JP6744962B2 - Compound, optical film and method for producing optical film - Google Patents

Description

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

A flat panel display device (FPD) includes a member using an optical film such as a polarizing plate and a retardation plate. Examples of the optical film include an optical film obtained by polymerizing a solution obtained by dissolving a polymerizable compound in a solvent on a supporting substrate. It is known that the retardation (Re(λ)) of the optical film given by the light of the wavelength λnm is determined by the product of the birefringence Δn and the film thickness d (Re(λ)=Δn). Xd). 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, and (Re (Λ)/Re(550)) has a wavelength range close to 1, and the reverse wavelength dispersibility 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, Volume 37, p.1673

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

The present invention is a compound represented by formula (1).
^{P 1 -F 1 - (B 1} -A 1) k -E 1 -G 1 -D 1 -Ar-D 2 -G 2 -E 2 - (A 2 -B 2) l -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 heterocycle, and a π electron contained in the aromatic ring in the Ar group. The number N _π of 12 is 12 or more.
D ¹ and D ² are each independently *-O-CO- (* represents a position at which Ar is bonded), -C(=S)-O-, -O-C(=S)-, ^{-CR 1 R 2 -, - CR} 1 R 2 -CR 3 R 4 -, - O-CR 1 R 2 -, - CR 1 R 2 -O -, - CR 1 R 2 -O-CR 3 R 4 - ^{, -CR 1 R 2 -O-CO} -, - O-CO-CR 1 R 2 -, - CR 1 R 2 -O-CO-R 3 R 4 -, - CR 1 R 2 -CO-O-CR ^{3 R 4 -, - NR 1} -CR 2 R 3 -, - CR 2 R 3 -NR 1 -, - CO-NR 1 -, or represents a ^-NR 1 -CO-. R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.
G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group. The hydrogen atom contained in the alicyclic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group. 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-, -OC(=S)-, -OC(=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.
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 with a group. The hydrogen atom contained in the alkyl group having 1 to 4 carbon atoms and the alkoxy group having 1 to 4 carbon atoms may be substituted with a fluorine atom.
k and l each independently 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 with an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom, and the methylene group contained in the alkylene group is -O. -Or-CO- may be substituted.
P ¹ and P ² each independently represent a hydrogen atom or a polymerizable group (provided that at least one of P ¹ and P ² represents a polymerizable group). ]

The compound of the present invention can provide an optical film capable of uniform polarization conversion in a wide wavelength range.

The compound of the present invention (hereinafter sometimes referred to as "compound (1)") is represented by formula (1).
^{P 1 -F 1 - (B 1} -A 1) k -E 1 -G 1 -D 1 -Ar-D 2 -G 2 -E 2 - (A 2 -B 2) l -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 heterocycle, and a π electron contained in the aromatic ring in the Ar group. The number N _π of 12 is 12 or more.
D ¹ and D ² are each independently *-O-CO- (* represents a position at which Ar is bonded), -C(=S)-O-, -O-C(=S)-, ^{-CR 1 R 2 -, - CR} 1 R 2 -CR 3 R 4 -, - O-CR 1 R 2 -, - CR 1 R 2 -O -, - CR 1 R 2 -O-CR 3 R 4 - ^{, -CR 1 R 2 -O-CO} -, - O-CO-CR 1 R 2 -, - CR 1 R 2 -O-CO-R 3 R 4 -, - CR 1 R 2 -CO-O-CR ^{3 R 4 -, - NR 1} -CR 2 R 3 -, - CR 2 R 3 -NR 1 -, - CO-NR 1 -, or represents a ^-NR 1 -CO-. R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.
G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group. The hydrogen atom contained in the alicyclic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group. 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-, -OC(=S)-, -OC(=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.
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 with a group. The hydrogen atom contained in the alkyl group having 1 to 4 carbon atoms and the alkoxy group having 1 to 4 carbon atoms may be substituted with a fluorine atom.
k and l each independently 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 with an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom, and the methylene group contained in the alkylene group is -O. -Or-CO- may be substituted.
P ¹ and P ² each independently represent a hydrogen atom or a polymerizable group (provided that at least one of P ¹ and P ² represents a polymerizable group). ]

The compound (1) preferably satisfies the requirements represented by the formula (2) and the formula (3).
(N _π -4)/3<k+l+4 (2)
12≦N _π ≦22 (3)
[In Formula (2) and Formula (3), N( _pi ), k, and l represent the same meaning as the above. ]

Examples of the aromatic hydrocarbon ring include a benzene ring, naphthalene ring, anthracene ring and phenanthroline ring, and 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. Examples include rings. Of these, a benzene ring, a thiazole ring and a benzothiazole ring are preferable.

Ar is a divalent group having at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles, and the total of π electrons of the aromatic rings 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 aromatic hydrocarbon rings and aromatic heterocycles.

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

[In Formula (Ar-1) to Formula (Ar-13), Z ¹ represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 6 carbon atoms, or a carbon number. 1-6 alkylsulfonyl group, carboxyl group, C1-C6 fluoroalkyl group, C1-C6 alkoxy group, C1-C6 alkylthio group, C1-C6 N-alkylamino group Represents an N,N-dialkylamino group having 2 to 12 carbon atoms, an N-alkylsulfamoyl group having 1 to 6 carbon atoms, or an N,N-dialkylsulfamoyl group having 2 to 12 carbon atoms.
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 an integer of 0 to 2. ]

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

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

Examples of the alkylsulfinyl group having 1 to 6 carbon atoms include methylsulfinyl group, ethylsulfinyl group, propylsulfinyl group, isopropylsulfinyl group, butylsulfinyl group, isobutylsulfinyl group, sec-butylsulfinyl group, tert-butylsulfinyl group, pentylsulfinyl group. Group, a hexyl group, sulfinyl, and the like, an alkylsulfinyl group having 1 to 4 carbon atoms is preferable, an alkylsulfinyl group having 1 to 2 carbon atoms is more preferable, and a methylsulfinyl group is particularly preferable.

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

Examples of the fluoroalkyl group having 1 to 6 carbon atoms include a fluoromethyl group, a trifluoromethyl group, a fluoroethyl group, a pentafluoroethyl group, a heptafluoropropyl group and a nonafluorobutyl group. A fluoroalkyl group is preferable, a fluoroalkyl group having 1 to 2 carbon atoms is more preferable, and a trifluoromethyl group is particularly preferable.

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

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

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

Examples of the N,N-dialkylamino group having 2 to 12 carbon atoms include N,N-dimethylamino group, N-methyl-N-ethylamino group, N,N-diethylamino group, N,N-dipropylamino group, Examples include 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 group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group and N- Butylsulfamoyl group, N-isobutylsulfamoyl group, N-sec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N-hexylsulfamoyl group, etc. And an N-alkylsulfamoyl group having 1 to 4 carbon atoms is preferable, an N-alkylsulfamoyl group having 1 to 2 carbon atoms is more preferable, and an N-methylsulfamoyl group is particularly preferable.

Examples of the N,N-dialkylsulfamoyl group having 2 to 12 carbon atoms include N,N-dimethylsulfamoyl group, N-methyl-N-ethylsulfamoyl group, N,N-diethylsulfamoyl group, N,N-dipropylsulfamoyl group, N,N-diisopropylsulfamoyl group, N,N-dibutylsulfamoyl group, N,N-diisobutylsulfamoyl group, N,N-dipentylsulfamoyl group, N,N-dihexylsulfamoyl group etc. are mentioned, C2-C8 N,N-dialkylsulfamoyl group is preferable and C2-C4 N,N-dialkylsulfamoyl group is more preferable. , N,N-dimethylsulfamoyl groups are particularly preferred.

Z ¹ is 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 in R ⁷ and R ⁸ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a tert-butyl group. An alkyl group is preferable, and a methyl group is more preferable.
Q ¹ is preferably -S-, -CO-, -NH-, -N(CH ₃ )-, and Q ³ is preferably -S- or -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, and a phenyl group. , A naphthyl group is preferable, and a phenyl group is more preferable. The aromatic heterocyclic group contains at least one hetero atom 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 or a sulfur atom, and has 4 to 20 carbon atoms. The aromatic heterocyclic group of is exemplified by furyl group, pyrrolyl group, thienyl group, pyridinyl group, and thiazolyl group.

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

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

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

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

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

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

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

[Formula (Ar-6a) ~ formula (Ar-6c), wherein (Ar-10a) and the formula ^{(Ar-10b), Z 1} , n, Q 1, Z 2, a 1 and ^{b 1} are as described above Have the same meaning. ]

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

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

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

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

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

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

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

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

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

D ¹ and ^{D 2} are, * - O-CO -, * - O-C (= S) -, * - O-CR 1 R 2 -, * - NR 1 -CR 2 R 3 - or * -NR ¹ -CO-(* represents a binding site with Ar.
) Is preferable. More preferably, D ¹ and D ² are *-O-CO-, *-O-C(=S)- or *-NR ¹ -CO- (* represents a binding site with Ar). .. R ¹ , R ² , R ³ and R ⁴ are preferably 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 formula (g-1) to formula (g-10), and include a 5-membered or 6-membered alicyclic ring. It is preferably a formula hydrocarbon group.

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

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

The divalent alicyclic hydrocarbon group or aromatic hydrocarbon group for A ¹ and A ² is, for example, a 5-membered ring or a 6-membered ring represented by the formula (g-1) to the formula (g-10). And a divalent aromatic hydrocarbon group having about 6 to 20 carbon atoms represented by formula (a-1) to formula (a-8).

In addition, as A ¹ and A ² , a part of hydrogen atoms of the above exemplified groups is an alkyl group having about 1 to 4 carbon atoms such as a methyl group, an ethyl group, an i-propyl group or a t-butyl group; methoxy. 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; a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom Good.

As A ¹ and A ^2, it is particularly preferable that both are the same type of group because the compound (1) can be easily produced. Further, A ¹ and A ² are preferably a monocyclic 1,4-phenylene group or a 1,4-cyclohexylene group, and particularly a 1,4-phenylene group because the compound (1) can be easily produced. Is preferred.

