JP2019215549A - Compound, optical film, and manufacturing method for optical film - Google Patents

Abstract

An optical film capable of performing uniform polarization conversion in a wide wavelength range.
An optical film composition containing cyclopentanone or cyclohexanone and a compound containing a group represented by the formula (A) and a polymerizable group. ^{-G a -D a -Ar a -D b} -G b - (A) [ in the formula (A), at least one aromatic ring Ar ^a is selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic represents a divalent group having, ^{D a} and ^{D b} are each independently a single bond, -CO-O -, - O -CO -, - C (= S) -O -, - O-C ( ^{= S) -, - CR1R 2} -, represents, ^{G a} and ^{G b} each independently represents a divalent alicyclic hydrocarbon group. ]
[Selection figure] None

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 a member using an optical film such as a polarizing plate or a retardation plate. Examples of the optical film include an optical film obtained by applying a solution obtained by dissolving a polymerizable compound in a solvent to a supporting base material and then polymerizing the solution. It is known that the retardation (Re (λ)) of an optical film given by light having a wavelength of λ nm is determined by the product of the birefringence Δn and the thickness d of the film (Re (λ) = Δn). × d). The wavelength dispersion characteristic is usually represented by a value (Re (λ) / Re (550)) obtained by dividing the retardation value Re (λ) at a certain wavelength λ by the retardation value Re (550) at 550 nm. (Λ) / Re (550)) and the inverse wavelength dispersion of [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, Vol. 37, p. 1673.

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

The present invention is a compound 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 _[pi of 12 or more.
D ¹ and D ² are each independently * -O-CO- (* represents a position bonding to Ar), -C (= S) -O-, -OC (= 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. It may be substituted, and 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 -, - 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.
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 the 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 by 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 by a fluorine atom.
k and l each independently represent an integer of 0 to 3.
F ¹ and F ² each independently represent an alkylene group having 1 to 12 carbon atoms. The hydrogen atom contained in the alkylene group may be substituted by 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 may be -O -Or -CO-.
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 performing 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 _[pi of 12 or more.
D ¹ and D ² are each independently * -O-CO- (* represents a position bonding to Ar), -C (= S) -O-, -OC (= 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. It may be substituted, and 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 -, - 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.
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 the 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 by 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 by a fluorine atom.
k and l each independently represent an integer of 0 to 3.
F ¹ and F ² each independently represent an alkylene group having 1 to 12 carbon atoms. The hydrogen atom contained in the alkylene group may be substituted by 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 may be -O -Or -CO-.
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). ]

Compound (1) preferably satisfies the requirements represented by formulas (2) and (3).
( _Nπ- 4) / 3 <k + 1 + 4 (2)
12 ≦ N _π ≦ 22 (3)
[In the formulas (2) and (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 heterocycle include a furan ring, a pyrrole ring, a thiophene ring, a pyridine ring, a thiazole ring, and a benzothiazole ring. And the like. Among them, 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 a total of π electrons of the aromatic ring contained in the divalent group. The number N _π 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 Formulas (Ar-1) to (Ar-13).

[In the formulas (Ar-1) to (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, and a carbon number. An alkylsulfonyl group having 1 to 6 carbon atoms, a 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, and an N-alkylamino group having 1 to 6 carbon atoms 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} are, each ^{independently, -CR 7 R 8 -, -} S -, - NR 7 -, - CO- or an -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 represent 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 to 6.
n represents the integer of 0-2. ]

  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 preferred.

  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 a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group, a butylsulfinyl group, an isobutylsulfinyl group, a sec-butylsulfinyl group, a tert-butylsulfinyl group, and a pentylsulfinyl group And a hexyl group sulfinyl, etc., preferably an alkylsulfinyl group having 1 to 4 carbon atoms, more preferably an alkylsulfinyl group having 1 to 2 carbon atoms, and particularly preferably a methylsulfinyl group.

  Examples of the alkylsulfonyl group having 1 to 6 carbon atoms include methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl, pentylsulfonyl And a hexylsulfonyl group, preferably an alkylsulfonyl group having 1 to 4 carbon atoms, more preferably an alkylsulfonyl group having 1 to 2 carbon atoms, and particularly preferably a methylsulfonyl group.

  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, a nonafluorobutyl group, and the like. A fluoroalkyl group is preferred, a fluoroalkyl group having 1 to 2 carbon atoms is more preferred, and a trifluoromethyl group is particularly preferred.

  Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, and a hexyloxy group. And 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, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, tert-butylthio, pentylthio, and hexylthio. , 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.

  The N-alkylamino group having 1 to 6 carbon atoms includes 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, N-alkylamino groups having 1 to 4 carbon atoms are preferable, and 1 to 4 carbon atoms are preferable. 2 is more preferably an N-alkylamino group, and particularly preferably an N-methylamino group.

  Examples of the N, N-dialkylamino group having 2 to 12 carbon atoms include N, N-dimethylamino, N-methyl-N-ethylamino, N, N-diethylamino, N, N-dipropylamino, N, N-diisopropylamino group, N, N-dibutylamino group, N, N-diisobutylamino group, N, N-dipentylamino group, N, N-dihexylamino group and the like. 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, N-ethylsulfamoyl, N-propylsulfamoyl, N-isopropylsulfamoyl, N- Butylsulfamoyl, N-isobutylsulfamoyl, N-sec-butylsulfamoyl, N-tert-butylsulfamoyl, N-pentylsulfamoyl, N-hexylsulfamoyl, etc. N-alkylsulfamoyl groups having 1 to 4 carbon atoms are preferred, N-alkylsulfamoyl groups having 1 to 2 carbon atoms are more preferred, and N-methylsulfamoyl groups are particularly preferred.

  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, An N, N-dihexylsulfamoyl group and the like are mentioned, and an N, N-dialkylsulfamoyl group having 2 to 8 carbon atoms is preferable, and an N, N-dialkylsulfamoyl group having 2 to 4 carbon atoms is more preferable. And N, N-dimethylsulfamoyl groups are 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- It is preferably a methylsulfamoyl group or an N, N-dimethylsulfamoyl group.

Examples of the alkyl group having 1 to 4 carbon atoms for R ⁷ and R ⁸ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a tert-butyl group. Alkyl groups are preferred, and methyl groups are more preferred.
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 includes at least one heteroatom such as a nitrogen atom such as a furyl group, a pyrrolyl group, a thienyl group, a pyridinyl group, a thiazolyl group, a benzothiazolyl group, an oxygen atom, and a sulfur atom, 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 preferred.

  Such an aromatic hydrocarbon group and an aromatic heterocyclic group may have at least one substituent, and the substituent includes 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 and the like, halogen atom, alkyl group having 1 to 2 carbon atoms, cyano group, nitro group, alkylsulfonyl group having 1 to 2 carbon atoms, fluoroalkyl group having 1 to 2 carbon atoms, carbon An alkoxy group having 1 to 2 carbon atoms, an alkylthio group having 1 to 2 carbon atoms, an N-alkylamino group having 1 to 2 carbon atoms, an N, N-dialkylamino group having 2 to 4 carbon atoms, and an alkyl having 1 to 2 carbon atoms Sulfamoyl groups are 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, Examples of the N-alkylsulfamoyl group and the N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms include those described above.

It is preferable that Y ¹ , Y ² and Y ³ are each independently any of the groups represented by the formulas (Y-1) to (Y-6).

[In the formulas (Y-1) to (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. C1-6 alkylsulfonyl group, carboxyl group, C1-6 fluoroalkyl group, C1-6 alkoxy group, C1-6 thioalkyl group, C1-6 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, R represents a hydrogen atom or a methyl group. . ]

The Z ^2, a halogen atom, a methyl group, a cyano group, a nitro group, a sulfonic group, a carboxyl group, a trifluoromethyl group, a methoxy group, thiomethyl group, N, N- dimethylamino group or N- methylamino group is preferable.

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

Preferably, W ¹ and W ² are each independently 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). Is more preferable.

[In the formulas (Ar-6a) to (Ar-6c), the formulas (Ar-10a) and the formulas (Ar-10b), Z ¹ , n, Q ¹ , Z ² , a ¹ and b ¹ are as defined above. Express the same meaning. ]

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

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

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

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

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

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

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

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

  Specific examples of the group represented by the formula (Ar-13) include groups represented by the formulas (ar-180) to (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 to Ar.
) Is preferable. D ¹ and D ² are more preferably * -O-CO-, * -OC (= S)-or * -NR ¹ -CO- (* represents a bonding site with Ar.). . Preferably, R ¹ , R ² , R ³ and R ⁴ are each independently 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 which may contain a hetero atom represented by any one of formulas (g-1) to (g-10), and include a 5-membered or 6-membered alicyclic ring. It is preferably a formula hydrocarbon group.

  Groups represented by the above formulas (g-1) to (g-10) are alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, isopropyl group and tert-butyl group; methoxy group, ethoxy group and the like. C 1-4 alkoxy group; C 1-4 fluoroalkyl group such as trifluoromethyl group; C 1-4 fluoroalkoxy group such as trifluoromethoxy group; cyano group; nitro group; , A chlorine atom, a bromine atom and the like.

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

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

In addition, as A ¹ and A ² , a part of the hydrogen atoms of the groups exemplified above 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; which is substituted by a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom; Is also good.

A ¹ and A ² are particularly preferably the same type of group, since the production of the 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 preferably a 1,4-phenylene group because of easy production of compound (1). Is preferred.

It is preferable that B ¹ and B ² are the same type of divalent group because the production of the compound (1) is easy. Further, since the production of compound (1) is easier, B ¹ and B ² bonded to only A ¹ and A ² among 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 particularly preferable. 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- More preferably, it is O-, -CO-NH-, -NH-CO- or a single bond.

  From the viewpoint of liquid crystallinity, k and l each independently preferably 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, 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, since 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, a p-stilbene group, an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group. Groups, carboxyl group, methylcarbonyl group, hydroxyl group, amide group, alkylamino group having 1 to 4 carbon atoms, amino group, epoxy group, oxetanyl group, aldehyde group, isocyanate group or thioisocyanate group. Further, the polymerizable group may include groups represented by B ¹ and B ² in order to bond the group exemplified above with E ¹ and E ² . For example, a radical polymerizable group or a cationic polymerizable group suitable for photopolymerization is preferable, and an acryloyl group or a methacryloyl group is preferable, and an acryloyl group is more preferable because handling is easy and production is easy. It is more preferable that both P ¹ and P ² are polymerizable groups, since the film hardness of the obtained 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 ) ₁ -F ² -P ² Specific examples include groups represented by formulas (R-1) to (R-134). * (Asterisk) indicates the bonding position with Ar. N in the formulas (R-1) to (R-134) represents an integer of 2 to 12.

Further, the compound (1) includes compounds (i) to (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.

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

  Further, compound (i), compound (ii), compound (iv), compound (v), compound (vi), compound (ix), compound (x), compound (xi), compound (xvi), compound in Table 1 (Xviii), compound (xix), compound (xx), compound (xxi), compound (xxiii), compound (xxiv), compound (xxv), compound (xxvi), compound (xxviii), compound (xxviii), And a typical structural formula of the compound (xxix) is 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-3) v-4), Expression (v-5), Expression (vi-1), Expression (ix-1), Expression (x-1), Expression (xi-1), Expression (xvi-1), Expression (xix) -1), formula (xx-1), formula (xxi-1), formula (xxiii-1), formula (xxiv- ), Formula (xxv-1), formula (xxvi-1), formula (xxvi-1), formula (xxviii-1), formula (xxix-1), formula (xxxiii-1), and formula (xxxiv- An example is shown in 1). In the optical film of the present invention, a plurality of different types of compounds (1) may be used.

  As the compound (1), for example, the following are further exemplified. However, in the formula, n1 and n2 each independently represent an integer of 2 to 12.

The method for producing the compound (A) will be described below using the compound (1) as an example.
Compound (1) can be synthesized by a known organic synthesis reaction (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, Hiyama reaction, Buchwald-Hartwig reaction, Friedel Craft reaction, Heck reaction, Aldol reaction, etc. ) Can be produced by appropriately combining them according to the structure.

