JP5880584B2 - Compound, optical film and method for producing optical film - Google Patents

Compound, optical film and method for producing optical film Download PDF

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JP5880584B2
JP5880584B2 JP2014008335A JP2014008335A JP5880584B2 JP 5880584 B2 JP5880584 B2 JP 5880584B2 JP 2014008335 A JP2014008335 A JP 2014008335A JP 2014008335 A JP2014008335 A JP 2014008335A JP 5880584 B2 JP5880584 B2 JP 5880584B2
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JP2014123134A (en
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大川 春樹
春樹 大川
哲郎 赤坂
哲郎 赤坂
鋼志郎 落合
鋼志郎 落合
忠弘 小林
忠弘 小林
ミア ブラボー ピアオ
ミア ブラボー ピアオ
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住友化学株式会社
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS, OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/30Polarising elements

Description

  The present invention relates to a compound, an optical film, and a method for producing an optical film.

A flat panel display (FPD) includes members using optical films such as a polarizing plate and a retardation plate. Examples of the optical film include an optical film obtained by polymerizing a solution obtained by dissolving a polymerizable compound in a solvent on a supporting substrate. It is known that the phase difference (Re (λ)) of the optical film given by the light of wavelength λnm is determined by the product of the birefringence Δn and the thickness d of the film (Re (λ) = Δn). Xd). The chromatic dispersion characteristic is usually represented by a value (Re (λ) / Re (550)) obtained by dividing the phase difference value Re (λ) at a certain wavelength λ by the phase difference value Re (550) at 550 nm. (Λ) / Re (550)) is close to 1, and [Re (450) / Re (550)] <1 and [Re (650) / Re (550)]> 1. It is known that uniform polarization conversion is possible in the wavelength range shown.
For example, LC242 (manufactured by BASF) is commercially available as the polymerizable compound (Non-Patent Document 1).

Cordula Mock-Knoblauch, Olivier S. Enger, Ulrich D. Schalkowsky, "L-7 Novel Polymerisable Liquid Crys talline Acrylates for the Manufacturing of Ultrathin Optical Films", SID Symposium Digest of Technical Papers, 2006, 37, p.1673

  An object of the present invention is to provide a new compound that provides an optical film capable of uniform polarization conversion in a wide wavelength range.

The present invention is a compound represented by formula (1).
P 1 -F 1- (B 1 -A 1 ) k -E 1 -G 1 -D 1 -Ar-D 2 -G 2 -E 2- (A 2 -B 2 ) 1 -F 2 -P 2 ( 1)
[In the formula (1), Ar represents a divalent group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and π electrons contained in the aromatic ring in the Ar group The number N π is 12 or more.
D 1 and D 2 are each independently * —O—CO— (* represents a position bonded to Ar), —C (═S) —O—, —O—C (═S) —, -CR 1 R 2 -, - CR 1 R 2 -CR 3 R 4 -, - O-CR 1 R 2 -, - CR 1 R 2 -O -, - CR 1 R 2 -O-CR 3 R 4 - , —CR 1 R 2 —O—CO—, —O—CO—CR 1 R 2 —, —CR 1 R 2 —O—CO—R 3 R 4 —, —CR 1 R 2 —CO—O—CR 3 R 4 -, - NR 1 -CR 2 R 3 -, - CR 2 R 3 -NR 1 -, - CO-NR 1 -, or represents a -NR 1 -CO-. R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.
G 1 and G 2 each independently represent a divalent alicyclic hydrocarbon group. The hydrogen atom contained in the alicyclic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group. The methylene group contained in the alicyclic hydrocarbon group may be substituted with —O—, —S—, or —NH—.
E 1, E 2, B 1 and B 2 are each independently, -CR 5 R 6 -, - CH 2 -CH 2 -, - O -, - S -, - CO-O -, - O-CO -, -O-CO-O-, -C (= S) -O-, -OC (= S)-, -O-C (= S) -O-, -CO-NR < 5 >-,- NR 5 —CO—, —O—CH 2 —, —CH 2 —O—, —S—CH 2 —, —CH 2 —S— or a single bond is represented. R 5 and R 6 each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.
A 1 and A 2 each independently represent a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group. The hydrogen atom contained in the divalent alicyclic hydrocarbon group and divalent aromatic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group. It may be substituted with a group. The hydrogen atom contained in the alkyl group having 1 to 4 carbon atoms and the alkoxy group having 1 to 4 carbon atoms may be substituted with a fluorine atom.
k and l each independently represents an integer of 0 to 3.
F 1 and F 2 each independently represents an alkylene group having 1 to 12 carbon atoms. The hydrogen atom contained in the alkylene group 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, and the methylene group contained in the alkylene group is -O -Or -CO- may be substituted.
P 1 and P 2 each independently represent a hydrogen atom or a polymerizable group (provided that at least one of P 1 and P 2 represents a polymerizable group). ]

  According to the compound of the present invention, an optical film capable of uniform polarization conversion in a wide wavelength range can be provided.

The compound of the present invention (hereinafter sometimes referred to as “compound (1)”) is represented by the formula (1).
P 1 -F 1- (B 1 -A 1 ) k -E 1 -G 1 -D 1 -Ar-D 2 -G 2 -E 2- (A 2 -B 2 ) 1 -F 2 -P 2 ( 1)
[In the formula (1), Ar represents a divalent group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and π electrons contained in the aromatic ring in the Ar group The number N π is 12 or more.
D 1 and D 2 are each independently * —O—CO— (* represents a position bonded to Ar), —C (═S) —O—, —O—C (═S) —, -CR 1 R 2 -, - CR 1 R 2 -CR 3 R 4 -, - O-CR 1 R 2 -, - CR 1 R 2 -O -, - CR 1 R 2 -O-CR 3 R 4 - , —CR 1 R 2 —O—CO—, —O—CO—CR 1 R 2 —, —CR 1 R 2 —O—CO—R 3 R 4 —, —CR 1 R 2 —CO—O—CR 3 R 4 -, - NR 1 -CR 2 R 3 -, - CR 2 R 3 -NR 1 -, - CO-NR 1 -, or represents a -NR 1 -CO-. R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.
G 1 and G 2 each independently represent a divalent alicyclic hydrocarbon group. The hydrogen atom contained in the alicyclic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group. The methylene group contained in the alicyclic hydrocarbon group may be substituted with —O—, —S—, or —NH—.
E 1, E 2, B 1 and B 2 are each independently, -CR 5 R 6 -, - CH 2 -CH 2 -, - O -, - S -, - CO-O -, - O-CO -, -O-CO-O-, -C (= S) -O-, -OC (= S)-, -O-C (= S) -O-, -CO-NR < 5 >-,- NR 5 —CO—, —O—CH 2 —, —CH 2 —O—, —S—CH 2 —, —CH 2 —S— or a single bond is represented. R 5 and R 6 each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.
A 1 and A 2 each independently represent a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group. The hydrogen atom contained in the divalent alicyclic hydrocarbon group and divalent aromatic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group. It may be substituted with a group. The hydrogen atom contained in the alkyl group having 1 to 4 carbon atoms and the alkoxy group having 1 to 4 carbon atoms may be substituted with a fluorine atom.
k and l each independently represents an integer of 0 to 3.
F 1 and F 2 each independently represents an alkylene group having 1 to 12 carbon atoms. The hydrogen atom contained in the alkylene group 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, and the methylene group contained in the alkylene group is -O -Or -CO- may be substituted.
P 1 and P 2 each independently represent a hydrogen atom or a polymerizable group (provided that at least one of P 1 and P 2 represents a polymerizable group). ]

It is preferable that a compound (1) satisfies the requirements represented by Formula (2) and Formula (3).
( Nπ- 4) / 3 <k + 1 + 4 (2)
12 ≦ N π ≦ 22 (3)
[In Formula (2) and Formula (3), N π , k, and l represent the same meaning as described above. ]

  Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthroline ring. Examples of the aromatic heterocyclic ring include a furan ring, a pyrrole ring, a thiophene ring, a pyridine ring, a thiazole ring, and a benzothiazole. A ring etc. are mentioned. Of these, a benzene ring, a thiazole ring, and a benzothiazole ring are preferable.

Ar is a divalent group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and the total of π electrons of the aromatic ring contained in the divalent group The number is 12 or more, preferably 12 or more and 22 or less, and more preferably 13 or more and 22 or less.

  Ar is preferably a divalent group having at least two aromatic rings selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring.

  In formula (1), Ar is preferably any divalent group represented by formula (Ar-1) to formula (Ar-13).

[In Formula (Ar-1) to Formula (Ar-13), Z 1 represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 6 carbon atoms, or a carbon number. 1-6 alkylsulfonyl groups, carboxyl groups, C1-C6 fluoroalkyl groups, C1-C6 alkoxy groups, C1-C6 alkylthio groups, C1-C6 N-alkylamino groups Represents an N, N-dialkylamino group having 2 to 12 carbon atoms, an N-alkylsulfamoyl group having 1 to 6 carbon atoms, or an N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms.
Q 1 and Q 3 each independently represent —CR 7 R 8 —, —S—, —NR 7 —, —CO— or —O—.
R 7 and R 8 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
Y 1 , Y 2 and Y 3 each independently represents an optionally substituted aromatic hydrocarbon group or aromatic heterocyclic group.
W 1 and W 2 each independently represent a hydrogen atom, a cyano group, a methyl group, or a halogen atom.
m represents an integer of 0-6.
n represents an integer of 0 to 2. ]

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom, a chlorine atom and a bromine atom are preferable.

  Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. An alkyl group having 1 to 4 carbon atoms is preferable, an alkyl group having 1 to 2 carbon atoms is more preferable, and a methyl group is particularly preferable.

  Examples of the alkylsulfinyl group having 1 to 6 carbon atoms include methylsulfinyl group, ethylsulfinyl group, propylsulfinyl group, isopropylsulfinyl group, butylsulfinyl group, isobutylsulfinyl group, sec-butylsulfinyl group, tert-butylsulfinyl group, pentylsulfinyl group Group, a hexyl group sulfinyl, etc. are mentioned, A C1-C4 alkylsulfinyl group is preferable, A C1-C2 alkylsulfinyl group is more preferable, A methylsulfinyl group is especially preferable.

  Examples of the alkylsulfonyl group having 1 to 6 carbon atoms include methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, butylsulfonyl group, isobutylsulfonyl group, sec-butylsulfonyl group, tert-butylsulfonyl group, pentylsulfonyl Group, a hexylsulfonyl group, etc. are mentioned, A C1-C4 alkylsulfonyl group is preferable, A C1-C2 alkylsulfonyl group is more preferable, A methylsulfonyl group is especially preferable.

  Examples of the fluoroalkyl group having 1 to 6 carbon atoms include a fluoromethyl group, a trifluoromethyl group, a fluoroethyl group, a pentafluoroethyl group, a heptafluoropropyl group, and a nonafluorobutyl group. A fluoroalkyl group is preferred, a C1-C2 fluoroalkyl group is more preferred, and a trifluoromethyl group is particularly preferred.

  Examples of the alkoxy group having 1 to 6 carbon atoms include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, and hexyloxy group. An alkoxy group having 1 to 4 carbon atoms is preferable, an alkoxy group having 1 to 2 carbon atoms is more preferable, and a methoxy group is particularly preferable.

  Examples of the alkylthio group having 1 to 6 carbon atoms include methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, sec-butylthio group, tert-butylthio group, pentylthio group, and hexylthio group. , An alkylthio group having 1 to 4 carbon atoms is preferable, an alkylthio group having 1 to 2 carbon atoms is more preferable, and a methylthio group is particularly preferable.

  Examples of the N-alkylamino group having 1 to 6 carbon atoms include N-methylamino group, N-ethylamino group, N-propylamino group, N-isopropylamino group, N-butylamino group, N-isobutylamino group, N-sec-butylamino group, N-tert-butylamino group, N-pentylamino group, N-hexylamino group and the like can be mentioned, and an N-alkylamino group having 1 to 4 carbon atoms is preferable, and 1 to The N-alkylamino group of 2 is more preferable, and the N-methylamino group is particularly preferable.

  Examples of the N, N-dialkylamino group having 2 to 12 carbon atoms include N, N-dimethylamino group, N-methyl-N-ethylamino group, N, N-diethylamino group, N, N-dipropylamino group, N, N-diisopropylamino group, N, N-dibutylamino group, N, N-diisobutylamino group, N, N-dipentylamino group, N, N-dihexylamino group and the like can be mentioned. An N, N-dialkylamino group is preferable, an N, N-dialkylamino group having 2 to 4 carbon atoms is more preferable, and an N, N-dimethylamino group is particularly preferable.

  Examples of the N-alkylsulfamoyl group having 1 to 6 carbon atoms include N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N- Butylsulfamoyl group, N-isobutylsulfamoyl group, N-sec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N-hexylsulfamoyl group, etc. N-alkylsulfamoyl group having 1 to 4 carbon atoms is preferable, N-alkylsulfamoyl group having 1 to 2 carbon atoms is more preferable, and N-methylsulfamoyl group is particularly preferable.

  Examples of the N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms include N, N-dimethylsulfamoyl group, N-methyl-N-ethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-dipropylsulfamoyl group, N, N-diisopropylsulfamoyl group, N, N-dibutylsulfamoyl group, N, N-diisobutylsulfamoyl group, N, N-dipentylsulfamoyl group, N, N-dihexylsulfamoyl group etc. are mentioned, N2-N-dialkylsulfamoyl group having 2 to 8 carbon atoms is preferable, and N, N-dialkylsulfamoyl group having 2 to 4 carbon atoms is more preferable. N, N-dimethylsulfamoyl group is particularly preferred.

Z 1 represents a halogen atom, methyl group, cyano group, nitro group, carboxyl group, methylsulfonyl group, trifluoromethyl group, methoxy group, methylthio group, N-methylamino group, N, N-dimethylamino group, N- A methylsulfamoyl group or an N, N-dimethylsulfamoyl group is preferred.

Examples of the alkyl group having 1 to 4 carbon atoms in R 7 and R 8 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, and the like. An alkyl group is preferable, and a methyl group is more preferable.
Q 1 is preferably —S—, —CO—, —NH—, —N (CH 3 ) —, and Q 3 is preferably —S—, —CO—.

Examples of the aromatic hydrocarbon group for Y 1 , Y 2 and Y 3 include an aromatic hydrocarbon group having 6 to 20 carbon atoms such as a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and a biphenyl group. A naphthyl group is preferred, and a phenyl group is more preferred. The aromatic heterocyclic group contains at least one hetero atom such as a furyl group, a pyrrolyl group, a thienyl group, a pyridinyl group, a thiazolyl group, a benzothiazolyl group, and the like, and has 4 to 20 carbon atoms. And a furyl group, a pyrrolyl group, a thienyl group, a pyridinyl group, and a thiazolyl group are preferable.

  Such aromatic hydrocarbon group and aromatic heterocyclic group may have at least one substituent, such as a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, C1-C6 alkylsulfinyl group, C1-C6 alkylsulfonyl group, carboxyl group, C1-C6 fluoroalkyl group, C1-C6 alkoxy group, C1-C6 alkylthio group N-alkylamino group having 1 to 6 carbon atoms, N, N-dialkylamino group having 2 to 12 carbon atoms, N-alkylsulfamoyl group having 1 to 6 carbon atoms, N, N having 2 to 12 carbon atoms -Dialkylsulfamoyl group etc. are mentioned, a halogen atom, a C1-C2 alkyl group, a cyano group, a nitro group, a C1-C2 alkylsulfonyl group, a C1-C2 fluoroalkyl group, carbon C 1-2 alkoxy group, C 1-2 alkylthio group, C 1-2 N-alkylamino group, C 2-4 N, N-dialkylamino group, C 1-2 alkyl A sulfamoyl group is preferred.

  Halogen atom, alkyl group having 1 to 6 carbon atoms, cyano group, nitro group, alkylsulfinyl group having 1 to 6 carbon atoms, alkylsulfonyl group having 1 to 6 carbon atoms, carboxyl group, fluoroalkyl group having 1 to 6 carbon atoms , An alkoxy group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, an N-alkylamino group having 1 to 6 carbon atoms, an N, N-dialkylamino group having 2 to 12 carbon atoms, and 1 to 6 carbon atoms Examples of the N-alkylsulfamoyl group and the N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms are the same as those described above.

Y 1 , Y 2 and Y 3 are preferably each independently any group represented by formula (Y-1) to formula (Y-6).

[In Formula (Y-1) to Formula (Y-6), Z 2 represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 6 carbon atoms, or a carbon number. 1-6 alkylsulfonyl group, carboxyl group, C1-C6 fluoroalkyl group, C1-C6 alkoxy group, C1-C6 thioalkyl group, C1-C6 N-alkylamino group Represents an N, N-dialkylamino group having 2 to 12 carbon atoms, an N-alkylsulfamoyl group having 1 to 6 carbon atoms, or an N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms.
a 1 is an integer of 0 to 5, a 2 is an integer of 0 to 4, b 1 is an integer of 0 to 3, b 2 is an integer of 0 to 2, and R is a hydrogen atom or a methyl group. . ]

Z 2 is preferably a halogen atom, methyl group, cyano group, nitro group, sulfone group, carboxyl group, trifluoromethyl group, methoxy group, thiomethyl group, N, N-dimethylamino group or N-methylamino group.

Further, Y 1 , Y 2 and Y 3 are each independently a group represented by the formula (Y-1) or the formula (Y-3) in terms of the production process and cost of the compound (1). Particularly preferred.

W 1 and W 2 are each independently preferably a hydrogen atom, a cyano group or a methyl group, and particularly preferably a hydrogen atom.
m is preferably 0 or 1. n is preferably 0.

  In formula (1), Ar is a divalent group represented by formula (Ar-6a), formula (Ar-6b), formula (Ar-6c), formula (Ar-10a) or (Ar-10b). It is more preferable that

[In Formula (Ar-6a) to Formula (Ar-6c), Formula (Ar-10a) and Formula (Ar-10b), Z 1 , n, Q 1 , Z 2 , a 1 and b 1 are Represents the same meaning. ]

  Examples of Ar are shown in Formula (ar-1) to Formula (ar-189).

  Specific examples of the groups represented by formula (Ar-1) to formula (Ar-4) include groups represented by formula (ar-1) to formula (ar-29).

  Specific examples of the group represented by the formula (Ar-5) include groups represented by the formula (ar-30) to the formula (ar-39).

  Specific examples of the group represented by formula (Ar-6) or formula (Ar-7) include groups represented by formula (ar-40) to formula (ar-119).


  Specific examples of the group represented by formula (Ar-8) or formula (Ar-9) include groups represented by formula (ar-120) to formula (ar-129).

  Specific examples of the group represented by formula (Ar-10) include groups represented by formula (ar-130) to formula (ar-149).

  Specific examples of the group represented by the formula (Ar-11) include groups represented by the formula (ar-150) to the formula (ar-159).

  Specific examples of the group represented by the formula (Ar-12) include groups represented by the formula (ar-160) to the formula (ar-179).

  Specific examples of the group represented by the formula (Ar-13) include groups represented by the formula (ar-180) to the formula (ar-189).

D 1 and D 2 are * —O—CO—, * —O—C (═S) —, * —O—CR 1 R 2 —, * —NR 1 —CR 2 R 3 — or * —NR 1. -CO-(* represents a binding site with Ar.
) Is preferable. More preferably, D 1 and D 2 are * —O—CO—, * —O—C (═S) —, or * —NR 1 —CO— (* represents a binding site with Ar). . R 1 , R 2 , R 3 and R 4 are each independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom, a methyl group or an ethyl group.

Examples of G 1 and G 2 include alicyclic hydrocarbon groups that may include a hetero atom represented by the formula (g-1) to the formula (g-10), and a 5-membered or 6-membered alicyclic ring. It is preferably a formula hydrocarbon group.

  The groups represented by the above formulas (g-1) to (g-10) are alkyl groups having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an isopropyl group and a tert-butyl group; An alkoxy group having 1 to 4 carbon atoms; a fluoroalkyl group having 1 to 4 carbon atoms such as a trifluoromethyl group; a fluoroalkoxy group having 1 to 4 carbon atoms such as a trifluoromethoxy group; a cyano group; a nitro group; May be substituted with a halogen atom such as a chlorine atom or a bromine atom.

G 1 and G 2 are preferably an alicyclic hydrocarbon group composed of a 6-membered ring represented by the formula (g-1), more preferably a 1,4-cyclohexylene group, and trans A -1,4-cyclohexylene group is particularly preferred.

Examples of the divalent alicyclic hydrocarbon group or aromatic hydrocarbon group in A 1 and A 2 include a 5-membered ring or a 6-membered ring represented by the above formula (g-1) to formula (g-10). And a divalent aromatic hydrocarbon group having about 6 to 20 carbon atoms represented by formula (a-1) to formula (a-8).

In addition, as A 1 and A 2 , a part of the hydrogen atoms of the exemplified groups is an alkyl group having about 1 to 4 carbon atoms such as a methyl group, an ethyl group, an i-propyl group, or a t-butyl group; An alkoxy group having about 1 to 4 carbon atoms such as a group or an ethoxy group; a trifluoromethyl group; a trifluoromethyloxy group; a cyano group; a nitro group; and a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom. Also good.

As A 1 and A 2, it is particularly preferable that both are the same type of group because the production of compound (1) is easy. A 1 and A 2 are preferably a monocyclic 1,4-phenylene group or a 1,4-cyclohexylene group, and particularly a 1,4-phenylene group since the production of the compound (1) is easy. Is preferred.

B 1 and B 2 are preferably the same type of divalent group because the production of the compound (1) is easy. Furthermore, since the production of the compound (1) is easier, B 1 and B 2 bonded to only A 1 and A 2 out of B 1 and B 2 are each independently —CH 2 —CH 2. —, —CO—O—, —O—CO—, —CO—NH—, —NH—CO—, —O—CH 2 —, —CH 2 —O— or a single bond is preferable, and particularly high. In view of liquid crystallinity, —CO—O— or —O—CO— is preferable. Of B 1 and B 2, B 1 and B 2 is bound to E 1 or E 2 are each independently, -O -, - CO-O -, - O-CO -, - O-CO- O-, -CO-NH-, -NH-CO- or a single bond is more preferable.

  From the viewpoint of liquid crystallinity, k and l preferably each independently represent an integer of 0 to 3, and k and l are more preferably 0 to 2. The total of k and l is preferably 5 or less, and more preferably 4 or less.

P 1 and P 2 each independently represent a hydrogen atom or a polymerizable group (provided that at least one of P 1 and P 2 represents a polymerizable group). It is preferable that both P 1 and P 2 are polymerizable groups because the film hardness of the obtained optical film tends to be excellent.
The polymerizable group is a substituent capable of polymerizing the compound (1) of the present invention, and specifically includes a vinyl group, p-stilbene group, acryloyl group, methacryloyl group, acryloyloxy group, and methacryloyloxy. Examples include a group, a carboxyl group, a methylcarbonyl group, a hydroxyl group, an amide group, an alkylamino group having 1 to 4 carbon atoms, an amino group, an epoxy group, an oxetanyl group, an aldehyde group, an isocyanate group, or a thioisocyanate group. Also the polymerizable group, in order to bind the above-exemplified group and E 1 and E 2, may include groups represented as B 1 and B 2. For example, radically polymerizable and cationically polymerizable groups suitable for photopolymerization are preferable, and acryloyl group or methacryloyl group is preferable, and acryloyl group is more preferable because it is easy to handle and easy to produce. It is more preferable that both P 1 and P 2 are polymerizable groups because the film hardness of the resulting optical film tends to be excellent.