B ¹ and B ² are preferably divalent groups of the same type, because the compound (1) can be easily produced. Furthermore, since compound (1) is easier to produce, B ¹ and B ² which are bonded to only A ¹ and A ^{2 of} B ¹ and B ² are independently —CH ₂ —CH ₂ respectively. -, - CO-O -, - O-CO -, - CO-NH -, - NH-CO -, - O-CH 2 -, - it is preferably CH 2 -O- or a single bond, particularly high -CO-O- or -O-CO- is preferable because it exhibits liquid crystallinity. 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- It is more preferably 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 sum 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 for both P ¹ and P ^{2 to} be a polymerizable group because the resulting optical film tends to have excellent film hardness.
The polymerizable group is a substituent capable of polymerizing the compound (1) of the present invention, and specifically, a vinyl group, p-stilbene group, acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy. Examples thereof include groups, carboxyl groups, methylcarbonyl groups, hydroxyl groups, amide groups, alkylamino groups having 1 to 4 carbon atoms, amino groups, epoxy groups, oxetanyl groups, aldehyde groups, isocyanate groups and thioisocyanate groups. Further, the polymerizable group may include groups represented by B ¹ and B ² in order to bond E ¹ and E ² to the above exemplified groups. For example, a radically polymerizable or cationically 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 it is particularly easy to handle and is easy to manufacture. It is more preferable that both P ¹ and P ² be a polymerizable group, since the obtained optical film tends to have excellent film hardness.

^{-D 1 -G 1 -E 1 - (} A 1 -B 1) k -F 1 -P 1, -D 2 -G 2 -E 2 - (A 2 -B 2) of l ^-F 2 -P ² Specific examples include groups represented by formula (R-1) to formula (R-134). * (Asterisk) indicates a bonding position with Ar. N in the formulas (R-1) to (R-134) represents an integer of 2 to 12.

Furthermore, examples of the compound (1) include compounds (i) to compounds (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 (R-57) to (R-57). R-120).
In Table 1 above, 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 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 the compound represented by the formula (ar-78) and the compound represented by the formula (ar-79).
In Table 2 above, the compound (xxx) is a compound in which the group represented by Ar is a group represented by the formula (ar-120), and a compound represented by Ar is a group represented by the formula (ar-121). Alternatively, it means that the group represented by Ar is a mixture of the compound represented by the formula (ar-120) and the compound represented by the formula (ar-121), and the compound (xxxi ) Is a compound in which the group represented by Ar is a group represented by formula (ar-122), a compound in which the group represented by Ar is a group represented by formula (ar-123) or a group represented by Ar is It means that it is either a mixture of the compound which is the group represented by (ar-122) and the compound which is the group represented by the formula (ar-123).

Furthermore, compound (i), compound (ii), compound (iv), compound (v), compound (vi), compound (ix), compound (x), compound (xi), compound (xvi), compound of Table 1 (Xviii), compound (xix), compound (xx), compound (xxi), compound (xxiii), compound (xxiv), compound (xxv), compound (xxvi), compound (xxvii), compound (xxviii), And, a typical structural formula of the compound (xxix) is represented by formula (ii-1), formula (iv-1), formula (v-1), formula (v-2), formula (v-3), formula ( v-4), formula (v-5), formula (vi-1), formula (ix-1), formula (x-1), formula (xi-1), formula (xvi-1), formula (xix). −1), formula (xx-1), formula (xxi-1), formula (xxiii-1), formula (xxiv-1), formula (xxv-1), formula (xxvi-1), formula (xxvii-). 1), formula (xxviii-1), formula (xxix-1), formula (xxxii-1), and formula (xxxiv-1). In the optical film of the present invention, a plurality of different types of compound (1) may be used.

Further examples of the compound (1) include the following. 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 by taking the compound (1) as an example.
The compound (1) is a known organic synthetic reaction (for example, condensation reaction, esterification reaction, Williamson reaction, described in Methoden der Organischen Chemie, Organic Reactions, Organic Syntheses, Comprehensive Organic Synthesis, New Experimental Chemistry Course, etc. 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-Crafts reaction, Heck reaction, Aldol reaction, etc. Can be produced by appropriately combining the above) depending on its 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 have the same meanings as described above.)
A 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 have the same meanings as described above.)
The compound of formula (1-3) and the compound of formula (1-4) are obtained.

（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。

(In the formula, R ¹ , R ² , G ² , E ² , A ² , B ² , F ² , P ² and l have the same meanings as described above.)
It can be produced by reacting with a compound represented by.
The reaction between the compound represented by formula (1-1) and the compound represented by formula (1-2) and the reaction between the compound represented by formula (1-3) and the compound represented by formula (1-4) are Preferably, it is carried out in the presence of an ester agent.

As the esterifying agent (condensing agent), 1-cyclohexyl-3-(2-morpholinoethyl)carbodiimide meth-para-toluenesulfonate, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, 1- Ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (partially water-soluble carbodiimide: commercially available as WSC), bis(2,6-diisopropylphenyl)carbodiimide, bis(trimethylsilyl)carbodiimide, bisisopropylcarbodiimide, Such as carbodiimide, 2-methyl-6-nitrobenzoic anhydride, 2,2′-carbonylbis-1H-imidazole, 1,1′-oxalyldiimidazole, diphenylphosphoryl azide, 1(4-nitrobenzenesulfonyl) -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 hexafluorophosphate, 2-bromo-1-ethylpyridinium tetrafluoroborate, 2-chloro-1,3-dimethylimidazolinium chloride, 2-chloro-1,3-dimethylimidazoli Examples include aluminum hexafluorophosphate, 2-chloro-1-methylpyridinium iodide, 2-chloro-1-methylpyridinium paraltoluene sulfonate, 2-fluoro-1-methylpyridinium paraltoluene sulfonate, and trichloroacetic acid pentachlorophenyl ester. From the viewpoint of reactivity, cost, and usable solvent, as the condensing agent, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride , Bis(2,6-diisopropylphenyl)carbodiimide, bis(trimethylsilyl)carbodiimide, bisisopropylcarbodiimide and 2,2′-carbonylbis-1H-imidazole are more preferred.

The composition of the present invention means a compound containing a group represented by the formula (A) and a polymerizable group (hereinafter sometimes referred to as “compound (A)”) and a liquid crystal compound (however, the compound (A) is Different).
^{-G a -D a -Ar a -D b} -G b - (A)
[In the formula (A), Ar ^a represents a divalent group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle, and is included in the aromatic ring in the Ar ^a group. The number of π electrons N _πa is 12 or more.
D ^a and ^{D b} are each independently a single bond, -CO-O -, - O -CO -, - C (= S) -O -, - O-C (= S) -, - CR 1 R ^{2 -, - CR 1 R 2} -CR 3 R 4 -, - O-CR 1 R 2 -, - CR 1 R 2 -O -, - CR 1 R 2 -O-CR 3 R 4 -, - CR 1 ^{R 2 -O-CO -, -} O-CO-CR 1 R 2 -, - CR 1 R 2 -O-CO-CR 3 R 4 -, - CR 1 R 2 -CO-O-CR 3 R 4 - ^{, -NR 1 -CR 2 R 3 -} , - CR 1 R 2 -NR 3 -, - CO-NR 1 -, or 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 ^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 Liquid Crystal Handbook (edited by the Liquid Crystal Handbook Editorial Committee, published by Maruzen Co., Ltd. on October 30, 2000), Chapter 3, Molecular structure and liquid crystal property, 3.2 Non-chiral rod-shaped liquid crystal molecules, 3 .3 Among the compounds described in the chiral rod-shaped liquid crystal molecule, compounds having a polymerizable group can be mentioned.
As the liquid crystal compound, a plurality of different compounds may be used together.

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

^{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 ( ═O)—CH═CH— or represents a single bond. R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms, and R ¹⁴ and R ¹⁵ may be linked to each other to form an alkylene group having 4 to 7 carbon atoms. Good.
E ¹¹ represents an alkylene group having 1 to 12 carbon atoms. The hydrogen atom contained in the alkylene group may be substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogen atom.
P ¹¹ represents a polymerizable group.
G is a hydrogen atom, a halogen atom, an alkyl group having 1 to 13 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, a fluoroalkyl group having 1 to 13 carbon atoms, an alkylamino group having 1 to 13 carbon atoms, a nitrile group, It represents a polymerizable group which is a nitro group or is bonded via an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom contained in the alkylene group is an alkyl group having 1 to 6 carbon atoms, or a hydrogen atom having 1 to 6 carbon atoms. It may be substituted with an alkoxy group or a halogen atom.
t represents an integer of 1 to 5. ]

In particular, the polymerizable group for P ¹¹ and G may be any group capable of polymerizing with the compound (A), such as vinyl group, vinyloxy group, p-stilbene group, acryloyl group, acryloyloxy group, methacroyl group, Methacroyloxy group, carboxyl group, acetyl group, hydroxyl group, carbamoyl group, amino group, alkylamino group having 1 to 4 carbon atoms, epoxy group, oxetanyl group, formyl group, -N=C=O or -N=C= S etc. are mentioned. Of these, radically polymerizable groups or cationically polymerizable groups are preferable in that they are suitable for photopolymerization, and they are easy to handle and can be easily produced into liquid crystal compounds, and thus have acryloyloxy groups, methacroyloxy groups or vinyloxy groups. Groups are preferred.

Further, the carbon number of the aromatic hydrocarbon group, the alicyclic hydrocarbon group and the heterocyclic group of A ¹¹ is, for example, 3 to 18, preferably 5 to 12, and preferably 5 or 6. Is particularly preferable.

Examples of compound (4) include compounds represented by formula (4-1) and 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)
Wherein (4-1) and the equation ^{(4-2), P 11, E} 11, B 11, A 11, B 12 is as defined above.
F ¹¹ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 13 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, a fluoroalkyl group having 1 to 13 carbon atoms, an alkylamino group having 1 to 13 carbon atoms, a nitrile group , Represents a nitro group.
E ¹² has the same meaning as E ¹¹ .
P ¹² has the same meaning as P ¹¹ .
t ¹ and t ² have the same meaning as t. ]

Furthermore, as the compounds represented by these formulas (4-1) and (4-2), those represented by formula (I), formula (II), formula (III), formula (IV) or 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)
Wherein (I) ~ formula ^{(V), A} 12 ^{~A 15 has} the same meaning as ^{A 11, B} 13 ^{~B 16 is B 11} as synonymous.