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

（式中、Ａｒは上記と同一の意味を表わす。）
で示される化合物と式（１−２）

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

（式中、Ｒ^１、Ｒ^２、Ｇ^１、Ｅ^１、Ａ^１、Ｂ^１、Ｆ^１、Ｐ^１およびｋは上記と同一の意味を表わす。）
で示される化合物とを反応させることにより、式（１−３）

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

（式中、Ａｒ、Ｒ^１、Ｒ^２、Ｇ^１、Ｅ^１、Ａ^１、Ｂ^１、Ｆ^１、Ｐ^１およびｋは上記と同一の意味を表わす。）
で示される化合物を得、得られた式（１−３）で示される化合物と式（１−４）

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

（式中、Ｒ^１、Ｒ^２、Ｇ^２、Ｅ^２、Ａ^２、Ｂ^２、Ｆ^２、Ｐ^２およびｌは上記と同一の意味を表わす。）
で示される化合物とを反応させることにより製造することができる。
式（１−１）で示される化合物と式（１−２）で示される化合物との反応および式（１−３）で示される化合物と式（１−４）で示される化合物との反応は、エステル剤の存在下に実施することが好ましい。

(Wherein, R ¹ , R ² , G ² , E ² , A ² , B ² , F ² , P ² and 1 have the same meaning as described above.)
The compound can be produced by reacting a compound represented by the following formula:
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 the reaction in the presence of an ester agent.

  Examples of the esterifying agent (condensing agent) include 1-cyclohexyl-3- (2-morpholinoethyl) carbodiimidemeth-para-toluenesulfonate, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide, Ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (partially water-soluble carbodiimide: commercially available as WSC), bis (2,6-diisopropylphenyl) carbodiimide, bis (trimethylsilyl) carbodiimide, bisisopropylcarbodiimide, 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, pentachlorophenyl trichloroacetate. From the viewpoints of reactivity, cost, and usable solvent, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide, and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride are used as condensing agents. , Bis (2,6-diisopropylphenyl) carbodiimide, bis (trimethylsilyl) carbodiimide, bisisopropylcarbodiimide, and 2,2′-carbonylbis-1H-imidazole are more preferred.

The composition of the present invention includes 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, compound (A) Different).
^{-G a -D a -Ar a -D b} -G b - (A)
Wherein (A), Ar ^a represents a divalent group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and aromatic heterocyclic ring are included in the aromatic ring in Ar ^a group The number N _{πa of} π electrons 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. It may be substituted, and the methylene group contained in the alicyclic hydrocarbon group may be substituted with -O-, -S- or -NH-. ]

Specific examples of the liquid crystal compound include a liquid crystal handbook (edited by the liquid crystal handbook editing committee, edited by Maruzen Co., Ltd., issued on October 30, 2000), Chapter 3, Molecular Structure and Liquid Crystallinity, 3.2 Non-chiral rod-shaped liquid crystal molecules, 0.3 Compounds having a polymerizable group among the compounds described in the chiral rod-shaped liquid crystal molecule.
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, may be 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, the alicyclic hydrocarbon group and the 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-, -OC (= O)-, -OC (= 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 ( ＯO) —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 even when R ¹⁴ and R ¹⁵ are linked 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, A nitro group or a polymerizable group bonded via an alkylene group having 1 to 12 carbon atoms, wherein a hydrogen atom contained in the alkylene group is an alkyl group having 1 to 6 carbon atoms, It may be substituted by an alkoxy group or a halogen atom.
t represents an integer of 1 to 5. ]

In particular, the polymerizable group in the P ¹¹ and G, may be any group which can be polymerized with the compound (A), a vinyl group, vinyloxy group, 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 and the like. Above all, a radical polymerizable group or a cationic polymerizable group is preferable in that it is suitable for photopolymerization, and an acryloyloxy group, a methacryloyloxy group, or a vinyloxy group is preferable in that it is easy to handle and easy to produce a liquid crystal compound. Groups are preferred.

The aromatic hydrocarbon group, alicyclic hydrocarbon group, and heterocyclic group represented by A ¹¹ each have, for example, 3 to 18 carbon atoms, preferably 5 to 12, and more preferably 5 or 6. Is particularly preferred.

  Examples of the compound (4) include compounds represented by the formula (4-1) and the formula (4-2).

^{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 the formulas (4-1) and (4-2), P ¹¹ , E ¹¹ , B ¹¹ , A ¹¹ , and B ¹² have the same meanings as described above.
F ¹¹ represents 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, and 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 are synonymous with 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). Including 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 the formulas (I) to (V), A ^{12 to} A ¹⁵ have the same meaning as A ¹¹ , and B ^{13 to} B ¹⁶ have the same meaning as B ¹¹ ].

In the compounds represented by the formulas (4-1), (4-2), (I), (II), (III), (IV) and (V), P ¹¹ and by appropriately selecting the combination of E ^11, by further appropriately selecting the combination of P ¹² and E ^12, it is preferable that they are bonded through an ether bond or an ester bond.

  Specific examples of the compound (4) include, for example, the following formulas (I-1) to (I-5), (II-1) to (II-6), (III-1) to ( III-19), compounds represented by formulas (IV-1) to (IV-14), and formulas (V-1) to (V-5). Here, k represents an integer of 1 to 11. These liquid crystal compounds are preferred because they are easily synthesized and are easily available, such as being commercially available.

  The amount of the liquid crystal compound used is, for example, 90 parts by weight or less based on 100 parts by weight of the total of the liquid crystal compound and the compound (A).

  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 and sulfonium salts, and more specifically, Irgacure 907. Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369 (all manufactured by Ciba Japan KK), Seikeall BZ, Seikeall Z, Seikeall BEE (all manufactured by 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 manufactured by ADEKA Corporation) and the like.

  The amount of the polymerization initiator to be used is, for example, 0.1 part by weight to 30 parts by weight, preferably 0.5 part by weight to 10 parts by weight based on 100 parts by weight of the total of the liquid crystal compound and the compound (A). Department. Within the above range, the compound (A) can be polymerized without disturbing the orientation of the liquid crystal compound.

  The optical film of the present invention is a film that can transmit light, and refers to a film having an optical function. The optical function means refraction, birefringence, or the like. A retardation film, which is a type of optical film, is used to convert linearly polarized light into circularly polarized light or elliptically polarized light, or vice versa.

  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 the formula (A) is preferably a group represented by the formula (B), more preferably a group represented by the formula (C), and represented by the 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 -, —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 have 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 the 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 by 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 by a fluorine atom. k and l each independently represent 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 _[pi of 12 or more.
D ¹ and D ² are each independently * -O-CO- (* represents a position bonding to Ar), -C (= S) -O-, -OC (= 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. It may be substituted, and 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 -, - 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.
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 the 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 by 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 by a fluorine atom.
k and l each independently represent an integer of 0 to 3.
F ¹ and F ² each independently represent an alkylene group having 1 to 12 carbon atoms. The hydrogen atom contained in the alkylene group may be substituted by 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 may be -O -Or -CO-.
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 characteristics of the optical film of the present invention can be arbitrarily determined by 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, a flatter wavelength dispersion characteristic and further a reverse wavelength dispersion characteristic are exhibited.

  Specifically, about a composition containing a liquid crystal compound and a compound (A), about 2 to 5 types of compositions having different contents of the structural unit derived from the compound (A) are prepared, and each composition will be described later. As described above, the retardation value of an optical film obtained by producing an optical film having the same thickness is determined, and the result is used to determine the difference between the content of the structural unit derived from the compound (A) and the retardation value of the optical film. The correlation may be obtained, and the content of the structural unit derived from the compound (A) necessary to give a desired retardation value to the optical film having the above film thickness may be determined from the obtained correlation.

The method for producing the optical film of the present invention will be described below.
First, an additive such as an organic solvent, the above-described liquid crystal compound serving as a host, the above-described polymerization initiator, a polymerization inhibitor, a photosensitizer, or a leveling agent is added to the compound (A), if necessary, and mixed. Prepare solution. It is particularly preferable to include an organic solvent to facilitate film formation at the time of film formation, and it is preferable to include a polymerization initiator because it has a function of curing the obtained optical film.

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

  The amount of the polymerization initiator to be used is, for example, 0.1 part by weight to 30 parts by weight, preferably 0.5 part by weight to 10 parts by weight based on 100 parts by weight of the total of the liquid crystal compound and the compound (A). Department. Within the above range, the compound (A) can be polymerized without disturbing the orientation of the liquid crystal compound.

(Polymerization inhibitor)
When 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 an alkyl ether, catechols having a substituent such as an alkyl ether such as butyl catechol, pyrogallols, 2,2,6,6-tetramethyl-1. Radical scavengers such as -piperidinyloxy radicals, thiophenols, β-naphthylamines and β-naphthols.

  By using the polymerization inhibitor, the polymerization of the liquid crystal compound or the compound (A) can be controlled, and the stability of the obtained optical film can be improved. The amount of the polymerization inhibitor to be used is, for example, 0.1 to 30 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the total of the liquid crystal compound and the compound (A). It is. Within the above range, the compound (A) can be polymerized without disturbing the orientation of the liquid crystal compound.

(Photosensitizer)
In preparing the optical film of the present invention, a photosensitizer may be used. Examples of the photosensitizer include xanthones such as xanthone and thioxanthone, anthracenes having a substituent such as anthracene or an alkyl ether, phenothiazine and rubrene.

  By using the photosensitizer, the polymerization of the liquid crystal compound or the compound (A) can be increased in sensitivity. The amount of the photosensitizer used is, for example, 0.1 to 30 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the total of the liquid crystal compound and the compound (A). Parts by weight. Within the above range, the compound (A) can be polymerized without disturbing the orientation of the liquid crystal compound.

(Leveling agent)
When preparing the optical film of the present invention, a leveling agent may be used. Examples of the leveling agent include additives for radiation curable paints (BYK-352, BYK-353, BYK-361N manufactured by BYK Japan), paint additives (SH28PA, DC11PA, ST80PA manufactured by Dow Corning Toray), Paint additives (KP321, KP323, X22-161A, KF6001 manufactured by Shin-Etsu Chemical Co., Ltd.) or fluorine-based additives (F-445, F-470, F-479 manufactured by Dainippon Ink and Chemicals, Inc.) Can be mentioned.

  By using a leveling agent, the optical film can be smoothed. Further, in the production process of the optical film, it is possible to control the fluidity of the mixed solution containing the compound (A) or to adjust the crosslink density of the optical film obtained by polymerizing the liquid crystal compound or the compound (A). it can. The specific amount of the leveling agent used is, for example, 0.1 part by weight to 30 parts by weight, preferably 0.5 part by weight, based on 100 parts by weight of the total of the liquid crystal compound and the compound (A). -10 parts by weight. Within the above range, the compound (A) can be polymerized without disturbing the orientation of the liquid crystal compound.

〔Organic solvent〕
The organic solvent used for preparing the mixed solution containing the compound (A) and the liquid crystal compound and the like is an organic solvent capable of dissolving 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 Ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone or methyl isobutyl ketone; aliphatic carbons 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 of two or more.
In particular, the composition of the present invention has excellent compatibility and can be dissolved in alcohols, ester solvents, ketone solvents, non-chlorine aliphatic hydrocarbon solvents, non-chlorine aromatic hydrocarbon solvents, and the like. Can be dissolved and applied without using halogenated hydrocarbons.

  It is preferable that the viscosity of the mixed solution containing the compound (A) and the liquid crystal compound is adjusted to, for example, 10 Pa · s or less, and preferably about 0.1 to 7 Pa · s, so as to facilitate application.

  The solid content in the mixed solution is, for example, 5 to 50% by weight. When the concentration of the solid content is 5% or more, the optical film does not become too thin, and the birefringence required for optical compensation of the liquid crystal panel tends to be given. In addition, when the content is 50% or less, the viscosity of the mixed solution is low, and the thickness of the optical film tends to be less likely to be uneven, which is preferable.

  Subsequently, the mixed solution is applied to the support substrate, dried and polymerized to obtain a target optical film on the support substrate.

[Unpolymerized film preparation process]
An unpolymerized film is obtained by applying a mixed solution containing the compound (A) on a supporting substrate and drying the mixed solution. When the unpolymerized film shows 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 at a low temperature of 25 to 80 ° C., it is possible to use a support base material having insufficient heat resistance as exemplified above as the alignment film. In addition, since it does not crystallize even after being cooled to about 30 to 10 ° C. after orientation, handling is easy.

  The film thickness can be adjusted so as to give a desired phase difference by appropriately adjusting the application amount and the 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 in the formula (7), and thus the desired Re value is obtained. In order to obtain (λ), the 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 index at a wavelength λnm.)

