: 43.8 g (intermediate B net 30 g (71.7 mmol)). The same operation was performed except for the above. As a result, when the amount of dropped methanol became 28% of the total amount of methanol, particles were generated and rapidly increased (condition (1)).
  • step (B) When the particle size distribution of the precipitated particles was measured immediately before filtration, the particles having a particle size of 50 to 2000 ⁇ m were 86% of the total number of particles. Then, a pale yellow solid was obtained by centrifugal filtration (step (B)). The obtained solid was dried in a vacuum dryer to obtain 32.98 g of the polymerizable compound 1 as a pale yellow solid. The yield was 86.5 mol% (based on 2,5-dihydroxybenzaldehyde).
  • Example 9 Synthesis of polymerizable compound 1
  • step 1 of Example 7 the same operation was carried out except that the dropping of methanol was changed from 1.5 hours to 3 hours. As a result, when the amount of dropped methanol became 27% of the total amount of methanol, particles were generated and rapidly increased (condition (1)). When the amount of dropped methanol reaches 30%, 35%, and 40% of the total amount of methanol, respectively, sampling is performed, and the mixture is filtered through a disk-type filter having a pore size of 0.45 ⁇ m in the filtrate.
  • the concentration of the polymerizable compound 1 was quantified, it was 135%, 140%, and 215% with respect to the saturated solubility in each solvent composition (condition (2)). Then, after dropping the entire amount of methanol, the mixture was cooled to 0 ° C. over 30 minutes and aged by stirring at 0 ° C. for 30 minutes as it was. When the particle size distribution of the precipitated particles was measured immediately before filtration, the particles having a particle size of 50 to 2000 ⁇ m were 85% of the total number of particles. Then, a pale yellow solid was obtained by centrifugal filtration (step (B)). The obtained solid was dried in a vacuum dryer to obtain 32.95 g of the polymerizable compound 1 as a pale yellow solid. The yield was 86.4 mol% (based on 2,5-dihydroxybenzaldehyde).
  • step 1 of Example 7 the mixture A: 32.4 g (intermediate B net 30 g (71.7 mmol)) is changed to the mixture B: 43.8 g (intermediate B net 30 g (71.7 mmol)).
  • step 1 of Example 7 the mixture A: 32.4 g (intermediate B net 30 g (71.7 mmol)) is changed to the mixture B: 43.8 g (intermediate B net 30 g (71.7 mmol)).
  • the dropping of methanol was changed from 1.5 hours to 3 hours.
  • the amount of dropped methanol became 28% of the total amount of methanol, particles were generated and rapidly increased (condition (1)).
  • step (B) When the particle size distribution of the precipitated particles was measured immediately before filtration, the particles having a particle size of 50 to 2000 ⁇ m were 85% of the total number of particles. Then, a pale yellow solid was obtained by centrifugal filtration (step (B)). The obtained solid was dried in a vacuum dryer to obtain 32.72 g of the polymerizable compound 1 as a pale yellow solid. The yield was 85.8 mol% (based on 2,5-dihydroxybenzaldehyde).
  • Step 1 Synthesis of Intermediate D> ...
  • Intermediate D In a three-port reactor equipped with a thermometer, 500.5 g (2.69 mol) of 1-naphthylacetic acid was added to 1049 g of toluene in a nitrogen stream. Further, 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 using a Dean-Stark apparatus, and azeotropic dehydration (internal temperature of about 95 ° C.) was carried out for 2 hours while discharging the produced water to the outside of the reaction system.
  • azeotropic dehydration internal temperature of about 95 ° C.
  • 275 g of a 9.1 mass% sodium chloride aqueous solution was added to the organic layer, the mixture was stirred at an internal temperature of 60 ° C. for 30 minutes, and then allowed to stand for 30 minutes to extract the aqueous layer.
  • 262.5 g of a 4.76 mass% sodium hydrogen carbonate aqueous solution was added to the organic layer, the mixture was stirred at an internal temperature of 60 ° C. for 30 minutes, and then allowed to stand for 30 minutes to extract the aqueous layer.
  • 250 g of water was added to the organic layer, the mixture was stirred at an internal temperature of 60 ° C. for 30 minutes, and then allowed to stand for 30 minutes to extract the aqueous layer.
  • the obtained organic layer was gradually cooled to 0 ° C. and stirred at 0 ° C. for 30 minutes.
  • the resulting solid was obtained by filtration.
  • 150 g of ethyl acetate was added to the obtained solid, the temperature was raised to 60 ° C. to prepare a uniform solution, and the mixture was stirred for 30 minutes.
  • the ethyl acetate solution was gradually cooled to 0 ° C., and the mixture was stirred at 0 ° C. for 1 hour.
  • the resulting solid was obtained by filtration and dried under reduced pressure to obtain 36.9 g of Intermediate E as a white solid.
  • the yield was 56.4 mol%.
  • Step 3 Synthesis of polymerizable compound 2> A mixture A containing the intermediate B synthesized in step 2 of Example 1 in the above-mentioned Example 1 step 2 as a main component in a three-port reactor equipped with a thermometer: 32.40 g (intermediate B net 30.00 g (71. 69 mmol)), 300 g of chloroform, and 10.47 g of dimethylformamide (DMF) were added and cooled to 10 ° C. or lower. 9.81 g (82.46 mmol) of thionyl chloride was added dropwise thereto under control so that the reaction temperature was 10 ° C. or lower. After completion of the dropping, the reaction solution was returned to 25 ° C. and stirred for 1 hour.