-D 1 -G 1 -E 1 - ( A 1 -B 1) k -F 1 -P 1, -D 2 -G 2 -E 2 - (A 2 -B 2) of l -F 2 -P 2 Specific examples include groups represented by formula (R-1) to formula (R-134). * (Asterisk) indicates the binding position with Ar. Moreover, n in a formula (R-1)-a formula (R-134) represents the integer of 2-12.

Furthermore, examples of compound (1) include compound (i) to compound (xxxiv). R1 in the table, -D 1 -G 1 -E 1 - a (A 1 -B 1) k -F 1 -P 1, R2 is, -D 2 -G 2 -E 2 - (A 2 -B 2) represents the l -F 2 -P 2.

Note that in the compound (xxx) and the compound (xxxi), any one of the group represented by the formula (1-A) and the group represented by the formula (1-B) is represented by (R-57) to ( R-120).
In Table 1, compound (xvii) is a compound in which the group represented by Ar is a group represented by formula (ar-78), and the compound in which the group represented by Ar is a group represented by formula (ar-79) Or it means that the group represented by Ar is any of a mixture of a compound which is a group represented by the formula (ar-78) and a compound which is a group represented by the formula (ar-79).
In Table 2, the compound (xxx) is a compound in which the group represented by Ar is a group represented by the formula (ar-120), and the compound in which the group represented by Ar is a group represented by the formula (ar-121). Or a group represented by Ar is any one of a mixture of a compound which is a group represented by the formula (ar-120) and a compound which is a group represented by the formula (ar-121), and the compound (xxxi ) Is a compound in which the group represented by Ar is a group represented by the formula (ar-122), a compound in which the group represented by Ar is a group represented by the formula (ar-123), or a group represented by Ar It means any of a mixture of a compound which is a group represented by (ar-122) and a compound which is a group represented by formula (ar-123).

  Further, compound (i), compound (ii), compound (iv), compound (v), compound (vi), compound (ix), compound (x), compound (xi), compound (xvi), compound of Table 1 (Xxviii), compound (xix), compound (xx), compound (xxi), compound (xxiii), compound (xxiv), compound (xxv), compound (xxvi), compound (xxvii), compound (xxviii), And representative structural formulas of the compound (xxix) are represented by the formula (ii-1), the formula (iv-1), the formula (v-1), the formula (v-2), the formula (v-3), the formula ( v-4), formula (v-5), formula (vi-1), formula (ix-1), formula (x-1), formula (xi-1), formula (xvi-1), formula (xix) -1), formula (xx-1), formula (xxi-1), formula (xxiii-1), formula (xxiv- ), Formula (xxv-1), formula (xxvi-1), formula (xxvii-1), formula (xxxviii-1), formula (xxxix-1), formula (xxxii-1), and formula (xxxiv- Illustrated in 1). In the optical film of the present invention, a plurality of different types of compounds (1) may be used.

  Examples of the compound (1) further include the following. However, n1 and n2 in a formula show the integer of 2-12 each independently.

The production method of compound (A) will be described below using compound (1) as an example.
Compound (1) is a known organic synthesis reaction described in Methoden der Organischen Chemie, Organic Reactions, Organic Syntheses, Comprehensive Organic Synthesis, New Experimental Chemistry Course, etc. (for example, condensation reaction, esterification reaction, Williamson reaction, Ullmann reaction, Wittig reaction, Schiff base formation reaction, benzylation reaction, Sonogashira reaction, Suzuki-Miyaura reaction, Negishi reaction, Kumada reaction, Kashiyama reaction, Buchwald-Heartwig reaction, Friedel-Craft reaction, Heck reaction, Aldol reaction, etc. ) Can be manufactured by appropriately combining depending on the structure.

For example, in the case of the compound (1) in which D 1 and D 2 are * —O—CO—, the formula (1-1)

(In the formula, Ar represents the same meaning as described above.)
And a compound represented by formula (1-2)

(In the formula, R 1 , R 2 , G 1 , E 1 , A 1 , B 1 , F 1 , P 1 and k have the same meaning as described above.)
Is reacted with a compound represented by formula (1-3)

(In the formula, Ar, R 1 , R 2 , G 1 , E 1 , A 1 , B 1 , F 1 , P 1 and k have the same meaning as described above.)
And the compound represented by the formula (1-3) and the formula (1-4)

(Wherein R 1 , R 2 , G 2 , E 2 , A 2 , B 2 , F 2 , P 2 and l have the same meaning as described above).
It can manufacture by making the compound shown by react.
The reaction between the compound represented by the formula (1-1) and the compound represented by the formula (1-2) and the reaction between the compound represented by the formula (1-3) and the compound represented by the formula (1-4) It is preferable to carry out in the presence of an ester agent.

  Examples of the esterifying agent (condensing agent) include 1-cyclohexyl-3- (2-morpholinoethyl) carbodiimide met-para-toluenesulfonate, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide, 1- Ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (partially water-soluble carbodiimide: commercially available as WSC), bis (2,6-diisopropylphenyl) carbodiimide, bis (trimethylsilyl) carbodiimide, bisisopropylcarbodiimide, Such as carbodiimide, 2-methyl-6-nitrobenzoic anhydride, 2,2′-carbonylbis-1H-imidazole, 1,1′-oxalyldiimidazole, diphenylphosphoryl azide, 1 (4-nitrobenzene Sulfonyl) -1H-1,2,4-triazole, 1H-benzotriazol-1-yloxytripyrrolidinophosphonium hexafluorophosphate, 1H-benzotriazol-1-yloxytris (dimethylamino) phosphonium hexafluorophosphate, N , N, N ′, N′-tetramethyl-O— (N-succinimidyl) uronium tetrafluoroborate, N- (1,2,2,2-tetrachloroethoxycarbonyloxy) succinimide, N-carbobenzoxysuccinimide , O- (6-chlorobenzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium tetrafluoroborate, O- (6-chlorobenzotriazol-1-yl) -N, N , N ', N'-Tetramethyluronium hexaf Orophosphate, 2-bromo-1-ethylpyridinium tetrafluoroborate, 2-chloro-1,3-dimethylimidazolinium chloride, 2-chloro-1,3-dimethylimidazolinium hexafluorophosphate, 2-chloro-1 -Methylpyridinium iodide, 2-chloro-1-methylpyridinium paratoluenesulfonate, 2-fluoro-1-methylpyridinium paratoluenesulfonate, trichloroacetic acid pentachlorophenyl ester. From the standpoint of reactivity, cost, and usable solvent, as the condensing agent, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride Bis (2,6-diisopropylphenyl) carbodiimide, bis (trimethylsilyl) carbodiimide, bisisopropylcarbodiimide, and 2,2′-carbonylbis-1H-imidazole are more preferable.

The composition of the present invention is a compound containing a group represented by the formula (A) and a polymerizable group (hereinafter sometimes referred to as “compound (A)”) and a liquid crystal compound (however, the compound (A) is Different).
-G a -D a -Ar a -D b -G b- (A)
[In the formula (A), Ar a represents a divalent group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and is included in the aromatic ring in the Ar a group The number of π electrons N πa is 12 or more.
D a and D b are each independently a single bond, —CO—O—, —O—CO—, —C (═S) —O—, —O—C (═S) —, —CR 1 R 2 -, - CR 1 R 2 -CR 3 R 4 -, - O-CR 1 R 2 -, - CR 1 R 2 -O -, - CR 1 R 2 -O-CR 3 R 4 -, - CR 1 R 2 —O—CO—, —O—CO—CR 1 R 2 —, —CR 1 R 2 —O—CO—CR 3 R 4 —, —CR 1 R 2 —CO—O—CR 3 R 4 — , —NR 1 —CR 2 R 3 —, —CR 1 R 2 —NR 3 —, —CO—NR 1 —, or —NR 1 —CO—. R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.
G a and G b each independently represent a divalent alicyclic hydrocarbon group. The hydrogen atom contained in the alicyclic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group. The methylene group contained in the alicyclic hydrocarbon group may be substituted with —O—, —S—, or —NH—. ]
Here, Ar a represents the same meaning as Ar.

Specific examples of liquid crystal compounds include: Chapter 3 of the Liquid Crystal Handbook (Edited by the Liquid Crystal Handbook Editorial Committee, published by Maruzen Co., Ltd., October 30, 2000). .3 Among compounds described in chiral rod-like liquid crystal molecules, compounds having a polymerizable group may be mentioned.
A plurality of different compounds may be used in combination as the liquid crystal compound.

  Examples of the liquid crystal compound include a compound represented by the formula (4) (hereinafter sometimes referred to as “compound (4)”).

P 11 -E 11 - (B 11 -A 11) t -B 12 -G (4)
[In the formula (4), A 11 represents an aromatic hydrocarbon group, an alicyclic hydrocarbon group or a heterocyclic group, and is included in the aromatic hydrocarbon group, alicyclic hydrocarbon group and heterocyclic group. The hydrogen atom may be substituted with a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylamino group having 1 to 6 carbon atoms, a nitro group, a nitrile group, or a mercapto group. .
B 11 and B 12 are each independently, -CR 14 R 15 -, - C≡C -, - CH = CH -, - CH 2 -CH 2 -, - O -, - S -, - C (= O)-, -C (= O) -O-, -O-C (= O)-, -O-C (= O) -O-, -C (= S)-, -C (= S). -O-, -O-C (= S)-, -CH = N-, -N = CH-, -N = N-, -C (= O) -NR < 14 >-, -NR < 14 > -C (= O) —, —OCH 2 —, —OCF 2 —, —NR 14 —, —CH 2 O—, —CF 2 O—, —CH═CH—C (═O) —O—, —O—C ( = O) -CH = CH- or a single bond. R 14 and R 15 each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms, and R 14 and R 15 may be connected to form an alkylene group having 4 to 7 carbon atoms. Good.
E 11 represents an alkylene group having 1 to 12 carbon atoms. The hydrogen atom contained in the alkylene group may be substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogen atom.
P 11 represents a polymerizable group.
G is a hydrogen atom, a halogen atom, an alkyl group having 1 to 13 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, a fluoroalkyl group having 1 to 13 carbon atoms, an alkylamino group having 1 to 13 carbon atoms, a nitrile group, It represents a polymerizable group that is a nitro group or bonded via an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom contained in the alkylene group is an alkyl group having 1 to 6 carbon atoms, or a carbon group having 1 to 6 carbon atoms. It may be substituted with an alkoxy group or a halogen atom.
t represents an integer of 1 to 5. ]

In particular, the polymerizable group in P 11 and G may be any group that can be polymerized with the compound (A), and includes a vinyl group, a vinyloxy group, a p-stilbene group, an acryloyl group, an acryloyloxy group, a methacryloyl group, Methacryloyloxy group, carboxyl group, acetyl group, hydroxyl group, carbamoyl group, amino group, alkylamino group having 1 to 4 carbon atoms, epoxy group, oxetanyl group, formyl group, -N = C = O or -N = C = S etc. are mentioned. Among them, a radical polymerizable group or a cationic polymerizable group is preferable in that it is suitable for photopolymerization, and it is easy to handle and easy to produce a liquid crystal compound, so that an acryloyloxy group, a methacryloyloxy group, or a vinyloxy group. Groups are preferred.

It aromatic hydrocarbon group A 11, the number of carbon atoms in the alicyclic hydrocarbon group and the heterocyclic group, respectively, for example, 3 to 18, preferably from 5 to 12, 5 or 6 Is particularly preferred.

  As a compound (4), the compound represented by Formula (4-1) and Formula (4-2) is mentioned, for example.

P 11 -E 11 - (B 11 -A 11) t1 -B 12 -E 12 -P 12 (4-1)
P 11 -E 11 - (B 11 -A 11) t2 -B 12 -F 11 (4-2)
[In Formula (4-1) and Formula (4-2), P 11 , E 11 , B 11 , A 11 , B 12 are as defined above.
F 11 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 13 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, a fluoroalkyl group having 1 to 13 carbon atoms, an alkylamino group having 1 to 13 carbon atoms, or a nitrile group. Represents a nitro group.
E 12 has the same meaning as E 11.
P 12 has the same meaning as P 11.
t 1 and t 2 have the same meanings as t. ]

  Further, the compounds represented by the formulas (4-1) and (4-2) are represented by the formula (I), the formula (II), the formula (III), the formula (IV), or the formula (V). Contains compounds.

P 11 -E 11 -B 11 -A 11 -B 12 -A 12 -B 13 -A 13 -B 14 -A 14 -B 15 -A 15 -B 16 -E 12 -P 12 (I)
P 11 -E 11 -B 11 -A 11 -B 12 -A 12 -B 13 -A 13 -B 14 -A 14 -B 15 -E 12 -P 12 (II)
P 11 -E 11 -B 11 -A 11 -B 12 -A 12 -B 13 -A 13 -B 14 -E 12 -P 12 (III)
P 11 -E 11 -B 11 -A 11 -B 12 -A 12 -B 13 -A 13 -B 14 -F 11 (IV)
P 11 -E 11 -B 11 -A 11 -B 12 -A 12 -B 13 -F 11 (V)
[In Formula (I) to Formula (V), A 12 to A 15 are synonymous with A 11 , and B 13 to B 16 are synonymous with B 11 ].

In the compounds represented by formula (4-1), formula (4-2), formula (I), formula (II), formula (III), formula (IV) and formula (V), P 11 It is preferable that both are bonded via an ether bond or an ester bond by appropriately selecting a combination of E 11 and E 11 and further selecting a combination of P 12 and E 12 as appropriate.

  Specific examples of the compound (4) include, for example, the following formulas (I-1) to (I-5), formulas (II-1) to (II-6), and formulas (III-1) to ( III-19), compounds represented by formula (IV-1) to formula (IV-14), formula (V-1) to formula (V-5), and the like. However, k represents the integer of 1-11 in a formula. These liquid crystal compounds are preferred because they are easy to synthesize and are commercially available.

  Moreover, the usage-amount of a liquid crystal compound is 90 weight part or less with respect to a total of 100 weight part of a liquid crystal compound and a compound (A), for example.

  The composition of the present invention is preferably a composition further containing a polymerization initiator. The polymerization initiator is preferably a photopolymerization initiator.

  Examples of the photopolymerization initiator include benzoins, benzophenones, benzyl ketals, α-hydroxyketones, α-aminoketones, iodonium salts, sulfonium salts, and the like. More specifically, Irgacure 907 , Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369 (all from Ciba Japan Co., Ltd.), Seiko All BZ, Seiko All Z, Seiko All BEE (all from Seiko Chemical Co., Ltd.), Kayacure BP100 (manufactured by Nippon Kayaku Co., Ltd.), Kayacure UVI-6992 (manufactured by Dow), Adeka optomer SP-152 or Adeka optomer SP-170 (all are made by ADEKA Corporation) and the like can be mentioned.

  Moreover, the usage-amount of a polymerization initiator is 0.1 weight part-30 weight part with respect to a total of 100 weight part of a liquid crystal compound and a compound (A), for example, Preferably, 0.5 weight part-10 weight part Part. If it is in the said range, a compound (A) can be polymerized, without disturbing the orientation of a liquid crystal compound.

  The optical film of the present invention refers to a film that can transmit light and has an optical function. The optical function means refraction, birefringence and the like. A retardation film, which is a kind of optical film, is used for converting linearly polarized light into circularly polarized light or elliptically polarized light, or conversely converting circularly polarized light or elliptically polarized light into linearly polarized light.

  The optical film of the present invention is obtained by polymerizing a compound containing a group represented by the formula (A) and a polymerizable group. The group represented by formula (A) is preferably a group represented by formula (B), more preferably a group represented by formula (C), and represented by formula (1). Particularly preferred is a group.

-E 1 -G a -D a -Ar a -D b -G b -E 2 - (B)
[In the formula (B), Ar a , D a , D b , G a and G b represent the same meaning as described above, and E 1 and E 2 each independently represent —CR 5 R 6 —, —CH 2 -CH 2 -, - O -, - S -, - CO-O -, - O-CO -, - O-CO-O -, - C (= S) -O -, - O-C (= S ) —, —O—C (═S) —O—, —CO—NR 5 —, —NR 5 —CO—, —O—CH 2 —, —CH 2 —O—, —S—CH 2 —, It represents a -CH 2 -S- or a single bond. R 5 and R 6 each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms. ]

- (B 1 -A 1) k -E 1 -G a -D a -Ar a -D b -G b -E 2 - (A 2 -B 2) l - (C)
[In the formula (C), Ar a , D a , D b , G a , G b , E 1 and E 2 represent the same meaning as described above.
B 1 and B 2 are each independently, -CR 5 R 6 -, - CH 2 -CH 2 -, - O -, - S -, - CO-O -, - O-CO -, - O-CO —O—, —C (═S) —O—, —O—C (═S) —, —O—C (═S) —O—, —CO—NR 5 —, —NR 5 —CO—, -O-CH 2 -, - CH 2 -O -, - S-CH 2 -, - represents a CH 2 -S- or a single bond. R 5 and R 6 represent the same meaning as described above.
A 1 and A 2 each independently represent a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group. The hydrogen atom contained in the divalent alicyclic hydrocarbon group and divalent aromatic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group. It may be substituted with a group. The hydrogen atom contained in the alkyl group having 1 to 4 carbon atoms and the alkoxy group having 1 to 4 carbon atoms may be substituted with a fluorine atom. k and l each independently represents an integer of 0 to 3. ]

P 1 -F 1- (B 1 -A 1 ) k -E 1 -G 1 -D 1 -Ar-D 2 -G 2 -E 2- (A 2 -B 2 ) 1 -F 2 -P 2 ( 1)
[In the formula (1), Ar represents a divalent group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and π electrons contained in the aromatic ring in the Ar group The number N π is 12 or more.
D 1 and D 2 are each independently * —O—CO— (* represents a position bonded to Ar), —C (═S) —O—, —O—C (═S) —, -CR 1 R 2 -, - CR 1 R 2 -CR 3 R 4 -, - O-CR 1 R 2 -, - CR 1 R 2 -O -, - CR 1 R 2 -O-CR 3 R 4 - , —CR 1 R 2 —O—CO—, —O—CO—CR 1 R 2 —, —CR 1 R 2 —O—CO—R 3 R 4 —, —CR 1 R 2 —CO—O—CR 3 R 4 -, - NR 1 -CR 2 R 3 -, - CR 2 R 3 -NR 1 -, - CO-NR 1 -, or represents a -NR 1 -CO-. R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.
G 1 and G 2 each independently represent a divalent alicyclic hydrocarbon group. The hydrogen atom contained in the alicyclic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group. The methylene group contained in the alicyclic hydrocarbon group may be substituted with —O—, —S—, or —NH—.
E 1, E 2, B 1 and B 2 are each independently, -CR 5 R 6 -, - CH 2 -CH 2 -, - O -, - S -, - CO-O -, - O-CO -, -O-CO-O-, -C (= S) -O-, -OC (= S)-, -O-C (= S) -O-, -CO-NR < 5 >-,- NR 5 —CO—, —O—CH 2 —, —CH 2 —O—, —S—CH 2 —, —CH 2 —S— or a single bond is represented. R 5 and R 6 each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.
A 1 and A 2 each independently represent a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group. The hydrogen atom contained in the divalent alicyclic hydrocarbon group and divalent aromatic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group. It may be substituted with a group. The hydrogen atom contained in the alkyl group having 1 to 4 carbon atoms and the alkoxy group having 1 to 4 carbon atoms may be substituted with a fluorine atom.
k and l each independently represents an integer of 0 to 3.
F 1 and F 2 each independently represents an alkylene group having 1 to 12 carbon atoms. The hydrogen atom contained in the alkylene group 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, and the methylene group contained in the alkylene group is -O -Or -CO- may be substituted.
P 1 and P 2 each independently represent a hydrogen atom or a polymerizable group (provided that at least one of P 1 and P 2 represents a polymerizable group). ]

  The wavelength dispersion characteristic of the optical film of the present invention can be arbitrarily determined depending on the content of the structural unit derived from the compound (A) in the optical film. When the content of the structural unit derived from the compound (A) among the structural units in the optical film is increased, flatter wavelength dispersion characteristics and further reverse wavelength dispersion characteristics are exhibited.

  Specifically, about the composition containing a liquid crystal compound and a compound (A), about 2 to 5 types of compositions having different content of structural units derived from the compound (A) are prepared, and each composition will be described later. Thus, the retardation value of the optical film obtained by producing an optical film having the same film thickness is obtained, and from the result, the content of the structural unit derived from the compound (A) and the retardation value of the optical film What is necessary is just to determine content of the structural unit derived from the compound (A) required in order to obtain | require a correlation and to give a desired retardation value to the optical film in the said film thickness from the obtained correlation.

The manufacturing method of the optical film of this invention is demonstrated below.
First, to the compound (A), an organic solvent, a liquid crystal compound serving as a host, an additive such as the polymerization initiator, a polymerization inhibitor, a photosensitizer, or a leveling agent are added and mixed as necessary. Prepare the solution. In particular, it is preferable to include an organic solvent that facilitates film formation during film formation, and it is preferable to include a polymerization initiator because it functions to cure the obtained optical film.

  The content of the liquid crystal compound is, for example, 90 parts by weight or less with respect to 100 parts by weight in total of the liquid crystal compound and the compound (A), for example.

  Moreover, the usage-amount of a polymerization initiator is 0.1 weight part-30 weight part with respect to a total of 100 weight part of a liquid crystal compound and a compound (A), for example, Preferably, 0.5 weight part-10 weight part Part. If it is in the said range, a compound (A) can be polymerized, without disturbing the orientation of a liquid crystal compound.

(Polymerization inhibitor)
In preparing the optical film of the present invention, a polymerization inhibitor may be used. Examples of the polymerization inhibitor include hydroquinones having a substituent such as hydroquinone or alkyl ether, catechols having a substituent such as alkyl ether such as butylcatechol, pyrogallols, 2,2,6,6-tetramethyl-1 -Radical scavengers such as piperidinyloxy radicals, thiophenols, β-naphthylamines or β-naphthols.

  By using a polymerization inhibitor, the polymerization of the liquid crystal compound and the compound (A) can be controlled, and the stability of the obtained optical film can be improved. The amount of the polymerization inhibitor used is, for example, 0.1 to 30 parts by weight, preferably 0.5 to 10 parts by weight with respect to 100 parts by weight as the total of the liquid crystal compound and the compound (A). It is. If it is in the said range, a compound (A) can be polymerized, without disturbing the orientation of a liquid crystal compound.

[Photosensitizer]
Moreover, when preparing the optical film of this invention, you may use a photosensitizer. Examples of the photosensitizer include xanthones such as xanthone or thioxanthone, anthracene having a substituent such as anthracene or alkyl ether, phenothiazine, or rubrene.

  By using a photosensitizer, the polymerization of the liquid crystal compound or the compound (A) can be made highly sensitive. The photosensitizer is used in an amount of, for example, 0.1 to 30 parts by weight, preferably 0.5 to 10 parts by weight with respect to 100 parts by weight as the total of the liquid crystal compound and the compound (A). Parts by weight. If it is in the said range, a compound (A) can be polymerized, without disturbing the orientation of a liquid crystal compound.

(Leveling agent)
Furthermore, a leveling agent may be used when preparing the optical film of the present invention. As a leveling agent, for example, an additive for radiation-curing coatings (by Big Chemie Japan: BYK-352, BYK-353, BYK-361N), coating additives (by Toray Dow Corning Co., Ltd .: SH28PA, DC11PA, ST80PA), Paint additives (Shin-Etsu Chemical Co., Ltd .: KP321, KP323, X22-161A, KF6001) or fluorine-based additives (Dainippon Ink Chemical Co., Ltd .: F-445, F-470, F-479), etc. Can be mentioned.