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

Specific examples of the compound (4) include, for example, the following formula (I-1) to formula (I-5), formula (II-1) to formula (II-6), formula (III-1) to formula (III). III-19), the compounds represented by formula (IV-1) to formula (IV-14), formula (V-1) to formula (V-5), and the like. However, in the formula, k represents an integer of 1 to 11. These liquid crystal compounds are preferable because they are easy to synthesize and 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 amount 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 or sulfonium salts, and more specifically, Irgacure 907. , Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369 (all manufactured by Ciba Japan Co., Ltd.), SEIQALL BZ, SEIQALL Z, SEIQALL BEE (all manufactured by Seiko Chemical Co., Ltd.), Kayacure Examples thereof include 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 Co., Ltd.).

The amount of the polymerization initiator used is, for example, 0.1 parts by weight to 30 parts by weight, preferably 0.5 parts by weight to 10 parts by weight, based on 100 parts by weight of the total amount of the liquid crystal compound and the compound (A). It is 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 capable of transmitting light and has an optical function. The optical function means refraction, birefringence and 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 conversely, to convert circularly polarized light or elliptically polarized light into linearly polarized light.

The optical film of the present invention is obtained by polymerizing a compound having a group represented by 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 Formula (B), Ar ^a , D ^a , D ^b , G ^a, and G ^b have the same meanings as described above, and E ¹ and E 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 -, It represents a -CH ₂ -S- or a single bond. R ⁵ and R ⁶ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms. ]

_{^{- (B 1 -A 1) k}} -E 1 -G a -D a -Ar a -D b -G b -E 2 - (A 2 -B 2) l - (C)
[In the formula (C), Ar ^a , D ^a , D ^b , G ^a , G ^b , E ¹ and E ² have the same meanings 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 meanings 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 with a group. The hydrogen atom contained in the alkyl group having 1 to 4 carbon atoms and the alkoxy group having 1 to 4 carbon atoms may be substituted with a fluorine atom. k and l each independently 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) l -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 heterocycle, and a π electron contained in the aromatic ring in the Ar group. The number N _π of 12 is 12 or more.
D ¹ and D ² are each independently *-O-CO- (* represents a position at which Ar is bonded), -C(=S)-O-, -O-C(=S)-, ^{-CR 1 R 2 -, - CR} 1 R 2 -CR 3 R 4 -, - O-CR 1 R 2 -, - CR 1 R 2 -O -, - CR 1 R 2 -O-CR 3 R 4 - ^{, -CR 1 R 2 -O-CO} -, - O-CO-CR 1 R 2 -, - CR 1 R 2 -O-CO-R 3 R 4 -, - CR 1 R 2 -CO-O-CR ^{3 R 4 -, - NR 1} -CR 2 R 3 -, - CR 2 R 3 -NR 1 -, - CO-NR 1 -, or represents a ^-NR 1 -CO-. R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.
G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group. The hydrogen atom contained in the alicyclic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group. 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-, -OC(=S)-, -OC(=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.
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 with a group. The hydrogen atom contained in the alkyl group having 1 to 4 carbon atoms and the alkoxy group having 1 to 4 carbon atoms may be substituted with a fluorine atom.
k and l each independently 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 with an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom, and the methylene group contained in the alkylene group is -O. -Or-CO- may be substituted.
P ¹ and P ² each independently represent a hydrogen atom or a polymerizable group (provided that at least one of P ¹ and P ² represents a polymerizable group). ]

The wavelength dispersion 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, flatter wavelength dispersion characteristics and further reverse wavelength dispersion characteristics are exhibited.

Specifically, with respect to the composition containing the liquid crystal compound and the compound (A), about 2 to 5 kinds of compositions having different content of the structural unit derived from the compound (A) are prepared, and each composition will be described later. Thus, the retardation value of the optical film obtained by producing the optical film of the same thickness is obtained, and from the result, the content of the structural unit derived from the compound (A) and the retardation value of the optical film The correlation may be obtained, and the content of the structural unit derived from the compound (A) necessary for giving the 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 organic solvent, the above-mentioned liquid crystal compound serving as a host, the above-mentioned polymerization initiator, polymerization inhibitor, photosensitizer or leveling agent and other additives are added to the compound (A), and mixed. Prepare the solution. In particular, it is preferable to include an organic solvent that facilitates film formation during film formation, and it is preferable to include a polymerization initiator because it 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 amount of the liquid crystal compound and the compound (A).

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

[Polymerization inhibitor]
A polymerization inhibitor may be used when preparing the optical film of the present invention. Examples of the polymerization inhibitor include hydroquinones having a substituent such as hydroquinone or alkyl ether, catechols having a substituent such as alkyl ether such as butylcatechol, pyrogallols, 2,2,6,6-tetramethyl-1. Examples thereof include radical scavengers such as piperidinyloxy radical, 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 used is, for example, 0.1 parts by weight to 30 parts by weight, preferably 0.5 parts by weight to 10 parts by weight, based on 100 parts by weight of the total amount of the liquid crystal compound and the compound (A). Is. Within the above range, the compound (A) can be polymerized without disturbing the orientation of the liquid crystal compound.

[Photosensitizer]
Further, a photosensitizer may be used when preparing the optical film of the present invention. Examples of the photosensitizer include xanthones such as xanthone and thioxanthone, anthracenes having a substituent such as anthracene and alkyl ether, phenothiazine, and rubrene.

By using the photosensitizer, the sensitivity of the polymerization of the liquid crystal compound or the compound (A) can be increased. 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 amount 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]
Further, a leveling agent may be used when preparing the optical film of the present invention. As the leveling agent, for example, an additive for radiation curable coating (manufactured by BYK Chemie Japan: BYK-352, BYK-353, BYK-361N), a coating additive (manufactured by Toray Dow Corning Co., Ltd.: SH28PA, DC11PA, ST80PA), 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.) and the like. Can be mentioned.

The optical film can be smoothed by using the leveling agent. Further, in the production process of the optical film, it is possible to control the fluidity of the mixed solution containing the compound (A) and 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 amount of the liquid crystal compound and the compound (A). 10 to 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 is an organic solvent capable of dissolving the compound (A) and the liquid crystal compound, and may be any solvent 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. -Based solvents; ketone-based solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone or methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane or heptane; aromatic hydrocarbons such as toluene, xylene or chlorobenzene Solvents, acetonitrile, propylene glycol monomethyl ether, tetrahydrofuran, dimethoxyethane, ethyl lactate, chloroform, phenol and the like can be mentioned. 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, etc. Even if the halogenated hydrocarbon is not used, it can be dissolved and applied.

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

The concentration of 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 necessary for optical compensation of the liquid crystal panel tends to be given. Further, when it is 50% or less, since the viscosity of the mixed solution is low, unevenness in the film thickness of the optical film tends not to occur, which is preferable.

Then, the mixed solution is applied to the supporting base material, dried and polymerized to obtain the target optical film on the supporting base material.

[Unpolymerized film preparation process]
An unpolymerized film is obtained by applying a mixed solution containing the compound (A) on a supporting substrate and drying it. When the unpolymerized film exhibits a liquid crystal phase such as a nematic phase, the resulting optical film has birefringence due to monodomain orientation. Since the unpolymerized film is oriented at a low temperature of about 0 to 120° C., preferably 25 to 80° C., it is possible to use a supporting substrate which is not necessarily sufficient in terms of heat resistance as an orientation film as described above. Further, since it does not crystallize even after being cooled to about 30 to 10° C. after orientation, it is easy to handle.

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

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

Examples of the coating method for the supporting substrate include an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a CAP coating method and a die coating method. Moreover, the method of applying using a coater, such as a dip coater, a bar coater, or a spin coater, can be used.

Examples of the supporting base material include glass, a plastic sheet, a plastic film, or a translucent film. Examples of the translucent film include polyolefin films such as polyethylene, polypropylene, norbornene-based polymers, polyvinyl alcohol films, polyethylene terephthalate films, polymethacrylate ester films, polyacrylate ester films, cellulose ester films, 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 the process of bonding the optical film of the present invention, the process of transporting the product, the process of storing the film, and the like, which require strength of the optical film, the support base material can be easily handled without tearing.

Further, it is preferable that an alignment film is formed on the supporting base material and the mixed solution containing the compound (A) is applied on the alignment film. The alignment film has solvent resistance that does not dissolve in the mixed solution when the mixed solution containing the compound (A) is applied, has heat resistance during removal of the solvent and heat treatment of liquid crystal alignment, and during rubbing It is preferable that peeling due to friction does not occur, and it is preferable that the polymer or the composition containing the polymer is used.

Examples of the polymer include polyamides and gelatins having an amide bond in the molecule, polyimide having an imide bond in the molecule, and polyamic acid which is a hydrolyzate thereof, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, polyoxazole, Polymers such as polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid or polyacrylic acid esters can be mentioned. These polymers may be used alone, two or more kinds may be mixed, or a copolymer may be used. These polymers can be easily obtained by polycondensation by dehydration, deamine, etc., chain polymerization such as radical polymerization, anionic polymerization, cationic polymerization, coordination polymerization, ring-opening polymerization and the like.

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

A commercially available alignment film material may be used as it is for forming the alignment film. Examples of commercially available alignment film materials include Sanever (registered trademark, manufactured by Nissan Chemical Industries, Ltd.) and Optomer (registered trademark, manufactured by JSR Corporation).

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

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

The thickness of the alignment film thus obtained is, for example, 10 nm to 10000 nm, 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 orientation film.

Further, these alignment films can be subjected to rubbing or polarized UV irradiation as required. By these, the compound (A) and 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 and a rotating rubbing roll is placed on a stage and brought into contact with the alignment film being transported can be used.

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

The solvent may be dried as the polymerization proceeds, but it is preferable to dry most of the solvent before the polymerization from the viewpoint of film forming property.

Examples of the method for drying the solvent include natural drying, ventilation drying, reduced pressure drying and the like. The specific heating temperature is preferably 10 to 120°C, more preferably 25 to 80°C. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes. If the heating temperature and the heating time are within the above ranges, a supporting base material that does not necessarily have sufficient heat resistance can be used as the supporting base material.