  • a thermometer 32.40 g (intermediate B net 30.00 g (71. 69 mmol)), 300 g of chloroform, and 10.47 g of dimethylformamide (DMF) were added and cooled to 10 ° C. or lower.
  • reaction was carried out for another 1 hour while keeping the reaction solution at 10 ° C. or lower. After that, 120 g of a 1.0 specified hydrochloric acid aqueous solution was further added, and the mixture was stirred at 10 ° C. or lower for 30 minutes to carry out the reaction. After completion of the reaction, 18.36 g (42.35 mmol) of the intermediate E synthesized in the above step 2 was further added to the obtained reaction solution at 10 ° C. or lower. Then, the temperature of the reaction solution was raised to 40 ° C., and the reaction was carried out for 5 hours. After completion of the reaction, the reaction solution was cooled to 25 ° C. and a liquid separation operation was performed.
  • Rocahelp # 479 manufactured by Mitsui Mining & Smelting Co., Ltd.
  • Rocahelp # 479 was washed with 15 g of chloroform and combined with the previously obtained filtrate to obtain an organic layer.
  • 600 g of methanol was added at 25 ° C. in a nitrogen stream to a three-port reactor equipped with a thermometer. The previously obtained organic layer was slowly added dropwise to this methanol at 25 ° C. over 30 minutes with stirring at 200 rpm. After completion of the dropping, the mixture was stirred as it was for 30 minutes.
  • step (B) a pale yellow solid was obtained by centrifugal filtration (step (B)).
  • the obtained solid was dried in a vacuum dryer to obtain 41.04 g of the polymerizable compound 2 as a pale yellow solid.
  • the yield was 93.0 mol% (based on 2,5-dihydroxybenzaldehyde).
  • step 3 of the eleventh embodiment 32.40 g of the mixture A containing the intermediate B synthesized in step 2 of the first embodiment as a main component (30.00 g (71.69 mmol) as the net of the intermediate B) was added. The same operation was carried out except that the mixture B synthesized in Example 2 was changed to 43.8 g (intermediate B net 30 g (71.7 mmol)) and the dropping of methanol was changed from 1.5 hours to 3 hours. .. As a result, when the amount of dropped methanol became 27% of the total amount of methanol, particles were generated and rapidly increased (condition (1)).
  • step (B) a pale yellow solid was obtained by centrifugal filtration (step (B)).
  • the obtained solid was dried in a vacuum dryer to obtain 40.16 g of the polymerizable compound 2 as a pale yellow solid.
  • the yield was 91.0 mol% (based on 2,5-dihydroxybenzaldehyde).
  • Example 13 Synthesis of polymerizable compound 2
  • Step 1 Synthesis of polymerizable compound 2> A mixture A containing the intermediate B synthesized in step 2 of Example 1 as a main component in a nitrogen stream in a three-port reactor equipped with a thermometer: 32.40 g (intermediate B net 30.00 g (71)). .69 mmol)), 300 g of chloroform, and 10.47 g of dimethylformamide (DMF) were added and cooled to 10 ° C. or lower. 9.81 g (82.46 mmol) of thionyl chloride was added dropwise thereto under control so that the reaction temperature was 10 ° C. or lower.
  • DMF dimethylformamide
  • reaction solution was returned to 25 ° C. and stirred for 1 hour.
  • 225 g of chloroform was extracted by an evaporator.
  • 75 g of chloroform was added to obtain a chloroform solution of the acid chloride of Intermediate B.
  • 4.5 g (32.58 mmol) of 2,5-dihydroxybenzaldehyde and 19.77 g (195.38 mmol) of triethylamine as a base were added to 150 g of chloroform in a nitrogen stream. Was dissolved in, and cooled to 10 ° C. or lower.
  • a chloroform solution of the acid chloride of Intermediate B previously synthesized was slowly added dropwise to this solution while maintaining the internal temperature of the reaction solution at 10 ° C. or lower. After completion of the dropping, the reaction was carried out for another 1 hour while keeping the reaction solution at 10 ° C. or lower. After that, 120 g of a 1.0 specified hydrochloric acid aqueous solution was further added, and the mixture was stirred at 10 ° C. or lower for 30 minutes to carry out the reaction. After completion of the reaction, 18.36 g (42.35 mmol) of Intermediate E: 18.36 g (42.35 mmol) was further added to the obtained reaction solution at 10 ° C. or lower.
  • condition (1) when the amount of dropped methanol became 24% of the total amount of methanol, particles were generated and rapidly increased (condition (1)).
  • condition (2) When the concentration of the polymerizable compound 2 was quantified, it was 142%, 145%, and 161% with respect to the saturated solubility in each solvent composition (condition (2)). Then, after dropping the entire amount of methanol, the mixture was cooled to 0 ° C.
  • step (B) The obtained solid was dried in a vacuum dryer to obtain 41.93 g of the polymerizable compound 2 as a pale yellow solid.
  • the yield was 95.0 mol% (based on 2,5-dihydroxybenzaldehyde).
  • Step 2 Synthesis of polymerizable compound 1>
  • Step 4 of Example 1 10.57 g (42.4 mmol) of Intermediate C synthesized in Step 3 is used as an intermediate C of 10.57 g (42.4 mmol) synthesized in Step 1 of Example 14.