  By using a leveling agent, the optical film can be smoothed. Furthermore, in the production process of the optical film, the fluidity of the mixed solution containing the compound (A) may be controlled, or the crosslinking density of the optical film obtained by polymerizing the liquid crystal compound or the compound (A) may be adjusted. it can. Moreover, the specific numerical value of the usage-amount of a leveling agent is 0.1 to 30 weight part with respect to a total of 100 weight part of a liquid crystal compound and a compound (A), for example, Preferably it is 0.5 weight part -10 parts by weight. If it is in the said range, a compound (A) can be polymerized, without disturbing the orientation of a liquid crystal compound.

〔Organic solvent〕
The organic solvent used for the preparation of the mixed solution containing the compound (A) and the liquid crystal compound is an organic solvent that can dissolve the compound (A) and the liquid crystal compound, and may be any solvent that is inert to the polymerization reaction. Specifically, alcohols such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl cellosolve or butyl cellosolve; esters such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, gamma-butyrolactone or propylene glycol methyl ether acetate Solvents; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone or methyl isobutyl ketone; aliphatic carbonization such as pentane, hexane or heptane Containing solvent; toluene, xylene or an aromatic hydrocarbon solvent such as chlorobenzene, acetonitrile, propylene glycol monomethyl ether, tetrahydrofuran, dimethoxyethane, ethyl lactate, chloroform, phenol. These organic solvents may be used alone or in combination.
In particular, the composition of the present invention is excellent in compatibility and can be dissolved in alcohols, ester solvents, ketone solvents, non-chlorine aliphatic hydrocarbon solvents, non-chlorine aromatic hydrocarbon solvents, etc., such as chloroform. Even if the halogenated hydrocarbon is not used, it can be dissolved and applied.

  The viscosity of the mixed solution containing the compound (A) and the liquid crystal compound is preferably adjusted to, for example, 10 Pa · s or less, and preferably about 0.1 to 7 Pa · s so as to be easily applied.

  Moreover, the density | concentration of the solid content in the said mixed solution is 5 to 50 weight%, for example. When the solid content is 5% or more, the optical film does not become too thin, and there is a tendency that a birefringence index necessary for optical compensation of the liquid crystal panel is provided. Moreover, since the viscosity of a mixed solution is low as it is 50% or less, since there exists a tendency for the nonuniformity to arise in the film thickness of an optical film, it is preferable.

  Subsequently, the mixed solution is applied to the supporting substrate, dried and polymerized, and the target optical film can be obtained on the supporting substrate.

[Unpolymerized film preparation process]
When a mixed solution containing the compound (A) is applied on a supporting substrate and dried, an unpolymerized film is obtained. When the unpolymerized film exhibits a liquid crystal phase such as a nematic phase, the obtained optical film has birefringence due to monodomain alignment. Since the unpolymerized film is oriented at a low temperature of about 0 to 120 ° C., preferably 25 to 80 ° C., a supporting substrate that is not necessarily sufficient with respect to heat resistance as exemplified above can be used as the orientation film. Moreover, even if it cools to about 30-10 degreeC after orientation, since it does not crystallize, handling is easy.

  The film thickness can be adjusted to give a desired phase difference by appropriately adjusting the coating amount and concentration of the mixed solution. In the case of a mixed solution in which the amount of the compound (A) is constant, the retardation value (retardation value, Re (λ)) of the obtained optical film is determined as shown in Equation (7). In order to obtain (λ), the film thickness d may be adjusted.

Re (λ) = d × Δn (λ) (7)
(In the formula, Re (λ) represents a retardation value at a wavelength λnm, d represents a film thickness, and Δn (λ) represents a birefringence at a wavelength λnm.)

  Examples of the application method to the supporting substrate include an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a CAP coating method, and a die coating method. Moreover, the method of apply | coating using coaters, such as a dip coater, a bar coater, or a spin coater, is mentioned.

  As said support base material, glass, a plastic sheet, a plastic film, or a translucent film can be mentioned, for example. Examples of the translucent film include polyolefin films such as polyethylene, polypropylene and norbornene polymers, polyvinyl alcohol films, polyethylene terephthalate films, polymethacrylate films, polyacrylate films, cellulose ester films, and polyethylene naphthalate films. , Polycarbonate film, polysulfone film, polyethersulfone film, polyetherketone film, polyphenylene sulfide film, or polyphenylene oxide film.

  For example, even a process that requires the strength of the optical film, such as a bonding process, a transport process, and a storage process of the optical film of the present invention, can be easily handled without tearing by using the support substrate.

  Moreover, it is preferable to form an alignment film on a support substrate and to apply a mixed solution containing the compound (A) on the alignment film. The alignment film has solvent resistance that does not dissolve in the mixed solution when the mixed solution containing the compound (A) or the like is applied, has heat resistance during the removal of the solvent or the heat treatment of liquid crystal alignment, and is rubbed. It is preferable that peeling due to friction or the like does not occur, and it is preferable that the polymer or a composition containing the polymer is used.

  Examples of the polymer include polyamides and gelatins having an amide bond in the molecule, polyimides having an imide bond in the molecule, and polyamic acid, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, polyoxazole, which are hydrolysates thereof. Mention may be made of polymers such as polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid or polyacrylates. These polymers may be used alone, or two or more kinds thereof may be mixed or copolymerized. These polymers can be easily obtained by polycondensation such as dehydration and deamination, chain polymerization such as radical polymerization, anion polymerization, and cation polymerization, coordination polymerization, and ring-opening polymerization.

  Further, these polymers can be applied after being dissolved in a solvent. The solvent is not particularly limited, but specifically, alcohol such as water, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl cellosolve or butyl cellosolve; ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, gamma Ester solvents such as butyrolactone or propylene glycol methyl ether acetate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone or methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane or heptane; toluene , Aromatic hydrocarbon solvents such as xylene or chlorobenzene, acetonitrile, propylene glycol monomethyl ether, tetrahydrofuran , Dimethoxyethane, ethyl lactate, chloroform and the like. These organic solvents may be used alone or in combination.

  In order to form the alignment film, a commercially available alignment film material may be used as it is. Examples of commercially available alignment film materials include Sunever (registered trademark, manufactured by Nissan Chemical Industries, Ltd.) or Optmer (registered trademark, manufactured by JSR Corporation).

  If such an alignment film is used, it is not necessary to control the refractive index by stretching, so that in-plane variation in birefringence is reduced. Therefore, it is possible to provide a large optical film that can cope with an increase in the size of the flat panel display (FPD) on the support substrate.

  As a method for forming an alignment film on the support substrate, for example, a commercially available alignment film material or a compound serving as an alignment film material is applied as a solution on the support substrate, and then annealed, An alignment film can be formed on the support substrate.

  The thickness of the alignment film thus obtained is, for example, 10 nm to 10000 nm, preferably 10 nm to 1000 nm. If it is the said range, a compound (A) etc. can be orientated on a desired angle on this alignment film.

  Further, these alignment films can be rubbed or irradiated with polarized UV rays as necessary. Thus, the compound (A) or the like can be oriented in a desired direction.

  As a method for rubbing the alignment film, for example, a method in which a rubbing cloth is wound and a rotating rubbing roll is placed on a stage and brought into contact with the alignment film being conveyed can be used.

  As described above, in the unpolymerized film preparation step, the unpolymerized film (liquid crystal layer) is laminated on the alignment film laminated on an arbitrary support substrate. Therefore, the production cost can be reduced as compared with a method of manufacturing a liquid crystal cell and injecting a liquid crystal compound into the liquid crystal cell. Furthermore, it is possible to produce a film using a roll film.

  The solvent may be dried while the polymerization proceeds, but it is preferable from the viewpoint of film formability that most of the solvent is dried before the polymerization.

  Examples of the solvent drying method include natural drying, ventilation drying, and vacuum drying. The specific heating temperature is preferably 10 to 120 ° C, more preferably 25 to 80 ° C. In addition, the heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes. As long as the heating temperature and the heating time are within the above ranges, a supporting substrate that does not necessarily have sufficient heat resistance can be used as the supporting substrate.

[Unpolymerized film polymerization process]
In the unpolymerized film polymerization step, the unpolymerized film obtained in the unpolymerized film preparation step is polymerized and cured. Thereby, a film in which the orientation of the compound (A) is fixed, that is, a polymerized film is obtained. Therefore, it is possible to produce a polymer film having a small change in refractive index in the plane direction of the film and a large change in refractive index in the normal direction of the film.

The method for polymerizing the unpolymerized film is determined according to the types of the liquid crystal compound and the compound (A). If P 1 and / or P 2 contained in the compound (A) and the polymerizable group contained in the liquid crystal compound are photopolymerizable, photopolymerization is performed, and if the polymerizable group is thermopolymerizable, thermal polymerization is performed. Unpolymerized films can be polymerized. In the present invention, it is particularly preferable to polymerize an unpolymerized film by photopolymerization. According to photopolymerization, an unpolymerized film can be polymerized at a low temperature, so that the selection range of the heat resistance of the supporting substrate is widened. In addition, it is easy to manufacture industrially. Photopolymerization is also preferred from the viewpoint of film formability. Photopolymerization is performed by irradiating an unpolymerized film with visible light, ultraviolet light, or laser light. From the viewpoint of handleability, the irradiation with ultraviolet light that is particularly preferable may be performed while heating the compound (A) to a temperature at which the liquid crystal phase is taken. At this time, the polymerized film can be patterned by masking or the like.

  Since the optical film of the present invention has good adhesion between the alignment film and the optical film, the production of the optical film is easy.

  Furthermore, the optical film of the present invention is a thin film as compared with a stretched film that gives a phase difference by stretching a polymer.

  In the manufacturing method of the optical film of this invention, the process of peeling a support base material may be included following the said process. By setting it as such a structure, the laminated body obtained becomes a film which consists of an oriented film and an optical film. Moreover, in addition to the process of peeling the said support base material, the process of peeling an alignment film may be further included. By setting it as such a structure, an optical film can be obtained.

  The optical film thus obtained is excellent in transparency and used as various display films. As described above, the thickness of the layer to be formed varies depending on the retardation value of the obtained optical film. In the present invention, the thickness is preferably 0.1 to 10 μm, and more preferably 0.5 to 3 μm from the viewpoint of reducing photoelasticity.

  In the case where the alignment film is used and has birefringence, for example, the retardation value is about 50 to 500 nm, preferably 100 to 300 nm.

  Such a thin film capable of uniform polarization conversion in a wider wavelength range can be used as an optical compensation film in all liquid crystal panels and FPDs such as organic EL.

  In order to use the optical film of the present invention as a broadband λ / 4 plate or λ / 2 plate, the content of the structural unit derived from the compound (A) is appropriately selected. In the case of a λ / 4 plate, the film thickness may be adjusted to Re (550) of the obtained optical film of 113 to 163 nm, preferably 135 to 140 nm, particularly preferably about 137.5 nm. In this case, the film thickness may be adjusted so that Re (550) of the obtained optical film is 250 to 300 nm, preferably 273 to 277 nm, particularly preferably about 275 nm.

  In order to use the optical film of the present invention as an optical film for a VA (vertical alignment) mode, the content of the structural unit derived from the compound (A) is appropriately selected. The film thickness may be adjusted so that Re (550) is preferably 40 to 100 nm, more preferably about 60 to 80 nm.

  By adding a small amount of the compound (A), the wavelength dispersion characteristic of the optical film can be shifted to a value close to 1, and the desired wavelength dispersion characteristic can be prepared by a simple method.

  The optical film of the present invention is used for an antireflection film such as an anti-reflection (AR) film, a polarizing film, a retardation film, an elliptically polarizing film, a viewing angle widening film, or an optical compensation film for compensating a viewing angle of a transmissive liquid crystal display. can do. Moreover, although the optical film of this invention shows the outstanding optical characteristic even if it is 1 sheet, you may laminate | stack several sheets.

  Moreover, you may combine with another film. Specifically, an elliptically polarizing plate in which the optical film of the present invention is bonded to a polarizing film, a broadband circularly polarizing plate in which the optical film of the present invention is further bonded to the elliptical polarizing plate as a broadband λ / 4 plate, and the like. It is done.

  Since the optical film of the present invention can be formed by coating on an alignment film and polymerizing by irradiation with ultraviolet rays, as shown in FIG. / 2 optical film can be formed.

FIG. 1 is a schematic view showing a color filter 1 according to the present invention.
The color filter 1 is a color filter in which the optical film 2 of the present invention is formed on the color filter layer 4 via an alignment film 3.

An example of a method for manufacturing the color filter 1 having the above configuration will be described. First, an alignment polymer is printed on the color filter layer 4 and a rubbing process is performed to form the alignment film 3.
Next, a mixed solution containing the compound (A) is prepared on the obtained alignment film 3 so as to have a desired wavelength dispersion characteristic, and applied while adjusting the thickness so as to obtain a desired retardation value. Film 2 is formed.

  On the other hand, if the color filter 1 is used, a thin liquid crystal display device with a reduced number of optical films 2 can be manufactured. As an example, there is a thin liquid crystal display device formed on the liquid crystal layer side of at least one substrate in a liquid crystal display element in which a liquid crystal layer is sandwiched and formed between a pair of substrates as shown in FIG.

FIG. 2 is a schematic view showing a liquid crystal display device 5 according to the present invention.
In the liquid crystal display device 5 shown in FIG. 2, a substrate 7 facing a backlight such as a glass substrate is fixed on a polarizing plate 6 via an adhesive, and a color filter layer 4 ′ formed on the substrate 7. An optical film 2 ′ is formed thereon via an alignment film 3 ′. Further, a counter electrode 8 is formed on the optical film 2 ′, and a liquid crystal phase 9 is formed on the counter electrode 8. On the backlight side, a substrate 11 such as a glass substrate is fixed to the polarizing plate 10 with an adhesive, and a thin film transistor (TFT) and an insulating layer 12 for actively driving a liquid crystal layer are formed on the substrate 11. Further, a transparent electrode 13 and / or a reflective electrode 13 ′ made of Ag, Al, or ITO (Indium Tin Oxide) is formed on the TFT. The configuration of the liquid crystal display device 5 shown in FIG. 2 can reduce the number of optical films as compared with a conventional liquid crystal display device, and enables the manufacture of a thinner liquid crystal display device.

Below, an example of the manufacturing method of the liquid crystal display device 5 in which color filter 1 'was formed in the liquid crystal layer side of one board | substrate is described. On the substrate on the backlight side, a gate electrode made of Mo, MoW or the like, a gate insulating film, and amorphous silicon are deposited and patterned on a borosilicate glass, and the amorphous silicon is crystallized by annealing with an excimer laser. A semiconductor thin film can be formed, and then n-channel and p-channel TFTs can be formed by doping P, B, and the like in regions on both sides of the gate electrode. By further forming an insulating film made of SiO 2, the backlight side of the substrate is obtained. Further, by sputtering ITO on the backlight side substrate 11, the transparent electrode 13 for the total transmission display device can be laminated on the backlight side substrate. Similarly, a reflective electrode 13 'for a total reflection display device can be obtained by using Ag, Al or the like instead of ITO. Further, a backlight electrode for a transflective liquid crystal display device can be obtained by appropriately combining a reflective electrode and a transparent electrode.

On the other hand, the color filter layer 4 ′ is formed on the opposing substrate 7. By using R, G, and B color filters in combination, a full-color liquid crystal display device can be obtained. Next, an orientation polymer is applied on the color filter layer 4 'and rubbed to form an orientation film 3'. A composition containing the compound (A) according to the present invention is applied onto the alignment film 3 ′, and polymerization and an optical film 2 ′ are formed by ultraviolet irradiation while heating to a temperature range that takes a liquid crystal phase.
After forming the optical film, the counter electrode 8 can be formed by sputtering ITO. Further, an alignment film is formed on the counter electrode, the liquid crystal phase 9 is formed, and finally the liquid crystal display device 5 can be produced by assembling together with the substrate on the backlight side. Further, the value of [Re (450) / Re (550)] and [Re (650) / Re (550)] of the compound (A) of the present invention is close to 1 or less than 1, so that the composition is changed. Thus, desired wavelength dispersion characteristics can be obtained, and the retardation value can be controlled from the film thickness, so that the lamination of the optical film can also be omitted.

  Furthermore, the optical film of the present invention can also be used for a retardation plate of a reflective liquid crystal display and an organic EL display, and an FPD including the retardation plate and the optical film. The FPD is not particularly limited, and examples thereof include a liquid crystal display (LCD) and an organic EL.

Thus, the film according to the present invention can be used in a wide range of applications. For example, a polarizing plate formed by laminating the optical film and the polarizing film according to the present invention and an FPD including the polarizing plate will be described below. The polarizing plate according to the present invention is a film having a polarizing function, that is, one side of the polarizing film. Alternatively, it is obtained by laminating the optical film directly on both sides or using an adhesive or a pressure-sensitive adhesive. In the following description of FIGS. 3 to 5, the adhesive and the pressure-sensitive adhesive may be collectively referred to as an adhesive.

Fig.3 (a)-FIG.3 (e) are schematic which shows the polarizing plate 1 which concerns on this invention.
In the polarizing plate 30 a shown in FIG. 3A, the laminate 14 and the polarizing film 15 are directly bonded, and the laminate 14 includes a support substrate 16, an alignment film 17, and an optical film 18.
The polarizing plate 30 a is laminated in the order of the support substrate 16, the alignment film 17, the optical film 18, and the polarizing film 15.

  In the polarizing plate 30 b shown in FIG. 3B, the laminate 14 and the polarizing film 15 are bonded together with an adhesive layer 19 interposed therebetween.

  In the polarizing plate 30c shown in FIG. 3C, the laminate 14 and the laminate 14 'are directly bonded, and the laminate 14' and the polarizing film 15 are directly bonded.

  In the polarizing plate 30d shown in FIG. 3D, the laminate 14 and the laminate 14 'are bonded together via the adhesive layer 19, and the polarizing film 15 is directly bonded onto the laminate 14'.

  In the polarizing plate 30e shown in FIG. 3 (e), the laminated body 14 and the laminated body 14 ′ are bonded through the adhesive layer 19, and the laminated body 14 ′ and the polarizing film 15 are further bonded through the adhesive layer 19 ′. To show the configuration.

  The polarizing plate of the present invention is a laminate of a polarizing film and a laminate containing the optical film of the present invention. Instead of the laminated body 14 and the laminated body 14 ′, an optical film 18 in which the supporting base material 16 and the alignment film 17 are peeled off from the laminated body 14 may be used, or the supporting base material 16 is peeled off from the laminated body 14. A film composed of the alignment film 17 and the optical film 18 may be used.

  The polarizing plate of the present invention may be formed by laminating a plurality of laminates, and the plurality of laminates may be all the same or different.

  The polarizing film 15 may be a film having a polarizing function. For example, a film obtained by adsorbing iodine or a dichroic dye on a polyvinyl alcohol film and drawn, or a film obtained by drawing a polyvinyl alcohol film to obtain iodine or a dichroic dye. Examples include adsorbed films.

  The adhesive used for the adhesive layer 19 and the adhesive layer 19 ′ is preferably an adhesive having high transparency and excellent heat resistance. As such an adhesive, for example, an acrylic, epoxy, or urethane adhesive is used.

  The flat panel display device of the present invention includes the optical film of the present invention. For example, a liquid crystal display device including a bonded product in which the polarizing film of the present invention and a liquid crystal panel are bonded, and the polarizing film of the present invention And an organic EL display device including an organic EL panel on which a light emitting layer is bonded.

  As embodiments of a flat panel display device according to the present invention, a liquid crystal display device and an organic EL display device will be described in detail below.

[Liquid Crystal Display]
FIG. 4 is a schematic view showing a bonded product 21 between the liquid crystal panel 20 and the polarizing plate 30 of the liquid crystal display device according to the present invention.

  As a liquid crystal display device, a liquid crystal display device provided with the bonding product 21 of the liquid crystal panel 20 and the polarizing plate 30 as shown, for example in FIG. 2 is mentioned. The bonded product 21 is obtained by bonding the polarizing plate 30 of the present invention and the liquid crystal panel 20 through an adhesive layer 22. By applying a voltage to the liquid crystal panel 20 using an electrode (not shown), the liquid crystal molecules are driven, and an optical shutter effect is produced.

[Organic EL display device]
FIG. 5 is a schematic view showing an organic EL panel 23 of the organic EL display device according to the present invention.

  Examples of the organic EL display device include an organic EL display device including the organic EL panel 23 shown in FIG. The organic EL panel 23 is formed by bonding the polarizing film 30 of the present invention and the light emitting layer 24 through an adhesive layer 25.

In the organic EL panel, the polarizing film 30 functions as a broadband circularly polarizing plate.
The light emitting layer 24 is at least one layer made of a conductive organic compound.

  Hereinafter, the present invention will be described in more detail with reference to examples. In the examples, “%” and “parts” are by weight and parts by weight unless otherwise specified.

  The compound was synthesized by the following scheme. The raw material monotetrahydropyranyl protected hydroquinone (a) was synthesized by the method described in the patent document (Japanese Patent Application Laid-Open No. 2004-262848).

(First route)

(Second route)

(Synthesis Example of Compound (b))
100.1 g (515 mmol) of monotetrahydropyranyl protected hydroquinone (a), 97.1 g (703 mmol) of potassium carbonate, and 64 g (468 mmol) of 6-bromohexanol were dissolved and dispersed in dimethylacetamide. The mixture was stirred at 90 ° C under a nitrogen atmosphere and then at 100 ° C. Thereafter, the mixture was cooled to room temperature, pure water and methyl isobutyl ketone were added, and the collected organic layer was dehydrated after washing with an aqueous sodium hydroxide solution and pure water, and concentrated under reduced pressure after filtration. Methanol was added to the residue, and the resulting precipitate was filtered and then vacuum dried to obtain 126 g (428 mmol) of compound (b). The yield was 91% based on 6-bromohexanol.

(Synthesis Example of Compound (c))
126 g (428 mmol) of compound (b), 1.40 g (6.42 mmol) of 3,5-ditertiarybutyl-4-hydroxytoluene (hereinafter referred to as BHT), 116.7 g (963 mmol) of N, N-dimethylaniline, 1 , 3-dimethyl-2-imidazolidinone 1.00 g and chloroform were mixed. Aquiroyl chloride (58.1 g, 642 mmol) was added dropwise to the mixture obtained under a nitrogen atmosphere and ice cooling, and pure water was added and stirred, and then the separated organic layer was recovered. The organic layer was washed with aqueous hydrochloric acid, saturated aqueous sodium carbonate solution and pure water. The organic layer was dried and filtered, and 1 g of BHT was added to the organic layer, followed by concentration under reduced pressure to obtain compound (c).

(Synthesis Example of Compound (d))
After mixing the compound (c) and 200 ml of tetrahydrofuran (hereinafter referred to as THF), 200 ml of THF was added to the resulting mixture. Further, aqueous hydrochloric acid and concentrated aqueous hydrochloric acid were added, and the mixture was stirred under a nitrogen atmosphere at 60 ° C. To the reaction solution, 500 ml of saturated brine was added and further stirred, and the separated organic layer was recovered. The collected organic layer was dehydrated, filtered and concentrated under reduced pressure. Further, hexane was added to the organic layer and stirred under ice-cooling, and the precipitated powder was filtered and dried under vacuum to obtain 90 g (339 mmol) of compound (d). The yield was 79% based on the compound (c).