[Unpolymerized film polymerization process]
In the unpolymerized film polymerization step, the unpolymerized film obtained in the unpolymerized film preparation step is polymerized and cured. This gives a film in which the orientation of the compound (A) is fixed, that is, a polymerized film. Therefore, it is possible to manufacture 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.

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. By photopolymerization, an unpolymerized film can be polymerized at a low temperature, so that the range of heat resistance of the supporting substrate can be widened. In addition, the manufacturing becomes easy industrially. Photopolymerization is also preferable from the viewpoint of film-forming property. Photopolymerization is performed by irradiating the unpolymerized film with visible light, ultraviolet light, or laser light. From the viewpoint of handleability, the irradiation of light, which is particularly preferably ultraviolet light, may be carried out while heating to a temperature at which the compound (A) takes a liquid crystal phase. At this time, the polymer 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, it is easy to manufacture the optical film.

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

The method for producing an optical film of the present invention may include a step of peeling the supporting base material after the above step. With such a structure, the obtained laminated body becomes a film including an alignment film and an optical film. Further, in addition to the step of peeling the supporting base material, a step of peeling the alignment film may be further included. With such a configuration, an optical film can be obtained.

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

When the alignment film is used to have birefringence, the retardation value is, for example, about 50 to 500 nm, preferably 100 to 300 nm.

Such a thin film capable of uniform polarization conversion in a wider wavelength range can be used as an optical compensation film in all 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 a 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 Re(550) of the obtained optical film may be adjusted to a film thickness of 113 to 163 nm, preferably 135 to 140 nm, and particularly preferably about 137.5 nm. In this case, the film thickness may be adjusted so that the Re(550) of the obtained optical film is 250 to 300 nm, preferably 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 VA (Vertical Alignment) mode, the content of the structural unit derived from the compound (A) is appropriately selected. The film thickness may be adjusted so that Re(550) is preferably about 40 to 100 nm, more preferably about 60 to 80 nm.

The wavelength dispersion characteristic of the optical film can be shifted to a value close to 1 by adding a small amount of the compound (A), and the 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 expanding film or an optical compensation film for viewing angle compensation of a transmissive liquid crystal display. can do. Although the optical film of the present invention exhibits excellent optical characteristics even with one sheet, a plurality of sheets 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 attached to a polarizing film, and a broadband circular polarizing plate in which the optical film of the present invention is further attached as a broadband λ/4 plate to the elliptically polarizing plate. To be

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

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

An example of a method of manufacturing the color filter 1 having the above structure 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 so as to obtain a desired retardation value. The film 2 is formed.

On the other hand, by using the color filter 1, it becomes possible to manufacture a thin liquid crystal display device in which the number of optical films 2 is reduced. As an example thereof, there is a thin liquid crystal display device formed on the liquid crystal layer side of at least one of the substrates in a liquid crystal display element formed by sandwiching a liquid crystal layer 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 the liquid crystal display device 5 shown in FIG. 2, a substrate 7 such as a glass substrate facing a backlight 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 on the top of the alignment film 3'. Further, the counter electrode 8 is formed on the optical film 2 ′, and the 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 with an adhesive, and a thin film transistor (TFT) and an insulating layer 12 for actively driving a liquid crystal layer are formed on the substrate 11. Further, a transparent electrode 13 and/or a reflective electrode 13' made of Ag, Al, or ITO (Indium Tin Oxide) is formed on the TFT. The configuration of the liquid crystal display device 5 shown in FIG. 2 can reduce the number of optical films as compared with the conventional liquid crystal display device, and enables the manufacture of a thinner liquid crystal display device.

An example of a method of 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 below. A gate electrode made of Mo, MoW, etc., a gate insulating film, and amorphous silicon are deposited and patterned on the borosilicate glass on the substrate on the backlight side, and the amorphous silicon is crystallized by annealing with an excimer laser. It is possible to form a semiconductor thin film and then dope P, B and the like into the regions on both sides of the gate electrode to form n-channel and p-channel TFTs. Further, a substrate on the backlight side can be obtained by forming an insulating film made of SiO ₂ . Further, by sputtering ITO on the backlight side substrate 11, the transparent electrode 13 for the total transmission type display device can be laminated on the backlight side substrate. Similarly, by using Ag, Al or the like instead of ITO, the reflection electrode 13' for the total reflection type display device can be obtained. Further, an electrode on the backlight side for a semi-transmissive liquid crystal display device can be obtained by appropriately combining a reflective electrode and a transparent electrode.

On the other hand, the color filter layer 4 ′ is formed on the opposing substrate 7. A full-color liquid crystal display device can also be obtained by using R, G, and B color filters together. Next, an alignment polymer is applied on the color filter layer 4'and rubbed to form an alignment film 3'. A composition containing the compound (A) according to the present invention is applied onto this alignment film 3', and while being heated to a temperature range where a liquid crystal phase is obtained, polymerization is performed by ultraviolet irradiation to form an optical film 2'.
After forming the optical film, the counter electrode 8 can be formed by sputtering ITO. Further, an alignment film is formed on the counter electrode, a liquid crystal phase 9 is formed, and finally, the liquid crystal display device 5 is assembled together with the backlight side substrate, whereby the liquid crystal display device 5 can be prepared. 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 should be changed. As a result, a desired wavelength dispersion characteristic can be obtained, and the retardation value can be controlled from the film thickness, so that lamination of optical films can be omitted.

Further, the optical film of the present invention can be used for a retardation plate of a reflection type liquid crystal display and an organic EL display, and an FPD equipped with the retardation plate and the optical film. The FPD is not particularly limited, and examples thereof include a liquid crystal display device (LCD) and an organic EL.

As described above, the film according to the present invention can be used in a wide range of applications. For example, of these, a polarizing plate formed by laminating an optical film and a polarizing film according to the present invention and an FPD including the polarizing plate will be described below. The polarizing plate according to the present invention is a film having a polarizing function, that is, one surface of a polarizing film. Alternatively, it can be obtained by directly laminating the optical film 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 the adhesive.

3A to 3E are schematic views showing the polarizing plate 1 according to the present invention.
In the polarizing plate 30a shown in FIG. 3A, the laminated body 14 and the polarizing film 15 are directly attached to each other, and the laminated body 14 is composed of a supporting base material 16, an alignment film 17, and an optical film 18.
The polarizing plate 30a includes a supporting base material 16, an alignment film 17, an optical film 18, and a polarizing film 15 which are laminated in this order.

In the polarizing plate 30b shown in FIG. 3B, the laminated body 14 and the polarizing film 15 are bonded together via the adhesive layer 19.

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

In the polarizing plate 30d shown in FIG. 3D, the laminated body 14 and the laminated body 14' are bonded together 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 laminated body 14 and the laminated body 14' are bonded together via the adhesive layer 19, and the laminated body 14' and the polarizing film 15 are further arranged via the adhesive layer 19'. The following shows a configuration in which they are pasted together.

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

The polarizing plate of the present invention may have a plurality of laminated bodies, and the plurality of laminated bodies may all be 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 to a polyvinyl alcohol-based film and stretching the film, or a polyvinyl alcohol-based film by stretching iodine or a dichroic dye. Examples include adsorbed films.

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

The flat panel display device of the present invention is provided with the optical film of the present invention, for example, a liquid crystal display device provided with a bonded product obtained by laminating the polarizing film of the present invention and a liquid crystal panel, and the polarizing film of the present invention. An organic EL display device including an organic EL panel in which a light emitting layer is attached can be given.

As an embodiment 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 device]
FIG. 4 is a schematic diagram 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.

Examples of the liquid crystal display device include a liquid crystal display device including a bonded product 21 of the liquid crystal panel 20 and the 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 the adhesive layer 22. By applying a voltage to the liquid crystal panel 20 using electrodes (not shown), the liquid crystal molecules are driven and the optical shutter effect is produced.

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

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

In the above 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. Unless otherwise specified, "%" and "parts" in the examples are% by weight and parts by weight.

The compound was synthesized by the following scheme. The starting material monotetrahydropyranyl-protected hydroquinone (a) was synthesized by the method described in the patent document (JP 2004-262884 A).

(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 taken and dissolved/dispersed in dimethylacetamide. The mixture was stirred under a nitrogen atmosphere at 90°C and then at 100°C. Thereafter, the mixture was cooled to room temperature, pure water and methyl isobutyl ketone were added, 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 generated 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 the compound (b), 3,5-ditert-butyl-4-hydroxytoluene (hereinafter referred to as BHT) 1.40 g (6.42 mmol), N,N-dimethylaniline 116.7 g (963 mmol), 1 , 3-dimethyl-2-imidazolidinone (1.00 g) and chloroform were mixed. Acryloyl chloride (58.1 g, 642 mmol) was added dropwise to the resulting mixed solution under a nitrogen atmosphere and ice cooling, and pure water was added and the mixture was stirred, and then the separated organic layer was recovered. The organic layer was washed with aqueous hydrochloric acid, saturated aqueous sodium carbonate solution and pure water. 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 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 mixed liquid. Further, hydrochloric acid water and concentrated hydrochloric acid water 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, and 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))
24.68 g (118 mmol) of transcyclohexanedicarboxylic acid and toluene were mixed, 74.91 g (590 mmol) of oxalyl dichloride and 0.5 mL of dimethylformamide were added to the resulting mixed solution, and the mixture was stirred under a nitrogen atmosphere. After reducing the pressure, chloroform was added to obtain solution 1.
On the other hand, 12 g (45.4 mmol) of compound (d) was dissolved in chloroform. A chloroform solution of the compound (d) and 12.6 g (159 mmol) of pyridine were mixed to obtain a solution 2. Solution 2 was added dropwise to solution 1 under ice cooling. The resulting solution was stirred under a nitrogen atmosphere, filtered, and concentrated under reduced pressure. The obtained solution was dropped into a mixed solvent of water/methanol (1/1 in volume ratio), and the generated precipitate was crushed, washed with pure water, filtered, and vacuum dried. After the obtained powder was pulverized again, n-heptane was added and stirred, and then toluene was further added. The insoluble component was removed by filtration, the obtained filtrate was concentrated under reduced pressure, and n-heptane was added. The generated precipitate was vacuum dried to obtain 7.8 g of compound (e). The yield was 40% based on the compound (d).