  • the same operation was performed except that it was changed to.
  • the amount of dropped methanol became 27% of the total amount of methanol, particles were generated and rapidly increased (condition (1)).
  • sampling is performed, and the mixture is filtered through a disk-type filter having a pore size of 0.45 ⁇ m in the filtrate.
  • the concentration of the polymerizable compound 1 was quantified, it was 139%, 141%, and 232% with respect to the saturated solubility in each solvent composition (condition (2)). Then, after dropping the entire amount of methanol, the mixture was aged by stirring at 15 ° C. for 30 minutes as it was. When the particle size distribution of the precipitated particles was measured immediately before filtration, the particles having a particle size of 50 to 2000 ⁇ m were 89% of the total number of particles. Then, a pale yellow solid was obtained by centrifugal filtration (step (B)). The obtained solid was dried in a vacuum dryer to obtain 39.76 g of the polymerizable compound 1 as a pale yellow solid. The yield was 90.1 mol% (based on 2,5-dihydroxybenzaldehyde).
  • Example 15 Production of polymerizable compound 1
  • step 4 of Example 1 an intermediate obtained by synthesizing 10.57 g (42.4 mmol) of the intermediate C synthesized in Step 3 in Step 1 of Example 14
  • the body C was changed to 10.57 g (42.4 mmol) and the dropping of methanol was changed from 1.5 hours to 3 hours.
  • condition (1) when the amount of dropped methanol became 27% of the total amount of methanol, particles were generated and rapidly increased
  • step (B) a pale yellow solid was obtained by centrifugal filtration (step (B)).
  • the obtained solid was dried in a vacuum dryer to obtain 33.90 g of the polymerizable compound 1 as a pale yellow solid.
  • the yield was 88.9 mol% (based on 2,5-dihydroxybenzaldehyde).
  • step 1 of Example 7 the mixture A: 32.4 g (intermediate B net 30 g (71.7 mmol)) is changed to the mixture B: 43.8 g (intermediate B net 30 g (71.7 mmol)).
  • step 3 the same operation except that the intermediate C: 10.57 g (42.4 mmol) synthesized in step 3 was changed to the intermediate C: 10.57 g (42.4 mmol) synthesized in step 1 of Example 14.
  • condition (1) when the amount of dropped methanol became 28% of the total amount of methanol, particles were generated and rapidly increased.
  • step (B) a pale yellow solid was obtained by centrifugal filtration.
  • the obtained solid was dried in a vacuum dryer to obtain 34.89 g of the polymerizable compound 1 as a pale yellow solid.
  • the yield was 91.5 mol% (based on 2,5-dihydroxybenzaldehyde).
  • the temperature of the reaction solution was raised to 40 ° C., and the reaction was carried out for 4 hours. After completion of the reaction, the aqueous layer was extracted. Further, 105 g of distilled water was added to the organic layer, and the organic layer was washed by stirring at 40 ° C. for 30 minutes. After extracting the aqueous layer, the organic layer was cooled to 25 ° C., 1.5 g of Rocahelp # 479 was added, and the mixture was stirred for 30 minutes. Then, filtration was performed with a Kiriyama funnel on which 1 g of Rocahelp # 479 was laid, and Rocahelp # 479 was removed.
  • the concentration of the polymerizable compound 1 was quantified, it was 161%, 155%, and 180% with respect to the saturated solubility in each solvent composition (condition (2)). Then, after dropping the entire amount of methanol, the mixture was cooled to 0 ° C. over 30 minutes and aged by stirring at 0 ° C. for 30 minutes as it was. When the particle size distribution of the precipitated particles was measured immediately before filtration, the particles having a particle size of 50 to 2000 ⁇ m were 86% of the total number of particles. Then, a pale yellow solid was obtained by centrifugal filtration (step (B)). The obtained solid was dried in a vacuum dryer to obtain 33.94 g of the polymerizable compound 1 as a pale yellow solid. The yield was 89.0 mol% (based on 2,5-dihydroxybenzaldehyde).
  • Example 18 Synthesis of polymerizable compound 1>
  • step 1 of Example 17 32.4 g of mixture A (30 g (71.7 mmol) as net of intermediate B) was synthesized in step 1 of Example 2 and 43.8 g of mixture B (net of intermediate B). The same operation was carried out except that the amount was changed to 30 g (71.7 mmol). As a result, when the amount of dropped methanol became 27% of the total amount of methanol, particles were generated and rapidly increased (condition (1)).
  • step (B) When the particle size distribution of the precipitated particles was measured immediately before filtration, the particles having a particle size of 50 to 2000 ⁇ m were 89% of the total number of particles. Then, a pale yellow solid was obtained by centrifugal filtration (step (B)). The obtained solid was dried in a vacuum dryer to obtain 33.90 g of the polymerizable compound 1 as a pale yellow solid. The yield was 88.9 mol% (based on 2,5-dihydroxybenzaldehyde).
  • Step 1 Production of polymerizable compound 1>
  • 10.57 g (42.4 mmol) of Intermediate C synthesized in Step 3 of Example 1 was combined with 10.57 g of Intermediate C synthesized in Step 1 of Example 14 (10.57 g).
  • the same operation was performed except that the value was changed to 42.4 mmol).