(Synthesis Example 1 of Compound (e))
To the resulting mixture obtained by mixing 24.68 g (118 mmol) of transcyclohexanedicarboxylic acid and toluene were added 74.91 g (590 mmol) of oxalyl dichloride and 0.5 mL of dimethylformamide, and the mixture was stirred under a nitrogen atmosphere. After decompression, chloroform was added to obtain Solution 1.
On the other hand, 12 g (45.4 mmol) of the compound (d) was dissolved in chloroform. A chloroform solution of the compound (d) and 12.6 g (159 mmol) of pyridine were mixed to obtain a solution 2. Solution 2 was added dropwise to Solution 1 under ice cooling. The resulting solution was stirred under a nitrogen atmosphere, filtered, and concentrated under reduced pressure. The obtained solution was dropped into a mixed solvent of water / methanol (1/1 by volume), and the produced precipitate was pulverized, washed with pure water, filtered, and vacuum-dried. The obtained powder was pulverized again, added with n-heptane, stirred, and further added with toluene. Insoluble components were removed by filtration, and the obtained filtrate was concentrated under reduced pressure, and n-heptane was added. The produced precipitate was vacuum-dried to obtain 7.8 g of compound (e). The yield was 40% based on the compound (d).

(Synthesis Example 2 of Compound (e))
Compound (e) can also be synthesized by the route shown below.

  Compound (d) 56.8 g (215 mmol), dimethylaminopyridine 2.65 g (22 mmol), trans 1,4-cyclohexanedicarboxylic acid monoethoxymethyl ester 50 g (217 mmol) and chloroform 300 mL were mixed. The obtained mixture was ice-cooled and stirred under a nitrogen atmosphere, and a solution consisting of 48.79 g (237 mol) of dicyclohexylcarbodiimide and 50 mL of chloroform was added dropwise. After completion of the dropwise addition, the resulting reaction solution was stirred at room temperature, and 200 mL of chloroform and 200 mL of heptane were added, and the precipitate was filtered. The filtrate was collected and washed with 2N aqueous hydrochloric acid. The separated organic layer was recovered, insoluble components were removed by filtration, anhydrous sodium sulfate was added, and after filtration, the solid obtained by removing the solvent was vacuum-dried to obtain 100 g of compound (e ′). .

  Compound (e ′) 100 g, pure water 3.64 g (202 mmol), paratoluenesulfonic acid monohydrate 3.84 g (20.2 mmol) and THF 200 mL were mixed. The resulting mixture was heated to 50 ° C. and stirred under a nitrogen atmosphere. The mixture was allowed to cool to room temperature, THF was removed under reduced pressure, and 200 mL of heptane was added to the residue. The deposited precipitate was collected by filtration, washed with pure water, and then vacuum dried. The obtained powder was dissolved in chloroform and filtered through silica gel. The filtrate was collected and dissolved in 400 mL of chloroform, the resulting solution was concentrated, and toluene was added. After the solution was concentrated under reduced pressure, heptane was added for crystallization, and the resulting powder was collected by filtration and dried in vacuo to obtain 64.1 g of compound (e). The yield was 76% based on the compound (d) in two steps.

(Production Example of Compound (ii-a))
Compound (ii-a) was synthesized according to the following scheme. The starting material 4,7-dimethoxy-2-phenylbenzothiazole is described in J. Org. Chem. Soc. Perkin Trans. It was synthesized by the method described in the first magazine, pages 205-210 (2000).

  4,8-Dimethoxy-2-phenylbenzothiazole 10.8 g (39.8 mmol) and pyridinium chloride 54.0 g (5 times mass) were mixed, and the resulting mixture was heated to 220 ° C. and stirred. . After cooling the mixture, water is added, and the resulting precipitate is filtered off, washed with water and hexane, and 4,7-dihydroxy-2-phenylbenzothiazole (compound (ii-a)) as a main component. 8.7 g of a solid was obtained. The yield was 89% based on 4,7-dimethoxy-2-phenylbenzothiazole.

(Production Example of Compound (vi-a))
Compound (vi-a) was synthesized according to the following scheme.

[Synthesis Example of Compound (vi-d)]
69.4 g (453 mmol) of 2,5-dimethoxyaniline, 91.7 g (906 mmol) of triethylamine and 994.3 g of dehydrated chloroform were mixed and stirred. Further, 99.4 g (453 mmol) of 4-bromobenzoyl chloride was added to the resulting mixture. Was added. Thereafter, the temperature was raised to 60 ° C., the mixture was stirred, cooled to room temperature, and the mixture was poured into water. The separated organic layer was washed with water and hydrochloric acid. The obtained organic layer was concentrated under reduced pressure, and the obtained solid was washed with hexane to obtain 139.6 g of a solid containing compound (vi-d) as a main component. The yield was 102% based on 2,5-dimethoxyaniline.

[Synthesis Example of Compound (vi-e)]
90.0 g (268.0 mmol) of compound (vi-d), 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetan-2,4-disulfide (Lawson reagent) 65 0.0 g (160.0 mmol) and 3132 g of toluene were mixed, and the resulting mixture was heated to 80 ° C. and stirred. After cooling, the mixture was concentrated, ethanol was added, and the resulting precipitate was washed with ethanol to obtain 93.8 g of a solid mainly composed of compound (vi-e). The yield was 99.5% based on the compound (vi-d).

[Synthesis Example of Compound (vi-f)]
Compound (vi-e) 93.8 g (266.3 mmol), sodium hydroxide 315 g (7875 mmol) and water 5250 g were mixed, and the resulting mixture was stirred under ice-cooling. Subsequently, an aqueous solution containing 174.3 g (529 mmol) of potassium ferricyanide was added under ice-cooling, the mixture was stirred, the precipitated solid was washed with cold water and hexane, and 88.2 g of a solid containing compound (vi-f) as a main component. Got. The yield was 95% based on the compound (vi-e).

[Synthesis Example of Compound (vi-a)]
11.2 g (32.0 mmol) of compound (vi-f) and 56.0 g (5 times mass) of pyridinium chloride were mixed, heated to 180 ° C. and stirred. After cooling the obtained mixed liquid, water was added, and the obtained precipitate was washed with water, hexane and chloroform to obtain 7.7 g of a solid containing compound (vi-a) as a main component. The yield was 74% based on the compound (vi-f).

(Synthesis Example of Compound (va))
After benzothiazole was synthesized in the same manner as for compound (vi-a), compound (va) was synthesized by demethylation reaction with pyridinium chloride or boron tribromide. An orange solid containing the compound (va) as a main component was obtained by washing with ethanol and washing with toluene. The reaction scheme is shown below.

(Synthesis Example of Compound (vb))
A solid containing compound (vb) as the main component was obtained in the same manner as in the synthesis example of compound (vi-d) except that the starting 4-bromobenzoyl chloride was changed to 4-nitrobenzoyl chloride. The yield was 98% based on 2,5-dimethoxyaniline.

(Synthesis Example of Compound (vc))
In the synthesis example of the compound (vi-e), a solid containing the compound (vc) as a main component was obtained in the same manner except that the starting compound (vi-d) was changed to the compound (vb). . The yield was 89% based on the compound (vb).

(Synthesis Example of Compound (vd))
In the synthesis example of compound (vi-f), a solid containing compound (vd) as the main component was obtained in the same manner except that the starting compound (vi-e) was changed to compound (vc). . The yield was 52% based on the compound (vc).

(Synthesis Example of Compound (va))
21.0 g (66.0 mmol) of compound (vd) and 441 g of dehydrated toluene were mixed and stirred. The obtained mixture was ice-cooled, 100 g (398 mmol) of boron tribromide was added, the temperature was raised to 70 ° C., and the mixture was stirred. After cooling to room temperature, the mixture was further cooled with ice, 1588 g of water was added, and the resulting precipitate was filtered off and washed with water and chloroform to obtain 16.5 g of a solid mainly composed of compound (va). It was. The yield was 86% based on the compound (vd).

(Production Example of Compound (ix-a))
Compound (ix-a) was synthesized according to the following scheme.

[Synthesis Example of Compound (ix-b)]
2,5-dimethoxyaniline 43.0 g (281 mmol), triethylamine 59.7 g (590 mmol) and dehydrated chloroform 499.7 g were mixed and stirred. 50.0 g (281 mmol) of isonicotinoyl chloride hydrochloride was further added to the obtained mixture, and the mixture was heated to 60 ° C. and stirred. The obtained mixed liquid was cooled and then poured into water, and the separated organic layer was recovered. Chloroform was added to the remaining aqueous layer and washed to recover the organic layer. The two organic layers were mixed and washed with water. The obtained mixed organic layer was concentrated under reduced pressure to obtain 71.5 g of a solid containing compound (ix-b) as a main component. The yield was 99% based on 2,5-dimethoxyaniline.

[Synthesis Example of Compound (ix-c)]
Compound (ix-b) 70.0 g (272.0 mmol), 2,4-bis (4-methoxyphenyl) -1,3-dithia 2,4-diphosphatan-2,4-disulfide (Lawson reagent) 65.8 g (162.0 mmol) and 2436 g of toluene were mixed, heated to 80 ° C. and stirred. The obtained mixed liquid was cooled and then concentrated to obtain a solid containing compound (ix-c) as a main component. Compound (ix-c) was used in the next step as it was without purification.

[Synthesis Example of Compound (ix-d)]
A solid containing compound (ix-c) as a main component, 333 g (8325 mmol) of sodium hydroxide and 5550 g of water were mixed and stirred under ice cooling. Subsequently, an aqueous solution containing 184.3 g (560 mmol) of potassium ferricyanide was added to the obtained mixture and stirred under ice cooling. The precipitated solid was separated by filtration and washed with cold water and hexane to obtain 25.9 g of a solid containing compound (ix-d) as a main component. The yield of the two steps combined with the previous step was 35% based on the compound (ix-c).

[Synthesis Example of Compound (ix-a)]
Compound (ix-d) 5.6g (21.0mmol) and pyridinium chloride 28.0g (5 times mass) were mixed, and it heated up at 180 degreeC and stirred. After cooling the obtained mixed liquid, water was added, and the obtained precipitate was washed with water and chloroform to obtain 3.4 g of a solid containing compound (ix-a) as a main component. The yield was 68% based on the compound (ix-d).

(Production Example of Compound (iv-a))
Compound (iv-a) was synthesized according to the following scheme.

  Compound (vi-a) 10.0 g (31 mmol), copper (I) cyanide 5.56 g (62 mmol), and N-methylpyrrolidone 100 g were mixed, heated to 200 ° C., and stirred in a nitrogen atmosphere. After cooling the obtained mixed liquid, water was added, and the resulting precipitate was taken out and washed well with water to obtain 6.6 g of a solid mainly composed of compound (iv-a). The yield was 79% based on the compound (vi-a).

<Synthesis Example of Compound (ii-1) in First Path>
Compound (ii-a) 2.55 g (11 mmol), compound (e) 9.67 g (23 mmol), dimethylaminopyridine 0.28 g (2 mmol) and chloroform 50 mL were mixed. To the obtained mixed solution, 40 mL of chloroform solution of 5.31 g (28 mmol) of dicyclohexylcarbodiimide was added dropwise under ice cooling. The obtained reaction solution was stirred and filtered, and then the separated organic layer was recovered. The organic layer was dried and concentrated under reduced pressure. Ethyl acetate was added to the residue for dissolution, and after concentration under reduced pressure, 200 mL of methanol was added and reprecipitated under ice cooling. The precipitate was collected by filtration, washed with n-heptane, filtered, and the obtained solid was vacuum-dried to obtain 6.1 g of compound (ii-1). The yield was 56% based on the compound (ii-a).

1 H-NMR (DMSO) of compound (ii-1): δ (ppm) 1.44 to 1.80 (m, 24H), 2.38 to 2.83 (m, 12H), 3.93 to 3 .97 (t, 4H), 4.11 to 4.14 (t, 4H), 5.89 to 5.94 (dd, 2H), 6.10 to 6.20 (m, 2H), 6.29 -6.36 (m, 2H), 6.91-7.03 (m, 8H), 7.36 (s, 2H), 7.60 (m, 3H), 8.06 (m, 2H)

  The phase transition temperature of the obtained compound (ii-1) was measured by texture observation with a polarizing microscope. Compound (ii-1) exhibited a smectic phase from 96 ° C. to 115 ° C. during the temperature increase, a nematic phase from 115 ° C. to 226 ° C., and a nematic phase from 226 ° C. to 50 ° C. during the temperature decrease. .

<Synthesis Example of Compound (v-1) in First Route>
2.88 g (10 mmol) of the compound (va), 8.37 g (20 mmol) of the compound (e), 0.24 g (2 mmol) of dimethylaminopyridine, and 75 mL of chloroform were mixed. To the obtained mixture, 40 mL of a chloroform solution of 4.95 g (24 mmol) of dicyclohexylcarbodiimide was added dropwise under ice cooling. The obtained reaction solution was stirred and filtered, and then the separated organic layer was recovered. The organic layer was dried and concentrated under reduced pressure. Ethyl acetate was added to the residue for dissolution, and after concentration under reduced pressure, 200 mL of methanol was added and reprecipitated under ice cooling. The precipitate was collected by filtration, further washed with methanol, filtered, and the obtained solid was vacuum-dried to obtain 10.3 g of compound (v-1). The yield was 94% based on the compound (va).

1 H-NMR (CDCl 3 ) of compound (v-1): δ (ppm) 1.45 to 1.86 (m, 24H), 2.35 to 2.83 (m, 12H), 3.93 to 3.97 (t, 4H), 4.15 to 4.20 (t, 4H), 5.80 to 5.84 (dd, 2H), 6.07 to 6.18 (m, 2H), 6. 37-6.44 (m, 2H), 6.87-7.02 (m, 8H), 7.27 (d, 2H), 8.19-8.23 (d, 2H), 8.34- 8.38 (d, 2H)

  The phase transition temperature of the obtained compound (v-1) was measured by texture observation with a polarizing microscope. Compound (v-1) exhibited a smectic phase from 160 ° C. to 169 ° C. at the time of temperature increase, a nematic phase from 169 ° C. to 224 ° C., and a nematic phase from 224 ° C. to 154 ° C. at the time of temperature decrease. .

<Synthesis Example of Compound (ix-1) in First Path>
Compound (ix-a) 2.24 g (10 mmol), compound (e) 8.37 g (20 mmol), dimethylaminopyridine 0.24 g (2 mmol) and chloroform 50 mL were mixed. To the obtained mixture, 30 mL of a chloroform solution of 4.95 g (24 mmol) of dicyclohexylcarbodiimide was added dropwise under ice cooling. The obtained reaction solution was stirred and filtered, and then the separated organic layer was recovered. The organic layer was dried and concentrated under reduced pressure. Ethyl acetate was added to the residue for dissolution, and after concentration under reduced pressure, 200 mL of methanol was added and reprecipitated under ice cooling. The precipitate was collected by filtration, washed with n-heptane, filtered, and the obtained solid was vacuum-dried to obtain 4.4 g of compound (ix-1). The yield was 43% based on the compound (ix-1).

1 H-NMR (CDCl 3 ) of compound (ix-1): δ (ppm) 1.43-1.84 (m, 24H), 2.29-2.83 (m, 12H), 3.93- 3.97 (t, 4H), 4.15 to 4.18 (t, 4H), 5.80 to 5.84 (dd, 2H), 6.07 to 6.18 (m, 2H), 6. 37-6.44 (m, 2H), 6.86-7.02 (m, 8H), 7.22 (m, 1H), 7.28 (d, 2H), 7.78-7.81 ( br, 2H), 8.14-8.17 (br, 1H)

<Synthesis Example of Compound (iv-1) in First Path>
Compound (iv-a) is used as a starting material in the same manner as described in the synthesis example of compound (ii-1) in the first route and the synthesis example of compound (ix-1) in the first route. Thus, compound (iv-1) is obtained.

1 H-NMR (CDCl 3 ) of compound (iv-1): δ (ppm) 1.43-1.83 (m, 24H), 2.29-2.82 (m, 12H), 3.93- 3.97 (t, 4H), 4.15 to 4.18 (t, 4H), 5.80 to 5.84 (dd, 2H), 6.07 to 6.18 (m, 2H), 6. 37-6.44 (m, 2H), 6.86-7.02 (m, 8H), 7.27 (s, 2H), 7.78-7.81 (d, 2H), 8.14- 8.17 (d, 2H)

  The phase transition temperature of the obtained compound (iv-1) was measured by texture observation with a polarizing microscope. Compound (iv-1) exhibited a smectic phase from 142 ° C. to 159 ° C. at the time of temperature increase, a nematic phase from 159 ° C. to 190 ° C. or more, and a nematic phase to 136 ° C. at the time of temperature decrease. .

<Synthesis Example of Compound (ii-1) in Second Route>
(Synthesis Example of Compound (f))
100 g (581 mmol) of transcyclohexanedicarboxylic acid and 500 mL of dimethylacetamide were mixed, and the resulting mixture was heated to 60 ° C. and dissolved. To the obtained mixture, 48.2 g (349 mmol) of potassium carbonate was added and stirred at 80 ° C. Further, 94.4 g (552 mmol) of benzyl bromide was added and stirred, and the resulting reaction solution was allowed to cool and poured into ice. The resulting precipitate was collected by filtration, washed with a water / methanol mixed solution (volume ratio 1/1), and vacuum dried. The obtained powder was dissolved in toluene and adsorbed onto silica gel while being concentrated under reduced pressure. The silica gel was placed on a silica gel column and eluted with 500 mL of a chloroform / heptane mixed solution (volume ratio 1/4), and then the solvent was replaced with the chloroform / heptane mixed solution (volume ratio 1/2) to elute the compound (f). . The collected solution was vacuum-dried to obtain 63 g of compound (f). The yield was 42% based on transcyclohexanedicarboxylic acid.

(Synthesis Example of Compound (ii-b))
Compound (ii-a) 4.87 g (20 mmol), compound (f) 11.54 g (44 mmol) and dimethylaminopyridine 0.54 g (4 mmol) were mixed with 50 mL of chloroform. To the obtained mixture, 60 mL of a chloroform solution of 10.89 g (53 mmol) of dicyclohexylcarbodiimide was added dropwise under ice cooling. The obtained reaction solution was stirred and filtered, and then the separated organic layer was recovered. The organic layer was dried and concentrated under reduced pressure. Ethyl acetate was added to the residue for dissolution, and after concentration under reduced pressure, methanol was added and reprecipitation was performed under ice cooling. The precipitate was collected by filtration and vacuum-dried to obtain 11.4 g of compound (ii-b). The yield was 78% based on the compound (ii-a).

(Synthesis Example of Compound (ii-c))
11.4 g (16 mmol) of compound (ii-b), 1.14 g of 10% palladium-carbon (containing 55% water), 0.1 mL of acetic acid and 200 mL of tetrahydrofuran were mixed. The obtained mixed solution was deoxygenated with nitrogen gas, and then the obtained reaction solution was decompressed and stirred under a hydrogen atmosphere. The reaction was filtered. The filtrate was collected and concentrated under reduced pressure. The solid obtained by adding n-heptane to the residue was collected by filtration and dried under vacuum to obtain 4.7 g of compound (ii-c). The yield was 55% based on compound (ii-b).

(Synthesis Example of Compound (ii-1))
Compound (ii-c) 4.41 g (8 mmol), compound (d) 4.65 g (18 mmol), dimethylaminopyridine 0.22 g (2 mmol) and chloroform 30 mL were mixed. To the obtained mixed solution, 20 mL of a chloroform solution of 4.36 g (21 mmol) of dicyclohexylcarbodiimide was added dropwise under ice cooling. The obtained reaction solution was stirred and filtered, and then the separated organic layer was recovered. The organic layer was dried and concentrated under reduced pressure. Ethyl acetate was added to the residue for dissolution, and after concentration under reduced pressure, methanol was added and reprecipitation was performed under ice cooling. The precipitate was collected by filtration and dried under vacuum to obtain 4.80 g of compound (ii-1). The yield was 58% based on the compound (ii-c).

<Synthesis Example of Compound (vi-1) in Second Route>
Compound (iv-1) was obtained by using compound (vi-a) as a starting material in the same manner as described in the synthesis example of compound (ii-1) in the second route.

  Similarly, the following compounds were obtained by the first route. The structure is shown below.

(Production Example of Compound (xa))
Compound (xa) was synthesized according to the following scheme.

  Compound (xb) was obtained in the same manner as in the synthesis example of compound (vb) except that 4-nitrobenzoyl chloride as a raw material was changed to thiophenecarbonyl chloride, and compound (vc), Compounds (xc), (xd), and (xa) were respectively obtained in the same manner as in the synthesis examples of (vd) and (va).

(Production Example of Compound (v′-a))
Compound (v′-a) was synthesized according to the following scheme.

[Synthesis Example of Compound (v′-b)]
170.0 g (940 mmol) of 3-methyl-4-nitrobenzoic acid, 238.7 g (1880 mmol) of oxalyl chloride, 2.2 g (18.8 mmol) of 1,3-dimethyl-2-imidazolidinone, and 1703 g of dehydrated chloroform Mix well and stir well at room temperature. The obtained mixed liquid was decompressed, and 608 g of dehydrated chloroform was added to the obtained solid.
To the chloroform solution, a mixed solution of 120.0 g (783 mmol) of 2,5-dimethoxyaniline, 158.5 g (1567 mmol) of triethylamine and 840 g of dehydrated chloroform was added. Then, it stirred at room temperature. The reaction solution was poured into 973 g of water and separated to take an organic layer. Further, this organic layer was washed with 973 g of 1N hydrochloric acid. The obtained organic layer was evaporated under reduced pressure to obtain 107.8 g of a solid containing the compound (v′-b) as a main component. The yield was 44% based on 2,5-dimethoxyaniline.

[Synthesis Example of Compound (v′-a)]
Compound (v′-c) was obtained in the same manner as in the synthesis example of compound (vc) except that the starting compound (vb) was changed to compound (v′-b). Compounds (v′-d) and (v′-a) were obtained in the same manner as in the synthesis examples of vd) and (va), respectively.

(Production Example of Compound (xa))
Compound (xa) was synthesized according to the following scheme.

  Compound (xb) was obtained in the same manner as in the synthesis example of compound (vb) except that 4-nitrobenzoyl chloride as a raw material was changed to thiophenecarbonyl chloride, and compound (vc), Compounds (xc), (xd), and (xa) were respectively obtained in the same manner as in the synthesis examples of (vd) and (va).

(Production Example of Compound (xi-a))
Compound (xi-a) was synthesized according to the following scheme.

[Synthesis Example of Compound (xi-b)]
2,5-dimethoxyaniline 52.3 g (341 mmol), triethylamine 69.0 g (682 mmol), and dehydrated chloroform 200 g were mixed and stirred, and 3-thenoyl chloride 50.0 g (341 mmol) was added to the resulting mixture. It was added dropwise under ice cooling. Thereafter, the mixture was warmed to room temperature and stirred for 1 hour, and then the mixture was poured into water. The separated organic layer was washed with water and hydrochloric acid. From the obtained organic layer, the solvent was distilled off under reduced pressure, and the obtained solid was washed with hexane to obtain 82.1 g of a solid containing the compound (xi-b) as a main component. The yield was 91% based on 2,5-dimethoxyaniline.

[Synthesis Example of Compound (xi-c)]
Compound (xi-b) 81 g (308.0 mmol), 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetan-2,4-disulfide (Lawson reagent) 64.7 g ( 160.0 mmol) and 500 g of toluene were mixed, heated to 80 ° C. and stirred. The obtained liquid mixture was cooled and then concentrated to obtain a red viscous liquid mainly composed of a decomposition product of Lawson's reagent and compound (xi-c).

[Synthesis Example of Compound (xi-d)]
A mixture containing the compound (xi-c) obtained in the previous item as a main component, 73.8 g (1845 mmol) of sodium hydroxide, and 750 g of water were mixed and stirred under ice cooling. Subsequently, an aqueous solution containing 257.8 g (783 mmol) of potassium ferricyanide is added to the obtained mixed solution under ice cooling, followed by stirring. The precipitated solid is washed with cold water and hexane, and ethanol is added for recrystallization. This gave 49.1 g of compound (xi-d). The yield was 58% based on the compound (xi-b).