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

56.8 g (215 mmol) of the 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 obtained mixed liquid was ice-cooled and stirred under a nitrogen atmosphere, and a solution of 48.79 g (237 mol) of dicyclohexylcarbodiimide and 50 mL of chloroform was added dropwise. After completion of dropping, 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-hydrochloric acid aqueous solution. The separated organic layer was collected, the insoluble component was removed by filtration, anhydrous sodium sulfate was added, the solvent was removed after filtration, and the solid obtained was vacuum dried 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 mixed liquid was heated to 50° C. under a nitrogen atmosphere and stirred. The mixture was allowed to cool to room temperature, THF was removed under reduced pressure, and 200 mL of heptane was added to the residue. The deposited precipitate was collected by filtration, washed with pure water, and vacuum dried. The powder obtained was dissolved in chloroform, passed through silica gel and then filtered. The filtrate was recovered, dissolved in 400 mL of chloroform, the resulting solution was concentrated, and toluene was added. The solution was concentrated under reduced pressure, heptane was added for crystallization, and the obtained powder was collected by filtration and vacuum dried to obtain 64.1 g of compound (e). The yield was 76% based on the compound (d) in two steps.

(Production Example of Compound (ii-a))
Compound (ii-a) was synthesized by the following scheme. The raw material 4,7-dimethoxy-2-phenylbenzothiazole is described in J. Chem. Soc. , Perkin Trans. It was synthesized by the method described in pp. 205-210 (2000), Vol.

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 obtained mixed liquid was heated to 220° C. and stirred. .. After cooling the mixed solution, water was added, the obtained precipitate was filtered off, washed with water and hexane, and 4,7-dihydroxy-2-phenylbenzothiazole (compound (ii-a)) was used 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))
The compound (vi-a) was synthesized by the following scheme.

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

[Synthesis Example of Compound (vi-e)]
90.0 g (268.0 mmol) of compound (vi-d), 2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulfide (Lawson's reagent) 65 0.0 g (160.0 mmol) and toluene 3132 g were mixed, and the obtained mixed liquid 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 mixed liquid 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 to give 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 compound (vi-f) and 56.0 g (5 times mass) of pyridinium chloride were mixed, heated to 180° C. and stirred. After cooling the obtained mixed liquid, water was added and the obtained precipitate was washed with water, hexane and chloroform to obtain 7.7 g of a solid containing the compound (vi-a) as a main component. The yield was 74% based on the compound (vi-f).

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

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

(Synthesis example of compound (vd))
A solid containing Compound (vd) as a main component was obtained in the same manner as in the Synthesis Example of Compound (vi-f) 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 compound (vd) and 441 g of dehydrated toluene were mixed and stirred. The obtained mixed liquid 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 ice-cooled, 1588 g of water was added, the obtained precipitate was filtered off and washed with water and chloroform to obtain 16.5 g of a solid containing the compound (va) as a main component. It was The yield was 86% based on the compound (vd).

(Production Example of Compound (ix-a))
The compound (ix-a) was synthesized by the following scheme.

[Synthesis Example of Compound (ix-b)]
2,5-Dimethoxyaniline 43.0 g (281 mmol), triethylamine 59.7 g (590 mmol) and dehydrated chloroform 499.7 g were mixed and stirred. Further, 50.0 g (281 mmol) of isonicotinoyl chloride hydrochloride was added to the obtained mixed liquid, the temperature was raised to 60° C., and the mixture was stirred. After cooling the obtained mixed liquid, it was poured into water and the separated organic layer was collected. Chloroform was added to the remaining aqueous layer and washed to collect the organic layer. The two organic layers were combined and washed with water. The obtained mixed organic layer was concentrated under reduced pressure to obtain 71.5 g of a solid containing the compound (ix-b) as a main component. 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), 2,4-bis(4-methoxyphenyl)-1,3-dithia 2,4-diphosphetan-2,4-disulfide (Lawson's reagent) 65.8 g (162.0 mmol) and 2436 g of toluene were mixed, heated to 80° C. and stirred. The obtained mixed liquid was cooled and then concentrated to obtain a solid mainly containing the compound (ix-c). The compound (ix-c) was used for the next step as it was 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 the mixture was stirred under ice cooling. Subsequently, an aqueous solution containing 184.3 g (560 mmol) of potassium ferricyanide was added to the obtained mixed solution under ice cooling and stirred. The precipitated solid was separated by filtration and washed with cold water and hexane to obtain 25.9 g of a solid containing the compound (ix-d) as a main component. The yield of the two steps combined with the previous step was 35% based on the compound (ix-c).

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

(Production Example of Compound (iv-a))
The compound (iv-a) was synthesized by the following scheme.

10.0 g (31 mmol) of 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 mixed liquid, water was added, and the obtained precipitate was taken out and washed thoroughly with water to obtain 6.6 g of a solid containing the compound (iv-a) as a main component. The yield was 79% based on the compound (vi-a).

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

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

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

<Synthesis Example of Compound (v-1) via 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 mixed solution under ice cooling. The obtained reaction solution was stirred and filtered, and then the separated organic layer was recovered. The organic layer was dried and then concentrated under reduced pressure. Ethyl acetate was added to the residue to dissolve it, the mixture was concentrated under reduced pressure, 200 mL of methanol was added, and reprecipitation was performed under ice cooling. The precipitate was collected by filtration, further washed with methanol and filtered, and the obtained solid was vacuum dried to obtain 10.3 g of compound (v-1). The yield was 94% based on the compound (va).

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

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

<Synthesis Example of Compound (ix-1) via 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 mixed solution under ice cooling. The obtained reaction solution was stirred and filtered, and then the separated organic layer was recovered. The organic layer was dried and then concentrated under reduced pressure. Ethyl acetate was added to the residue to dissolve it, the mixture was concentrated under reduced pressure, 200 mL of methanol was added, and reprecipitation was performed under ice cooling. The precipitate was collected by filtration, washed with n-heptane and filtered, and the obtained solid was vacuum dried to obtain 4.4 g of compound (ix-1). The yield was 43% based on the compound (ix-1).

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

<Synthesis Example of Compound (iv-1) via First Route>
Compound (iv-a) was used as a starting material in the same manner as in the above-mentioned synthesis example of compound (ii-1) by the first route and synthesis example of compound (ix-1) by the first route. Then, the 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. 3.97 (t, 4H), 4.15 to 4.18 (t, 4H), 5.80 to 5.84 (dd, 2H), 6.07 to 6.18 (m, 2H), 6. 37 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 observed by texture observation with a polarizing microscope. The compound (iv-1) exhibited a smectic phase from 142° C. to 159° C. at the time of temperature increase, a nematic phase from 159° C. to 190° C. or higher, and a nematic phase at the temperature decrease to 136° C. to be crystallized. ..

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

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

(Synthesis example of compound (ii-c))
11.4 g (16 mmol) of compound (ii-b), 1.14 g of 10% palladium-carbon (containing 55% water), 0.1 mL of acetic acid and 200 mL of tetrahydrofuran were mixed. The resulting mixed solution was deoxygenated with nitrogen gas, the resulting reaction solution was depressurized, and then stirred under a hydrogen atmosphere. The reaction solution was filtered. The filtrate was collected, concentrated under reduced pressure, n-heptane was added to the residue, and the obtained solid was collected by filtration and dried in vacuum 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 compound (ii-c), 4.65 g (18 mmol) of compound (d), 0.22 g (2 mmol) of dimethylaminopyridine and 30 mL of chloroform were mixed. 20 mL of a chloroform solution of 4.36 g (21 mmol) of dicyclohexylcarbodiimide was added dropwise to the obtained mixed solution under ice cooling. The obtained reaction solution was stirred and filtered, and then the separated organic layer was recovered. The organic layer was dried and then concentrated under reduced pressure. Ethyl acetate was added to the residue to dissolve it, the mixture was concentrated under reduced pressure, methanol was added, and the mixture was reprecipitated under ice cooling. The precipitate was collected by filtration and vacuum dried to obtain 4.80 g of compound (ii-1). The yield was 58% based on the compound (ii-c).

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

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

(Production Example of Compound (xa))
The compound (xa) was synthesized by the following scheme.

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

(Production Example of Compound (v'-a))
The compound (v'-a) was synthesized by 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 were added. Mix and stir well at room temperature. The pressure of the obtained mixed liquid was reduced, 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. Then, it stirred at room temperature. The reaction solution was poured into 973 g of water, the layers were separated, and the organic layer was taken. Further, this organic layer was washed with 973 g of 1N hydrochloric acid. The solvent of the obtained organic layer was distilled off under reduced pressure to obtain 107.8 g of a solid containing the compound (v′-b) as a main component. The yield was 44% based on 2,5-dimethoxyaniline.

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

(Production Example of Compound (xa))
The compound (xa) was synthesized by the following scheme.

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

(Production Example of Compound (xi-a))
The compound (xi-a) was synthesized by 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 mixed solution. It was added dropwise under ice cooling. After that, the temperature was raised to room temperature, the mixture was stirred for 1 hour, and then the mixed solution was poured into water. The separated organic layer was washed with water and hydrochloric acid. The solvent was distilled off under reduced pressure from the obtained organic layer, and the obtained solid was washed with hexane to obtain 82.1 g of a solid containing the compound (xi-b) as a main component. The yield was 91% based on 2,5-dimethoxyaniline.

[Synthesis Example of Compound (xi-c)]
81 g (308.0 mmol) of compound (xi-b), 64.7 g of 2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetan-2,4-disulfide (Lawson's reagent) ( 160.0 mmol) and 500 g of toluene were mixed, the temperature was raised to 80° C., and the mixture was stirred. The obtained mixed liquid was cooled and then concentrated to obtain a red viscous liquid containing a decomposition product of Lawesson's reagent and the 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 the mixture was stirred under ice cooling. Subsequently, an aqueous solution containing 257.8 g (783 mmol) of potassium ferricyanide was added to the obtained mixed solution under ice cooling and stirred, and the precipitated solid was washed with cold water and hexane and recrystallized by adding ethanol. Thus, 49.1 g of compound (xi-d) was obtained. The yield was 58% based on the compound (xi-b).

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

(Production Example of Compound (xvi-a))
The compound (xvi-a) was synthesized by the following scheme.

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

(Production Example of Compound (xvii-a))
The compound (xvii-a) was synthesized by the following scheme.