  Examples of the method of applying 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. In addition, a coating method using a coater such as a dip coater, a bar coater, or a spin coater may be used.

  Examples of the support substrate include glass, a plastic sheet, a plastic film, and a translucent film. Examples of the light-transmitting film include polyolefin films such as polyethylene, polypropylene and norbornene polymers, polyvinyl alcohol films, polyethylene terephthalate films, polymethacrylic ester films, polyacrylic ester films, cellulose ester films, and polyethylene naphthalate films. , A polycarbonate film, a polysulfone film, a polyethersulfone film, a polyetherketone film, a polyphenylene sulfide film or a polyphenylene oxide film.

  For example, even in a step requiring strength of the optical film, such as a bonding step, a transporting step, and a storage step of the optical film of the present invention, by using the supporting substrate, it can be easily handled without breaking.

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

  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 acids which are hydrolysates thereof, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, polyoxazole, Examples include polymers such as polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid and polyacrylates. These polymers may be used alone, or two or more of them may be mixed or copolymerized. These polymers can be easily obtained by polycondensation by dehydration or deamination, chain polymerization such as radical polymerization, anionic polymerization, or cationic polymerization, coordination polymerization, or ring-opening polymerization.

  These polymers can be applied after dissolving in a solvent. The solvent is not particularly limited, but specific examples include water, alcohols such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl cellosolve and butyl cellosolve; ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, and gamma-solvent. 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 , Xylene or aromatic hydrocarbon solvents such as chlorobenzene, acetonitrile, propylene glycol monomethyl ether, tetrahydrofura , Dimethoxyethane, ethyl lactate, chloroform and the like. These organic solvents may be used alone or in combination of two or more.

  Further, 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 Sanever (registered trademark, manufactured by Nissan Chemical Industries, Ltd.) and Optmer (registered trademark, manufactured by JSR Corporation).

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

  As a method of forming an alignment film on the support substrate, for example, on the support substrate, a commercially available alignment film material or a compound to be a material of the alignment film is applied in a solution, and thereafter, by annealing, 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, and preferably 10 nm to 1000 nm. Within the above range, the compound (A) or the like can be oriented at a desired angle on the alignment film.

  In addition, these alignment films can be subjected to rubbing or polarized UV irradiation as needed. Thus, the compound (A) or the like can be oriented in a desired direction.

  As a method of rubbing the alignment film, for example, a method in which a rubbing cloth is wound around 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, an unpolymerized film (liquid crystal layer) is laminated on an alignment film laminated on an arbitrary supporting 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, film production with roll film is possible.

  The drying of the solvent may be performed while the polymerization proceeds, but it is preferable to dry most of the solvent before the polymerization from the viewpoint of film-forming properties.

  Examples of the method for drying the solvent include methods such as natural drying, ventilation drying, and drying under reduced pressure. The specific heating temperature is preferably from 10 to 120C, more preferably from 25 to 80C. The heating time is preferably from 10 seconds to 60 minutes, more preferably from 30 seconds to 30 minutes. If the heating temperature and the heating time are within the above ranges, a support base material having insufficient heat resistance can be used as the support base material.

[Unpolymerized film polymerization process]
In the unpolymerized film polymerization step, the unpolymerized film obtained in the above-described unpolymerized film preparation step is polymerized and cured. As a result, a film in which the orientation of the compound (A) is fixed, that is, a polymerized film is obtained. Therefore, a polymer film having a small change in the refractive index in the plane direction of the film and a large change in the refractive index in the normal direction of the film can be produced.

The method of polymerizing the unpolymerized film is determined according to the types of the liquid crystal compound and the compound (A). When 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 when the polymerizable group is thermopolymerizable, thermal polymerization is performed. The unpolymerized film can be polymerized. In the present invention, it is particularly preferable to polymerize the unpolymerized film by photopolymerization. According to the photopolymerization, the unpolymerized film can be polymerized at a low temperature, so that the selection range of the heat resistance of the supporting base material is expanded. In addition, production becomes easy industrially. Photopolymerization is also preferable from the viewpoint of film formation. Photopolymerization is performed by irradiating an unpolymerized film with visible light, ultraviolet light, or laser light. From the viewpoint of handleability, irradiation with ultraviolet light, which is particularly preferable, may be performed while heating the compound (A) to a temperature at which the compound (A) takes a liquid crystal phase. 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.

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

  The method for producing an optical film of the present invention may include a step of peeling off the supporting substrate, following the above step. With such a configuration, the obtained laminate is a film including the alignment film and the optical film. In addition to the step of peeling the support substrate, the method may further include a step of peeling the alignment film. With such a configuration, an optical film can be obtained.

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

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

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

  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 of the obtained optical film may be adjusted to 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 about 250 to 300 nm, preferably about 273 to 277 nm, and particularly preferably about 275 nm.

  In order to use the optical film of the present invention as an optical film for a VA (Vertical Almentment) 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 about 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 a desired wavelength dispersion characteristic can be prepared by a simple method.

  The optical film of the present invention is used as 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 transmission type liquid crystal display. can do. Although the optical film of the present invention exhibits excellent optical characteristics even when it is a single film, a plurality of films may be laminated.

  Moreover, you may combine with another film. Specific examples include an elliptically polarizing plate in which the optical film of the present invention is bonded to a polarizing film, and a broadband circularly polarizing plate in which the optical film of the present invention is further bonded to the elliptically polarizing plate as a broadband λ / 4 plate. Can be

  Since the optical film of the present invention can be formed by coating on an alignment film and polymerizing by irradiating ultraviolet rays, as shown in FIG. 1, a wider band of, for example, λ / 4, λ / 2 optical film can be formed.

FIG. 1 is a schematic diagram 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 the 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 subjected to a rubbing treatment 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 is applied while adjusting the thickness to a desired retardation value. A film 2 is formed.

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

FIG. 2 is a schematic diagram showing the liquid crystal display device 5 according to the present invention.
In a 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 with an adhesive, and a color filter layer 4 ′ formed on the substrate 7 is formed. An optical film 2 ′ is formed thereon with an alignment film 3 ′ therebetween. 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 a polarizing plate 10 via 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) are 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 a thinner liquid crystal display device to be manufactured.

Hereinafter, an example of a method for manufacturing the liquid crystal display device 5 in which the color filter 1 'is formed on the liquid crystal layer side of one substrate will be described. On the substrate on the backlight side, a gate electrode made of Mo or MoW, a gate insulating film, and amorphous silicon are deposited and patterned on borosilicate glass, and the amorphous silicon is crystallized by annealing with an excimer laser. A semiconductor thin film is formed, and then P and B are doped into regions on both sides of the gate electrode to form n-channel and p-channel TFTs. Further, by forming an insulating film made of SiO _2, a substrate on the backlight side can be obtained. Furthermore, by sputtering ITO on the backlight-side substrate 11, the transparent electrode 13 for a full-transmission display device can be laminated on the backlight-side substrate. Similarly, by using Ag, Al, or the like instead of ITO, a reflective electrode 13 'for a total reflection type display device can be obtained. Further, by appropriately combining the reflective electrode and the transparent electrode, a backlight-side electrode for a transflective liquid crystal display device can be obtained.

On the other hand, the color filter layer 4 ′ is formed on the opposing substrate 7. By using the R, G, and B color filters together, 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 is polymerized by ultraviolet irradiation to form an optical film 2 ′ while being heated to a temperature range in which a liquid crystal phase is obtained.
After forming the optical film, the counter electrode 8 can be formed by sputtering ITO. Further, by forming an alignment film on the counter electrode, forming a liquid crystal phase 9, and finally assembling the liquid crystal phase 9 with the substrate on the backlight side, the liquid crystal display device 5 can be manufactured. Further, since the values of [Re (450) / Re (550)] and [Re (650) / Re (550)] of the compound (A) of the present invention are close to 1 or smaller than 1, the composition may be changed. As a result, 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 films can be omitted.

  Further, the optical film of the present invention can be used also for a retardation plate of a reflection type liquid crystal display and an organic EL display, and an FPD provided with 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 has a wide range of applications. For example, among them, a polarizing plate obtained by laminating an optical film and a polarizing film according to the present invention and an FPD provided with the polarizing plate will be described below. Alternatively, it can be obtained by bonding the optical film directly on both surfaces 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.

FIGS. 3A to 3E are schematic views showing a polarizing plate 1 according to the present invention.
A polarizing plate 30a shown in FIG. 3A has a laminate 14 and a polarizing film 15 directly bonded to each other. The laminate 14 includes a support base material 16, an alignment film 17, and an optical film 18.
The polarizing plate 30a 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 30b shown in FIG. 3B, the laminate 14 and the polarizing film 15 are bonded via an adhesive layer 19.

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

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

  In the polarizing plate 30e shown in FIG. 3 (e), the laminate 14 and the laminate 14 'are bonded together via the adhesive layer 19, and the laminate 14' and the polarizing film 15 are further bonded via the adhesive layer 19 '. This shows a configuration in which the components are bonded together.

  The polarizing plate of the present invention is obtained by laminating a polarizing film and a laminate including the optical film of the present invention. Instead of the laminate 14 and the laminate 14 ′, an optical film 18 from which the support base material 16 and the alignment film 17 are separated from the laminate 14 may be used, or the support base material 16 is separated from the laminate 14, A film composed of the alignment film 17 and the optical film 18 may be used.

  In the polarizing plate of the present invention, a plurality of laminates may be laminated, 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-based film, or a film obtained by stretching a polyvinyl alcohol-based film to obtain iodine or a dichroic dye. An adsorbed film may be used.

  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 obtained by bonding the polarizing film of the present invention and a liquid crystal panel, and the polarizing film of the present invention. And an organic EL display device having an organic EL panel on which a light emitting layer is bonded.

  As embodiments of the 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 of the liquid crystal panel 20 and the polarizing plate 30 of the liquid crystal display device according to the present invention.

  As the liquid crystal display device, for example, a liquid crystal display device including a bonded product 21 of a liquid crystal panel 20 and a polarizing plate 30 as shown in FIG. The bonded product 21 is obtained by bonding the polarizing plate 30 of the present invention and the liquid crystal panel 20 via an adhesive layer 22. When a voltage is applied to the liquid crystal panel 20 using electrodes (not shown), the liquid crystal molecules are driven, and an optical shutter effect is achieved.

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

  As the organic EL display device, an organic EL display device including the organic EL panel 23 shown in FIG. The organic EL panel 23 is formed by laminating the polarizing film 30 of the present invention and the light emitting layer 24 via the 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. “%” And “parts” in the examples are% by weight and parts by weight unless otherwise specified.

  The compound was synthesized according to the following scheme. The starting material monotetrahydropyranyl-protected hydroquinone (a) was synthesized by the method described in Patent Document (JP-A-2004-262883).

(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. and then at 100 ° C. under a nitrogen atmosphere. Thereafter, the mixture was cooled to room temperature, pure water and methyl isobutyl ketone were added, and the collected organic layer was washed with an aqueous sodium hydroxide solution and pure water, dehydrated, filtered and concentrated under reduced pressure. Methanol was added to the residue, and the resulting precipitate was filtered and dried under vacuum 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-ditert-butyl-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. Aqueiroyl chloride (58.1 g, 642 mmol) was added dropwise to the mixture obtained under ice-cooling under a nitrogen atmosphere, and pure water was further added. After stirring, the separated organic layer was collected. The organic layer was washed with aqueous hydrochloric acid, saturated aqueous sodium carbonate and pure water. After the organic layer was dried and filtered, 1 g of BHT was added to the organic layer and the mixture was concentrated under reduced pressure to obtain a 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 obtained mixture. Further, aqueous hydrochloric acid and concentrated aqueous hydrochloric acid were added, and the mixture was stirred under a nitrogen atmosphere at 60 ° C. 500 ml of saturated saline was added to the reaction solution, and the mixture was further stirred, and the separated organic layer was collected. The collected organic layer was dehydrated, filtered and concentrated under reduced pressure. Hexane was further added to the organic layer, and the mixture was stirred under ice-cooling. The precipitated powder was filtered and vacuum dried 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 a mixture obtained by mixing 24.68 g (118 mmol) of transcyclohexanedicarboxylic acid and toluene, 74.91 g (590 mmol) of oxalyl dichloride and 0.5 mL of dimethylformamide were added, and the mixture was stirred under a nitrogen atmosphere. After reduced pressure, chloroform was added to obtain a solution 1.
On the other hand, 12 g (45.4 mmol) of the compound (d) was dissolved in chloroform. A solution 2 was obtained by mixing a chloroform solution of the compound (d) and 12.6 g (159 mmol) of pyridine. Solution 2 was added dropwise to Solution 1 under ice cooling. The obtained solution was stirred under a nitrogen atmosphere, filtered, and concentrated under reduced pressure. The obtained solution was added dropwise to a mixed solvent of water / methanol (1/1 by volume), and the resulting precipitate was pulverized, washed with pure water, filtered and dried in vacuo. After the obtained powder was pulverized again, n-heptane was added, and after stirring, toluene was further added. Insoluble components were removed by filtration, and the obtained filtrate was concentrated under reduced pressure, and n-heptane was added. The resulting precipitate was dried under vacuum 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 following route.