  • the amount of dropped methanol became 24% of the total amount of methanol, particles were generated and rapidly increased (condition (1)).
  • step (B) When the particle size distribution of the precipitated particles was measured immediately before filtration, the particles having a particle size of 50 to 2000 ⁇ m were 85% of the total number of particles. Then, a pale yellow solid was obtained by centrifugal filtration (step (B)). The obtained solid was dried in a vacuum dryer to obtain 33.98 g of the polymerizable compound 1 as a pale yellow solid. The yield was 89.1 mol% (based on 2,5-dihydroxybenzaldehyde).
  • Step 1 Synthesis of polymerizable compound 1>
  • 32.4 g of mixture A (30 g (71.7 mmol) as net of intermediate B) was synthesized in step 1 of Example 2 and 43.8 g of mixture B (net of intermediate B). 30 g (71.7 mmol)), and the intermediate C: 10.57 g (42.4 mmol) synthesized in step 3 of Example 1 was synthesized as an intermediate C: 10.
  • the same operation was performed except that the content was changed to 57 g (42.4 mmol).
  • the amount of dropped methanol became 25% of the total amount of methanol, particles were generated and rapidly increased (condition (1)).
  • step (B) When the particle size distribution of the precipitated particles was measured immediately before filtration, the particles having a particle size of 50 to 2000 ⁇ m were 87% of the total number of particles. Then, a pale yellow solid was obtained by centrifugal filtration (step (B)). The obtained solid was dried in a vacuum dryer to obtain 33.25 g of the polymerizable compound 1 as a pale yellow solid. The yield was 87.2 mol% (based on 2,5-dihydroxybenzaldehyde).
  • Step 2 Synthesis of polymerizable compound 1> Obtained by dissolving 4.13 g (29.9 mmol) of 2,5-dihydroxybenzaldehyde and 7.62 g (75.4 mmol) of triethylamine in 150 g of THF in a nitrogen stream in a three-port reactor equipped with a thermometer.
  • the solution was cooled to 10 ° C. or lower.
  • a solution of 150 g of toluene of Intermediate F synthesized in Step 1 was slowly added dropwise to this solution while maintaining the reaction temperature at 10 ° C. or lower.
  • the whole volume was further stirred at 5 to 10 ° C. for 1 hour.
  • the reaction solution became creamy because the hydrochloride salt of triethylamine produced by the reaction was precipitated.
  • 9.7 g (38.9 mmol) of the intermediate C synthesized in step 3 of Example 1 and 30 g of a 1.0 specified hydrochloric acid aqueous solution were added to the reaction solution while keeping the temperature at 10 ° C. or lower. It was.
  • the temperature of the reaction solution was raised to 40 ° C., and the reaction was carried out for 5 hours.
  • the precipitated triethylamine hydrochloride was dissolved to form a transparent two-layer solution of toluene and water.
  • the reaction solution was cooled to 25 ° C., 300 g of ethyl acetate and 300 g of 10 wt% saline solution were added to carry out a liquid separation operation.
  • the obtained organic layer was further washed twice with 300 g of 2 wt% saline solution. From the obtained organic layer, about 15% of the total weight was extracted by an evaporator and concentrated.
  • a mixed solvent of 300 g of methanol and 60 g of water was added dropwise to the solution over 1.5 hours with stirring at 200 rpm. Then, the solid was precipitated by cooling to 10 ° C. and stirring for 30 minutes as it was. At this time, when the mixed solvent of 300 g of methanol and 60 g of water dropped was 19% with respect to the total amount of the mixed solvent, particles were generated and rapidly increased (condition (1)). When the amount of the dropped mixed solvent becomes 30%, 35%, and 40%, respectively, with respect to the total amount of the mixed solvent, sampling is performed, and filtration is performed with a disk-type filter having a pore size of 0.45 ⁇ m.
  • step 2 of Comparative Example 1 the same operation was carried out except that the dropping of the mixed solvent of 300 g of methanol and 60 g of water was changed from 1.5 hours to 3 hours.
  • the amount of the dropped mixed solvent was 19% of the total amount of the mixed solvent, particles were generated and rapidly increased (condition (1)).
  • the amount of the dropped mixed solvent becomes 30%, 35%, and 40%, respectively, with respect to the total amount of the mixed solvent, sampling is performed, and filtration is performed with a disk-type filter having a pore size of 0.45 ⁇ m.
  • Step 2 Synthesis of polymerizable compound 1> In a three-port reactor equipped with a thermometer, 4.13 g (29.90 mmol) of 2,5-dihydroxybenzaldehyde and 0.7 g (3.01 mmol) of ( ⁇ ) -10-camphorsulfonic acid were added to 300 g of chloroform in a nitrogen stream. Was dissolved in.
  • the mixture was stirred at 2 ° C. for 1 hour, the reaction solution was returned to 25 ° C., and the mixture was further stirred for 1 hour.
  • 150 ml of a 1N hydrochloric acid aqueous solution was added to the reaction solution to separate the layers, and the organic layer was separated.
  • 1350 g of methanol was added dropwise to the obtained organic layer over 1.5 hours with stirring at 200 rpm to precipitate a solid.
  • the mixture was cooled to 10 ° C. and stirred as it was for 30 minutes to precipitate a solid.
  • condition (1) when the amount of the dropped methanol became 31% of the total amount of methanol, particles were generated and rapidly increased (condition (1)).