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

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

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

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

(Production Example of Compound (xix-a))
The compound (xix-a) was synthesized by the following scheme.

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

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

[Synthesis Example of Compound (xix-d)]
A mixture containing the compound (xix-c) obtained in the previous section as a main component, 38.8 g (971 mmol) of sodium hydroxide and 700 g of water were mixed and stirred under ice cooling. An aqueous solution containing 145.3 g (441 mmol) of potassium ferricyanide was added to the obtained mixed solution under ice-cooling and stirred, and the precipitated solid was washed with cold water and hexane, washed with methanol, and recrystallized from ethanol. Thus, 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)]
Compound (xix-d) 9.00 g (34.4 mmol) and pyridinium chloride 45.0 g (5 times mass) were mixed, heated to 180° C. and stirred. After cooling the obtained mixed liquid, water was added, and the obtained precipitate was washed with water, hexane, and toluene to obtain 7.68 g of a solid containing the compound (xix-a) as a main component. The yield was 96% based on the compound (xix-d).

(Synthesis example of compound (xx-a))
After benzothiazole was synthesized by a method similar to that for compound (xx-a), compound (xx-a) was synthesized by demethylation reaction with pyridinium chloride. A solid containing the compound (xx-a) as a main component was obtained by washing with heptane and washing with toluene. The reaction scheme is shown below.

(Production Example of Compound (xxi-a))
The compound (xxi-a) was synthesized by 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 were mixed and stirred, and 57.1 g (387 mmol) of 3-thiazolecarboxylic acid chloride was added to an ice-cooled mixture. It was added dropwise under cold conditions. Then, 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, the obtained solid was washed with hexane, and crystallized with heptane-ethyl acetate 3/1 (v/v). Further, by washing with heptane-ethyl acetate 4/1 (v/v), 77.2 g of a solid containing the compound (xxi-b) as a main component was obtained. The yield was 75% based on 2,5-dimethoxyaniline.

[Synthesis Example of Compound (xxi-c)]
77 g (291.0 mmol) of the compound (xxi-b), 2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetan-2,4-disulfide (Lawson's reagent) 61.3 g (151.0 mmol) and 500 g of toluene were mixed, the temperature was raised to 80° C., and the mixture was stirred. After cooling, the mixture was concentrated to obtain an orange viscous liquid containing a decomposition product of Lawesson's reagent and a 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 mixed solution under ice cooling and stirred, and the precipitated solid was washed with cold water and hexane, and washed with hot ethanol to give the compound (xxi- d) 45.9 g was obtained. The yield was 57% based on the compound (xxb-d).

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

(Production Example of Compound (xxiii-a))
The compound (xxiii-a) was synthesized by the following scheme.

[Synthesis Example of Compound (xxiii-b)]
2,5-Dimethoxyaniline 38.3 g (250 mmol), triethylamine 50.5 g (500 mmol) and dehydrated chloroform 200 g were mixed and stirred, and further 4-methylsulfonylbenzoic acid chloride 54.6 g (250 mmol) was cooled with ice. added. Then, 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, the obtained solid was washed with hexane, and crystallized with heptane-ethyl acetate 3/1 (v/v). Further, by washing with heptane-ethyl acetate 3/1 (v/v), 52.2 g of the compound (xxiii-b) was obtained as white crystals. The yield was 62% based on 2,5-dimethoxyaniline.

[Synthesis Example of Compound (xxiii-c)]
54.5 g (155.0 mmol) of compound (xxiii-b), 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 mixed liquid was cooled and then 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 previous section as a main component, 37.2 g (930 mmol) of sodium hydroxide and 380 g of water were mixed and stirred under ice cooling. An aqueous solution containing 163.5 g (497 mmol) of potassium ferricyanide was added to the obtained mixed solution under ice cooling and stirred, and the precipitated solid was washed with cold water and hexane, washed with hot ethanol, and recrystallized from toluene. Thus, 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 compound (xxiii-d) and 100.0 g (10 times mass) of pyridinium chloride were mixed, heated to 180° C. and stirred for 2 hours. The obtained mixed liquid was cooled, 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 a 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 converted to compound (xxiv-a) according to the following reaction scheme by the same method except that 4-fluorobenzoyl chloride was used instead of 4-bromobenzoyl chloride as a starting material. Synthesized.

(Synthesis example of compound (xxv-a))
In the synthesis example of compound (vi-a), 4-trifluoromethylbenzoyl chloride was used in place of 4-bromobenzoyl chloride as a starting material, and the same procedure was followed according to the following reaction scheme, according to the following reaction scheme. ) Was synthesized.

<Synthesis Example of Compound (v′-1) via First Route>
A compound (v′-1) was obtained in the same manner as in the synthesis example of the compound (v-1) except that the starting compound (va) was changed to the 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 observed by texture observation with a polarizing microscope. The compound (v′-1) exhibits a smectic phase from 127° C. to 154° C. during heating, exhibits a nematic phase from 154° C. to 217° C., and exhibits a nematic phase from 217° C. to 113° C. during cooling. did.

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

<Synthesis Example of First Route of Compound (x-1)>
A compound (x-1) was obtained in the same manner as in the synthesis example of the compound (v-1) except that the starting compound (va) was changed to the 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 to 6.44 (m, 2H), 6.86 to 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 observed by texture observation with a polarizing microscope. The compound (x-1) exhibits a smectic phase from 101° C. to 106° C. at a temperature increase, a nematic phase from 106° C. to 180° C. or higher, and a nematic phase up to 81° C. at a temperature decrease to be crystallized. ..

<Synthesis Example of Compound (xi-1) via First Route>
Compound (xi-1) was obtained in the same manner as in the synthesis example of compound (v-1) except that the starting compound (va) was changed to compound (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 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), 5.81 to 5.85 (dd, 2H), 6.08 to 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 measured by texture observation with a polarizing microscope. The compound (xi-1) exhibited a smectic phase from 111° C. to 125° C. during heating, a nematic phase from 125° C. to 242° C., and a nematic phase from 242° C. to 82° C. during cooling. ..

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

¹ H-NMR of Compound _{(xvi-1) (CDCl 3} ): δ (ppm) 1.45~1.86 (m, 24H), 2.35~2.83 (m, 18H), 3.92~ 3.97 (t, 4H), 4.15 to 4.19 (t, 4H), 5.80 to 5.84 (dd, 2H), 6.07 to 6.18 (m, 2H), 6. 37 to 6.44 (m, 2H), 6.86 to 7.01 (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 observed by texture observation with 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 heating, and was thermally polymerized.

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

¹ H-NMR (CDCl ₃ ): δ (ppm) 1.45 to 1.86 (m, 24H), 2.35 to 2.83 (m, 12H), 3.93 to of compound (xvii-1). 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 measured by texture observation with a polarizing microscope. The compound (xvii-1) exhibited a smectic phase from 129° C. to 148° C. during heating, a nematic phase from 148° C. to 186° C., and a nematic phase from 186° C. to 105° C. during cooling. ..

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

¹ H-NMR (CDCl ₃ ): δ (ppm) 1.45 to 1.86 (m, 24H) of compound (xviii-1), 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 to 6.44 (m, 2H), 6.86 to 7.00 (m, 8H), 7.32 to 7.35 (d, 2H)

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

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

¹ H-NMR (CDCl ₃ ): δ (ppm) 1.45 to 1.82 (m, 24H), 2.34 to 2.83 (m, 12H), 3.92 to of Compound (xix-1). 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), 6.59 (br, m, 1H), 6.86 to 7.00 (m, 8H), 7.20 (2s, 3H), 7.59 (s, 1H)

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

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

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

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

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

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

The phase transition temperature of the obtained compound (xxi-1) was observed by texture observation with a polarizing microscope. The 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.

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

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

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

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

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

The phase transition temperature of the compound (xxiv-1) was measured by texture observation with a polarizing microscope. As the temperature was raised, it changed to a nematic phase near 95°C. When the temperature was further increased, it changed to an isotropic phase at around 212°C. When the temperature was lowered from here, it 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) exhibits a nematic phase from 95° C. to 212° C. at the time of temperature increase, and exhibits a nematic phase from 212° C. to 86° C. at the time of temperature decrease.

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

¹ H-NMR of Compound _{(xxv-1) (CDCl 3} ): 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), 8.13-8.17 (d, 2H)

The phase transition temperature of the compound (xxv-1) was observed by texture observation with a polarizing microscope. As the temperature was raised, it changed to a nematic phase at around 135°C. When the temperature was further increased, it changed to an isotropic phase at around 193°C. When the temperature was lowered from here, it 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) exhibits a nematic phase from 135° C. to 193° C. at the time of temperature increase, and exhibits a nematic phase from 193° C. to 114° C. at the time of temperature decrease.

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

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

(Synthesis example of compound (xxvi-b))
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 mixed liquid and stirred, and the organic layer was taken out. The obtained organic layer was concentrated under reduced pressure, the solvent was removed, and the residue was vacuum dried to obtain 8.5 g (42.6 mmol) of compound (xxvi-b). The yield was 68% based on 2,3-dicyanohydroquinone.

(Synthesis example of compound (xxvi-a))
2.5 g (12.6 mmol) of 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 mixed liquid was cooled to room temperature, 3.1 g (15.1 mmol) of N,N′-dicyclohexylcarbodiimide was dissolved in 9.4 g of tetrahydrofuran, and the mixture was added dropwise at room temperature and then heated at 60° C. with stirring. The obtained mixed solution was filtered, the obtained organic layer was concentrated under reduced pressure, the solvent was removed, and then methanol was added and stirred. The generated precipitate was filtered and then vacuum dried to obtain 0.4 g (1.6 mmol) of 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 compound (xxvi-a), 0.03 (0.3 mmol) of 4-dimethylaminopyridine, 1.2 g (2.8 mmol) of compound (e), and 24 g of chloroform were mixed. Subsequently, a solution prepared by dissolving 0.9 g (4.2 mmol) of N,N′-dicyclohexylcarbodiimide in 4.7 g of chloroform was added dropwise to the obtained mixed solution at room temperature and stirred. After filtering the obtained mixed liquid, 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 formed precipitate was filtered and then vacuum dried to obtain 0.7 g of the compound (xxvi-1).
The yield was 54% based on xxvi-a.