[Synthesis Example of Compound (xi-a)]
Compound (xi-f) 40.0 g (144.2 mmol) and pyridinium chloride 200.0 g (5 times mass) were mixed, heated to 180 ° C. and stirred for 2 hours. After cooling the obtained mixed liquid, water was added, and the obtained precipitate was washed with water and hexane to obtain 36.4 g of a solid mainly composed of the compound (xi-a). The yield was 101% based on the compound (xi-d).

(Production Example of Compound (xvi-a))
Compound (xvi-a) was synthesized according to the following scheme.

  A compound (xvi-b) compound was obtained in the same manner as in the synthesis example of the compound (vb) except that the starting material 4-nitrobenzoyl chloride was changed to 3,5-dimethylbenzoyl chloride. Compound (xvi-c), (xvi-d), and (xvi-a) were respectively obtained in the same manner as in the synthesis examples of -c), (vd), and (va).

(Production Example of Compound (xvii-a))
Compound (xvii-a) was synthesized according to the following scheme.

[Synthesis Example of Compound (xvii-d)]
4,7-dimethoxy-2-phenylbenzothiazole (11.0 g) and glacial acetic acid (288 g) were mixed, and a mixed solution of concentrated nitric acid (4.0 g) and glacial acetic acid (14.4 g) was added dropwise. The resulting mixture was stirred at room temperature, and the reaction solution was poured into 1154 g of ice water. The obtained solid was separated by filtration to obtain 11.8 g of a solid containing the compound (xi-d) as a main component. Compound (xvii-d) was a mixture of two isomers having different nitro group substitution positions. The yield was 92% based on 4,7-dimethoxy-2-phenylbenzothiazole.

[Synthesis Example of Compound (xvii-a)]
Compound (xvii-a) was obtained in the same manner as in the synthesis example of compound (va) except that the starting compound (vd) was changed to compound (xvii-d). Compound (xvii-a) was a mixture of two isomers having different nitro group substitution positions.

(Compound (Production Example of (xviii-a))
The compound ((xviii-a) was synthesized according to the following scheme.

  Compound ((xviii-b) was obtained in the same manner as in the synthesis example of compound (vb) except that 4-nitrobenzoyl chloride as a raw material was changed to pentafluorobenzoyl chloride, and compound (vc) The compounds ((xviii-c), ((xviii-d), and ((xviii-a)) were obtained in the same manner as in the synthesis examples of (vd) and (va).

(Production Example of Compound (xix-a))
Compound (xix-a) was synthesized according to the following scheme.

[Synthesis Example of Compound (xix-b)]
2,8.7-Dimethoxyaniline (58.7 g, 383 mmol), triethylamine (77.5 g, 766 mmol) and dehydrated chloroform (400 g) were mixed and stirred. The resulting mixture was further mixed with 2-furancarboxylic acid chloride (50.0 g, 383 mmol). Was added under ice cooling. Thereafter, the mixture was heated to room temperature, stirred for 1 hour, and then poured into water. The separated organic layer was washed with water and hydrochloric acid. From the obtained organic layer, the solvent was concentrated under reduced pressure and crystallized with hexane to obtain 86.3 g of compound (xix-b). The yield was 91% based on 2,5-dimethoxyaniline.

[Synthesis Example of Compound (xix-c)]
Compound (xix-b) 40 g (162.0 mmol), 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetan-2,4-disulfide (Lawson reagent) 34.0 g ( 84.0 mmol) and 120 g of toluene were mixed, heated to 80 ° C. and stirred for 8 hours. The obtained mixed liquid was cooled and concentrated to obtain a red viscous liquid containing partially white crystals mainly composed of a decomposition product of Lawson's reagent and compound (xix-c).

[Synthesis Example of Compound (xix-d)]
A mixture containing the compound (xix-c) obtained in the previous item as a main component, 38.8 g (971 mmol) of sodium hydroxide and 700 g of water were mixed and stirred under ice cooling. An aqueous solution containing 145.3 g (441 mmol) of potassium ferricyanide is added to the obtained mixed solution under ice cooling, followed by stirring. The precipitated solid is washed with cold water and hexane, washed with methanol, and recrystallized from ethanol. As a result, 19.5 g of the compound (xix-d) was obtained. The yield was 46% based on the compound (xix-b).

[Synthesis Example of Compound (xix-a)]
Compound (xix-d) 9.00 g (34.4 mmol) and pyridinium chloride 45.0 g (5 times mass) were mixed, heated to 180 ° C. and stirred. After cooling the obtained mixture, water was added, and the resulting precipitate was washed with water, hexane, and toluene to obtain 7.68 g of a solid containing compound (xix-a) as a main component. The yield was 96% based on the compound (xix-d).

(Synthesis Example of Compound (xx-a))
After benzothiazole was synthesized in the same manner as for compound (xa), compound (xx-a) was synthesized by demethylation reaction with pyridinium chloride. A solid containing the compound (xx-a) as a main component was obtained by washing with heptane and washing with toluene. The reaction scheme is shown below.

(Production Example of Compound (xxi-a))
Compound (xxi-a) was synthesized according to the following scheme.

[Synthesis Example of Compound (xxi-b)]
2,5-dimethoxyaniline 59.3 g (387 mmol), triethylamine 78.4 g (774 mmol) and dehydrated chloroform 500 g were mixed and stirred, and 3-thiazolecarboxylic acid chloride 57.1 g (387 mmol) was added to ice. Add dropwise under cooling. Thereafter, the mixture was heated to room temperature and stirred, and then poured into water. The separated organic layer was washed with water and hydrochloric acid. The solvent was distilled off from the obtained organic layer under reduced pressure, and the obtained solid was washed with hexane and crystallized with heptane-ethyl acetate 3/1 (v / v). The solid was further washed with heptane-ethyl acetate 4/1 (v / v) to obtain 77.2 g of a solid containing compound (xxi-b) as a main component. The yield was 75% based on 2,5-dimethoxyaniline.

[Synthesis Example of Compound (xxi-c)]
77 g (291.0 mmol) of the compound (xxi-b), 61.3 g of 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetan-2,4-disulfide (Lawson reagent) (151.0 mmol) and 500 g of toluene were mixed, heated to 80 ° C. and stirred. After cooling, the mixture was concentrated to obtain an orange viscous liquid mainly composed of a decomposition product of Lawesson's reagent and compound (xxi-c).

[Synthesis Example of Compound (xxi-d)]
A mixture containing the compound (xxi-c) obtained in the previous item as a main component, 70.0 g (1748 mmol) of sodium hydroxide, and 750 g of water were mixed and stirred under ice cooling. An aqueous solution containing 245.0 g (744 mmol) of potassium ferricyanide was added to the obtained mixed solution under ice-cooling, the mixture was stirred, and the precipitated solid was washed with cold water and hexane, and washed with hot ethanol to give compound (xxi- d) 45.9 g was obtained. The yield was 57% based on the compound (xxb-d).

[Synthesis Example of Compound (xxi-a)]
45.0 g (144.2 mmol) of compound (xxi-d) and 225.0 g (5 times mass) of pyridinium chloride were mixed, heated to 180 ° C. and stirred for 2 hours. After cooling, water was added, and the resulting precipitate was washed with water, hexane, and toluene to obtain 39.9 g of a solid containing the compound (xxi-a) as a main component. The yield was 100% based on the compound (xxi-d).

(Production Example of Compound (xxiii-a))
Compound (xxiii-a) was synthesized according to the following scheme.

[Synthesis Example of Compound (xxiii-b)]
2,5-dimethoxyaniline 38.3 g (250 mmol), triethylamine 50.5 g (500 mmol) and dehydrated chloroform 200 g were mixed and stirred, and further, 4-methylsulfonylbenzoic acid chloride 54.6 g (250 mmol) was added under ice cooling. added. Thereafter, the mixture was heated to room temperature and stirred, and then poured into water. The separated organic layer was washed with water and hydrochloric acid. The solvent was distilled off from the obtained organic layer under reduced pressure, and the obtained solid was washed with hexane and crystallized with heptane-ethyl acetate 3/1 (v / v). Furthermore, it was washed with heptane-ethyl acetate 3/1 (v / v) to obtain 52.2 g of compound (xxiii-b) as white crystals. The yield was 62% based on 2,5-dimethoxyaniline.

[Synthesis Example of Compound (xxiii-c)]
Compound (xxiii-b) 54.5 g (155.0 mmol), 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetan-2,4-disulfide (Lawson reagent) 64 0.7 g (160.0 mmol) and 500 g of toluene were mixed, heated to 80 ° C. and stirred. The obtained mixed liquid was cooled and concentrated to obtain a red viscous liquid mainly composed of a decomposition product of Lawson's reagent and compound (xxiii-c).

[Synthesis Example of Compound (xxiii-d)]
A mixture containing the compound (xxiii-c) obtained in the previous item as a main component, 37.2 g (930 mmol) of sodium hydroxide and 380 g of water were mixed and stirred under ice cooling. An aqueous solution containing 163.5 g (497 mmol) of potassium ferricyanide is added to the obtained mixed solution under ice cooling, followed by stirring. The precipitated solid is washed with cold water and hexane, washed with hot ethanol, and recrystallized from toluene. This gave 25.2 g of compound (xxiii-d). The yield was 47% based on the compound (xxiii-b).

[Synthesis Example of Compound (xxiii-a)]
Compound (xxiii-d) 10.0 g (28.6 mmol) and pyridinium chloride 100.0 g (10 times mass) were mixed, heated to 180 ° C. and stirred for 2 hours. After cooling the obtained mixed liquid, water was added, and the obtained precipitate was washed with water, hexane, and toluene to obtain 7.8 g of an off-white solid containing the compound (xxiii-a) as a main component. The yield was 85% based on the compound (xxiii-d).

(Synthesis Example of Compound (xxiv-a))
In the synthesis example of compound (vi-a), compound (xxiv-a) was prepared according to the following reaction scheme in the same manner except that 4-fluorobenzoyl chloride was used instead of the starting 4-bromobenzoyl chloride. Synthesized.

(Synthesis Example of Compound (xxv-a))
In the synthesis example of compound (vi-a), compound (xxv-a) was prepared according to the following reaction scheme in the same manner except that 4-trifluoromethylbenzoyl chloride was used instead of starting material 4-bromobenzoyl chloride. ) Was synthesized.

<Synthesis Example of Compound (v′-1) in First Path>
Compound (v′-1) was obtained in the same manner except that the raw material compound (va) in the synthesis example of compound (v-1) was changed to compound (v′-a). The yield was 73% based on the compound (v′-a).

1 H-NMR (CDCl 3 ) of the compound (v′-1): δ (ppm) 1.45 to 1.90 (m, 24H), 2.29 to 2.83 (m, 15H), 3.92 To 3.97 (t, 4H), 4.15 to 4.20 (t, 4H), 5.80 to 5.84 (dd, 2H), 6.07 to 6.18 (m, 2H), 6 .37 to 6.44 (m, 2H), 6.86 to 7.01 (m, 8H), 7.23 (m, 2H), 7.98 to 8.11 (m, 3H)

  The phase transition temperature of the obtained compound (v′-1) was measured by texture observation with a polarizing microscope. Compound (v′-1) exhibits a smectic phase from 127 ° C. to 154 ° C. at the time of temperature increase, exhibits a nematic phase from 154 ° C. to 217 ° C., and exhibits a nematic phase from 217 ° C. to 113 ° C. at the time of temperature decrease. did.

<Synthesis Example of Compound (vi-1) in First Route>
Compound (vi-1) was obtained in the same manner except that the raw material compound (va) in the synthesis example of compound (v-1) was changed to compound (vi-a). The yield was 84% based on the compound (vi-a).

<Synthesis Example of Compound (x-1) in First Path>
Compound (x-1) was obtained in the same manner except that the starting compound (va) in the synthesis example of compound (v-1) was changed to compound (xa). The yield was 84% based on the compound (xa).

1 H-NMR (CDCl 3 ) of compound (x-1): δ (ppm) 1.43-1.83 (m, 24H), 2.29-2.82 (m, 12H), 3.92- 3.97 (t, 4H), 4.15 to 4.20 (t, 4H), 5.80 to 5.84 (dd, 2H), 6.07 to 6.18 (m, 2H), 6. 37-6.44 (m, 2H), 6.86-7.02 (m, 8H), 7.12 (dt, 1H), 7.18 (s, 2H), 7.51 (dd, 1H) 7.63 (dd, 1H)

  The phase transition temperature of the obtained compound (x-1) was measured by texture observation with a polarizing microscope. The compound (x-1) exhibits a smectic phase from 101 ° C. to 106 ° C. at the time of temperature increase, a nematic phase from 106 ° C. to 180 ° C. or more, and a nematic phase to 81 ° C. at the time of temperature decrease. .

<Synthesis Example of Compound (xi-1) in First Path>
Compound (xi-1) was obtained in the same manner except that the starting compound (va) in the synthesis example of compound (v-1) was changed to compound (xi-a). The yield was 55% based on the compound (xi-a).

1 H-NMR (CDCl 3 ) of compound (xi-1): δ (ppm) δ (ppm) 1.43-1.83 (m, 24H), 2.29-2.82 (m, 12H), 3.92 to 3.97 (t, 4H), 4.15 to 4.20 (t, 4H), 5.81 to 5.85 (dd, 2H), 6.08 to 6.18 (m, 2H) ), 6.37-6.45 (m, 2H), 6.86-7.03 (m, 8H), 7.12 (dt, 1H), 7.19 (s, 2H), 7.44 ( dd, 1H), 7.62 (dd, 1H), 7.98 (dd, 1H)

  The phase transition temperature of the obtained compound (xi-1) was measured by texture observation with a polarizing microscope. Compound (xi-1) exhibited a smectic phase from 111 ° C. to 125 ° C. during the temperature increase, a nematic phase from 125 ° C. to 242 ° C., and a nematic phase from 242 ° C. to 82 ° C. during the temperature decrease. .

<Synthesis Example of Compound (xvi-1) in First Path>
Compound (xvi-1) was obtained by the same method except that the starting compound (va) in the synthesis example of compound (v-1) was changed to compound (xvi-a). The yield was 78% based on the compound (xvi-a).

1 H-NMR (CDCl 3 ) of compound (xvi-1): δ (ppm) 1.45 to 1.86 (m, 24H), 2.35 to 2.83 (m, 18H), 3.92 to 3.97 (t, 4H), 4.15 to 4.19 (t, 4H), 5.80 to 5.84 (dd, 2H), 6.07 to 6.18 (m, 2H), 6. 37-6.44 (m, 2H), 6.86-7.01 (m, 8H), 7.13 (s, 1H), 7.20 (s, 2H), 7.66 (s, 2H)

  The phase transition temperature of the obtained compound (xvi-1) was measured by texture observation with a polarizing microscope. Compound (xvi-1) exhibited a smectic phase from 91 ° C. to 100 ° C. and a nematic phase from 100 ° C. to 210 ° C. at the time of temperature increase, and was thermally polymerized.

<Synthesis Example of Compound (xvii-1) in First Path>
Compound (xvii-1) was obtained in the same manner as in the synthesis example of compound (v-1) except that the starting compound (va) was changed to compound (xvii-a). The yield was 53% based on the compound (xvii-a).

1 H-NMR (CDCl 3 ) of compound (xvii-1): δ (ppm) 1.45 to 1.86 (m, 24H), 2.35 to 2.83 (m, 12H), 3.93 to 3.97 (t, 4H), 4.15 to 4.20 (t, 4H), 5.80 to 5.84 (dd, 2H), 6.07 to 6.18 (m, 2H), 6. 37-6.44 (m, 2H), 6.87-7.00 (m, 8H), 7.44 (2s, 1H), 7.50 (m, 3H), 8.02-8.06 ( m, 2H)

  The phase transition temperature of the obtained compound (xvii-1) was measured by texture observation with a polarizing microscope. The compound (xvii-1) exhibited a smectic phase from 129 ° C. to 148 ° C. during the temperature increase, a nematic phase from 148 ° C. to 186 ° C., and a nematic phase from 186 ° C. to 105 ° C. during the temperature decrease. .

<Synthesis Example of Compound (xviii-1) in First Route>
Compound (xviii-1) was obtained in the same manner as in the synthesis example of compound (v-1) except that the starting compound (va) was changed to compound (xviii-a). The yield was 82% based on the compound (xviii-a).

1 H-NMR (CDCl 3 ) of compound (xviii-1): δ (ppm) 1.45 to 1.86 (m, 24H), 2.35 to 2.87 (m, 18H), 3.92 to 3.97 (t, 4H), 4.15 to 4.20 (t, 4H), 5.80 to 5.84 (dd, 2H), 6.07 to 6.18 (m, 2H), 6. 37-6.44 (m, 2H), 6.86-7.00 (m, 8H), 7.32-7.35 (d, 2H)

  The phase transition temperature of the obtained compound (xvii-1) was measured by texture observation with a polarizing microscope. Compound (xvii-1) exhibited a smectic phase from 124 ° C. to 166 ° C. at the time of temperature increase, a nematic phase from 166 ° C. to 199 ° C., and a nematic phase from 199 ° C. to 79 ° C. at the time of temperature decrease. .

<Synthesis Example of Compound (xix-1) in First Path>
Compound (xix-1) was obtained in the same manner except that the starting compound (va) in the synthesis example of compound (v-1) was changed to compound (xix-a). The yield was 78% based on the compound (xix-a).

1 H-NMR (CDCl 3 ) of compound (xix-1): δ (ppm) 1.45 to 1.82 (m, 24H), 2.34 to 2.83 (m, 12H), 3.92 to 3.97 (t, 4H), 4.15 to 4.20 (t, 4H), 5.80 to 5.84 (dd, 2H), 6.07 to 6.18 (m, 2H), 6. 37-6.44 (m, 2H), 6.59 (br, m, 1H), 6.86-7.00 (m, 8H), 7.20 (2s, 3H), 7.59 (s, 1H)

  The phase transition temperature of the obtained compound (xix-1) was measured by texture observation with a polarizing microscope. Compound (xix-1) exhibits a smectic phase from 91 ° C. to 130 ° C. at the time of temperature increase, a nematic phase from 130 ° C. to 180 ° C. or more, and a nematic phase to 62 ° C. at the time of temperature decrease. .

<Synthesis Example of Compound (xx-1) in First Path>
Compound (xx-1) was obtained in the same manner as in the synthesis example of compound (v-1) except that the starting compound (va) was changed to compound (xx-a). The yield was 40% based on the compound (xx-a).

1 H-NMR (CDCl 3 ) of compound (xx-1): δ (ppm) 1.45 to 1.86 (m, 24H), 2.35 to 2.80 (m, 12H), 3.92 to 3.97 (t, 4H), 4.15 to 4.20 (t, 4H), 5.80 to 5.84 (dd, 2H), 6.07 to 6.18 (m, 2H), 6. 37-6.44 (m, 2H), 6.86-7.02 (m, 8H), 7.19 (s, 2H), 7.40 (d, 2H)

  The phase transition temperature of the obtained compound (xx-1) was observed by texture observation with a polarizing microscope. Compound (xx-1) exhibits a smectic phase from 110 ° C. to 114 ° C. at the time of temperature increase, a nematic phase from 114 ° C. to 160 ° C. or more, and a nematic phase from 69 ° C. to a temperature of 69 ° C. at the time of temperature decrease. .

<Synthesis Example of Compound (xxi-1) in First Path>
Compound (xxi-1) was obtained in the same manner as in the synthesis example of compound (v-1) except that the starting compound (va) was changed to compound (xxi-a). The yield was 71% based on the compound (xxi-a).

1 H-NMR (CDCl 3 ) of the compound (xxi-1): δ (ppm) 1.43 to 1.86 (m, 24H), 2.35 to 2.84 (m, 12H), 3.90 to 3.97 (t, 4H), 4.15 to 4.19 (t, 4H), 5.80 to 5.84 (dd, 2H), 6.07 to 6.18 (m, 2H), 6. 37-6.44 (m, 2H), 6.86-7.00 (m, 8H), 7.22 (s, 2H), 8.21 (d, 1H), 8.88 (d, 1H)

  The phase transition temperature of the obtained compound (xxi-1) was measured by texture observation with a polarizing microscope. Compound (xxi-1) exhibited a nematic phase from 162 ° C. to 246 ° C. when the temperature was increased, and exhibited a nematic phase from 246 ° C. to 120 ° C. when the temperature was decreased.

<Synthesis Example of Compound (xxiii-1) in First Path>
Compound (xxiii-1) was obtained in the same manner except that the starting compound (va) in the synthesis example of compound (v-1) was changed to compound (xxiii-a). The yield was 46% based on the compound (xxiii-a).

1 H-NMR (CDCl 3 ) of the compound (xxiii-1): δ (ppm) 1.44 to 1.86 (m, 24H), 2.35 to 2.84 (m, 12H), 3.11 ( s, 3H), 3.92 to 3.97 (t, 4H), 4.15 to 4.20 (t, 4H), 5.80 to 5.84 (dd, 2H), 6.07 to 6. 18 (m, 2H), 6.37 to 6.44 (m, 2H), 6.86 to 7.02 (m, 8H), 7.25 (s, 2H), 8.08 (d, 2H) 8.23 (d, 2H)

  The phase transition temperature of the obtained compound (xxiii-1) was measured by texture observation with a polarizing microscope. The compound (xxiii-1) exhibits a smectic phase from 137 ° C. to 146 ° C. during the temperature increase, exhibits a nematic phase from 146 ° C. to 170 ° C. or more, and exhibits a nematic phase up to 78 ° C. during the temperature decrease. .

<Synthesis Example of Compound (xxiv-1) in First Path>
Compound (xxiv-1) was obtained in the same manner as in the synthesis example of compound (v-1) except that the starting compound (va) was changed to compound (xxiv-a). The yield was 54% based on the compound (xxiv-a).

1 H-NMR (CDCl 3 ) of the compound (xxiv-1): δ (ppm) 1.44 to 1.90 (m, 24H), 2.34 to 2.81 (m, 12H), 3.92 to 4.00 (t, 4H), 4.15 to 4.20 (t, 4H), 5.79 to 5.84 (m, 2H), 6.07 to 6.18 (m, 2H), 6. 36 to 6.44 (m, 2H), 6.86 to 7.02 (m, 8H), 7.14 to 7.21 (m, 4H), 8.00 to 8.07 (m, 2H)

The phase transition temperature of compound (xxiv-1) was measured by texture observation with a polarizing microscope. As the temperature was raised, it changed to a nematic phase around 95 ° C. When the temperature was further increased, it changed to an isotropic phase around 212 ° C. When the temperature was lowered from here, it changed to a nematic phase around 212 ° C., and changed to a crystal around 86 ° C. That is, it was found that the compound (xxiv-1) exhibited a nematic phase from 95 ° C. to 212 ° C. when the temperature was raised and a nematic phase from 212 ° C. to 86 ° C. when the temperature was lowered.

<Synthesis Example of Compound (xxv-1) in First Path>
<Synthesis Example of Compound (xxv-1) in First Path>
Compound (xxv-1) was obtained in the same manner except that the starting compound (va) in the synthesis example of compound (v-1) was changed to compound (xxv-a). The yield was 77% based on the compound (xxv-a).