  • condition (2) When the concentration of the polymerizable compound 1 was quantified, it was 118%, 120%, and 135% with respect to the saturated solubility in each solvent composition (condition (2)).
  • condition (2) When the particle size distribution of the precipitated particles was measured immediately before filtration, the particles having a particle size of 50 to 2000 ⁇ m were 75% of the total number of particles.
  • step (B) a pale yellow solid was obtained by centrifugal filtration (step (B)).
  • the obtained solid was dried in a vacuum dryer to obtain 27.68 g of the polymerizable compound 1 as a pale yellow solid.
  • the yield was 79.1 mol% (based on 2,5-dihydroxybenzaldehyde).
  • step 2 of Comparative Example 3 the same operation was performed except that the dropping of methanol was changed from 1.5 hours to 3 hours. As a result, when the amount of dropped methanol became 31% of the total amount of methanol, particles were generated and rapidly increased (condition (1)). When the amount of dropped methanol reaches 30%, 35%, and 40% of the total amount of methanol, respectively, sampling is performed, filtration is performed with a disk-type filter having a pore size of 0.45 ⁇ m, and the mixture is contained in the filtrate.
  • reaction solution was concentrated by an evaporator until the amount of the reaction solution was halved. Then, the same amount of toluene as the extracted amount was added, and the mixture was concentrated with an evaporator until the amount of the reaction solution was halved. This operation was repeated 5 times to obtain reaction solution 1.
  • 4.36 g (31.57 mmol) of 2,5-dihydroxybenzaldehyde and 9.60 g (94.87 mmol) of triethylamine were dissolved in 160 g of THF in a nitrogen stream, and 10 It was cooled to below ° C.
  • the reaction solution 1 was slowly added dropwise to this solution while maintaining the internal temperature of the reaction solution at 10 ° C. or lower. After completion of the dropping, the reaction was carried out for another 1 hour while keeping the reaction solution at 10 ° C. or lower. After completion of the reaction, 10.26 g (41.14 mmol) of the intermediate C synthesized in step 3 of Example 1 was added to the reaction solution at 10 ° C. or lower, and 40 g of a 1.0 specified hydrochloric acid aqueous solution was further added. It was. Then, the temperature of the reaction solution was raised to 40 ° C., and the reaction was carried out for 5 hours. The hydrochloride salt of triethylamine that was precipitated when the temperature was raised to 40 ° C.
  • condition (1) when the amount of the dropped methanol became 19% of the total amount of methanol, particles were generated and rapidly increased (condition (1)).
  • condition (2) When the amount of the mixed solvent of 300 g of the dropped methanol and 80 g of water became 30%, 35%, and 40% of the total mixed solvent amount, respectively, sampling was performed to obtain a disk-type filter having a pore size of 0.45 ⁇ m.
  • the concentration of the polymerizable compound 1 in the filtrate was quantified, it was 105%, 108%, and 111% with respect to the saturated solubility in each solvent composition (condition (2)).
  • step (B) When the particle size distribution of the precipitated particles was measured immediately before filtration, the particles having a particle size of 50 to 2000 ⁇ m were 64% of the total number of particles. Then, a pale yellow solid was obtained by centrifugal filtration (step (B)). The obtained solid was dried in a vacuum dryer to obtain 19.40 g of the polymerizable compound 1 as a pale yellow solid. The yield was 52.5 mol% (based on 2,5-dihydroxybenzaldehyde).
  • step 1 of Comparative Example 5 the same operation was carried out except that the dropping of the mixed solvent of 300 g of methanol and 80 g of water was changed from 1.5 hours to 3 hours.
  • the amount of the mixed solvent of 300 g of methanol and 80 g of water became 18% with respect to the total amount of the mixed solvent, particles were generated and rapidly increased (condition (1)).
  • the amount of the dropped mixed solvent becomes 30%, 35%, and 40%, respectively, with respect to the total amount of the mixed solvent, sampling is performed, and filtration is performed with a disk-type filter having a pore size of 0.45 ⁇ m.
  • the reaction was carried out for another 1 hour while keeping the reaction solution at 10 ° C. or lower.
  • 10.13 g (40.62 mmol) of the intermediate C synthesized in step 3 of Example 1 above was added to the reaction solution at 10 ° C. or lower, and 113 g of a 1.0 specified hydrochloric acid aqueous solution was further added. added.
  • the temperature of the reaction solution was raised to 40 ° C., and the reaction was carried out for 3 hours.
  • the reaction solution was cooled to 25 ° C. and a liquid separation operation was performed.
  • a pale yellow solid was obtained by centrifugal filtration.
  • 300 g of THF, Rocahelp # 479: 5.3 g, and 275 mg of 2,6-di-t-butyl-4-methylphenol were added, and the mixture was stirred for 30 minutes, and then Rocahelp # 479 was filtered off.
  • 100 g of THF was distilled off from the obtained reaction solution by an evaporator.
  • 335 g of methanol was added dropwise to the obtained solution at 25 ° C. with stirring at 200 rpm for 1.5 hours, then cooled to 0 ° C. over 30 minutes and stirred as it was for 30 minutes to precipitate a solid.
  • condition (1) when the amount of dropped methanol became 31% of the total amount of methanol, particles were generated and rapidly increased.