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

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

(Synthesis example of compound (xxvii-a))
2.5 g (12.6 mmol) of 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 mixed solution was cooled to room temperature, and a solution prepared by dissolving 3.1 g (15.1 mmol) of N,N′-dicyclohexylcarbodiimide in 9.4 g of tetrahydrofuran was added dropwise at room temperature and then stirred. The obtained mixed solution was filtered, the obtained organic layer was concentrated under reduced pressure, the solvent was removed, and then methanol was added and stirred. The generated precipitate was filtered and then vacuum dried to obtain 0.4 g (1.5 mmol) of 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 prepared by dissolving 0.9 g (4.2 mmol) of N,N′-dicyclohexylcarbodiimide in 4.6 g of chloroform was added dropwise to the obtained mixed solution at room temperature and stirred. The obtained mixed liquid was filtered, 12 g of 2N hydrochloric acid was added, and the mixture was 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 generated precipitate was filtered and then vacuum dried to obtain 0.3 g of the compound (xxvii-1). The yield was 25% based on xxvii-a.

¹ H-NMR (CDCl ₃ ): δ (ppm) of the compound (xxvii-1): 6.6 (m, 14H), 2.72 (m, 4H), 2.57 (m, 2H), 3.94. (T, 4H), 4.17 (t, 4H), 5.80 (d, 2H), 6.14 (m, 2H), 6.43 (d, 2H), 6.91 (m, 8H). , 7.26 (d, 1H), 7.49 (s, 2H), 7.80 (d, 1H)

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

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

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

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

<Synthesis Example of Compound (xxviii-1) via First Route>
Compound (e) 12.5 g (30 mmol), 4-dimethylaminopyridine 0.4 (3 mmol), 1,5-dihydroxyanthraquinone 2.9 g (12 mmol), and chloroform 100 g were mixed. A liquid prepared by dissolving 9.3 g (45 mmol) of N,N′-dicyclohexylcarbodiimide in 25 g of chloroform was added dropwise to the obtained mixed liquid at room temperature and stirred. 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 obtain an organic layer. After distilling off the solvent of this organic layer, methanol was added and the solid matter was taken out by filtration. The obtained solid was dried to obtain 10.5 g of compound (xxviii-1). The yield was 84% based on 1,5-dihydroxyanthraquinone.

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

<Synthesis Example of Compound (xxix-1) via First Route>
Compound (e) 12.5 g (30 mmol), 4-dimethylaminopyridine 0.4 (3 mmol), 1,2-dihydroxyanthraquinone 2.9 g (12 mmol), and chloroform 100 g were mixed. A solution prepared by dissolving 9.3 g (45 mmol) of N,N'-dicyclohexylcarbodiimide in 25 g of chloroform was added dropwise to the obtained mixed solution at room temperature and stirred. Thereafter, 124 g of 1N hydrochloric acid was added, and the mixture was stirred, filtered to remove solids, and the obtained liquid was separated to obtain an organic layer. After distilling off the solvent of this organic layer, methanol was added and the solid matter was taken out by filtration. The obtained solid was dried to obtain 10.3 g of compound (xxix-1). The yield was 82% based on 1,2-dihydroxyanthraquinone. When this compound was heated and the phase transition temperature was confirmed, no liquid crystal phase was observed and the compound melted at 105°C.

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

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

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

[Synthesis Example of Compound (xxxii-c)]
30 g (106.0 mmol) of 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 mixed liquid was cooled and then concentrated to obtain a red viscous solid containing a decomposition product of Lawesson's reagent and the compound (xxxii-c) as main components.

[Synthesis Example of Compound (xxxii-d)]
A mixture containing the compound (xxxii-c) obtained in the previous section as a main component, 25.4 g (636 mmol) of sodium hydroxide and 750 g of water were mixed and stirred under ice cooling. Subsequently, an aqueous solution containing 95.1 g (289 mmol) of potassium ferricyanide was added to the obtained mixed solution under ice cooling, and the solid precipitated was washed with cold water and hexane, and suspended with hot methanol. This gave 17.7 g of the compound (xxxii-d) 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 compound (xxxii-d) and 106.0 g (10 times mass) of pyridinium chloride were mixed, heated to 180° C. and stirred for 2 hours. The obtained mixed liquid was cooled, water was added, and the obtained precipitate was washed with water and hexane to obtain 10.8 g of a solid containing the compound (xxxii-a) as a main component. The yield was 110% based on the compound (xxxii-d).

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

¹ H-NMR (CDCl ₃ ): δ (ppm) 1.44 to 1.83 (m, 24H), 2.34 to 2.84 (m, 12H), 3.92 to the compound (xxxii-1). 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 observed by texture observation with a polarizing microscope. The compound (xxxii-1) exhibited a nematic phase from 125° C. to 180° C. or higher at the time of temperature increase, and a nematic phase up to 55° C. at the time of temperature decrease, and was crystallized.

Further, similarly, by changing the alkyl chain length of the compound (e), the compounds (v-2), (v-3) and (v-4) can be synthesized by the same method as in the first route. The synthesis examples of each compound are shown below.

The compound (b') could be synthesized in exactly the same manner as the compound (b) which differs only in the alkyl chain length. Similarly, compound (d') and compound (e') were synthesizable by the same method as compound (d) and 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 under a nitrogen atmosphere at 90°C and then 110°C. Thereafter, the mixture was cooled to room temperature, the mixed solution was poured into 1680 g of pure water, and the deposited precipitate was collected by filtration. Next, the precipitate was washed with 400 mL of 6N aqueous sodium hydroxide solution, washed with heptane, and dried in 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 the compound (b″), 1.40 g (6.42 mmol) of 3,5-ditertiarybutyl-4-hydroxytoluene, 61.2 g (505 mmol) of N,N-dimethylaniline, 1,3- Dimethyl-2-imidazolidinone (1.00 g) and chloroform were mixed. 29.8 g (329 mmol) of acryloyl chloride was added dropwise to the obtained mixed solution 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, 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 for crystallization, and this was recovered. The resulting white powder was washed with water-methanol 2/1 (v/v) by suspension, further washed with heptane, and vacuum dried 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 mixed liquid was ice-cooled and stirred under a nitrogen atmosphere, and a 50 mL chloroform solution of 27.3 g (132 mmol) of dicyclohexylcarbodiimide was added dropwise. After completion of dropping, 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-hydrochloric acid aqueous solution. The organic layer was collected, 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, pure water 2.34 g (130 mmol), 3,5-ditertiarybutyl-4-hydroxytoluene 1.40 g (6.42 mmol), paratoluenesulfonic acid monohydrate 3.95 g( 20.8 mmol) and 200 mL of THF were mixed. The obtained mixed liquid was heated to 70° C. under a nitrogen atmosphere and then stirred for 3 hours. After allowing to cool to room temperature, the precipitate was removed by filtration, and the solution was concentrated under reduced pressure at room temperature. 200 mL of heptane was added to the residue. The deposited precipitate was collected by filtration, washed with pure water, and vacuum dried. The powder obtained was redissolved in chloroform and filtered through silica gel. The filtrate was recovered, and 400 mL of chloroform and heptane were added for crystallization. The obtained powder was collected by filtration and vacuum dried to obtain 44.4 g of compound (e″). The yield was 82% in two steps based on the compound (d″).

(Synthesis example of compound (b'''))
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 mixed liquid was stirred under a nitrogen atmosphere at 90° C. and then at 100° C. for 2 hours. Then, the mixture was cooled to room temperature, the mixed solution was poured into 600 g of pure water, and the deposited precipitate was collected by filtration. Then, the precipitate was washed with 400 mL of 6N aqueous sodium hydroxide solution, washed with heptane, and vacuum dried to obtain 132 g of compound (b″′). The yield was 90% based on 8-chlorooctanol.

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

(Synthesis example of compound (e'''))
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 mixed liquid was ice-cooled and stirred under a nitrogen atmosphere, and a 50 mL chloroform solution of 19.5 g (95 mmol) of dicyclohexylcarbodiimide was added dropwise. After completion of dropping, 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-hydrochloric acid aqueous solution. The organic layer was collected, the insoluble component was filtered, dried over anhydrous sodium sulfate, filtered, and the solvent was removed to obtain an intermediate.

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

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

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

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

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

The phase transition temperature of the obtained compound (v-3) was measured by texture observation with a polarizing microscope. The compound (v-3) exhibits a smectic phase from 164° C. to 174° C. during heating, exhibits a nematic phase from 174° C. to 195° C., and exhibits a nematic phase from 195° C. to 167° C. during cooling. It exhibited a smectic phase from 167°C to 151°C and was crystallized.

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

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

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

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

<Synthesis Example of Compound (v-5) via Second Route>
The compound (v-5) was synthesized by the following scheme.

(Synthesis example of compound (g))
12.5 g (43.3 mmol) of compound (va), 1.06 g (8.7 mmol) of 4-dimethylaminopyridine, 20.0 g (86.7 mmol) of compound (f), and 50 g of chloroform were mixed. A solution prepared by dissolving 19.7 g (95.4 mmol) of N,N′-dicyclohexylcarbodiimide in 30 g of chloroform was added dropwise to the obtained mixed solution at room temperature and stirred. The obtained mixed liquid was filtered, 12 g of 2N hydrochloric acid was added, and the mixture was stirred, the liquid was separated, and the organic layer was taken out. After distilling off the solvent of this organic layer, 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 vacuum to obtain the compound (g) as a pale yellow powder.

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

(Synthesis example of compound (i))
25.36 g (85 mmol) of triphosgene and 125 g of tetrahydrofuran 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 mixed liquid. 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 compound (a) and 49.9 g (282 mmol) of pyridine were dissolved was added dropwise to the intermediate solution. The mixture was stirred overnight at room temperature, the white precipitate was removed by filtration, and then concentrated under reduced pressure. After 120 mL of ethanol was added 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, the lower layer liquid was further washed by suspending with water-ethanol 1/3, and the supernatant was removed by decantation. Further, after washing with heptane and decantation, a 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 compound (g), 6.0 g (21 mmol) of 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 mixed solution under ice cooling. The reaction solution was stirred and dicyclohexylurea was filtered, a 2N aqueous hydrochloric acid solution was added, the separated organic layer was dried, filtered through Celite and concentrated under reduced pressure. Methanol was added to the residue for crystallization. The resulting precipitate was collected and redissolved in chloroform. After adding 500 mg of activated carbon and leaving it to stand overnight, it was filtered with acetic acid and celite and reprecipitated in ethanol. The precipitate was collected by filtration, washed with heptane by suspension, and vacuum dried to obtain 2.8 g of compound (v-5). The yield was 25% based on the compound (g).