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

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

(Production Example of Compound (ii-a))
Compound (ii-a) was synthesized according to the following scheme. 4,7-dimethoxy-2-phenylbenzothiazole as a raw material is described in J. Am. Chem. Soc. Perkin Trans. The compound was synthesized according to the method described in one journal, pages 205-210 (2000).

  10.8 g (39.8 mmol) of 4,7-dimethoxy-2-phenylbenzothiazole and 54.0 g (5 times mass) of pyridinium chloride were mixed, and the resulting mixture was heated to 220 ° C. and stirred. . After cooling the mixture, water was added, and the obtained precipitate was separated by filtration, washed with water and hexane, and containing 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, and 99.4 g (453 mmol) of 4-bromobenzoyl chloride was added to the obtained mixture. Was added. Thereafter, the temperature was raised to 60 ° C., and after stirring, the mixture was 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 mainly containing the compound (vi-d). 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-diphosphetane-2,4-disulfide (Lawson's 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 containing the compound (vi-e) as a main component. The yield was 99.5% based on the compound (vi-d).

[Synthesis Example of Compound (vi-f)]
93.8 g (266.3 mmol) of compound (vi-e), 315 g (7875 mmol) of sodium hydroxide, and 5250 g of water were mixed, and the obtained mixture was stirred under ice-cooling. Subsequently, an aqueous solution containing 174.3 g (529 mmol) of potassium ferricyanide was added under ice cooling and stirred, and the precipitated solid was washed with cold water and hexane, and 88.2 g of a solid containing the 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 the 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 mixture, water was added, and the obtained precipitate was washed with water, hexane and chloroform to obtain 7.7 g of a solid mainly containing the compound (vi-a). The yield was 74% based on the compound (vi-f).

(Synthesis example of compound (va))
After synthesizing benzothiazole in the same manner as for compound (vi-a), compound (va) was synthesized by demethylation 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 having compound (vb) as a main component was obtained in the same manner as in the synthesis example of compound (vi-d) except that 4-bromobenzoyl chloride as a raw material was changed to 4-nitrobenzoyl chloride. The yield was 98% based on 2,5-dimethoxyaniline.

(Synthesis example of compound (vc))
A solid containing a compound (vc) as a main component was obtained in the same manner as in the synthesis example of the compound (vi-e), except that the compound (vi-d) as a raw material 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 a main component was obtained by the same method except that compound (vi-e) as a raw material 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 the 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 obtained precipitate was separated by filtration and washed with water and chloroform to obtain 16.5 g of a solid containing compound (va) as a main component. 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)]
43.0 g (281 mmol) of 2,5-dimethoxyaniline, 59.7 g (590 mmol) of triethylamine and 499.7 g of dehydrated chloroform 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. After cooling the obtained mixture, it was poured into water, and the separated organic layer was recovered. Chloroform was added to the remaining aqueous layer, and the organic layer was recovered by washing. 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 mainly containing the compound (ix-b). The yield was 99% based on 2,5-dimethoxyaniline.

[Synthesis Example of Compound (ix-c)]
70.0 g (272.0 mmol) of the compound (ix-b), 65.8 g of 2,4-bis (4-methoxyphenyl) -1,3-dithia2,4-diphosphetane-2,4-disulfide (Lawson's reagent) (162.0 mmol) and 2436 g of toluene were mixed, heated to 80 ° C., and stirred. The obtained mixture was cooled and then concentrated to obtain a solid mainly containing the compound (ix-c). The compound (ix-c) was used in the next step without purification without purification.

[Synthesis Example of Compound (ix-d)]
A solid containing the 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 under ice-cooling, followed by stirring. After the precipitated solid was separated by filtration, the solid was washed with cold water and hexane to obtain 25.9 g of a solid mainly containing the compound (ix-d). The yield for the two steps combined with the previous step was 35% based on the compound (ix-c).

[Synthesis Example of Compound (ix-a)]
5.6 g (21.0 mmol) of the compound (ix-d) and 28.0 g (5 times mass) of pyridinium chloride were mixed, heated to 180 ° C., and stirred. After cooling the obtained mixture, water was added, and the obtained precipitate was washed with water and chloroform to obtain 3.4 g of a solid mainly containing the compound (ix-a). 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.

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

<Synthesis example of compound (ii-1) in the first route>
2.55 g (11 mmol) of the compound (ii-a), 9.67 g (23 mmol) of the compound (e), 0.28 g (2 mmol) of dimethylaminopyridine, and 50 mL of chloroform were mixed. A chloroform solution (40 mL) of 5.31 g (28 mmol) of dicyclohexylcarbodiimide was added dropwise to the obtained mixture under ice-cooling. After the obtained reaction solution was stirred and filtered, the separated organic layer was recovered. The organic layer was dried and concentrated under reduced pressure. Ethyl acetate was added to the residue to dissolve it, 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, and filtered, and the obtained solid was dried under vacuum 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 ６6.36 (m, 2H), 6.91 to 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 determined by texture observation using a polarizing microscope. Compound (ii-1) exhibited a smectic phase from 96 ° C. to 115 ° C. at the time of temperature rise, exhibited a nematic phase from 115 ° C. to 226 ° C., and exhibited a nematic phase from 226 ° C. to 50 ° C. at the time of temperature decrease. .

<Synthesis example of compound (v-1) in the first route>
2.88 g (10 mmol) of compound (va), 8.37 g (20 mmol) of compound (e), 0.24 g (2 mmol) of dimethylaminopyridine, and 75 mL of chloroform were mixed. 40 mL of a chloroform solution of 4.95 g (24 mmol) of dicyclohexylcarbodiimide was added dropwise to the obtained mixture under ice-cooling. After the obtained reaction solution was stirred and filtered, the separated organic layer was recovered. The organic layer was dried and concentrated under reduced pressure. Ethyl acetate was added to the residue to dissolve it, 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 methanol, filtered, and dried in vacuo 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 to 6.44 (m, 2H), 6.87 to 7.02 (m, 8H), 7.27 (d, 2H), 8.19 to 8.23 (d, 2H), 8.34 to 8.38 (d, 2H)

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

<Synthesis example of compound (ix-1) in the first route>
2.24 g (10 mmol) of compound (ix-a), 8.37 g (20 mmol) of compound (e), 0.24 g (2 mmol) of dimethylaminopyridine, and 50 mL of chloroform were mixed. 30 mL of a chloroform solution of 4.95 g (24 mmol) of dicyclohexylcarbodiimide was added dropwise to the obtained mixture under ice cooling. After the obtained reaction solution was stirred and filtered, the separated organic layer was recovered. The organic layer was dried and concentrated under reduced pressure. Ethyl acetate was added to the residue to dissolve it, 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, and filtered, and the obtained solid was dried under vacuum 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 to 1.84 (m, 24H), 2.29 to 2.83 (m, 12H), 3.93 to 5.97 (t, 4H), 4.15-4.18 (t, 4H), 5.80-5.84 (dd, 2H), 6.07-6.18 (m, 2H), 37 to 6.44 (m, 2H), 6.86 to 7.02 (m, 8H), 7.22 (m, 1H), 7.28 (d, 2H), 7.78 to 7.81 ( br, 2H), 8.14-8.17 (br, 1H)

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

¹ H-NMR (CDCl ₃ ) of compound (iv-1): δ (ppm) 1.43 to 1.83 (m, 24H), 2.29 to 2.82 (m, 12H), 3.93 to 5.97 (t, 4H), 4.15-4.18 (t, 4H), 5.80-5.84 (dd, 2H), 6.07-6.18 (m, 2H), 37 to 6.44 (m, 2H), 6.86 to 7.02 (m, 8H), 7.27 (s, 2H), 7.78 to 7.81 (d, 2H), 8.14 to 8.17 (d, 2H)

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

<Synthesis Example of Compound (ii-1) by 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. 48.2 g (349 mmol) of potassium carbonate was added to the obtained mixture, and the mixture was stirred at 80 ° C. After further adding 94.4 g (552 mmol) of benzyl bromide and stirring, 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 dried under vacuum. The obtained powder was dissolved in toluene and adsorbed on silica gel while being concentrated under reduced pressure. The silica gel was placed on a silica gel column, eluted with 500 mL of a mixed solution of chloroform / heptane (1/4 by volume), and then the solvent was replaced with a mixed solution of chloroform / heptane (1/2 by volume) to elute the compound (f). . The collected solution was vacuum-dried to obtain 63 g of a compound (f). The yield was 42% based on transcyclohexanedicarboxylic acid.

(Synthesis example of compound (ii-b))
4.87 g (20 mmol) of the compound (ii-a), 11.54 g (44 mmol) of the compound (f) and 0.54 g (4 mmol) of dimethylaminopyridine were mixed with 50 mL of chloroform. 60 mL of a chloroform solution of 10.89 g (53 mmol) of dicyclohexylcarbodiimide was added dropwise to the obtained mixture under ice cooling. After the obtained reaction solution was stirred and filtered, the separated organic layer was recovered. The organic layer was dried and concentrated under reduced pressure. Ethyl acetate was added to the residue to dissolve it, and after concentration under reduced pressure, methanol was added and reprecipitated under ice-cooling. The precipitate was collected by filtration and dried in vacuo to give 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 the 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. After the resulting mixture was deoxygenated with nitrogen gas, the resulting reaction solution was depressurized and then stirred under a hydrogen atmosphere. The reaction was filtered. The filtrate was collected and concentrated under reduced pressure, and the solid obtained by adding n-heptane to the residue was collected by filtration and dried in vacuo to obtain 4.7 g of compound (ii-c). The yield was 55% based on the compound (ii-b).

(Synthesis example of compound (ii-1))
4.41 g (8 mmol) of the compound (ii-c), 4.65 g (18 mmol) of the compound (d), 0.22 g (2 mmol) of dimethylaminopyridine and 30 mL of chloroform were mixed. To the obtained mixture, 20 mL of a chloroform solution of 4.36 g (21 mmol) of dicyclohexylcarbodiimide was added dropwise under ice cooling. After the obtained reaction solution was stirred and filtered, the separated organic layer was recovered. The organic layer was dried and concentrated under reduced pressure. Ethyl acetate was added to the residue to dissolve it, and after concentration under reduced pressure, methanol was added and reprecipitated under ice-cooling. The precipitate was collected by filtration and dried in vacuo to give 4.80 g of compound (ii-1). The yield was 58% based on the compound (ii-c).

<Synthesis example of compound (vi-1) through the 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.

  In a similar manner, the following compound was obtained by the first route. The structure is shown below.

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

  In the synthesis example of compound (vb), compound (xb) was obtained in the same manner except that 4-nitrobenzoyl chloride as a raw material was changed to thiophenecarbonyl chloride, and compound (vc), Compounds (xc), (xd), and (xa) were 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 mixture was depressurized, and 608 g of dehydrated chloroform was added to the obtained solid.
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 to the chloroform solution. Thereafter, the mixture was stirred at room temperature. The reaction solution was poured into 973 g of water, and the layers were separated to obtain an organic layer. Further, this organic layer was washed with 973 g of 1 N hydrochloric acid. The solvent was distilled off from the obtained organic layer 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 of compound (vc) except that compound (vb) as a raw material was changed to compound (v'-b) to obtain compound (v'-c). Compounds (v′-d) and (v′-a) were obtained in the same manner as in the synthesis examples of vd) and (va).