  • the amount of dropped methanol reaches 30%, 35%, and 40% of the total amount of methanol, respectively, sampling is performed, and the mixture is filtered through a disk-type filter having a pore size of 0.45 ⁇ m and contained in the filtrate.
  • the concentration of the polymerizable compound 1 was quantified, it was 121%, 125%, and 131% with respect to the saturated solubility in each solvent composition (condition (2)).
  • condition (2) When the particle size distribution of the precipitated particles was measured immediately before filtration, the particles having a particle size of 50 to 2000 ⁇ m were 65% of the total number of particles.
  • step (B) a pale yellow solid was obtained by centrifugal filtration.
  • the obtained solid was dried in a vacuum dryer to obtain 28.24 g of the polymerizable compound 1 as a pale yellow solid.
  • the yield was 77.5 mol% (based on 2,5-dihydroxybenzaldehyde).
  • step 1 of Comparative Example 7 the same operation was performed except that the dropping of methanol was changed from 1.5 hours to 3 hours. As a result, when the amount of the dropped methanol solvent became 30% of the total amount of the mixed solvent, particles were generated and rapidly increased (condition (1)). When the amount of dropped methanol reaches 30%, 35%, and 40% of the total amount of methanol, respectively, sampling is performed, and the mixture is filtered through a disk-type filter having a pore size of 0.45 ⁇ m in the filtrate.
  • the concentration of the polymerizable compound 1 was quantified, it was 111%, 118%, and 121% with respect to the saturated solubility in each solvent composition (condition (2)).
  • the particle size distribution of the precipitated particles was measured immediately before filtration, the particles having a particle size of 50 to 2000 ⁇ m were 58% of the total number of particles.
  • a pale yellow solid was obtained by centrifugal filtration (step (B)).
  • the obtained solid was dried in a vacuum dryer to obtain 27.26 g of the polymerizable compound 1 as a pale yellow solid.
  • the yield was 74.8 mol% (based on 2,5-dihydroxybenzaldehyde).
  • the reaction mixture was concentrated with an evaporator until the amount of the reaction solution was reduced to 1/4. Then, 75 g of chloroform was added to obtain a chloroform solution.
  • a chloroform solution Separately, in a three-port reactor equipped with a thermometer, 4.50 g (32.58 mmol) of 2,5-dihide-mouth xibendaldehyde and 20.94 g (195.41 mmol) of 2,6-lutidine as a base in a nitrogen stream. ) was dissolved in 150 g of chloroform and cooled to 10 ° C. or lower. The chloroform solution was slowly added dropwise to this solution while maintaining the internal temperature of the reaction solution at 10 ° C. or lower.
  • the reaction was carried out for another 1 hour while keeping the reaction solution at 10 ° C. or lower. Further, at 10 ° C. or lower, 10.56 g (42.35 mmol) of the intermediate C synthesized in step 3 of Example 1 was added to the obtained reaction solution, and 120 g of a 1.0 specified hydrochloric acid aqueous solution was added. Was added. Then, the temperature of the reaction solution was raised to 40 ° C., and the reaction was carried out for 3 hours. After completion of the reaction, the reaction solution was cooled to 25 ° C. and a liquid separation operation was performed.
  • Mouth Help # 479 manufactured by Mitsui Mining & Smelting Co., Ltd.
  • Mouth Help # 479 was filtered off.
  • about 80% of the total weight was extracted from the obtained reaction solution by an evaporator and concentrated.
  • the mixture was stirred for 1 hour.
  • 240 g of normal hexane was added dropwise to this solution with stirring at 200 rpm, cooled to 0 ° C. over 30 minutes, and stirred as it was for 30 minutes to precipitate a solid.
  • a pale yellow solid was obtained by centrifugal filtration.
  • 324 g of THF, mouth force help # 479: 5.4 g, and 300 mg of 2,6-di-t-butyl-4-methylphenol were added, and the mixture was stirred for 30 minutes, and then Rocahelp # 479 was filtered off. did.
  • 108 g of THF was distilled off from the obtained reaction solution by an evaporator.
  • 351 g of methanol was added dropwise to the obtained solution at 25 ° C. with stirring at 200 rpm for 1.5 hours, then cooled to 0 ° C. over 30 minutes and stirred as it was for 30 minutes to precipitate a solid.
  • condition (1) when the amount of dropped methanol became 30% of the total amount of methanol, particles were generated and rapidly increased.
  • the amount of dropped methanol reaches 30%, 35%, and 40% of the total amount of methanol, respectively, sampling is performed, and the mixture is filtered through a disk-type filter having a pore size of 0.45 ⁇ m and contained in the filtrate.
  • the concentration of the polymerizable compound 1 was quantified, it was 123%, 128%, and 134% with respect to the saturated solubility in each solvent composition (condition (2)).
  • condition (2) When the particle size distribution of the precipitated particles was measured immediately before filtration, the particles having a particle size of 50 to 2000 ⁇ m were 70% of the total number of particles.
  • step (B) a pale yellow solid was obtained by centrifugal filtration.
  • the obtained solid was dried in a vacuum dryer to obtain 30.62 g of the polymerizable compound 1 as a pale yellow solid.
  • the yield was 80.3 mol% (based on 2,5-dihydroxybenzaldehyde).