1 H-NMR (CDCl 3 ) of compound (xxv-1): δ (ppm) 1.44 to 1.90 (m, 24H), 2.35 to 2.82 (m, 12H), 3.92 to 3.98 (t, 4H), 4.15 to 4.21 (t, 4H), 5.79 to 5.84 (m, 2H), 6.07 to 6.18 (m, 2H), 6. 36-6.44 (m, 2H), 6.86-7.02 (m, 8H), 7.21-7.29 (m, 2H), 7.74-7.78 (d, 2H), 8.13-8.17 (d, 2H)

The phase transition temperature of compound (xxv-1) was measured by texture observation with a polarizing microscope. As the temperature increased, it changed to a nematic phase around 135 ° C. When the temperature was further increased, it changed to an isotropic phase around 193 ° C. When the temperature was lowered from this point, it changed to a nematic phase around 193 ° C. and changed to crystals around 114 ° C. That is, it was found that the compound (xxiv-1) exhibits a nematic phase from 135 ° C. to 193 ° C. when the temperature is increased, and exhibits a nematic phase from 193 ° C. to 114 ° C. when the temperature is decreased.

Similarly, polymerizable liquid crystals other than benzothiazole could be synthesized by the first route.
A method for synthesizing liquid crystal molecules is shown below.

Compound xxvi-1 was prepared according to the following scheme.

(Synthesis Example of Compound (xxvi-b))
2,3-dicyanohydroquinone 10.0 g (62 mmol), potassium hydroxide 35.0 g (624 mmol) and water 70.0 g were mixed, and the mixture was heated at 100 ° C. with stirring. The obtained mixture was cooled to room temperature, 40.0 g of sulfuric acid was added, and the mixture was further stirred. Ethyl acetate was added to the resulting mixture and stirred, and the organic layer was taken out. The obtained organic layer was concentrated under reduced pressure, the solvent was removed, and the residue was vacuum-dried to obtain 8.5 g (42.6 mmol) of compound (xxvi-b). The yield was 68% based on 2,3-dicyanohydroquinone.

(Synthesis Example of Compound (xxvi-a))
Compound (xxvi-b) 2.5 g (12.6 mmol), aniline 2.5 g (26.5 mmol) and tetrahydrofuran 50.0 g were mixed, and the mixture was heated at 100 ° C. with stirring. The obtained mixture was cooled to room temperature, 3.1 g (15.1 mmol) of N, N′-dicyclohexylcarbodiimide was dissolved in 9.4 g of tetrahydrofuran, added dropwise at room temperature, and then heated at 60 ° C. with stirring. After filtering the obtained mixed liquid, the obtained organic layer was concentrated under reduced pressure, the solvent was removed, and methanol was added and stirred. The produced precipitate was filtered and then dried under vacuum to obtain 0.4 g (1.6 mmol) of the compound (xxvi-a). The yield was 12% based on the compound (xxvi-b).

(Synthesis Example of Compound (xxvi-1))
Compound (xxvi-a) 0.3 g (1.2 mmol), 4-dimethylaminopyridine 0.03 (0.3 mmol), compound (e) 1.2 g (2.8 mmol), and chloroform 24 g were mixed. Subsequently, a solution obtained by dissolving 0.9 g (4.2 mmol) of N, N′-dicyclohexylcarbodiimide in 4.7 g of chloroform was added dropwise to the obtained mixed solution at room temperature and stirred. After filtering the obtained mixture, 12 g of 2N hydrochloric acid was added and stirred, the liquid was separated, and the organic layer was taken out. After the solvent of this organic layer was distilled off, methanol was added and stirred. The produced precipitate was filtered and then vacuum-dried to obtain 0.7 g of compound (xxvi-1).
The yield was 54% based on xxvi-a.

1 H-NMR (CDCl 3 ) of the compound (xxvi-1): δ (ppm) 1.66 (m, 14H), 2.72 (m, 4H), 2.57 (m, 2H), 3.94 (T, 4H), 4.17 (t, 4H), 5.80 (d, 2H), 6.12 (m, 2H), 6.43 (d, 2H), 6.91 (m, 8H) 7.42 (m, 7H)

  Compound xxvii-1 was prepared according to the following scheme.

(Synthesis Example of Compound (xxvii-a))
Compound (xxvi-b) 2.5 g (12.6 mmol), 2-aminothiazole 2.7 g (26.5 mmol) and tetrahydrofuran 50.0 g were mixed, and the resulting mixture was heated at 100 ° C. with stirring. . The obtained mixed solution was cooled to room temperature, and a solution prepared by dissolving 3.1 g (15.1 mmol) of N, N′-dicyclohexylcarbodiimide in 9.4 g of tetrahydrofuran was added dropwise at room temperature, followed by stirring. After filtering the obtained mixed liquid, the obtained organic layer was concentrated under reduced pressure, the solvent was removed, and methanol was added and stirred. The produced precipitate was filtered and then vacuum-dried to obtain 0.4 g (1.5 mmol) of the compound (xxvii-a). The yield was 13% based on the compound (xxvi-b).

(Synthesis Example of Compound (xxvii-1))
Compound (xxvii-a) 0.3 g (1.1 mmol), 4-dimethylaminopyridine 0.03 (0.3 mmol), compound (e) 1.2 g (2.8 mmol), and chloroform 23 g were mixed. A solution prepared by dissolving 0.9 g (4.2 mmol) of N, N′-dicyclohexylcarbodiimide in 4.6 g of chloroform was added dropwise to the obtained mixed solution at room temperature and stirred. The obtained mixture was filtered, 12 g of 2N hydrochloric acid was added and stirred, the liquid was separated, and the organic layer was taken out. After the solvent of this organic layer was distilled off, methanol was added and stirred. The produced precipitate was filtered and then vacuum-dried to obtain 0.3 g of compound (xxvii-1). The yield was 25% based on xxvii-a.

1 H-NMR (CDCl 3 ) of the compound (xxvii-1): δ (ppm) 1.66 (m, 14H), 2.72 (m, 4H), 2.57 (m, 2H), 3.94 (T, 4H), 4.17 (t, 4H), 5.80 (d, 2H), 6.14 (m, 2H), 6.43 (d, 2H), 6.91 (m, 8H) 7.26 (d, 1H), 7.49 (s, 2H), 7.80 (d, 1H)

  The phase transition temperature of the obtained compound (xxvii-1) was measured by texture observation with a polarizing microscope. The compound (xxvii-1) exhibited a smectic phase from 143 ° C. to 152 ° C. during the temperature increase, a nematic phase from 152 ° C. to 186 ° C., and exhibited a nematic phase from 99 ° C. during the temperature decrease and crystallized.

<Synthesis Example of Compound (i-1) in First Path>
<Synthesis Example of Compound (xxv-1) in First Path>
Compound (i-1) was obtained in the same manner as in the synthesis example of compound (v-1) except that the starting compound (va) was changed to compound 1,4-dihydroxyanthraquinone. The yield was 34% based on 1,4-dihydroxyanthraquinone.

1 H-NMR (CDCl 3 ) of compound (i-1): δ (ppm) 1.43 to 1.86 (m, 24H), 2.35 to 2.84 (m, 12H), 3.90 to 3.97 (t, 4H), 4.15 to 4.19 (t, 4H), 5.80 to 5.84 (dd, 2H), 6.07 to 6.18 (m, 2H), 6. 37 to 6.44 (m, 2H), 6.86 to 7.00 (m, 8H), 7.40 to 7.48 (m, 2H), 7.74 to 7.79 (m, 2H) 8 .17-8.25 (m, 2H)

  The phase transition temperature of the obtained compound (i-1) was measured by texture observation with a polarizing microscope. Compound (i-1) exhibits a smectic phase from 125 ° C. to 128 ° C. at the time of temperature increase, exhibits a nematic phase from 128 ° C. to 200 ° C. or more, and exhibits a nematic phase to 106 ° C. at the time of temperature decrease. .

<Synthesis Example of Compound (xxviii-1) in First Route>
Compound (e) 12.5 g (30 mmol), 4-dimethylaminopyridine 0.4 (3 mmol), 1,5-dihydroxyanthraquinone 2.9 g (12 mmol), and chloroform 100 g were mixed. A solution obtained by dissolving 9.3 g (45 mmol) of N, N′-dicyclohexylcarbodiimide in 25 g of chloroform was added dropwise to the obtained mixed solution at room temperature and stirred. Thereafter, 124 g of 1N hydrochloric acid was added and stirred, and the liquid obtained by filtering to remove solids was separated, and the organic layer was taken out. After the solvent of this organic layer was distilled off, methanol was added and filtered to take out a solid matter. When the obtained solid was dried, 10.5 g of compound (xxviii-1) was obtained. The yield was 84% based on 1,5-dihydroxyanthraquinone.

1 H-NMR (CDCl 3 ) of the compound (xxviii-1): δ (ppm) 1 H NMR (CDCl 3 ); δ 1.44-1.89 (m, 24H), 2.31-2.81 ( m, 12H), 3.92 to 3.97 (m, 4H), 4.15 to 4.21 (m, 4H), 5.79 to 5.85 (m, 2H), 6.07 to 6. 18 (m, 2H), 636-6.44 (m, 2H), 6.86-7.02 (m, 8H), 7.36-7.40 (m, 2H), 7.74-7. 81 (m, 2H) 8.17-8.22 (m, 2H)

<Synthesis Example of Compound (xxix-1) in First Path>
Compound (e) 12.5 g (30 mmol), 4-dimethylaminopyridine 0.4 (3 mmol), 1,2-dihydroxyanthraquinone 2.9 g (12 mmol), and chloroform 100 g were mixed. A solution obtained by dissolving 9.3 g (45 mmol) of N, N′-dicyclohexylcarbodiimide in 25 g of chloroform was added dropwise to the obtained mixed solution at room temperature and stirred. Thereafter, 124 g of 1N hydrochloric acid was added and stirred, and the liquid obtained by filtering to remove solids was separated, and the organic layer was taken out. After the solvent of the organic layer was distilled off, methanol was added and filtered to take out a solid. When the obtained solid was dried, 10.3 g of compound (xxix-1) was obtained. The yield was 82% based on 1,2-dihydroxyanthraquinone. When this compound was heated and the phase transition temperature was confirmed, the liquid crystal phase was not observed and it melt | dissolved at 105 degreeC.

1 H-NMR (CDCl 3 ) of compound (xxix-1): δ (ppm) 1.44 to 1.83 (m, 24H), 2.29 to 2.82 (m, 12H), 3.91 to 3.97 (m, 4H), 4.14 to 4.20 (m, 4H), 5.79 to 5.84 (m, 2H), 6.07 to 6.18 (m, 2H), 6. 36 to 6.44 (m, 2H), 6.85 to 7.02 (m, 8H), 7.59 to 7.64 (d, 1H), 7.75 to 7.83 (m, 2H) 8 .20-8.34 (m, 3H)

<Synthesis Example of Compound (xxxii-1) in First Path>
Compound (xxxii-1) was produced according to the following scheme.

[Synthesis Example of Compound (xxxii-b)]
Trans-cinnamic acid 23 g (155 mmol), 1H-benzotriazol-1-yloxytripyrrolidinophosphonium hexafluorophosphate 75.5 g (171 mmol), triethylamine 15.7 g (155 mmol), dimethylaminopyridine 1.9 g (15.5 mmol) ), And 200 g of dehydrated dimethylacetamide were mixed with ice-cooling under light-cooling, and 24.6 g (155 mmol) of 2,5-dimethoxyaniline was added to the resulting mixture, followed by room temperature at 0 ° C. for 8 hours. And stirred overnight. The resulting solution was extracted with methyl isobutyl ketone and separated three times with a saturated aqueous sodium carbonate solution. The organic layer was collected, concentrated under reduced pressure, and crystallized from methanol. The crystals were collected by filtration and dried in vacuo. On the other hand, the methanol solution was allowed to stand overnight at room temperature for recrystallization. Crystals were similarly collected and dried in vacuo.
The two were combined, washed again with cold methanol and dried to obtain 38.6 g of a light gray powder mainly composed of the compound (xxxii-b). The yield was 88% based on 2,5-dimethoxyaniline.

[Synthesis Example of Compound (xxxii-c)]
30 g (106.0 mmol) of the compound (xxxii-b), 22.27 g of 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetan-2,4-disulfide (Lawson reagent) (55.0 mmol) and 500 g of toluene were mixed, heated to 80 ° C. and stirred. The obtained mixed solution was cooled and concentrated to obtain a red viscous solid mainly composed of a decomposition product of Lawesson's reagent and compound (xxxii-c).

[Synthesis Example of Compound (xxxii-d)]
A mixture containing the compound (xxxii-c) obtained in the previous item as a main component, 25.4 g (636 mmol) of sodium hydroxide and 750 g of water were mixed and stirred under ice cooling. Subsequently, an aqueous solution containing 95.1 g (289 mmol) of potassium ferricyanide is added to the obtained mixed solution under ice cooling, followed by stirring. The precipitated solid is washed with cold water and hexane, and then washed with hot methanol. Gave 17.7 g of compound (xxxii-d) as a yellow powder. The yield was 56% based on the compound (xxxii-b).

[Synthesis Example of Compound (xxxii-a)]
Compound (xxxii-d) 10.6g (35.7mmol) and pyridinium chloride 106.0g (10 times mass) were mixed, and it heated up at 180 degreeC, and stirred for 2 hours. After cooling the obtained mixed liquid, water was added, and the obtained precipitate was washed with water and hexane to obtain 10.8 g of a solid containing the compound (xxxii-a) as a main component. The yield was 110% based on the compound (xxxii-d).

(Synthesis Example of Compound (xxxii-1))
Compound (xxxii-a) 0.54 g (2.01 mmol), 4-dimethylaminopyridine 0.02 (0.2 mmol), compound (e) 1.76 g (4.21 mmol), and chloroform 30 g were mixed. To the obtained mixture, 0.92 g (4.81 mmol) of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride was added and stirred. The resulting mixture was filtered through celite and concentrated under reduced pressure. The crude product was developed by column chromatography using chloroform 100% as an eluent, and then developed with an eluent of 95% chloroform and 5% acetone. The orange adsorption band was collected, concentrated under reduced pressure, and crystallized with ethanol. The crystals were collected by filtration, further washed with heptane and vacuum dried to obtain 1.21 g of compound (xxxii-1) as a white powder. The yield was 56% based on xxxii-a.

1 H-NMR (CDCl 3 ) of the compound (xxxii-1): δ (ppm) 1.44 to 1.83 (m, 24H), 2.34 to 2.84 (m, 12H), 3.92 to 3.97 (t, 4H), 4.15 to 4.20 (t, 4H), 5.79 to 5.84 (dd, 2H), 6.07 to 6.18 (m, 2H), 6. 37-6.43 (m, 2H), 6.87-7.01 (m, 8H), 7.19 (s, 2H), 7.34-7.59 (m, 7H)

  The phase transition temperature of the obtained compound (xxxii-1) was measured by texture observation with a polarizing microscope. Compound (xxxii-1) exhibited a nematic phase from 125 ° C. to 180 ° C. or higher when the temperature was raised, and exhibited a nematic phase up to 55 ° C. when the temperature was lowered and crystallized.

  Similarly, if the alkyl chain length of the compound (e) is changed, the compounds (v-2), (v-3) and (v-4) can be synthesized by the same method as in the first route. The synthesis example of each compound is shown below.

  Compound (b ′) could be synthesized in exactly the same manner as compound (b) which differs only in alkyl chain length. Similarly, compound (d ′), compound (d) and compound (e ′) could be synthesized in the same manner as compound (e), respectively.

(Synthesis Example of Compound (b ″))
Monotetrahydropyranyl protected hydroquinone (a) 59.5 g (307 mmol), sodium hydroxide 21.7 g (543 mmol), 11-bromoundecanol 70 g (279 mmol) and dimethylacetamide 280 g were mixed. The resulting mixture was stirred at 90 ° C. and then at 110 ° C. under a nitrogen atmosphere. Thereafter, the mixture was cooled to room temperature, the mixture was poured into 1680 g of pure water, and the deposited precipitate was collected by filtration. Next, the precipitate was washed with 400 mL of 6N aqueous sodium hydroxide solution, washed with heptane, and dried in vacuo to obtain 83 g of compound (b ″). The yield was 82% based on 11-bromoundecanol.

(Synthesis Example of Compound (d ″))
80 g (219 mmol) of compound (b ″), 1.40 g (6.42 mmol) of 3,5-ditertiarybutyl-4-hydroxytoluene, 61.2 g (505 mmol) of N, N-dimethylaniline, 1, 3- 1.00 g of dimethyl-2-imidazolidinone and chloroform were mixed. To the obtained mixed solution, 29.8 g (329 mmol) of aquiroyl chloride was added dropwise under a nitrogen atmosphere and ice cooling, and the mixture was returned to room temperature and stirred. After confirming the completion of the reaction, the reaction mixture was washed with a 2N aqueous hydrochloric acid solution and a saturated aqueous sodium carbonate solution, and the collected organic layer was concentrated to obtain an intermediate. 700 ml of methanol was added to the obtained intermediate, and 3.34 g (18 mmol) of paratoluenesulfonic acid and 3 g of water were added. The solution was stirred at 60 ° C. for 3 hours. After confirming the completion of the reaction, 1400 g of pure water was added to the solution to cause crystallization, and this was recovered. The obtained white powder was washed with water-methanol 2/1 (v / v), further washed with heptane, and dried under vacuum to obtain 62 g of compound (d ″). The yield was 84% based on the compound (b ″).

(Synthesis Example of Compound (e ″))
40.3 g (120 mmol) of compound (d ″), 1.49 g (12.2 mmol) of dimethylaminopyridine, 28 g (122 mmol) of trans 1,4-cyclohexanedicarboxylic acid monoethoxymethyl ester (compound (f)), and 150 mL of chloroform was mixed. The resulting mixture was ice-cooled and stirred under a nitrogen atmosphere, and a solution of 27.3 g (132 mmol) of dicyclohexylcarbodiimide in 50 mL of chloroform was added dropwise. After completion of dropping, the mixture was stirred at room temperature. Chloroform 200mL and heptane 200mL were added to the reaction solution, and the precipitate was filtered. The filtrate was collected and washed with 2N aqueous hydrochloric acid. The organic layer was collected, insoluble components were filtered, dried over anhydrous sodium sulfate, filtered, and then the solvent was removed to obtain an intermediate.

  The intermediate obtained in the previous section, 2.34 g (130 mmol) of pure water, 1.40 g (6.42 mmol) of 3,5-ditertiarybutyl-4-hydroxytoluene, 3.95 g of paratoluenesulfonic acid monohydrate ( 20.8 mmol) and 200 mL of THF were mixed. The resulting mixture was heated to 70 ° C. under a nitrogen atmosphere and stirred for 3 hours. After allowing to cool to room temperature, the precipitate was removed by filtration, and the solution was concentrated under reduced pressure at room temperature. 200 mL of heptane was added to the residue. The deposited precipitate was collected by filtration, washed with pure water, and then vacuum-dried. The obtained powder was redissolved in chloroform and filtered through silica gel. The filtrate was collected and crystallized by adding 400 mL of chloroform and heptane. The obtained powder was collected by filtration and vacuum-dried to obtain 44.4 g of compound (e ″). The yield was 82% in two steps based on the compound (d ″).

(Synthesis Example of Compound (b ′ ″))
Monotetrahydropyranyl protected hydroquinone (a) 88.5 g (455 mmol), sodium hydroxide 35.5 g (888 mmol), 8-chlorooctanol 75 g (455 mmol), and dimethylacetamide 300 g were mixed. The resulting mixture was stirred at 90 ° C. under a nitrogen atmosphere and then at 100 ° C. for 2 hours. Thereafter, the mixture was cooled to room temperature, the mixed solution was poured into 600 g of pure water, and the deposited precipitate was collected by filtration. Subsequently, the precipitate was washed with 400 mL of 6N aqueous sodium hydroxide solution, washed with heptane, and dried in vacuo to obtain 132 g of compound (b ′ ″). The yield was 90% based on 8-chlorooctanol.

(Synthesis Example of Compound (d ′ ″))
Compound (b ′ ″) 100 g (310 mmol), 3,5-ditertiarybutyl-4-hydroxytoluene 1.40 g (6.42 mmol), N, N-dimethylaniline 86.4 g (713 mmol), 1, 3 -Dimethyl-2-imidazolidinone 1.00g and chloroform were mixed. Aquiroyl chloride (42.11 g, 465 mmol) was added dropwise to the obtained mixed solution under a nitrogen atmosphere and ice cooling, and the mixture was returned to room temperature and stirred for 2 hours. After confirming the completion of the reaction, the organic layer was washed with a 2N aqueous hydrochloric acid solution and a saturated aqueous sodium carbonate solution, and the collected organic layer was concentrated to obtain an intermediate. To the obtained intermediate, 300 ml of methanol was added, and 3.34 g (18 mmol) of paratoluenesulfonic acid and 3 g of water were added. The solution was allowed to stir at 60 ° C. for 3 hours. After confirming the completion of the reaction, 1400 g of pure water was added for crystallization, and this was recovered. The obtained powder was washed with water-methanol 2/1 (v / v), further washed with heptane, and vacuum-dried to obtain 72 g of compound (d ′ ″). The yield was 79% based on the compound (b ′ ″).

(Synthesis Example of Compound (e ′ ″))
Compound (d ′ ″) 25.1 g (86 mmol), dimethylaminopyridine 1.06 g (8.7 mmol), trans 1,4-cyclohexanedicarboxylic acid monoethoxymethyl ester (compound (f)) 20 g (86.9 mmol) ) And 70 mL of chloroform. The obtained mixture was ice-cooled and stirred under a nitrogen atmosphere, and a solution of 19.5 g (95 mmol) of dicyclohexylcarbodiimide in 50 mL of chloroform was added dropwise. After completion of dropping, the mixture was stirred at room temperature. Chloroform 200mL and heptane 200mL were added to the reaction solution, and the precipitate was filtered. The filtrate was collected and washed with 2N aqueous hydrochloric acid. The organic layer was collected, insoluble components were filtered, dried over anhydrous sodium sulfate, filtered, and then the solvent was removed to obtain an intermediate.

  The intermediate obtained in the previous section, 1.46 g (81 mmol) of pure water, 1.40 g (6.42 mmol) of 3,5-ditertiarybutyl-4-hydroxytoluene, 2.46 g of paratoluenesulfonic acid monohydrate ( 12.9 mmol) and 200 mL of THF were mixed. The resulting mixture was heated to 70 ° C. under a nitrogen atmosphere and stirred for 2 hours. After allowing to cool to room temperature, the precipitate was removed by filtration, concentrated under reduced pressure at room temperature, and 800 mL of pure water was added to the residue. The deposited precipitate was collected by filtration, washed with pure water, and then vacuum dried. The obtained powder was washed with ethanol / water 2/3 (v / v) and further washed with heptane. The obtained powder was collected by filtration and dried in vacuo to obtain 30.1 g of a compound (e ″ ″). The yield was 84% in two steps based on the compound (d ′ ″).

<Synthesis Example of Compound (v-2) in First Route>
Compound (v-2) was obtained in the same manner except that the starting compound (e) in the synthesis example of compound (v-1) was changed to compound (e ′). The yield was 72% based on the compound (va).

1 H-NMR (CDCl 3 ) of compound (v-2): δ (ppm) 1.45 to 1.83 (m, 16H), 2.35 to 2.85 (m, 12H), 3.94 to 3.97 (t, 4H), 4.16 to 4.21 (t, 4H), 5.81 to 5.84 (dd, 2H), 6.07 to 6.18 (m, 2H), 6. 37-6.44 (m, 2H), 6.87-7.02 (m, 8H), 7.27 (d, 2H), 8.19-8.23 (d, 2H), 8.34- 8.38 (d, 2H)

<Synthesis Example of Compound (v-3) in First Route>
Compound (v-3) was obtained by the same method except that the starting compound (e) in the synthesis example of compound (v-1) was changed to compound (e ″). The yield was 82% based on the compound (va).