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

  In the synthesis example of compound (vb), compound (xb) was obtained in the same manner except that 4-nitrobenzoyl chloride as a raw material was changed to thiophenecarbonyl chloride, and compound (vc), Compounds (xc), (xd), and (xa) were 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)]
52.3 g (341 mmol) of 2,5-dimethoxyaniline, 69.0 g (682 mmol) of triethylamine, and 200 g of dehydrated chloroform were mixed and stirred, and 50.0 g (341 mmol) of 3-thenoyl chloride was added to the obtained mixture. The mixture was added dropwise under ice cooling. Thereafter, the temperature was raised to room temperature, and the mixture was stirred for one hour. 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 to obtain 82.1 g of a solid mainly containing the compound (xi-b). The yield was 91% based on 2,5-dimethoxyaniline.

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

[Synthesis Example of Compound (xi-d)]
A mixture containing the compound (xi-c) obtained in the preceding section 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 mixture under ice-cooling, and the mixture is stirred. The precipitated solid is washed with cold water and hexane, and recrystallized by adding ethanol. As a result, 49.1 g of a compound (xi-d) was obtained. The yield was 58% based on the compound (xi-b).

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

  Compound (xvi-b) was obtained in the same manner as in the synthesis of compound (vb), except that the starting material 4-nitrobenzoyl chloride was changed to 3,5-dimethylbenzoyl chloride, to obtain compound (v-b). Compounds (xvi-c), (xvi-d), and (xvi-a) were 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)]
A mixture of 4.0 g of concentrated nitric acid and 14.4 g of glacial acetic acid was added dropwise to 11.0 g of 4,7-dimethoxy-2-phenylbenzothiazole and 288 g of glacial acetic acid. The obtained 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 mainly containing the compound (xi-d). 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 of compound (va), except that compound (vd) as a raw material was changed to compound (xvii-d). Compound (xvii-a) was a mixture of two isomers having different nitro group substitution positions.

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

  A compound ((xviii-b) was obtained in the same manner as in the synthesis of compound (vb) except that 4-nitrobenzoyl chloride as a raw material was changed to pentafluorobenzoyl chloride to obtain compound (vc). Compounds ((xviii-c), ((xviii-d), ((xviii-a)) were obtained in the same manner as in the synthesis examples of (v-d) and (v-a).

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

[Synthesis Example of Compound (xix-b)]
58.7 g (383 mmol) of 2,5-dimethoxyaniline, 77.5 g (766 mmol) of triethylamine and 400 g of dehydrated chloroform were mixed and stirred, and the obtained mixture was further mixed with 50.0 g (383 mmol) of 2-furancarboxylic acid chloride. 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 from hexane to obtain 86.3 g of a compound (xix-b). The yield was 91% based on 2,5-dimethoxyaniline.

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

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

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

(Synthesis example of compound (xx-a))
After synthesizing benzothiazole in the same manner as for compound (xx-a), compound (xx-a) was synthesized by demethylation with pyridinium chloride. A solid containing 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)]
59.3 g (387 mmol) of 2,5-dimethoxyaniline, 78.4 g (774 mmol) of triethylamine and 500 g of dehydrated chloroform are mixed and stirred, and 57.1 g (387 mmol) of 3-thiazolecarboxylic acid chloride is added to the obtained mixed solution with ice. Under cooling, it was added dropwise. Thereafter, the mixture was heated to room temperature, 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 from heptane-ethyl acetate 3/1 (v / v). Further, the solid was washed with heptane-ethyl acetate 4/1 (v / v) to obtain 77.2 g of a solid containing the 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 compound (xxi-b), 61.3 g of 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetane-2,4-disulfide (Lawson's 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 containing a decomposition product of the Lawson reagent and the compound (xxi-c) as main components.

[Synthesis Example of Compound (xxi-d)]
A mixture containing the compound (xxi-c) obtained in the preceding section 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 mixture under ice-cooling, and the mixture was stirred. The precipitated solid was washed with cold water and hexane, and washed with hot ethanol to obtain a compound (xxi- d) 45.9 g were obtained. The yield was 57% based on the compound (xxb-d).

[Synthesis Example of Compound (xxi-a)]
45.0 g (144.2 mmol) of the compound (xxi-d) and 225.0 g (5 times by mass) of pyridinium chloride were mixed, heated to 180 ° C., and stirred for 2 hours. After cooling, water was added, and the obtained precipitate was washed with water, hexane, and toluene to obtain 39.9 g of a solid mainly containing the compound (xxi-a). 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)]
38.3 g (250 mmol) of 2,5-dimethoxyaniline, 50.5 g (500 mmol) of triethylamine and 200 g of dehydrated chloroform were mixed and stirred, and 54.6 g (250 mmol) of 4-methylsulfonylbenzoic acid chloride was further added under ice-cooling. added. Thereafter, the mixture was heated to room temperature, 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 from heptane-ethyl acetate 3/1 (v / v). Further washing with heptane-ethyl acetate 3/1 (v / v) gave 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-diphosphetane-2,4-disulfide (Lawson's reagent) 64 0.7 g (160.0 mmol) and 500 g of toluene were mixed, heated to 80 ° C., and stirred. The obtained mixture was cooled and concentrated to obtain a red viscous liquid containing a decomposition product of Lawesson's reagent and the compound (xxiii-c) as main components.

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

[Synthesis Example of Compound (xxiii-a)]
10.0 g (28.6 mmol) of the compound (xxiii-d) and 100.0 g (10-fold mass) of pyridinium chloride were mixed, heated to 180 ° C., and stirred for 2 hours. After cooling the obtained mixture, 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 produced according to the following reaction scheme in the same manner except that 4-fluorobenzoyl chloride was used instead of 4-bromobenzoyl chloride as a raw material. 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 4-bromobenzoyl chloride as a raw material. ) Was synthesized.

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

¹ H-NMR (CDCl ₃ ) of compound (v′-1): δ (ppm) 1.45 to 1.90 (m, 24H), 2.29 to 2.83 (m, 15H), 3.92 -3.97 (t, 4H), 4.15-4.20 (t, 4H), 5.80-5.84 (dd, 2H), 6.07-6.18 (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 determined by texture observation using a polarizing microscope. Compound (v′-1) exhibits a smectic phase from 127 ° C. to 154 ° C. and a nematic phase from 154 ° C. to 217 ° C. when the temperature is raised, and a nematic phase from 217 ° C. to 113 ° C. when the temperature is lowered. did.

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

<Synthesis example of compound (x-1) in the first route>
Compound (x-1) was obtained in the same manner as in the synthesis of compound (v-1) except that compound (va) as a raw material 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 to 1.83 (m, 24H), 2.29 to 2.82 (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), 7.12 (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 determined by texture observation using a polarizing microscope. Compound (x-1) exhibited a smectic phase from 101 ° C. to 106 ° C. at the time of temperature increase, exhibited a nematic phase from 106 ° C. to 180 ° C. or more, and crystallized at the time of temperature decrease to 81 ° C. .

<Synthesis Example of Compound (xi-1) in First Route>
Compound (xi-1) was obtained in the same manner as in the synthesis of compound (v-1), except that compound (va) as a raw material 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), 3.92-3.97 (t, 4H), 4.15-4.20 (t, 4H), 5.81-5.85 (dd, 2H), 6.08-6.18 (m, 2H) ), 6.37 to 6.45 (m, 2H), 6.86 to 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 determined by texture observation using a polarizing microscope. Compound (xi-1) exhibited a smectic phase from 111 ° C. to 125 ° C. when heated, exhibited a nematic phase from 125 ° C. to 242 ° C., and exhibited a nematic phase from 242 ° C. to 82 ° C. when cooled. .

<Synthesis example of compound (xvi-1) in first route>
Compound (xvi-1) was obtained in the same manner as in the synthesis of compound (v-1), except that compound (va) as a raw material 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), 4.15-4.19 (t, 4H), 5.80-5.84 (dd, 2H), 6.07-6.18 (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 determined by texture observation using a polarizing microscope. The 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 the first route>
Compound (xvi-1) was obtained in the same manner as in the synthesis example of compound (v-1), except that compound (va) as a raw material 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 to 6.44 (m, 2H), 6.87 to 7.00 (m, 8H), 7.44 (2s, 1H), 7.50 (m, 3H), 8.02 to 8.06 ( m, 2H)

  The phase transition temperature of the obtained compound (xvii-1) was determined by texture observation using a polarizing microscope. Compound (xvii-1) exhibited a smectic phase from 129 ° C. to 148 ° C. at the time of temperature rise, exhibited a nematic phase from 148 ° C. to 186 ° C., and exhibited a nematic phase from 186 ° C. to 105 ° C. at the time of temperature decrease. .

<Synthesis example of compound (xviii-1) in the first route>
Compound (xviii-1) was obtained in the same manner as in the synthesis of compound (v-1), except that compound (va) as a raw material 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 determined by texture observation using a polarizing microscope. The compound (xvii-1) exhibited a smectic phase from 124 ° C. to 166 ° C. and a nematic phase from 166 ° C. to 199 ° C. when the temperature was raised, and a nematic phase from 199 ° C. to 79 ° C. when the temperature was lowered. .

<Synthesis example of compound (xix-1) in the first route>
Compound (xix-1) was obtained in the same manner as in the synthesis of compound (v-1) except that compound (va) as a raw material 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 determined by texture observation using a polarizing microscope. The compound (xix-1) exhibits a smectic phase from 91 ° C. to 130 ° C. at the time of temperature rise, exhibits a nematic phase from 130 ° C. to 180 ° C. or more, and exhibits a nematic phase up to 62 ° C. at the time of temperature decrease and crystallized. .

<Synthesis example of compound (xx-1) in the first route>
Compound (xx-1) was obtained in the same manner as in the synthesis of compound (v-1), except that compound (va) as a raw material 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 determined by texture observation using a polarizing microscope. The compound (xx-1) exhibited a smectic phase from 110 ° C. to 114 ° C. when heated, exhibited a nematic phase from 114 ° C. to 160 ° C. or more, and crystallized from 69 ° C. when cooled. .

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

¹ H-NMR (CDCl ₃ ) of 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), 4.15-4.19 (t, 4H), 5.80-5.84 (dd, 2H), 6.07-6.18 (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 determined by texture observation using a polarizing microscope. Compound (xxi-1) exhibited a nematic phase from 162 ° C. to 246 ° C. when the temperature was raised, and a nematic phase from 246 ° C. to 120 ° C. when the temperature was lowered.

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

¹ H-NMR (CDCl ₃ ) of compound (xxiii-1): δ (ppm) 1.44 to 1.86 (m, 24H), 2.35 to 2.84 (m, 12H), 3.11 ( s, 3H), 3.92-3.97 (t, 4H), 4.15-4.20 (t, 4H), 5.80-5.84 (dd, 2H), 6.07-6. 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 determined by texture observation using a polarizing microscope. The compound (xxiii-1) exhibited a smectic phase from 137 ° C. to 146 ° C. at the time of temperature increase, exhibited a nematic phase from 146 ° C. to 170 ° C. or more, and crystallized at the time of temperature decrease to 78 ° C. .

<Synthesis example of compound (xxiv-1) in the first route>
Compound (xxiv-1) was obtained in the same manner as in the synthesis of compound (v-1), except that compound (va) as a raw material was changed to compound (xxiv-a). The yield was 54% based on the compound (xxiv-a).

¹ H-NMR (CDCl ₃ ) of compound (xxiv-1): δ (ppm) 1.44-1.90 (m, 24H), 2.34-2.81 (m, 12H), 3.92- 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 the compound (xxiv-1) was determined by texture observation using a polarizing microscope. As the temperature was raised, it changed to a nematic phase at around 95 ° C. When the temperature was further increased, the phase changed to an isotropic phase at around 212 ° C. When the temperature was lowered from this point, the phase changed to a nematic phase at around 212 ° C. and changed to a crystal at 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 route>
<Synthesis example of compound (xxv-1) in first route>
Compound (xxv-1) was obtained in the same manner as in the synthesis of compound (v-1), except that compound (va) as a raw material 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) 1.44-1.90 (m, 24H), 2.35-2.82 (m, 12H), 3.92- 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 to 6.44 (m, 2H), 6.86 to 7.02 (m, 8H), 7.21 to 7.29 (m, 2H), 7.74 to 7.78 (d, 2H), 8.13 to 8.17 (d, 2H)

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

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

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

(Synthesis example of compound (xxvi-b))
10.0 g (62 mmol) of 2,3-dicyanohydroquinone, 35.0 g (624 mmol) of potassium hydroxide and 70.0 g of water 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 obtained mixture and stirred, and the organic layer was taken out. The obtained organic layer was concentrated under reduced pressure to remove the solvent, and then dried under vacuum to obtain 8.5 g (42.6 mmol) of a compound (xxvi-b). The yield was 68% based on 2,3-dicyanohydroquinone.