  • step 1 of Comparative Example 9 the same operation was performed except that the dropping of methanol was changed from 1.5 hours to 3 hours. As a result, when the amount of the dropped methanol solvent became 30% of the total amount of the mixed solvent, particles were generated and rapidly increased (condition (1)). When the amount of dropped methanol reaches 30%, 35%, and 40% of the total amount of methanol, respectively, sampling is performed, and the mixture is filtered through a disk-type filter having a pore size of 0.45 ⁇ m and contained in the filtrate.
  • the reaction mixture was concentrated with an evaporator until the amount of the reaction solution was reduced to 1/4. Then, 75 g of chloroform was added to obtain a chloroform solution.
  • a chloroform solution Separately, in a three-port reactor equipped with a thermometer, 4.50 g (32.58 mmol) of 2,5-dihide-mouth xibendaldehyde and 20.94 g (195.41 mmol) of 2,6-lutidine as a base in a nitrogen stream. ) was dissolved in 150 g of chloroform and cooled to 10 ° C. or lower. The chloroform solution was slowly added dropwise to this solution while maintaining the internal temperature of the reaction solution at 10 ° C. or lower.
  • the reaction was carried out for another 1 hour while keeping the reaction solution at 10 ° C. or lower. Further, the intermediate E: 16.98 g (39.16 mmol) synthesized in step 2 of Example 11 was added to the obtained reaction solution at 10 ° C. or lower, and 120 g of a 1.0 specified hydrochloric acid aqueous solution was further added. Was added. Then, the temperature of the reaction solution was raised to 40 ° C., and the reaction was carried out for 3 hours. After completion of the reaction, the reaction solution was cooled to 25 ° C. and a liquid separation operation was performed.
  • Rocahelp # 479 manufactured by Mitsui Mining & Smelting Co., Ltd.
  • Rocahelp # 479 was filtered off.
  • about 60% of the total weight was extracted from the obtained reaction solution by an evaporator and concentrated.
  • the mixture was cooled to 15 ° C. and stirred for 30 minutes.
  • 210 g of normal hexane was added dropwise to this solution over 1.5 hours while stirring at 200 rpm, and the mixture was stirred as it was for 30 minutes to precipitate a solid.
  • condition (1) when the amount of dropped methanol became 25% of the total amount of methanol, particles were generated and rapidly increased.
  • the amount of dropped methanol reaches 30%, 35%, and 40% of the total amount of methanol, respectively, sampling is performed, and the mixture is filtered through a disk-type filter having a pore size of 0.45 ⁇ m and contained in the filtrate.
  • condition (2) When the concentration of the polymerizable compound 1 was quantified, it was 118%, 121%, and 135% with respect to the saturated solubility in each solvent composition.
  • condition (2) When the particle size distribution of the precipitated particles was measured immediately before filtration, the particles having a particle size of 50 to 2000 ⁇ m were 72% of the total number of particles.
  • step (B) a pale yellow solid was obtained by centrifugal filtration (step (B)).
  • the obtained solid was dried in a vacuum dryer to obtain 35.17 g of the polymerizable compound 2 as a pale yellow solid.
  • the yield was 79.7 mol% (based on 2,5-dihydroxybenzaldehyde).
  • Step 1 Synthesis of Polymerizable Compound 1>
  • step 1 of Comparative Example 9 30.8 g (71.69 mmol) of intermediate B synthesized in step 1 of Example 3 was synthesized in step 1 of Example 2 and 43.8 g (intermediate) of the mixture.
  • the same operation was carried out except that the net body B was changed to 30 g (71.7 mmol)) and the dropping of methanol was changed from 1.5 hours to 3 hours.
  • the amount of the dropped methanol solvent was 28% of the total amount of the mixed solvent (condition (1)).
  • step 4 of Example 1 Production of Polymerizable Compound 1 ⁇ Step 1: Synthesis of Polymerizable Compound 1>
  • step 4 of Example 1 the same operation was performed except that the dropping of methanol was changed from 1.5 hours to 30 minutes.
  • the amount of dropped methanol became 32% of the total amount of methanol, particles were generated and rapidly increased (condition (1)).
  • the amount of dropped methanol reaches 30%, 35%, and 40% of the total amount of methanol, respectively, sampling is performed, and the mixture is filtered through a disk-type filter having a pore size of 0.45 ⁇ m in the filtrate.
  • the concentration of the polymerizable compound 1 was quantified, it was 198%, 235%, and 320% with respect to the saturated solubility in each solvent composition (condition (2)). Then, after the total amount of methanol was added dropwise, the mixture was aged by stirring for 30 minutes as it was. When the particle size distribution of the precipitated particles was measured immediately before filtration, the particles having a particle size of 50 to 2000 ⁇ m were 77% of the total number of particles. Then, a pale yellow solid was obtained by centrifugal filtration (step (B)). The obtained solid was dried in a vacuum dryer to obtain 32.15 g of the polymerizable compound 1 as a pale yellow solid. The yield was 84.3 mol% (based on 2,5-dihydroxybenzaldehyde).
  • step 4 of Example 1 the same operation was performed except that the dropping of methanol was changed from 1.5 hours to 5 hours. As a result, when the amount of dropped methanol became 24% of the total amount of methanol, particles were generated and rapidly increased (condition (1)). When the amount of dropped methanol reaches 30%, 35%, and 40% of the total amount of methanol, respectively, sampling is performed, and the mixture is filtered through a disk-type filter having a pore size of 0.45 ⁇ m and contained in the filtrate.