1 H-NMR (CDCl 3 ) of compound (v-3): δ (ppm) 1.45 to 1.90 (m, 44H), 2.34 to 2.87 (m, 12H), 3.93 to 3.97 (t, 4H), 4.15 to 4.20 (t, 4H), 5.81 to 5.84 (dd, 2H), 6.07 to 6.18 (m, 2H), 6. 37-6.44 (m, 2H), 6.87-7.02 (m, 8H), 7.27 (d, 2H), 8.18-8.23 (d, 2H), 8.33- 8.37 (d, 2H)

  The phase transition temperature of the obtained compound (v-3) was observed by texture observation with a polarizing microscope. Compound (v-3) exhibits a smectic phase from 164 ° C. to 174 ° C. at the time of temperature increase, exhibits a nematic phase from 174 ° C. to 195 ° C., and exhibits a nematic phase from 195 ° C. to 167 ° C. at the time of temperature decrease, From 167 ° C. to 151 ° C., a smectic phase was exhibited and crystallized.

<Synthesis Example of Compound (v-4) in First Path>
Compound (v-4) was obtained in the same manner as in the synthesis example of compound (v-1) except that the starting compound (e) was changed to compound (e ′ ″). The yield was 69% based on the compound (va).

1 H-NMR (CDCl 3 ) of compound (v-4): δ (ppm) 1.45 to 1.90 (m, 32H), 2.34 to 2.87 (m, 12H), 3.94 to 3.98 (t, 4H), 4.15 to 4.20 (t, 4H), 5.81 to 5.84 (dd, 2H), 6.07 to 6.18 (m, 2H), 6. 35 to 6.44 (m, 2H), 6.88 to 7.02 (m, 8H), 7.27 (d, 2H), 8.19 to 8.22 (d, 2H), 8.33 to 8.37 (d, 2H)

  The phase transition temperature of the obtained compound (v-4) was measured by texture observation with a polarizing microscope. Compound (v-4) exhibits a smectic phase from 163 ° C. to 167 ° C. at the time of temperature increase, exhibits a nematic phase from 167 ° C. to 220 ° C., and exhibits a nematic phase from 220 ° C. to 156 ° C. at the time of temperature decrease, Crystallized.

Furthermore, if the compound (f) is applied to the second route, it becomes possible to synthesize compound v-1 derivatives having various linking groups. The synthesis example of compound v-5 is shown below.

<Synthesis Example of Compound (v-5) in Second Route>
Compound (v-5) was synthesized according to the following scheme.

(Synthesis Example of Compound (g))
12.5 g (43.3 mmol) of the compound (va), 1.06 g (8.7 mmol) of 4-dimethylaminopyridine, 20.0 g (86.7 mmol) of the compound (f), and 50 g of chloroform were mixed. A solution obtained by dissolving 19.7 g (95.4 mmol) of N, N′-dicyclohexylcarbodiimide in 30 g of chloroform was added dropwise to the obtained mixture at room temperature and stirred. The obtained mixture was filtered, 12 g of 2N hydrochloric acid was added and stirred, the liquid was separated, and the organic layer was taken out. After the solvent of the organic layer was distilled off, tetrahydrofuran was added and stirred. The produced precipitate was removed by filtration, concentrated under reduced pressure, and crystallized with heptane. This was collected by filtration and dried in vacuo to give compound (g) as a pale yellow powder.

(Synthesis Example of Compound (h))
Liquid obtained by dissolving the intermediate (g) obtained in the previous item in tetrahydrofuran, 1.18 g (65 mmol) of pure water, 1.40 g (6.42 mmol) of 3,5-ditertiarybutyl-4-hydroxytoluene, paratoluene 1.55 g (8.2 mmol) of sulfonic acid monohydrate and 115 mL of tetrahydrofuran were mixed. The resulting mixture was heated to 70 ° C. under a nitrogen atmosphere and stirred for 2 hours. After cooling to room temperature, the produced precipitate was collected by filtration. The obtained powder was washed with tetrahydrofuran and further washed with heptane. The obtained powder was collected by filtration and dried in vacuo to obtain 18 g of compound (h). The yield was 70% based on the compound (va) based on the two steps.

(Synthesis Example of Compound (i))
Triphosgene (25.36 g, 85 mmol) and tetrahydrofuran (125 g) were mixed under ice cooling. To the resulting mixture, 37 g (257 mmol) of 4-hydroxybutyl acrylate and 28.0 g (231 mmol) of N, N′dimethylaniline were added dropwise. The reaction solution was stirred at room temperature for 2 hours to obtain a chloroformate intermediate. To the intermediate solution, 50 mL of tetrahydrofuran in which 49.9 g (257 mmol) of compound (a) and 49.9 g (282 mmol) of pyridine were dissolved was added dropwise. The mixture was stirred overnight at room temperature, and the white precipitate was removed by filtration and concentrated under reduced pressure. 120 mL of ethanol was added to the residue, and then 44 g of paratoluenesulfonic acid monohydrate was added to adjust the pH of the solution to 4. The mixture was stirred at room temperature for 1 hour, and the ethanol solution was poured into 1000 g of ice. The supernatant was removed by decantation, and the lower layer liquid was further washed with water-ethanol 1/3, and the supernatant was also removed by decantation. Further, the compound (i) was obtained through washing with heptane and decantation. The yield was 50.0 g, and the yield was 70% based on 4-hydroxybutyl acrylate.

<Synthesis Example of Compound (v-5)>
Compound (g) 6.1 g (10 mmol), compound (i) 6.0 g (21 mmol), dimethylaminopyridine 0.26 g (2.1 mmol) and chloroform 20 mL were mixed. To the resulting mixture, 10 mL of a chloroform solution of 5.30 g (26 mmol) of dicyclohexylcarbodiimide was added dropwise under ice cooling. The reaction solution was stirred, dicyclohexylurea was filtered, a 2N aqueous hydrochloric acid solution was added, the separated organic layer was dried, filtered through celite, and concentrated under reduced pressure. Methanol was added to the residue for crystallization. The resulting precipitate was collected and redissolved in chloroform. 500 mg of activated carbon was added and allowed to stand overnight, then filtered through acetic acid and celite, and reprecipitated in ethanol. The precipitate was collected by filtration, washed with heptane, and vacuum dried to obtain 2.8 g of compound (v-5). The yield was 25% based on the compound (g).

1 H-NMR (CDCl 3 ) of the compound (v-5): δ (ppm) 1.72-1.88 (m, 16H), 2.35-2.84 (m, 12H), 4.21- 4.25 (t, 4H), 4.28 to 4.33 (t, 4H), 5.82 to 5.86 (dd, 2H), 6.08 to 6.19 (m, 2H), 6. 39 to 6.46 (m, 2H), 7.13 to 7.24 (m, 8H), 7.29 (d, 2H), 8.19 to 8.22 (d, 2H), 8.35 to 8.38 (d, 2H)

  The phase transition temperature of the obtained compound (v-5) was observed by texture observation with a polarizing microscope. Compound (v-5) exhibited a smectic phase from 142 ° C. to 163 ° C. at the time of temperature increase, a nematic phase from 163 ° C. to 224 ° C., and a nematic phase from 108 ° C. to the temperature of 108 ° C. when crystallized.

However, compound v-1 derivatives having different linking groups can also be synthesized by the same method as in the first route. The structure and synthesis example of compound v-6 are shown below.

<Synthesis Example of Compound (v-6) in First Route>
Compound (v-6) was synthesized according to the following scheme. The structure of compound (v-6) is as follows.

(Synthesis Example of Compound (j))
30.73 g (135 mmol) of parahydroxybenzoic acid benzyl ester, 31 g (135 mmol) of trans 1,4-cyclohexanedicarboxylic acid monoethoxymethyl ester (compound (f)), 31.95 g (155 mmol) of N, N′-dicyclohexylcarbodiimide , N, N-dimethylaminopyridine (1.64 g, 13.5 mmol) and 200 ml of dehydrated chloroform were mixed. The resulting mixture was stirred at room temperature under a nitrogen atmosphere. 100 mL of heptane was added to the reaction solution, the resulting precipitate was filtered, and the filtrate was recovered. The filtrate was washed with 1N hydrochloric acid aqueous solution. The collected organic layer was dried and filtered, and 50% by volume aqueous methanol solution was added to the residue, and the resulting crystals were collected by filtration. The crystals were washed with heptane and pure water and then vacuum dried to obtain 58.0 g of Compound (j). The yield was 98% based on parahydroxybenzoic acid benzyl ester.

(Synthesis Example of Compound (k))
50.0 g (114 mmol) of the compound (j) obtained in the previous item and 150 ml of tetrahydrofuran were mixed. Acetic acid (catalytic amount, 2 g) and 7.5 g of palladium carbon were added to the obtained mixed solution, and the mixture was stirred under a nitrogen atmosphere. The reaction solution was depressurized and then stirred under a hydrogen atmosphere. When hydrogen consumption ceased, the solution was filtered through Celite under a nitrogen atmosphere. After removing the solvent with an evaporator, the residue was washed with 50 vol% aqueous methanol solution and dried in vacuo to obtain 32.0 g of compound (k). The yield was 80% based on the compound (j).

(Synthesis Example of Compound (l))
Compound (j) 16 g (46 mmol), acrylic acid (4-hydroxybutyl) 6.91 g (48 mmol)), N, N′-dicyclohexylcarbodiimide 10.88 g (53 mmol), N, N-dimethyl obtained in the previous section 0.56 g (4.6 mmol) of aminopyridine, 10 mg of 2,6-ditertiarybutyl-4-methylphenol, and 80 ml of dehydrated chloroform were mixed. The resulting mixture was stirred at room temperature under a nitrogen atmosphere. 40 mL of heptane was added to the reaction solution, the resulting precipitate was filtered, and the filtrate was recovered. The filtrate was washed with 1N hydrochloric acid aqueous solution. The recovered organic layer was dried and filtered to obtain 18.5 g of compound (l). The yield was 85% based on the compound (j).

<Production Example of Compound (m)>
18.5 g of compound (l), 0.87 g of pure water, 0.87 g (4.6 mmol) of paratoluenesulfonic acid monohydrate, and 80 mL of THF were mixed. The resulting mixture was heated to 60 ° C. under a nitrogen atmosphere and stirred. After allowing to cool to room temperature, THF was removed, and 200 mL of heptane was added to the residue. The deposited precipitate was collected by filtration, washed with pure water, and then vacuum dried to obtain 7.5 g of compound (m). The yield was 40% based on the compound (1) in two steps.

(Synthesis Example of Compound (v-6))
4.95 g (11.8 mmol) of the compound (m) obtained in the previous item, 1.70 g (5.9 mmol) of the compound (va), 2.95 g (14.2 mmol) of N, N′-dicyclohexylcarbodiimide, N, N-dimethylaminopyridine (0.29 g, 2.4 mmol) and dehydrated chloroform (40 ml) were mixed. The resulting mixture was stirred at room temperature under a nitrogen atmosphere. 20 mL of heptane was added to the reaction solution, the resulting precipitate was filtered, and the filtrate was recovered. The filtrate was washed with 1N hydrochloric acid aqueous solution. The organic layer was dried, filtered, and concentrated under reduced pressure using an evaporator. Ethyl acetate was added, and the mixture was concentrated again under reduced pressure. The obtained powder was washed with heptane and then vacuum-dried to obtain 2.9 g of compound (v-6). The yield was 45% based on the compound (m).

1 H-NMR (CDCl 3 ) of compound (v-6): δ (ppm) 1.75 to 1.88 (m, 16H), 2.37 to 2.84 (m, 12H), 4.22 to 4.27 (t, 4H), 4.31 to 4.37 (t, 4H), 5.82 to 5.86 (dd, 2H), 6.08 to 6.18 (m, 2H), 6. 38 to 6.45 (m, 2H), 7.17 to 7.21 (dd, 4H), 7.29 (d, 2H), 8.07 to 8.11 (d, 4H), 8.19 to 8.22 (d, 2H), 8.34 to 8.38 (d, 2H)

  The phase transition temperature of the obtained compound (v-6) was measured by texture observation with a polarizing microscope. Compound (v-6) exhibits a smectic phase from 124 ° C. to 135 ° C. at the time of temperature increase, a nematic phase from 135 ° C. to 220 ° C., and exhibits a nematic phase from 220 ° C. to 103 ° C. at the time of temperature decrease, Crystallized.

Furthermore, a compound (v-1) derivative having a different polymerizable substituent and a compound (v-1) derivative having a side substituent can also be synthesized by the same method as in the first route. The chemical structures and synthesis examples of compound (v-7) and compound (v-8) are shown below.

<Synthesis Example of Compound (v-7) in First Route>
Compound (v-7) was synthesized according to the following scheme.

(Synthesis Example of Compound (n))
30 g (102 mmol) of compound (b), 1.40 g (6.42 mmol) of 3,5-ditertiarybutyl-4-hydroxytoluene, 15.5 g (153 mmol) of triethylamine, 1,3-dimethyl-2-imidazolidinone 1.00 g was taken and dissolved in 300 mL of tetrahydrofuran. Under nitrogen atmosphere and ice-cooling, 16.0 g (153 mmol) of metaquinoyl chloride was added dropwise, and the mixture was returned to room temperature and stirred for 3 hours. After confirming the completion of the reaction, p-toluenesulfonic acid monohydrate was added to adjust the pH to 2. 1.47 g of pure water was added to the reaction solution and stirred at room temperature for 3 hours. After confirming the completion of the reaction, 100 mL of heptane was added, and the mixture was separated from a 2N aqueous hydrochloric acid solution to recover the organic layer. The organic layer was concentrated under reduced pressure, 1000 g of ice was added, and the mixture was vigorously stirred to crystallize and recovered. The obtained white powder was washed with water-methanol 2/1 (v / v), further washed with heptane and pure water, and dried under vacuum to obtain 12.4 g of compound (n). The yield was 44% based on the compound (b).

(Synthesis Example of Compound (o))
Take 12.0 g (43 mmol) of compound (n), 0.53 g (4.3 mmol) of dimethylaminopyridine, and 10.0 g (44 mmol) of trans 1,4-cyclohexanedicarboxylic acid monoethoxymethyl ester (compound (f)). And dissolved in 50 mL of chloroform. Under nitrogen atmosphere, the mixture was ice-cooled and stirred, and a 20 mL chloroform solution of 9.8 g (48 mmol) of dicyclohexylcarbodiimide was added dropwise. After completion of dropping, the mixture was stirred at room temperature.
Chloroform 200mL and heptane 200mL were added to the reaction solution, and the precipitate was filtered. The filtrate was collected and washed with 2N aqueous hydrochloric acid. The organic layer was collected, insoluble components were filtered, dried over anhydrous sodium sulfate, filtered, and then the solvent was removed to obtain an intermediate.

Intermediate obtained in the previous section, 0.73 g (40 mmol) of pure water, 1.40 g (6.42 mmol) of 3,5-ditertiarybutyl-4-hydroxytoluene, 1.15 g of paratoluenesulfonic acid monohydrate ( 6.1 mmol) and dissolved in 100 mL of THF. The mixture was heated to 70 ° C. under a nitrogen atmosphere and stirred for 3 hours. After allowing to cool to room temperature, the precipitate was removed by filtration and concentrated under reduced pressure at room temperature. 200 mL of heptane was added to the residue. The deposited precipitate was collected by filtration, washed with pure water, and then vacuum-dried. The obtained powder was redissolved in chloroform and filtered through silica gel. The filtrate was collected, dissolved in 400 mL of chloroform, and crystallized by adding heptane. The obtained powder was collected by filtration and vacuum dried to obtain 12.2 g of compound (o).
The yield was 68% based on the compound (n) in two steps.

<Synthesis Example of Compound (v-7)>
6.7g of compound (v-7) was obtained by the same method except having changed the raw material compound (e) into the compound (n) in the synthesis example of the compound (v-1). The yield was 55% based on the compound (va).

1 H-NMR (CDCl 3 ) of the compound (v-7): δ (ppm) 1.40 to 1.85 (m, 24H), 1.95 (d, 6H), 2.36 to 2.85 ( m, 12H), 3.93-3.97 (t, 4H), 4.14-4.19 (t, 4H), 5.46-5.55 (t, 2H), 6.10-6. 10 (br, t, 2H), 6.90-7.00 (m, 8H), 7.27 (d, 2H), 8.20-8.23 (d, 2H), 8.35-8. 38 (d, 2H)

<Synthesis Example of Compound (v-8) in First Path>
Compound (v-8) was synthesized according to the following scheme.

(Synthesis Example of Compound (p))
119 g (713 mmol) of 2-tertiarybutylhydroquinone, 0.23 g (1.2 mmol) of paratoluenesulfonic acid monohydrate and 480 mL of tetrahydrofuran were mixed, and 50 g of dihydropyran was added to the resulting mixture under ice cooling. 594 mmol) was added dropwise. After stirring at room temperature, 500 mL of heptane was added followed by saturated sodium hydroxide.
After discarding the separated aqueous layer, the organic layer was recovered and allowed to stand. The precipitated crystals were collected by filtration, washed with pure water, filtered and dried under vacuum to obtain 39 g of compound (p) as a light purple powder. The yield was 26% based on dihydropyran.

(Synthesis Example of Compound (q))
Compound (p) 39 g (156 mmol), sodium hydroxide 12.2 g (304 mmol), 6-chlorohexanol 21.3 g (156 mmol), and dimethylacetamide 86 g were mixed. The resulting mixture was stirred at 100 ° C. for 6 hours under a nitrogen atmosphere. Thereafter, the mixture was cooled to room temperature, and the mixture was poured into 580 g of pure water. After removing the supernatant aqueous solution by decantation, the precipitated oily crude purified product was dissolved in methyl isobutyl ketone and separated from pure water. The organic layer was collected, concentrated and vacuum dried to obtain 42 g of compound (q) as a pale red viscous liquid. The yield was 77% based on the compound (p).

(Synthesis Example of Compound (r))
Compound (q) was mixed with 40 g (114 mmol), 3,5-ditertiarybutyl-4-hydroxytoluene 1.40 g (6.42 mmol), N, N-dimethylaniline 31.8 g (262 mmol), and chloroform. Aquiroyl chloride (15.5 g, 171 mmol) was added dropwise to the obtained mixture under a nitrogen atmosphere and ice cooling, and the mixture was returned to room temperature and stirred for 3 hours. After confirming the completion of the reaction, paratoluenesulfonic acid monohydrate was added to adjust the pH to 2. 1.64 g of pure water was added to the reaction solution and stirred at room temperature for 1 hour. After confirming the completion of the reaction, 100 mL of heptane was added, 2N hydrochloric acid aqueous solution was added until dimethylaniline was completely removed, and the separated organic layer was recovered. The organic layer was treated with activated carbon, filtered through celite, concentrated under reduced pressure, poured into heptane, and the supernatant heptane layer was removed by decantation. The precipitated pale red viscous liquid was vacuum-dried for 2 days to obtain 26.0 g of compound (r). The yield was 71% based on the compound (q).

(Synthesis Example of Compound (s))
15.0 g (47 mmol) of compound (r), 0.58 g (4.7 mmol) of dimethylaminopyridine, 10.9 g (47 mmol) of trans 1,4-cyclohexanedicarboxylic acid monoethoxymethyl ester (compound (f)), and Chloroform 40mL was mixed. The obtained mixture was ice-cooled and stirred in a nitrogen atmosphere, and a 10 mL chloroform solution of 10.6 g (52 mmol) of dicyclohexylcarbodiimide was added dropwise. After completion of dropping, the mixture was stirred at room temperature. A precipitate formed by adding 100 mL of heptane to the reaction solution was filtered. The filtrate was collected and washed with 2N aqueous hydrochloric acid. The separated organic layer was collected, insoluble components were filtered, dried over anhydrous sodium sulfate, filtered through silica gel, and the solvent was removed to obtain an intermediate.

  Intermediate obtained in the previous section, 0.79 g (44 mmol) of pure water, 1.40 g (6.42 mmol) of 3,5-ditertiarybutyl-4-hydroxytoluene, 1.25 g of paratoluenesulfonic acid monohydrate ( 6.6 mmol) and 150 mL of THF were mixed. The resulting mixture was heated to 70 ° C. under a nitrogen atmosphere and stirred for 3 hours. After cooling to room temperature, the formed precipitate was removed by filtration and concentrated under reduced pressure at room temperature. 300 g of ice was added to the residue and stirred, and the deposited precipitate was collected by filtration, washed with heptane, collected, and dried in vacuo. The obtained powder was redissolved in chloroform and filtered through silica gel. The filtrate was recovered, redissolved in 400 mL of chloroform, and crystallized by adding heptane. The obtained powder was washed with ethanol / water 2/3 (v / v) and collected by filtration, followed by vacuum drying to obtain 17.9 g of compound (o). The yield was 86% based on the compound (r) in two steps.

<Synthesis Example of Compound (v-7)>
0.7 g of compound (v-7) was obtained in the same manner as in the synthesis example of compound (v-1), except that the starting compound (e) was changed to compound (s). The yield was 4.5% based on the compound (va).

1 H-NMR (CDCl 3 ) of the compound (v-8): δ (ppm) 1.38 (s, 18H), 1.47 to 1.85 (m, 24H), 2.36 to 2.83 ( m, 12H), 3.95 to 4.00 (t, 4H), 4.16 to 4.21 (t, 4H), 5.80 to 5.84 (dd, 2H), 6.08 to 6. 18 (m, 2H), 6.37 to 6.44 (dd, 2H), 6.84 to 6.91 (m, 4H), 6.95 (t, 2H), 7.28 (d, 2H) 8.20-8.23 (d, 2H), 8.35-8.38 (d, 2H)

  Furthermore, a polymerizable liquid crystal compound in which cyclohexane is used instead of the benzene ring can be synthesized by the following scheme.

<Synthesis Example of Compound (iv-9) and Compound (v-9) in the First Route>
Compound (iv-9) and compound (v-9) have the following structures.

  The compound was synthesized by the following scheme.

(Synthesis Example of Compound (t))
The compound (t) was synthesized in the same manner as the compound (m) by DCC condensation reaction using trans-4-hydroxycyclohexanecarboxylic acid and monoacrylate (4-hydroxybutyl: manufactured by Tokyo Chemical Industry Co., Ltd.) as raw materials. . The overall yield was 45%. The reaction scheme is shown below.

<Production Example of Compound (u)>
Trans-4-hydroxycyclohexanecarboxylic acid (125 g (867 mmol)), potassium carbonate 143.8 g (1.04 mol), benzyl bromide 140.87 g (824 mmol) and dimethylacetamide 700 ml were mixed. The resulting mixture was heated to 80 ° C. and stirred under a nitrogen atmosphere. After allowing the reaction solution to cool to room temperature, the reaction solution was poured into 1000 g of water and 500 g of a solution consisting of methyl isobutyl ketone / heptane (weight ratio 3/2). After stirring the resulting solution, the separated organic layer was recovered and washed with pure water. The organic layer was dried over anhydrous sodium sulfate and filtered, and then heptane was added to the obtained residue, followed by filtration and vacuum drying to obtain 150 g of compound (u). The yield was 75% based on trans-4-hydroxycyclohexanecarboxylic acid.

<Production Example of Compound (v)>
Compound (u) 30.5 g (130 mmol), dimethylaminopyridine 1.59 g (13 mmol), trans 1,4-cyclohexanedicarboxylic acid monoethoxymethyl ester 30 g (130 mmol) and chloroform 200 mL were mixed. The resulting mixture was ice-cooled and stirred under a nitrogen atmosphere, and 29.57 g (143 mol) of dicyclohexylcarbodiimide was added dropwise. It stirred after completion | finish of dripping. To the resulting reaction solution, 200 mL of chloroform and 200 mL of heptane were added, and the generated precipitate was filtered. The filtrate was collected and washed 3 times with pure water. The organic layer was collected, dried over anhydrous sodium sulfate and filtered. Methanol was added to the resulting residue and stirred, and the resulting powder was collected by filtration and further added with methanol and stirred.
The obtained powder was collected by filtration and vacuum-dried to obtain 42 g of compound (v). The yield was 90% based on the compound (u).