(Synthesis Example of Compound (xxvi-a))
2.5 g (12.6 mmol) of the compound (xxvi-b), 2.5 g (26.5 mmol) of aniline and 50.0 g of tetrahydrofuran were mixed, and the mixture was heated at 100 ° C. with stirring. The obtained mixture was cooled to room temperature, and 3.1 g (15.1 mmol) of N, N'-dicyclohexylcarbodiimide was dissolved in 9.4 g of tetrahydrofuran, added dropwise at room temperature, and heated at 60 ° C with stirring. After filtering the obtained mixture, the obtained organic layer was concentrated under reduced pressure, the solvent was removed, methanol was added, and the mixture was stirred. The resulting precipitate was filtered and 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))
0.3 g (1.2 mmol) of the compound (xxvi-a), 0.03 (0.3 mmol) of 4-dimethylaminopyridine, 1.2 g (2.8 mmol) of the compound (e), and 24 g of chloroform 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 mixture at room temperature, followed by stirring. 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 the mixture was stirred. The resulting precipitate was filtered and dried under vacuum to obtain 0.7 g of compound (xxvi-1).
The yield was 54% based on xxvi-a.

¹ H-NMR (CDCl ₃ ) of 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 produced according to the following scheme.

(Synthesis example of compound (xxvii-a))
2.5 g (12.6 mmol) of the compound (xxvi-b), 2.7 g (26.5 mmol) of 2-aminothiazole and 50.0 g of tetrahydrofuran were mixed, and the resulting mixture was heated at 100 ° C. with stirring. . The obtained mixture was cooled to room temperature, and a solution in which 3.1 g (15.1 mmol) of N, N'-dicyclohexylcarbodiimide was dissolved in 9.4 g of tetrahydrofuran was added dropwise at room temperature, followed by stirring. After filtering the obtained mixture, the obtained organic layer was concentrated under reduced pressure, the solvent was removed, methanol was added, and the mixture was stirred. The resulting precipitate was filtered and dried under vacuum 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))
0.3 g (1.1 mmol) of the compound (xxvii-a), 0.03 (0.3 mmol) of 4-dimethylaminopyridine, 1.2 g (2.8 mmol) of the compound (e), and 23 g of chloroform were mixed. A solution in which 0.9 g (4.2 mmol) of N, N'-dicyclohexylcarbodiimide was dissolved in 4.6 g of chloroform was added dropwise to the obtained mixture at room temperature, followed by stirring. After filtering the obtained mixture, 12 g of 2N hydrochloric acid was added and stirred, then 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 the mixture was stirred. The resulting precipitate was filtered and dried under vacuum to obtain 0.3 g of compound (xxvii-1). The yield was 25% based on xxvii-a.

¹ H-NMR (CDCl ₃ ) of 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 determined by texture observation using a polarizing microscope. The compound (xxvii-1) exhibited a smectic phase from 143 ° C to 152 ° C at the time of temperature rise, exhibited a nematic phase from 152 ° C to 186 ° C, and exhibited a nematic phase from 99 ° C to crystallization at the time of temperature decrease.

<Synthesis example of compound (i-1) in the first route>
<Synthesis example of compound (xxv-1) in first route>
Compound (i-1) was obtained in the same manner as in the synthesis of compound (v-1) except that compound (va) as a raw material 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), 4.15-4.19 (t, 4H), 5.80-5.84 (dd, 2H), 6.07-6.18 (m, 2H), 6. 37-6.44 (m, 2H), 6.86-7.00 (m, 8H), 7.40-7.48 (m, 2H), 7.74-7.79 (m, 2H) 8 .17-8.25 (m, 2H)

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

<Synthesis example of compound (xxviii-1) in the first route>
12.5 g (30 mmol) of compound (e), 0.4 (3 mmol) of 4-dimethylaminopyridine, 2.9 g (12 mmol) of 1,5-dihydroxyanthraquinone, and 100 g of chloroform were mixed. A solution in which 9.3 g (45 mmol) of N, N'-dicyclohexylcarbodiimide was dissolved in 25 g of chloroform was added dropwise to the obtained mixture at room temperature, followed by stirring. Thereafter, 124 g of 1N hydrochloric acid was added and the mixture was stirred, filtered to remove solids, and the obtained liquid was separated to take out an organic layer. After the solvent in the organic layer was distilled off, methanol was added, and the mixture was filtered to take out a solid. 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 compound (xxviii-1): δ (ppm) ¹ H NMR (CDCl ₃ ); δ 1.44 to 1.89 (m, 24H), 2.31 to 2.81 ( m, 12H), 3.92-3.97 (m, 4H), 4.15-4.21 (m, 4H), 5.79-5.85 (m, 2H), 6.07-6. 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 to 8.22 (m, 2H)

<Synthesis example of compound (xxix-1) in the first route>
12.5 g (30 mmol) of compound (e), 0.4 (3 mmol) of 4-dimethylaminopyridine, 2.9 g (12 mmol) of 1,2-dihydroxyanthraquinone, and 100 g of chloroform were mixed. A solution in which 9.3 g (45 mmol) of N, N'-dicyclohexylcarbodiimide was dissolved in 25 g of chloroform was added dropwise to the obtained mixture at room temperature, followed by stirring. Thereafter, 124 g of 1N hydrochloric acid was added and the mixture was stirred, filtered to remove solids, and the obtained liquid was separated to take out an organic layer. After the solvent of the organic layer was distilled off, methanol was added, and the mixture was filtered to remove 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. The compound was heated and the phase transition temperature was confirmed. As a result, no liquid crystal phase was observed, and the compound was melted at 105 ° C.

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 to 8.34 (m, 3H)

<Synthesis example of compound (xxxii-1) in the first route>
Compound (xxxii-1) was produced according to the following scheme.

[Synthesis Example of Compound (xxxii-b)]
23 g (155 mmol) of trans-cinnamic acid, 75.5 g (171 mmol) of 1H-benzotriazol-1-yloxytripyrrolidinophosphonium hexafluorophosphate, 15.7 g (155 mmol) of triethylamine, 1.9 g (15.5 mmol) of dimethylaminopyridine ) And 200 g of dehydrated dimethylacetamide were mixed, and the mixture was stirred under ice-cooling and shielded from light. To the resulting mixture, 24.6 g (155 mmol) of 2,5-dimethoxyaniline was added, and the mixture was stirred at 0 ° C for 8 hours at room temperature. And stirred overnight. The obtained solution was extracted with methyl isobutyl ketone, and separated with a saturated aqueous solution of sodium carbonate three times. The organic layer was collected, concentrated under reduced pressure, and crystallized from methanol. The crystals were collected by filtration and dried under vacuum. On the other hand, the methanol solution was allowed to stand at room temperature overnight and recrystallized. The crystals were similarly collected and dried under vacuum.
The two were combined, washed again with cold methanol, and dried to obtain 38.6 g of a pale 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-diphosphetane-2,4-disulfide (Lawson's reagent) (55.0 mmol) and 500 g of toluene were mixed, heated to 80 ° C., and stirred. The obtained mixture was cooled and then concentrated to obtain a red viscous solid mainly composed of a decomposition product of Lawesson's reagent and the compound (xxxii-c).

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

[Synthesis Example of Compound (xxxii-a)]
10.6 g (35.7 mmol) of the compound (xxxii-d) and 106.0 g (10-fold mass) of pyridinium chloride were mixed, heated to 180 ° C., and stirred for 2 hours. After cooling the obtained mixture, water was added, and the obtained precipitate was washed with water and hexane to obtain 10.8 g of a solid mainly containing the compound (xxxii-a). The yield was 110% based on the compound (xxxii-d).

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

¹ H-NMR (CDCl ₃ ) of 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 determined by texture observation using a polarizing microscope. The compound (xxxii-1) exhibited a nematic phase from 125 ° C. to 180 ° C. or more when the temperature was raised, and exhibited a nematic phase up to 55 ° C. when the temperature was lowered and crystallized.

  Furthermore, if the alkyl chain length of the compound (e) is similarly changed, the compounds (v-2), (v-3) and (v-4) can be synthesized in the same manner as in the first route. Hereinafter, synthesis examples of each compound will be described.

  Compound (b ') could be synthesized in exactly the same manner as compound (b) differing only in alkyl chain length. Similarly, compound (d '), compound (d), and compound (e') could be synthesized by the same method as compound (e), respectively.

(Synthesis example of compound (b ''))
59.5 g (307 mmol) of monotetrahydropyranyl-protected hydroquinone (a), 21.7 g (543 mmol) of sodium hydroxide, 70 g (279 mmol) of 11-bromoundecanol and 280 g of dimethylacetamide 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 1,680 g of pure water, and the deposited precipitate was collected by filtration. Next, the precipitate was washed with 400 mL of a 6 N aqueous sodium hydroxide solution, washed with heptane, and dried under vacuum 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-ditert-butyl-4-hydroxytoluene, 61.2 g (505 mmol) of N, N-dimethylaniline, 1,3- 1.00 g of dimethyl-2-imidazolidinone and chloroform were mixed. 29.8 g (329 mmol) of aquiloyl chloride was added dropwise to the obtained mixture under ice-cooling under a nitrogen atmosphere, and the mixture was returned to room temperature and stirred. After confirming the completion of the reaction, the 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 suspended and 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 obtained mixture was stirred under ice-cooling under a nitrogen atmosphere, and a solution of 27.3 g (132 mmol) of dicyclohexylcarbodiimide in 50 mL of chloroform was added dropwise. After the addition, the mixture was stirred at room temperature. 200 mL of chloroform and 200 mL of heptane were added to the reaction solution, and the precipitate was filtered. The filtrate was collected and washed with a 2N aqueous hydrochloric acid solution. The organic layer was recovered, the insoluble component was filtered, dried over anhydrous sodium sulfate, filtered, and the solvent was removed to obtain an intermediate.

  2.34 g (130 mmol) of pure water obtained in the preceding section, 1.40 g (6.42 mmol) of 3,5-ditert-butyl-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. in a nitrogen atmosphere and then stirred for 3 hours. After cooling to room temperature, the precipitate was removed by filtration, and the solution was concentrated under reduced pressure at room temperature. Heptane (200 mL) was added to the residue. The deposited precipitate was collected by filtration, washed with pure water, and dried in vacuum. The resulting 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 dried under vacuum to obtain 44.4 g of a compound (e ''). The yield was 82% in two steps based on compound (d '').

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

(Synthesis example of compound (d '''))
100 g (310 mmol) of compound (b ′ ″), 1.40 g (6.42 mmol) of 3,5-ditert-butyl-4-hydroxytoluene, 86.4 g (713 mmol) of N, N-dimethylaniline, 1, 3 -Dimethyl-2-imidazolidinone (1.00 g) and chloroform were mixed. 42.11 g (465 mmol) of aquiloyl chloride was added dropwise to the resulting mixture under ice-cooling under a nitrogen atmosphere, and the mixture was returned to room temperature and stirred for 2 hours. After confirming the completion of the reaction, the 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. 300 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 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 suspended and washed with water / methanol 2/1 (v / v), further washed with heptane, and dried under vacuum to obtain 72 g of compound (d ′ ″). The yield was 79% based on the compound (b ′ ″).

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

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

<Synthesis Example of Compound (v-2) in First Route>
Compound (v-2) was obtained in the same manner as in the synthesis example of compound (v-1) except that compound (e) as a raw material 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), 37 to 6.44 (m, 2H), 6.87 to 7.02 (m, 8H), 7.27 (d, 2H), 8.19 to 8.23 (d, 2H), 8.34 to 8.38 (d, 2H)

<Synthesis example of compound (v-3) in the first route>
Compound (v-3) was obtained in the same manner as in the synthesis of compound (v-1), except that compound (e) as a raw material 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 5.97 (t, 4H), 4.15-4.20 (t, 4H), 5.81-5.84 (dd, 2H), 6.07-6.18 (m, 2H), 37 to 6.44 (m, 2H), 6.87 to 7.02 (m, 8H), 7.27 (d, 2H), 8.18 to 8.23 (d, 2H), 8.33 to 8.37 (d, 2H)

  The phase transition temperature of the obtained compound (v-3) was determined by texture observation using a polarizing microscope. Compound (v-3) exhibits a smectic phase from 164 ° C. to 174 ° C. and a nematic phase from 174 ° C. to 195 ° C. when the temperature is raised, and shows a nematic phase from 195 ° C. to 167 ° C. when the temperature is decreased. It showed a smectic phase from 167 ° C. to 151 ° C. and crystallized.