  • the concentration of the polymerizable compound 1 was quantified, it was 110%, 117%, and 128% with respect to the saturated solubility in each solvent composition (condition (2)). Then, after the total amount of methanol was added dropwise, the mixture was aged by stirring for 30 minutes as it was. When the particle size distribution of the precipitated particles was measured immediately before filtration, the particles having a particle size of 50 to 2000 ⁇ m were 63% of the total number of particles. Then, a pale yellow solid was obtained by centrifugal filtration (step (B)). The obtained solid was dried in a vacuum dryer to obtain 29.29 g of the polymerizable compound 1 as a pale yellow solid. The yield was 76.8 mol% (based on 2,5-dihydroxybenzaldehyde).
  • step 1 of Example 17 the same operation was performed except that the dropping of methanol was changed from 1.5 hours to 30 minutes. As a result, when the amount of dropped methanol became 33% of the total amount of methanol, particles were generated and rapidly increased (condition (1)). When the amount of dropped methanol reaches 30%, 35%, and 40% of the total amount of methanol, respectively, sampling is performed, and the mixture is filtered through a disk-type filter having a pore size of 0.45 ⁇ m and contained in the filtrate.
  • the concentration of the polymerizable compound 1 was quantified, it was 205%, 234%, and 328% with respect to the saturated solubility in each solvent composition (condition (2)). Then, after the total amount of methanol was added dropwise, the mixture was aged by stirring for 30 minutes as it was. When the particle size distribution of the precipitated particles was measured immediately before filtration, the particles having a particle size of 50 to 2000 ⁇ m were 74% of the total number of particles. Then, a pale yellow solid was obtained by centrifugal filtration (step (B)). The obtained solid was dried in a vacuum dryer to obtain 32.49 g of the polymerizable compound 1 as a pale yellow solid. The yield was 85.2 mol% (based on 2,5-dihydroxybenzaldehyde).
  • step 1 of Example 17 the same operation was performed except that the dropping of methanol was changed from 1.5 hours to 5 hours. As a result, when the amount of dropped methanol became 23% of the total amount of methanol, particles were generated and rapidly increased (condition (1)). When the amount of dropped methanol reaches 30%, 35%, and 40% of the total amount of methanol, respectively, sampling is performed, filtration is performed with a disk-type filter having a pore size of 0.45 ⁇ m, and the mixture is contained in the filtrate.
  • the concentration of the polymerizable compound 1 was quantified, it was 119%, 120%, and 131% with respect to the saturated solubility in each solvent composition (condition (2)). Then, after the total amount of methanol was added dropwise, the mixture was aged by stirring for 30 minutes as it was. When the particle size distribution of the precipitated particles was measured immediately before filtration, the particles having a particle size of 50 to 2000 ⁇ m were 60% of the total number of particles. Then, a pale yellow solid was obtained by centrifugal filtration (step (B)). The obtained solid was dried in a vacuum dryer to obtain 28.94 g of the polymerizable compound 1 as a pale yellow solid. The yield was 75.9 mol% (based on 2,5-dihydroxybenzaldehyde).
  • the liquid crystal compound contained in the solution can be obtained as particles having excellent filterability and a large particle size.

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Abstract

L'invention fournit une technique selon laquelle un composé cristallin liquide contenu dans une solution, est acquis par précipitation en tant que grosses particules d'un diamètre particulaire excellent en termes de propriétés de filtration. Le procédé de fabrication de composé cristallin liquide de l'invention inclut : une étape (A) au cours de laquelle un solvant pauvre est additionné à une solution dans laquelle un composé cristallin liquide est dissous, et des particules de composé cristallin liquide sont mises en croissance ; et une étape (B) au cours de laquelle les particules sont séparées par filtration. La quantité selon laquelle le solvant pauvre est additionné lorsque la précipitation du composé cristallin liquide commence lors de l'étape (A), est inférieure à 30% de la quantité de l'ensemble du solvant pauvre additionné lors de l'étape (A). À l'étape (A), au moment où la quantité selon laquelle le solvant pauvre est additionné atteint 30% ou plus à 40% ou moins de la quantité de l'ensemble du solvant pauvre additionné lors de l'étape (A), la solution est agitée simultanément à une addition de solvant pauvre de sorte que la supersaturation est comprise à l'intérieur d'une plage supérieure ou égale à 125% et inférieure ou égale à 300%.
PCT/JP2020/046554 2019-12-27 2020-12-14 Procédé de fabrication de composé cristallin liquide WO2021131856A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018025770A (ja) * 2016-07-28 2018-02-15 富士フイルム株式会社 液晶混合物の製造方法
WO2018128084A1 (fr) * 2017-01-06 2018-07-12 Dic株式会社 Composé polymérisable et corps optiquement anisotrope
WO2019230848A1 (fr) * 2018-06-01 2019-12-05 日本ゼオン株式会社 Procédé de production d'un composé polymérisable

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018025770A (ja) * 2016-07-28 2018-02-15 富士フイルム株式会社 液晶混合物の製造方法
WO2018128084A1 (fr) * 2017-01-06 2018-07-12 Dic株式会社 Composé polymérisable et corps optiquement anisotrope
WO2019230848A1 (fr) * 2018-06-01 2019-12-05 日本ゼオン株式会社 Procédé de production d'un composé polymérisable

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