<Production Example of Compound (w)>
23 g of the compound (v) obtained in the previous step was dissolved in 150 ml of THF. Under a nitrogen atmosphere, 1.2 g of 10% palladium-carbon (containing 50% water) was added to the obtained mixture. The resulting mixture was depressurized and stirred at room temperature, normal pressure, and hydrogen atmosphere. Filtered under a nitrogen atmosphere. Toluene was added to the obtained residue, insoluble components were removed by filtration, and then the solvent was removed. The residue was washed with water / methanol 1: 1 (v / v) and then with water. The obtained crystal was separated by filtration and vacuum-dried to obtain 17.8 g of compound (w). The yield was 97% based on the compound (v).

<Production Example of Compound (x)>
16 g (44.9 mmol) of the compound (w), 0.55 g (13 mmol) of dimethylaminopyridine, 6.47 g (44.9 mmol) of 4-hydroxybutyl acrylate, and 100 mL of chloroform were mixed. The resulting mixture was ice-cooled and stirred under a nitrogen atmosphere, and a 50 mL chloroform solution of 10.19 g (49.4 mmol) of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride was added dropwise. It stirred after completion | finish of dripping. 200 mL of toluene was added to the resulting reaction solution, and then the filtrate was collected, concentrated under reduced pressure, and toluene was added. The resulting solution was washed with a 1N hydrochloric acid aqueous solution. The organic layer was collected, dried over anhydrous sodium sulfate, filtered, and the residue was vacuum dried to obtain 18.5 g of compound (x).

<Production Example of Compound (t)>
18.5 g of compound (x), 0.97 g (53.9 mmol) of pure water, 0.85 g (4.5 mmol) of paratoluenesulfonic acid monohydrate and 100 mL of THF were mixed. The resulting mixture was heated to 50 ° C. under a nitrogen atmosphere and stirred. After allowing to cool to room temperature, THF was removed, and 200 mL of heptane was added to the residue. The deposited precipitate was collected by filtration, washed with pure water, and then vacuum-dried to obtain 15.4 g of compound (t). The yield was 81% in two steps based on the compound (x).

(Synthesis Example of Compound (v-9))
Compound (va) 1.44 g (5 mmol), compound (k) 4.24 g (10 mmol), dimethylaminopyridine 0.12 g (1 mmol) and chloroform were mixed. A chloroform solution of 2.48 g (12 mmol) of dicyclohexylcarbodiimide was added dropwise to the obtained mixture under ice cooling. The obtained reaction solution was stirred and filtered, and then the separated organic layer was recovered. The organic layer was dried and concentrated under reduced pressure. Ethyl acetate was added to the residue, and after concentration under reduced pressure, methanol was added for reprecipitation. The precipitate was collected by filtration, further washed with ethanol, filtered, and vacuum dried to obtain 4.65 g of compound (v-9). The yield was 85% based on the compound (va).

  The phase transition temperature of the obtained compound (v-9) was observed by texture observation with a polarizing microscope. Compound (v-9) exhibited a smectic phase from 146 ° C. to 159 ° C. at the time of temperature increase and exhibited a melting point, and exhibited a nematic phase from 159 ° C. to 121 ° C. at the time of temperature decrease, and crystallized.

(Synthesis Example of Compound (iv-9))
Compound (iv-9) was synthesized in the same manner as compound (v-9) using compound (iv-a) and compound (t) as raw materials.

<Example of optical film production>
Example 1
A 2% by weight aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified type, manufactured by Wako Pure Chemical Industries, Ltd.) was applied to a glass substrate, and after heating and drying, a 89 nm thick film was obtained. Subsequently, after rubbing the surface of the obtained film, a coating solution having the composition shown in Table 2 was applied to the surface subjected to the rubbing process by a spin coating method. After drying on a 100 ° C. hot plate for 1 minute, an ultraviolet ray of 1200 mJ / cm 2 was irradiated while heating at 100 ° C. to produce an optical film having a thickness of 1.04 μm.
In Table 2, “% by weight” in the table other than the solvent means “% by weight” of the solid content with the coating solution being 100% by weight.

A: LC242 (liquid crystal compound commercially available from BASF)
Photopolymerization initiator: Irgacure 907, Irgacure 819 (manufactured by Ciba Specialty Chemicals)
Leveling agent: BYK361N (manufactured by Big Chemie Japan)

(Example 2)
An optical film having a thickness of 1.28 μm was produced in the same manner as in Example 1 except that the coating liquid (mixed solution) having the composition shown in Table 2 was used.

(Example 3)
A coating solution (mixed solution) having the composition shown in Table 2 was applied on the polyvinyl alcohol substrate subjected to the rubbing treatment described in Example 1 by a spin coating method. After drying on an 80 ° C. hot plate for 1 minute, it was further dried at 210 ° C. for 1 minute. The obtained unpolymerized film was cooled to 190 ° C., and irradiated with 1200 mJ / cm 2 of ultraviolet rays while being kept at the same temperature, to produce an optical film having a thickness of 2.43 μm.

Example 4
An optical film having a thickness of 1.52 μm was produced in the same manner as in Example 3 except that the coating liquid (mixed solution) having the composition shown in Table 2 was used.

(Example 5)
A coating solution (mixed solution) having the composition shown in Table 2 was applied on the polyvinyl alcohol substrate subjected to the rubbing treatment described in Example 1 by a spin coating method. After drying on an 80 ° C. hot plate for 1 minute, the temperature was further raised to 160 ° C. for drying. The obtained unpolymerized film was irradiated with ultraviolet rays of 1200 mJ / cm 2 while keeping the temperature at the same temperature to produce an optical film having a thickness of 2.27 μm.

(Example 6)
A coating solution (mixed solution) having the composition shown in Table 2 was applied onto the polyvinyl alcohol substrate subjected to the rubbing treatment described in Example 1 by a spin coating method. After drying on an 80 ° C. hot plate for 1 minute, the temperature was further raised to 140 ° C. for drying. The obtained unpolymerized film was irradiated with ultraviolet rays of 1200 mJ / cm 2 while keeping the temperature at the same temperature to produce an optical film having a thickness of 1.59 μm.

(Example 7)
A coating solution (mixed solution) having the composition shown in Table 2 was applied on the polyvinyl alcohol substrate subjected to the rubbing treatment described in Example 1 by a spin coating method. After drying on an 80 ° C. hot plate for 1 minute, the temperature was further raised to 150 ° C. for drying. The obtained unpolymerized film was irradiated with ultraviolet rays of 1200 mJ / cm 2 while being kept at the same temperature to produce an optical film having a thickness of 2.11 μm.

(Example 8)
An optical film having a film thickness of 1.56 μm was produced in the same manner as in Example 5 except that the coating liquid (mixed solution) having the composition shown in Table 2 was used.

Example 9
A coating solution (mixed solution) having the composition shown in Table 2 was applied on the polyvinyl alcohol substrate subjected to the rubbing treatment described in Example 1 by a spin coating method. After drying on an 80 ° C. hot plate for 1 minute, the temperature was further raised to 170 ° C. for drying. The obtained unpolymerized film was irradiated with ultraviolet rays of 1200 mJ / cm 2 while keeping the temperature at the same temperature to produce an optical film having a thickness of 1.40 μm.

(Example 10)
An optical film having a thickness of 1.50 μm was produced in the same manner as in Example 6 except that the coating liquid (mixed solution) having the composition shown in Table 2 was used.

(Comparative Example 1)
A coating solution (mixed solution) having the composition shown in Table 2 was applied on the polyvinyl alcohol substrate subjected to the rubbing treatment described in Example 1 by a spin coating method. After drying on an 80 ° C. hot plate for 1 minute, it was further dried at 150 ° C. for 1 minute. The obtained unpolymerized film was cooled to 100 ° C. and irradiated with ultraviolet rays of 1200 mJ / cm 2 while being kept at the same temperature to produce an optical film having a thickness of 0.88 μm.

<Measurement of optical properties>
In the wavelength range from 450 nm to 700 nm, the retardation value of the produced optical film is measured using a measuring instrument (KOBRA-WR, manufactured by Oji Scientific Instruments), and the retardation value Re (450) at a wavelength of 450 nm is measured with the program attached to the apparatus. The retardation value Re (550) at a wavelength of 550 nm and the retardation value Re (650) at a wavelength of 650 nm were calculated. The results are shown in Table 3.

<Production Example of Compound (TM-1)>
The synthesis route and structure of compound (TM-1) are as follows.

(Synthesis Example of Compound (TC-1))
In a container, 4.9 g (17.0 mmol) of compound (va), 1.7 g (8.5 mmol) of trans-4-n-pentylcyclohexanecarboxylic acid, 0.21 g (1.7 mmol) of 4-dimethylaminopyridine , And 392 g of dehydrated pyridine, followed by dropwise addition of a solution prepared by dissolving 46.2 g (224.4 mmol) of N, N′-dicyclohexylcarbodiimide (DCC) in 98 g of dehydrated pyridine, and the resulting mixture was heated to 60 ° C. The mixture was heated to and stirred.
After the precipitated solid was filtered off, the solution was concentrated, and 196 g of chloroform was added to the solution. The chloroform solution was washed with 196 g of 2N hydrochloric acid, and the separated organic layer was taken out. The organic layer was purified with a silica gel column under reduced pressure to obtain 2.8 g of a solid containing the compound (TC-1) as a main component. The yield was 70% based on trans-4-n-pentylcyclohexanecarboxylic acid.

(Synthesis Example of Compound (TM-1))
In a container, 2.6 g (5.6 mmol) of compound (TC-1), 2.3 g (5.6 mmol) of compound (e), 0.07 g (0.56 mmol) of 4-dimethylaminopyridine, and 75 g of chloroform are mixed. Subsequently, a solution prepared by dissolving 1.4 g (6.7 mmol) of N, N′-dicyclohexylcarbodiimide (DCC) in 19 g of chloroform was dropped, and the resulting mixture was stirred at room temperature. After the precipitated solid was filtered off, chloroform was added to the solution.
The chloroform solution was washed with 94 g of 2N hydrochloric acid, and the separated organic layer was taken out. Methanol was added to the organic layer under reduced pressure to obtain a solid. The obtained solid was washed with methanol to obtain 1.2 g of Compound (TM-1). The yield was 24% based on the compound (TC-1).
1 H-NMR (CDCl 3 ) of compound (TM-1): δ (ppm) 0.9 (3Hy), 1.0 (2Hx), 1.2-2.0 (2Hu + 2Hv + 2Hw + 2Hq + 2Hr + 2Hp + 2Hs + 2Hh + 2Hm + 4Hl + Hk + 2Hi), 2.2-2 .5 (2Hh + 2Hm + 2Hi), 2.6-2.8 (Hg + Hn + Hj), 3.9 (2Ht), 4.2 (2Ho), 5.8 (Hz 3 ), 6.1 (Hz 1 ), 6.4 (Hz 2), 6.9-7.0 (2He + 2Hf), 7.3 (Ha + Hb), 8.2-8.4 (2Hc + 2Hd)

  The phase transition temperature of the obtained compound (TM-1) was observed by texture observation with a polarizing microscope. As the temperature was raised, the crystal phase changed to a smectic phase around 148 ° C, and further changed to a nematic phase around 153 ° C. When the temperature was further increased, the phase changed to an isotropic phase around 173 ° C. When the temperature was lowered from here, it changed to a nematic phase around 170 ° C. and changed to a crystalline phase around 102 ° C. That is, the compound (TM-1) exhibits a smectic phase from 148 ° C. to 153 ° C. at a temperature rise, a nematic phase from 153 ° C. to 173 ° C., and a nematic phase from 170 ° C. to 102 ° C. at a temperature drop. I found out that

<Example of optical film production>
(Example 11)
A 2% by weight aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified type, manufactured by Wako Pure Chemical Industries, Ltd.) was applied to a glass substrate, and after heating and drying, a 89 nm thick film was obtained. Subsequently, after rubbing the surface of the obtained film, a coating solution having the composition shown in Table 4 was applied to the surface subjected to the rubbing process by a spin coating method. After drying on a 170 ° C. hot plate for 1 minute, an ultraviolet ray of 9600 mJ / cm 2 was irradiated while heating at 130 ° C. to produce an optical film with a thickness of 1.353 μm.
In Table 4, “wt%” in the table other than the solvent means “wt%” of the solid content with the coating solution being 100 wt%.

A: LC242 (liquid crystal compound commercially available from BASF)
Photopolymerizable initiator: Irgacure 819 (manufactured by Ciba Specialty Chemicals) Leveling agent: BYK361N (manufactured by Big Chemie Japan)

(Comparative Example 2)
An optical film was prepared in the same manner as in Example 1 except that the coating liquid shown in Table 4 was applied by spin coating, dried on a 45 ° C. hot plate for 1 minute, and irradiated with ultraviolet rays at room temperature. About the obtained optical film, the phase difference value was measured like Example 1 using the measuring machine (KOBRA-WR, Oji Scientific Instruments company make). The results are shown in Table 5.

<Measurement of optical properties>
About the created optical film, the phase difference value in wavelength 547nm was measured using the measuring machine (KOBRA-WR, Oji Scientific Instruments company make). Moreover, the film thickness derived from the polymeric compound of an optical film was measured using the laser microscope (LEXT, Olympus Corporation make). Δn was calculated from the retardation value and the film thickness at a wavelength of 547 nm. Similarly, retardation values at wavelengths of 447 nm and 628 nm were measured, and wavelength dispersion characteristics Re (447) / Re (547) and Re (628) / Re (547) were calculated. The results are shown in Table 5.

  The optical film obtained in Example 11 contains [Re (447) / Re (547)] and [Re (628) / Re (547) as compared with Comparative Example 2 by containing the compound (TM-1). )] Is closer to 1 and has excellent wavelength dispersion.

<Example of optical film production>
(Examples 12 to 28, Comparative Example 3)
A 2% by weight aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified type, manufactured by Wako Pure Chemical Industries, Ltd.) was applied to a glass substrate, and after drying, a film having a thickness of 89 nm was formed. Subsequently, the surface of the obtained film was subjected to a rubbing treatment, and a coating solution having the composition shown in Table 6 was applied to the surface subjected to the rubbing treatment by a spin coating method and dried. Thereafter, ultraviolet rays were irradiated. Thereby, the optical film was able to be created on the glass substrate.

In Table 6, “% by weight” in the tables other than the solvent means “% by weight” with the coating solution being 100% by weight.

LC242: liquid crystal compound photopolymerizable initiator commercially available from BASF: Irgacure 907, Irgacure 819 (manufactured by Ciba Specialty Chemicals)
Leveling agent: BYK361N (manufactured by Big Chemie Japan)

<Measurement of optical properties>
The front retardation value of the produced optical film was measured using a measuring machine (KOBRA-WR, manufactured by Oji Scientific Instruments). In addition, since the glass substrate used for the base material has no birefringence, the front retardation value of the optical film produced on the glass substrate can be obtained by measuring the film with the glass substrate with a measuring machine. . The obtained optically measured front phase difference values were measured at wavelengths of 447.3 nm, 546.9 nm, and 627.8 nm, respectively, and [Re (447.3) / Re (546.9)] (referred to as α). And [Re (627.8) / Re (546.9)] (referred to as β) were calculated. Moreover, the film thickness (micrometer) of the part originating in an optical film was measured using the laser microscope (LEXT, Olympus company make). The results are shown in Table 7. Δn was calculated by dividing the value of Re (546.9) by the film thickness.

The optical films obtained in Examples 12 to 28 were compared with Comparative Example 3 [Re (447.
3) / Re (546.9)] (α in the table) was closer to 1 or less than 1. Further, the value of [Re (627.8) / Re (546.9)] (β in the table) was closer to 1 or 1 or more. That is, since the wavelength dependency of the refractive index is small or so-called reverse wavelength dispersion is exhibited, when used in a liquid crystal panel, it has excellent optical compensation characteristics.

  According to the compound of the present invention, an optical film capable of uniform polarization conversion in a wide wavelength range can be provided.

It is the schematic which shows the color filter 1 which concerns on this invention. It is the schematic which shows the liquid crystal display device 5 which concerns on this invention. It is the schematic which shows the polarizing plate 30 which concerns on this invention. It is the schematic which shows the bonding product 21 of the liquid crystal panel 20 and the polarizing plate 30 of the liquid crystal display device which concerns on this invention. It is the schematic which shows the organic electroluminescent panel 23 of the organic electroluminescent display apparatus which concerns on this invention.

DESCRIPTION OF SYMBOLS 1,1 'Color filter 2,2' Optical film 3,3 'Orientation film 4,4' Color filter layer 5 Liquid crystal display device 6,10 Polarizing plate 7,11 Substrate 8 Counter electrode 9 Liquid crystal layer 12 TFT, Insulating layer 13 Transparent electrode 13 'Reflective electrode 30, 30a, 30b, 30c, 30d, 30e Polarizing plate 14, 14' Laminated body 15 Polarizing film 16, 16 'Supporting substrate 17, 17' Alignment film 18, 18 'Optical film 19, 19 ', 22, 25 Adhesive layer 20 Liquid crystal panel 21 Bonded product 23 Organic EL panel 24 Light emitting layer

Claims (11)

  1. An optical film obtained by polymerizing a compound containing a group represented by the formula (C) and a polymerizable group, and having a thickness of 0.1 to 10 μm.
    - (B 1 -A 1) k -E 1 -G a -D a -Ar a -D b -G b -E 2 - (A 2 -B 2) l - (C)
    [In Formula (C), Ar a represents a divalent group having a benzothiazole ring, and the number N πa of π electrons contained in the aromatic ring in the Ar a group is 12 or more and 22 or less. D a and D b are each independently a single bond, —CO—O—, —O—CO—, —C (═S) —O—, —O—C (═S) —, —CR 1 R 2 -, - CR 1 R 2 -CR 3 R 4 -, - O-CR 1 R 2 -, - CR 1 R 2 -O -, - CR 1 R 2 -O-CR 3 R 4 -, - CR 1 R 2 —O—CO—, —O—CO—CR 1 R 2 —, —CR 1 R 2 —O—CO—CR 3 R 4 —, —CR 1 R 2 —CO—O—CR 3 R 4 — , —NR 1 —CR 2 R 3 —, —CR 1 R 2 —NR 3 —, —CO—NR 1 —, or —NR 1 —CO—. R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.
    G a and G b each independently represent a divalent alicyclic hydrocarbon group. The hydrogen atom contained in the alicyclic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group. The methylene group contained in the alicyclic hydrocarbon group may be substituted with —O—, —S—, or —NH—.
    E 1 and E 2, each independently, -CR 5 R 6 -, - CH 2 -CH 2 -, - O -, - S -, - CO-O -, - O-CO -, - O-CO —O—, —C (═S) —O—, —O—C (═S) —, —O—C (═S) —O—, —CO—NR 5 —, —NR 5 —CO—, -O-CH 2 -, - CH 2 -O -, - S-CH 2 -, - represents a CH 2 -S- or a single bond. R 5 and R 6 each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.
    B 1 and B 2 are each independently, -CR 5 R 6 -, - CH 2 -CH 2 -, - O -, - S -, - CO-O -, - O-CO -, - O-CO —O—, —C (═S) —O—, —O—C (═S) —, —O—C (═S) —O—, —CO—NR 5 —, —NR 5 —CO—, -O-CH 2 -, - CH 2 -O -, - S-CH 2 -, - represents a CH 2 -S- or a single bond.
    A 1 and A 2 each independently represent a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group. The hydrogen atom contained in the divalent alicyclic hydrocarbon group and divalent aromatic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group. It may be substituted with a group. The hydrogen atom contained in the alkyl group having 1 to 4 carbon atoms and the alkoxy group having 1 to 4 carbon atoms may be substituted with a fluorine atom. k and l each independently represents an integer of 0 to 3. ]
  2. The optical film according to claim 1, wherein the number N πa of π electrons contained in the aromatic ring in the Ar a group is 13 or more and 22 or less.
  3. 3. The optical film according to claim 1, wherein G a and G b are 1,4-cyclohexylene groups.
  4. The optical film according to any one of claims 1 to 3 , wherein the compound containing a group represented by formula (C) and a polymerizable group is a compound represented by formula (1).
    P 1 -F 1- (B 1 -A 1 ) k -E 1 -G 1 -D 1 -Ar-D 2 -G 2 -E 2- (A 2 -B 2 ) 1 -F 2 -P 2 ( 1)
    [In the formula (1), Ar represents a divalent group having a benzothiazole ring, and the number Nπ of π electrons contained in the aromatic ring in the Ar group is 12 or more and 22 or less.
    D 1 and D 2 are each independently * —O—CO— (* represents a position bonded to Ar), —C (═S) —O—, —O—C (═S) —, -CR 1 R 2 -, - CR 1 R 2 -CR 3 R 4 -, - O-CR 1 R 2 -, - CR 1 R 2 -O -, - CR 1 R 2 -O-CR 3 R 4 - , —CR 1 R 2 —O—CO—, —O—CO—CR 1 R 2 —, —CR 1 R 2 —O—CO—R 3 R 4 —, —CR 1 R 2 —CO—O—CR 3 R 4 -, - NR 1 -CR 2 R 3 -, - CR 2 R 3 -NR 1 -, - CO-NR 1 -, or represents a -NR 1 -CO-. R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.
    G 1 and G 2 each independently represent a divalent alicyclic hydrocarbon group. The hydrogen atom contained in the alicyclic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group. The methylene group contained in the alicyclic hydrocarbon group may be substituted with —O—, —S—, or —NH—.
    E 1, E 2, B 1 and B 2 are each independently, -CR 5 R 6 -, - CH 2 -CH 2 -, - O -, - S -, - CO-O -, - O-CO -, -O-CO-O-, -C (= S) -O-, -OC (= S)-, -O-C (= S) -O-, -CO-NR < 5 >-,- NR 5 —CO—, —O—CH 2 —, —CH 2 —O—, —S—CH 2 —, —CH 2 —S— or a single bond is represented. R 5 and R 6 each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.
    A 1 and A 2 each independently represent a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group. The hydrogen atom contained in the divalent alicyclic hydrocarbon group and divalent aromatic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group. It may be substituted with a group. The hydrogen atom contained in the alkyl group having 1 to 4 carbon atoms and the alkoxy group having 1 to 4 carbon atoms may be substituted with a fluorine atom.
    k and l each independently represents an integer of 0 to 3.
    F 1 and F 2 each independently represents an alkylene group having 1 to 12 carbon atoms. The hydrogen atom contained in the alkylene group 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, and the methylene group contained in the alkylene group is -O -Or -CO- may be substituted.
    P 1 and P 2 each independently represent a hydrogen atom or a polymerizable group (provided that at least one of P 1 and P 2 represents a polymerizable group). ]
  5. The optical film according to any one of claims 1 to 4 , which is for a λ / 4 plate having a retardation value (Re (550)) of 113 to 163 nm at a wavelength of 550 nm.
  6. The optical film according to any one of claims 1-4 retardation value (Re (550)) is for lambda / 2 plate of 250~300nm at a wavelength of 550 nm.
  7. The optical film in any one of Claims 1-6 , and the polarizing plate containing a polarizing film.
  8. A color filter in which the optical film according to any one of claims 1 to 6 is formed by forming on the alignment polymer coated directly on the color filter substrate.
  9. A flat panel display comprising a liquid crystal panel comprising the polarizing plate according to claim 7 .
  10. An organic EL display device comprising an organic electroluminescence panel comprising the polarizing plate according to claim 7 .
  11. A liquid crystal display device comprising the color filter according to claim 8 .
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