<Synthesis example of compound (v-4) in the first route>
Compound (v-4) was obtained in the same manner as in the synthesis of compound (v-1), except that compound (e) as a raw material 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), 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 determined by texture observation using a polarizing microscope. Compound (v-4) exhibits a smectic phase from 163 ° C. to 167 ° C. when heated, exhibits a nematic phase from 167 ° C. to 220 ° C., and exhibits a nematic phase from 220 ° C. to 156 ° C. when cooled. Crystallized.

Further, if the compound (f) is applied to the second route, it becomes possible to synthesize a compound v-1 derivative having more various linking groups. The following shows a synthesis example of compound v-5.

<Synthesis example of compound (v-5) by 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 in which 19.7 g (95.4 mmol) of N, N'-dicyclohexylcarbodiimide was dissolved in 30 g of chloroform was added dropwise to the obtained mixture at room temperature, followed by stirring. After filtering the obtained mixture, 12 g of 2N hydrochloric acid was added and stirred, then the liquid was separated, and the organic layer was taken out. After the solvent of this organic layer was distilled off, tetrahydrofuran was added and the mixture was stirred. The generated 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))
A solution obtained by dissolving the intermediate (g) obtained in the preceding section in tetrahydrofuran, 1.18 g (65 mmol) of pure water, 1.40 g (6.42 mmol) of 3,5-ditert-butyl-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 then stirred for 2 hours. After cooling to room temperature, the resulting precipitate was collected by filtration. The obtained powder was suspended and 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% in two steps based on compound (va).

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

<Synthesis example of compound (v-5)>
6.1 g (10 mmol) of the compound (g), 6.0 g (21 mmol) of the compound (i), 0.26 g (2.1 mmol) of dimethylaminopyridine and 20 mL of chloroform were mixed. 10 mL of a chloroform solution of 5.30 g (26 mmol) of dicyclohexylcarbodiimide was added dropwise to the obtained mixture 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. The residue was crystallized by adding methanol. The resulting precipitate was collected and redissolved in chloroform. After 500 mg of activated carbon was added, the mixture was allowed to stand overnight, filtered with acetic acid and celite, and reprecipitated in ethanol. The precipitate was collected by filtration, washed with heptane, and dried under vacuum to obtain 2.8 g of compound (v-5). The yield was 25% based on the compound (g).

¹ H-NMR (CDCl ₃ ) of compound (v-5): δ (ppm) 1.72 to 1.88 (m, 16H), 2.35 to 2.84 (m, 12H), 4.21 to 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 determined by texture observation using a polarizing microscope. The compound (v-5) exhibited a smectic phase from 142 ° C. to 163 ° C. at the time of temperature rise, exhibited a nematic phase from 163 ° C. to 224 ° C., and exhibited a nematic phase up to 108 ° C. at the time of temperature decrease and crystallized.

However, a compound v-1 derivative having a different linking group can also be synthesized in the same manner as in the first route. The structure and synthesis example of compound v-6 are shown below.

<Example of synthesis of compound (v-6) in the 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 benzyl parahydroxybenzoate, 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 dehydrated chloroform 200 ml were mixed. The resulting mixture was stirred at room temperature under a nitrogen atmosphere. Heptane (100 mL) was added to the reaction solution, and the resulting precipitate was filtered and the filtrate was collected. The filtrate was washed with a 1N aqueous hydrochloric acid solution. After the collected organic layer was dried and filtered, a crystal obtained by adding a 50 vol% aqueous solution of methanol to the residue was collected by filtration. The crystals were washed with heptane and pure water, and dried under vacuum to obtain 58.0 g of compound (j). The yield was 98% based on benzyl parahydroxybenzoate.

(Synthesis example of compound (k))
50.0 g (114 mmol) of the compound (j) obtained in the preceding section and 150 ml of tetrahydrofuran were mixed. Acetic acid (catalyst amount: 2 g) and palladium carbon (7.5 g) were added to the obtained mixture, and the mixture was stirred under a nitrogen atmosphere. The reaction solution was depressurized and then stirred under a hydrogen atmosphere. Once the hydrogen consumption ceased, the solution was filtered through celite under a nitrogen atmosphere. After the solvent was removed with an evaporator, the residue was washed with a 50 vol% methanol aqueous solution and dried under vacuum to obtain 32.0 g of a compound (k). The yield was 80% based on the compound (j).

(Synthesis example of compound (l))
16 g (46 mmol) of compound (j), 6.91 g (48 mmol) of (4-hydroxybutyl) acrylate, 10.88 g (53 mmol) of N, N'-dicyclohexylcarbodiimide obtained in the preceding section, N, N-dimethyl 0.56 g (4.6 mmol) of aminopyridine, 10 mg of 2,6-ditert-butyl-4-methylphenol, and 80 ml of dehydrated chloroform were mixed. The resulting mixture was stirred at room temperature under a nitrogen atmosphere. Heptane (40 mL) was added to the reaction solution, and the resulting precipitate was filtered and the filtrate was collected. The filtrate was washed with a 1N aqueous hydrochloric acid solution. After drying and filtering the collected organic layer, 18.5 g of compound (l) was obtained. 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 then stirred. After cooling 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 dried under vacuum to obtain 7.5 g of compound (m). The yield was 40% in two steps based on compound (l).

(Synthesis example of compound (v-6))
4.95 g (11.8 mmol) of compound (m) obtained in the preceding section, 1.70 g (5.9 mmol) of compound (va), 2.95 g (14.2 mmol) of N, N′-dicyclohexylcarbodiimide, 0.29 g (2.4 mmol) of N, N-dimethylaminopyridine and 40 ml of dehydrated chloroform were mixed. The resulting mixture was stirred at room temperature under a nitrogen atmosphere. Heptane (20 mL) was added to the reaction solution, and the formed precipitate was filtered and the filtrate was collected. The filtrate was washed with a 1N aqueous hydrochloric acid solution. The organic layer was dried, filtered, concentrated under reduced pressure by an evaporator, added with ethyl acetate, concentrated again under reduced pressure, and reprecipitated by adding 300 mL of methanol cooled in an ice bath. The obtained powder was washed with heptane and then dried under vacuum 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 determined by texture observation using a polarizing microscope. Compound (v-6) exhibits a smectic phase from 124 ° C. to 135 ° C. and a nematic phase from 135 ° C. to 220 ° C. when the temperature is raised, and shows a nematic phase from 220 ° C. to 103 ° C. when the temperature is decreased. Crystallized.

Further, a compound (v-1) derivative having a different polymerizable substituent and a compound (v-1) derivative having a lateral substituent can be synthesized in the same manner 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 the 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-ditert-butyl-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 a nitrogen atmosphere and ice-cooling, 16.0 g (153 mmol) of methacryloyl chloride was added dropwise, and the mixture was returned to room temperature and stirred for 3 hours. After confirming the completion of the reaction, the pH was adjusted to 2 by adding paratoluenesulfonic acid monohydrate. 1.47 g of pure water was added to the reaction solution, and the mixture was 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 an organic layer. After the organic layer was concentrated under reduced pressure, 1000 g of ice was added, and the mixture was vigorously stirred to crystallize, and this was collected. The obtained white powder was suspended and 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))
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)) were taken. Was dissolved in 50 mL of chloroform. Under a nitrogen atmosphere, the mixture was stirred under ice cooling, and a solution of 9.8 g (48 mmol) of dicyclohexylcarbodiimide in 20 mL of chloroform was added dropwise. After the addition, the mixture was stirred at room temperature.
200 mL of chloroform and 200 mL of heptane were added to the reaction solution, and the precipitate was filtered. The filtrate was collected and washed with a 2N aqueous hydrochloric acid solution. The organic layer was recovered, the insoluble component was filtered, dried over anhydrous sodium sulfate, filtered, and the solvent was removed to obtain an intermediate.

0.73 g (40 mmol) of pure water obtained in the preceding section, 1.40 g (6.42 mmol) of 3,5-ditert-butyl-4-hydroxytoluene, 1.15 g of paratoluenesulfonic acid monohydrate (1.45 g) 6.1 mmol) and dissolved in 100 mL of THF. Under a nitrogen atmosphere, the mixture was heated to 70 ° C. 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. Heptane (200 mL) was added to the residue. The deposited precipitate was collected by filtration, washed with pure water, and dried in vacuum. The resulting 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 dried under vacuum to obtain 12.2 g of compound (o).
The yield was 68% in two steps based on compound (n).

<Synthesis example of compound (v-7)>
6.7 g of compound (v-7) was obtained in the same manner as in the synthesis of compound (v-1), except that compound (e) as a raw material was changed to compound (n). The yield was 55% based on the compound (va).

¹ H-NMR (CDCl ₃ ) of 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 to 7.00 (m, 8H), 7.27 (d, 2H), 8.20 to 8.23 (d, 2H), 8.35 to 8. 38 (d, 2H)

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

(Synthesis example of compound (p))
119 g (713 mmol) of 2-tert-butylhydroquinone, 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 obtained mixture under ice-cooling. 594 mmol) was added dropwise. After stirring at room temperature, 500 mL of heptane was added, and then saturated sodium hydroxide was added.
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 vacuum dried to obtain 39 g of compound (p) as a light purple powder. The yield was 26% based on dihydropyran.

(Synthesis example of compound (q))
39 g (156 mmol) of compound (p), 12.2 g (304 mmol) of sodium hydroxide, 21.3 g (156 mmol) of 6-chlorohexanol, and 86 g of dimethylacetamide were mixed. The obtained 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 crude oily purified product was dissolved in methyl isobutyl ketone and separated from pure water. The organic layer was collected, concentrated and dried under vacuum to obtain 42 g of the compound (q) as a pale red viscous liquid. The yield was 77% based on the compound (p).

(Synthesis example of compound (r))
40 g (114 mmol) of compound (q), 1.40 g (6.42 mmol) of 3,5-ditert-butyl-4-hydroxytoluene, 31.8 g (262 mmol) of N, N-dimethylaniline, and chloroform were mixed. Aqueiroyl 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, the pH was adjusted to 2 by adding paratoluenesulfonic acid monohydrate. 1.64 g of pure water was added to the reaction solution, and the mixture was stirred at room temperature for 1 hour. After confirming the completion of the reaction, 100 mL of heptane was added, and a 2N aqueous hydrochloric acid solution was added until dimethylaniline was completely removed, and the separated organic layer was collected. The organic layer was treated with activated carbon, filtered through celite, concentrated under reduced pressure, poured into heptane, and decanted to remove the supernatant heptane layer. The precipitated pale red viscous liquid was dried under vacuum 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 40 mL of chloroform was mixed. The obtained mixture was stirred under ice-cooling under a nitrogen atmosphere, and a solution of 10.6 g (52 mmol) of dicyclohexylcarbodiimide in 10 mL of chloroform was added dropwise. After the addition, 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 a 2N aqueous hydrochloric acid solution. The separated organic layer was collected, the insoluble component was filtered, dried over anhydrous sodium sulfate, filtered through silica gel, and the solvent was removed to obtain an intermediate.

  The intermediate obtained in the preceding section, 0.79 g (44 mmol) of pure water, 1.40 g (6.42 mmol) of 3,5-ditert-butyl-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 then stirred for 3 hours. After allowing to cool to room temperature, the generated precipitate was removed by filtration, and concentrated under reduced pressure at room temperature. 300 g of ice was added to the residue and the mixture was stirred, and the deposited precipitate was collected by filtration, washed with heptane, collected, and dried in vacuum. The resulting powder was redissolved in chloroform and filtered through silica gel. The filtrate was collected, redissolved in 400 mL of chloroform, and crystallized by adding heptane. The resulting powder was washed with ethanol / water 2/3 (v / v), filtered, and dried under vacuum to obtain 17.9 g of compound (o). The yield was 86% in two steps based on compound (r).

<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 compound (e) as a raw material was changed to compound (s). The yield was 4.5% based on the compound (va).

¹ H-NMR (CDCl ₃ ) of compound (v-8): δ (ppm) 1.38 (s, 18H), 1.47 to 1.85 (m, 24H), 2.36 to 2.83 ( m, 12H), 3.95-4.00 (t, 4H), 4.16-4.21 (t, 4H), 5.80-5.84 (dd, 2H), 6.08-6. 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)

  Further, a polymerizable liquid crystal compound using cyclohexane instead of a benzene ring can also be synthesized according to 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 according to the following scheme.

(Synthesis example of compound (t))
Compound (t) was synthesized from trans-4-hydroxycyclohexanecarboxylic acid and monoacrylate (4-hydroxybutyl: manufactured by Tokyo Kasei Kogyo Co., Ltd.) by DCC condensation reaction and the like in the same manner as compound (m). . 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 1,000 g of water and 500 g of a liquid composed of methyl isobutyl ketone / heptane (weight ratio: 3/2). After stirring the obtained solution, the separated organic layer was recovered and washed with pure water. After the organic layer was dried over anhydrous sodium sulfate and filtered, 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)>
30.5 g (130 mmol) of compound (u), 1.59 g (13 mmol) of dimethylaminopyridine, 30 g (130 mmol) of trans-1,4-cyclohexanedicarboxylic acid monoethoxymethyl ester, and 200 mL of chloroform were mixed. The obtained mixture was stirred under ice-cooling under a nitrogen atmosphere, and 29.57 g (143 mol) of dicyclohexylcarbodiimide was added dropwise. After completion of the dropwise addition, the mixture was stirred. 200 mL of chloroform and 200 mL of heptane were added to the obtained reaction solution, and the formed precipitate was filtered. The filtrate was collected and washed three times with pure water. The organic layer was recovered, dried over anhydrous sodium sulfate, filtered, and the obtained residue was added with methanol and stirred. The obtained powder was collected by filtration, and further added with methanol and stirred.
The obtained powder was collected by filtration and dried in vacuo 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. After the resulting mixture was depressurized, the mixture was stirred at room temperature, normal pressure and in a hydrogen atmosphere. Filtered under a nitrogen atmosphere. Toluene was added to the obtained residue, the 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 crystals were separated by filtration and dried under vacuum 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 obtained mixture was stirred under ice-cooling under a nitrogen atmosphere, and a solution of 10.19 g (49.4 mmol) of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride in 50 mL of chloroform was added dropwise. After completion of the dropwise addition, the mixture was stirred. After adding 200 mL of toluene to the obtained reaction solution, the filtrate was collected, concentrated under reduced pressure, and toluene was added. The obtained solution was washed with a 1N aqueous hydrochloric acid solution. The organic layer was recovered, dried over anhydrous sodium sulfate and filtered, and the residue was dried under vacuum 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. in a nitrogen atmosphere and then stirred. After cooling 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 dried under vacuum to obtain 15.4 g of compound (t). The yield was 81% in two steps based on compound (x).

(Synthesis example of compound (v-9))
1.44 g (5 mmol) of the compound (va), 4.24 g (10 mmol) of the compound (k), 0.12 g (1 mmol) of dimethylaminopyridine 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. After the obtained reaction solution was stirred and filtered, 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 to cause reprecipitation. The precipitate was collected by filtration, further washed with ethanol, filtered, and dried under vacuum 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 determined by texture observation using a polarizing microscope. The compound (v-9) exhibited a smectic phase from 146 ° C. to 159 ° C. and showed a melting point when the temperature was raised, and showed a nematic phase from 159 ° C. to 121 ° C. and was crystallized when the temperature was lowered.

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

<Production example of optical film>
(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 then heated and dried to obtain a film having a thickness of 89 nm. Subsequently, after a rubbing treatment was performed on the surface of the obtained film, a coating solution having a composition shown in Table 2 was applied to the rubbed surface by a spin coating method. After drying on a hot plate at 100 ° C. for 1 minute, an ultraviolet film 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, wt% in the tables other than the solvent means wt% of the solid content based on 100 wt% of the coating solution.

A: LC242 (liquid crystal compound commercially available from BASF)
Photopolymerizable initiator: Irgacure 907, Irgacure 819 (manufactured by Ciba Specialty Chemicals Co., Ltd.)
Leveling agent: BYK361N (manufactured by BYK Japan)

(Example 2)
An optical film having a thickness of 1.28 μm was prepared in the same manner as in Example 1 except that the coating solution (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 to the rubbed polyvinyl alcohol substrate described in Example 1 by spin coating. After drying for 1 minute on a hot plate at 80 ° C., it was further dried for 1 minute at 210 ° C. The obtained unpolymerized film was cooled to 190 ° C., and irradiated with 1200 mJ / cm ² ultraviolet rays while keeping the temperature 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 solution (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 to the rubbed polyvinyl alcohol substrate described in Example 1 by spin coating. After drying for 1 minute on a hot plate at 80 ° C., the temperature was further raised to 160 ° C. and dried. 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 to the rubbed polyvinyl alcohol substrate described in Example 1 by spin coating. After drying on a hot plate at 80 ° C for 1 minute, the temperature was further raised to 140 ° C and dried. 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 to the rubbed polyvinyl alcohol substrate described in Example 1 by spin coating. After drying on a hot plate at 80 ° C. for 1 minute, the temperature was further raised to 150 ° C. and dried. The obtained unpolymerized film was irradiated with ultraviolet rays of 1200 mJ / cm ² while keeping the same temperature at the same temperature to produce an optical film having a thickness of 2.11 μm.

(Example 8)
An optical film having a thickness of 1.56 μm was produced in the same manner as in Example 5, except that the coating solution (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 to the rubbed polyvinyl alcohol substrate described in Example 1 by spin coating. After drying on a hot plate at 80 ° C. for 1 minute, the temperature was further raised to 170 ° C. and dried. The obtained unpolymerized film was irradiated with an ultraviolet ray of 1200 mJ / cm ² while keeping the temperature at the same temperature to prepare 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 solution (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 to the rubbed polyvinyl alcohol substrate described in Example 1 by spin coating. After drying on a hot plate at 80 ° C. 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 1200 mJ / cm ² ultraviolet rays while keeping the temperature at the same temperature to produce an optical film having a thickness of 0.88 μm.

<Measurement of optical characteristics>
In the wavelength range of 450 nm to 700 nm, the retardation value of the produced optical film is measured using a measuring device (KOBRA-WR, manufactured by Oji Scientific Instruments), and the retardation value Re (450) at a wavelength of 450 nm is measured by a program attached to the device. The phase difference value Re (550) at a wavelength of 550 nm and the phase difference 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 of 46.2 g (224.4 mmol) of N, N'-dicyclohexylcarbodiimide (DCC) dissolved in 98 g of dehydrated pyridine. And stirred.
After the precipitated solid was separated by filtration, 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 by a silica gel column under reduced pressure to obtain 2.8 g of a solid containing compound (TC-1) as a main component. The yield was 70% based on trans-4-n-pentylcyclohexanecarboxylic acid.

化合物（ＴＭ−１）の^１Ｈ−ＮＭＲ（ＣＤＣｌ_３）：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） (Synthesis example of compound (TM-1))
In a vessel, 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. Then, a solution in which 1.4 g (6.7 mmol) of N, N'-dicyclohexylcarbodiimide (DCC) was dissolved in 19 g of chloroform was added dropwise, and the resulting mixture was stirred at room temperature. After the precipitated solid was separated by filtration, 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 a 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 determined by texture observation using a polarizing microscope. As the temperature was increased, the crystal phase changed to a smectic phase at around 148 ° C, and further changed to a nematic phase at around 153 ° C. When the temperature was further increased, the phase changed to an isotropic phase at around 173 ° C. When the temperature was lowered from this point, the phase changed to a nematic phase at around 170 ° C., and changed to a crystalline phase at around 102 ° C. That is, the compound (TM-1) exhibits a smectic phase from 148 ° C. to 153 ° C. at the time of temperature rise, exhibits a nematic phase from 153 ° C. to 173 ° C., and exhibits a nematic phase from 170 ° C. to 102 ° C. at the time of temperature decrease. It was found to present.

<Production example of optical film>
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 then heated and dried to obtain a film having a thickness of 89 nm. Subsequently, after a rubbing treatment was performed on the surface of the obtained film, a coating solution having a composition shown in Table 4 was applied to the rubbed surface by a spin coating method. After drying on a hot plate at 170 ° C. for 1 minute, ultraviolet rays of 9600 mJ / cm ² were irradiated while heating at 130 ° C. to produce an optical film having a thickness of 1.353 μm.
The weight% in the tables other than the solvent in Table 4 means the weight% of the solid content with the coating liquid being 100% by weight.

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

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

<Measurement of optical characteristics>
About the produced optical film, the phase difference value at a wavelength of 547 nm was measured using a measuring device (KOBRA-WR, manufactured by Oji Scientific Instruments). The thickness of the optical film derived from the polymerizable compound was measured using a laser microscope (LEXT, manufactured by Olympus Corporation). Δn was calculated from the phase difference 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 contained [Compound (TM-1)], and thus, compared to Comparative Example 2, [Re (447) / Re (547)] and [Re (628) / Re (547). )] Is closer to 1 and has excellent performance in wavelength dispersion.

<Production example of optical film>
(Examples 12 to 28, Comparative Example 3)
A 2 wt% aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000, completely saponified, manufactured by Wako Pure Chemical Industries, Ltd.) was applied to a glass substrate, and dried to form a film having a thickness of 89 nm. Subsequently, the surface of the obtained film was subjected to a rubbing treatment, and a coating solution having a composition shown in Table 6 was applied to the rubbed surface by a spin coating method and dried. Thereafter, ultraviolet light was applied. As a result, an optical film could be formed on the glass substrate.

In Table 6, the weight% in the tables other than the solvent means the weight% based on 100% by weight of the coating solution.

LC242: Liquid crystal compound photopolymerizable initiator commercially available from BASF: Irgacure 907, Irgacure 819 (manufactured by Ciba Specialty Chemicals Co., Ltd.)
Leveling agent: BYK361N (manufactured by BYK Japan)

<Measurement of optical characteristics>
The front retardation value of the produced optical film was measured using a measuring device (KOBRA-WR, manufactured by Oji Scientific Instruments). In addition, since the glass substrate used for the base material does not have 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 instrument. . The obtained optical measurement 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. The thickness (μm) of the portion derived from the optical film was measured using a laser microscope (LEXT, manufactured by Olympus Corporation). 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 by [Re (447.
3) / Re (546.9)] (α in the table) was closer to 1 or less than 1. The value of [Re (627.8) / Re (546.9)] (β in the table) was closer to 1 or 1 or more. In other words, since the wavelength dependence of the refractive index is small or a so-called inverse wavelength dispersion property is exhibited, when used for a liquid crystal panel, the liquid crystal panel has excellent characteristics in optical compensation.

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

FIG. 1 is a schematic diagram showing a color filter 1 according to the present invention. FIG. 1 is a schematic diagram showing a liquid crystal display device 5 according to the present invention. FIG. 2 is a schematic view showing a polarizing plate 30 according to the present invention. It is the schematic which shows the bonded article 21 of the liquid crystal panel 20 and the polarizing plate 30 of the liquid crystal display device which concerns on this invention. FIG. 2 is a schematic diagram showing an organic EL panel 23 of the organic EL display device according to the present 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 Polarizer 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' Laminate 15 Polarizing film 16, 16 'Support base 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 (5)

An optical film-forming composition comprising cyclopentanone or cyclohexanone, and a compound containing a group represented by the formula (A) and a polymerizable group.
^{-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 Nπa of π electrons 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. It may be substituted, and the methylene group contained in the alicyclic hydrocarbon group may be substituted with -O-, -S- or -NH-. ]   The composition for forming an optical film according to claim 1, further comprising a polymerization initiator.   A method for producing an unpolymerized film, comprising applying the composition for forming an optical film according to claim 1 on an alignment film formed on a support substrate, and drying the applied film.   A method for producing an optical film, comprising curing an unpolymerized film obtained by the method for producing an unpolymerized film according to claim 3 by polymerization.   An optical film comprising a cured product of the composition for forming an optical film according to claim 1.

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