¹ H-NMR (CDCl ₃ ): δ (ppm) 1.72 to 1.88 (m, 16H), 2.35 to 2.84 (m, 12H), 4.21 of compound (v-5). 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 8.38 (d, 2H)

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

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

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

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

(Synthesis example of compound (k))
50.0 g (114 mmol) of the compound (j) obtained in the previous 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 mixed liquid, and the mixture was stirred under a nitrogen atmosphere. The reaction solution was depressurized and then stirred under a hydrogen atmosphere. When the consumption of hydrogen ceased, the solution was filtered through Celite under a nitrogen atmosphere. After the solvent was removed by an evaporator, the residue was washed with a 50 vol% methanol aqueous solution and vacuum dried to obtain 32.0 g of 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 acrylic acid (4-hydroxybutyl) obtained in the previous section, 10.88 g (53 mmol) of N,N'-dicyclohexylcarbodiimide, N,N-dimethyl 0.56 g (4.6 mmol) of aminopyridine, 10 mg of 2,6-ditertiarybutyl-4-methylphenol and 80 ml of dehydrated chloroform were mixed. The obtained mixed liquid was stirred at room temperature under a nitrogen atmosphere. 40 mL of heptane was added to the reaction solution, the generated precipitate was filtered, and the filtrate was collected. The filtrate was washed with 1N-hydrochloric acid aqueous solution. The collected organic layer was dried and filtered to obtain 18.5 g of compound (l). The yield was 85% based on the compound (j).

<Production Example of Compound (m)>
Compound (1) 18.5 g, pure water 0.87 g, paratoluenesulfonic acid monohydrate 0.87 g (4.6 mmol), and THF 80 mL were mixed. The obtained mixed liquid was heated to 60° C. under a nitrogen atmosphere and then stirred. After allowing to cool to room temperature, THF was removed and 200 mL of heptane was added to the residue. The deposited precipitate was collected by filtration, washed with pure water, and vacuum dried 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 the compound (m) obtained in the previous section, 1.70 g (5.9 mmol) of the 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 obtained mixed liquid was stirred at room temperature under a nitrogen atmosphere. 20 mL of heptane was added to the reaction solution, the generated precipitate was filtered, and the filtrate was collected. The filtrate was washed with 1N-hydrochloric acid aqueous solution. The organic layer was dried, filtered, concentrated under reduced pressure with an evaporator, ethyl acetate was added, concentrated again under reduced pressure, and 300 mL of methanol cooled in an ice bath was added to reprecipitate. The obtained powder was washed with heptane and vacuum dried to obtain 2.9 g of compound (v-6). The yield was 45% based on the compound (m).

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

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

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

<Synthesis Example of Compound (v-7) via First Route>
Compound (v-7) was synthesized by the following scheme.

(Synthesis example of compound (n))
Compound (b) 30 g (102 mmol), 3,5-ditertiarybutyl-4-hydroxytoluene 1.40 g (6.42 mmol), triethylamine 15.5 g (153 mmol), 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 after returning to room temperature, the mixture was 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 collect an organic layer. The organic layer was concentrated under reduced pressure, 1000 g of ice was added, and the mixture was vigorously stirred to crystallize and collected. The obtained white powder was washed with water-methanol 2/1 (v/v) by suspension, further washed with heptane and pure water, and vacuum dried to obtain 12.4 g of compound (n). The yield was 44% based on the compound (b).

(Synthesis example of compound (o))
Taking 12.0 g (43 mmol) of compound (n), 0.53 g (4.3 mmol) of dimethylaminopyridine, and 10.0 g (44 mmol) of trans 1,4-cyclohexanedicarboxylic acid monoethoxymethyl ester (compound (f)). , And dissolved in 50 mL of chloroform. In a nitrogen atmosphere, the mixture was ice-cooled and stirred, and a 20 mL chloroform solution of 9.8 g (48 mmol) of dicyclohexylcarbodiimide was added dropwise. After completion of dropping, the mixture was stirred at room temperature.
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-hydrochloric acid aqueous solution. The organic layer was collected, the insoluble component was filtered, dried over anhydrous sodium sulfate, filtered, and the solvent was removed to obtain an intermediate.

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

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

¹ H-NMR (CDCl ₃ ): δ (ppm) 1.40 to 1.85 (m, 24H), 1.95 (d, 6H), 2.36 to 2.85 () of the compound (v-7). 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) via First Route>
Compound (v-8) was synthesized by 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 resulting mixed solution 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, suspended in pure water, filtered, and vacuum dried to obtain 39 g of the compound (p) as light purple powder. The yield was 26% based on dihydropyran.

(Synthesis example of compound (q))
39 g (156 mmol) of the 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 mixed liquid was stirred at 100° C. for 6 hours under a nitrogen atmosphere. Then, the mixture was cooled to room temperature, and the mixed solution was poured into 580 g of pure water. After removing the supernatant aqueous solution by decantation, the precipitated oily crude product was dissolved in methyl isobutyl ketone, and the solution was separated from pure water. The organic layer was collected, concentrated and dried in 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 the compound (q), 1.40 g (6.42 mmol) of 3,5-ditertiarybutyl-4-hydroxytoluene, 31.8 g (262 mmol) of N,N-dimethylaniline, and chloroform were mixed. 15.5 g (171 mmol) of acryloyl chloride was added dropwise to the obtained mixed solution under ice cooling in a nitrogen atmosphere, and the mixture was returned to room temperature and stirred for 3 hours. After confirming the completion of the reaction, p-toluenesulfonic acid monohydrate was added to adjust the pH to 2. 1.64 g of pure water was added to the reaction solution and stirred at room temperature for 1 hour. After confirming the completion of the reaction, 100 mL of heptane was added, a 2N aqueous hydrochloric acid solution was added until dimethylaniline was completely removed, and the separated organic layer was recovered. The organic layer was treated with activated carbon, filtered through Celite, concentrated under reduced pressure, poured into heptane, and the supernatant heptane layer was removed by decantation. The precipitated pale red viscous liquid was vacuum dried for 2 days to obtain 26.0 g of compound (r). The yield was 71% based on the compound (q).

(Synthesis example of compound (s))
15.0 g (47 mmol) of compound (r), 0.58 g (4.7 mmol) of dimethylaminopyridine, 10.9 g (47 mmol) of trans 1,4-cyclohexanedicarboxylic acid monoethoxymethyl ester (compound (f)), and 40 mL of chloroform was mixed. The obtained mixed liquid was ice-cooled and stirred under a nitrogen atmosphere, and a 10 mL chloroform solution of 10.6 g (52 mmol) of dicyclohexylcarbodiimide was added dropwise. After completion of dropping, the mixture was stirred at room temperature. 100 mL of heptane was added to the reaction solution, and the generated precipitate was filtered. The filtrate was collected and washed with a 2N-hydrochloric acid aqueous 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 paragraph, pure water 0.79 g (44 mmol), 3,5-ditertiarybutyl-4-hydroxytoluene 1.40 g (6.42 mmol), paratoluenesulfonic acid monohydrate 1.25 g( 6.6 mmol) and 150 mL of THF were mixed. The obtained mixed liquid 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 the mixture was concentrated under reduced pressure at room temperature. 300 g of ice was added to the residue and stirred, and the deposited precipitate was collected by filtration, washed with heptane, collected, and dried under vacuum. The powder obtained was redissolved in chloroform and filtered through silica gel. The filtrate was recovered and redissolved in 400 mL of chloroform, and heptane was added for crystallization. The obtained powder was washed with ethanol/water 2/3 (v/v), collected by filtration, and vacuum dried to obtain 17.9 g of compound (o). The yield was 86% in two steps based on the 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 the starting compound (e) was changed to compound (s). The yield was 4.5% based on the compound (va).

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

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

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

The compound was synthesized by the following scheme.

(Synthesis example of compound (t))
The compound (t) was synthesized by a method similar to that of the compound (m) by a DCC condensation reaction or the like using trans-4-hydroxycyclohexanecarboxylic acid or mono-acrylic acid (4-hydroxybutyl: manufactured by Tokyo Chemical Industry Co., Ltd.) as a raw material. .. 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 obtained mixed liquid was heated to 80° C. under a nitrogen atmosphere and stirred. After allowing the reaction solution to cool to room temperature, the reaction solution was poured into 1000 g of water and 500 g of a liquid containing methyl isobutyl ketone/heptane (weight ratio 3/2). After stirring the obtained solution, the separated organic layer was collected and washed with pure water. The organic layer was dried over anhydrous sodium sulfate and filtered, heptane was added to the obtained residue, filtered and vacuum dried 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 mixed liquid was ice-cooled and stirred under a nitrogen atmosphere, and 29.57 g (143 mol) of dicyclohexylcarbodiimide was added dropwise. After the completion of dropping, the mixture was stirred. 200 mL of chloroform and 200 mL of heptane were added to the obtained reaction solution, and the generated precipitate was filtered. The filtrate was collected and washed with pure water three times. The organic layer was collected, dried over anhydrous sodium sulfate and filtered, methanol was added to the obtained residue and the mixture was stirred, and the obtained powder was collected by filtration, further methanol was added and the mixture was stirred.
The obtained powder was collected by filtration and vacuum dried to obtain 42 g of compound (v). The yield was 90% based on the compound (u).

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

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

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

(Synthesis example of compound (v-9))
1.44 g (5 mmol) of compound (va), 4.24 g (10 mmol) of 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 mixed solution under ice cooling. The obtained reaction solution was stirred and filtered, and then the separated organic layer was recovered. The organic layer was dried and then concentrated under reduced pressure. Ethyl acetate was added to the residue, the mixture was concentrated under reduced pressure, and then methanol was added to cause reprecipitation. The precipitate was collected by filtration, washed with ethanol, filtered, and dried in 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 measured by texture observation with a polarizing microscope. The compound (v-9) was crystallized by exhibiting a smectic phase from 146° C. to 159° C. at the time of temperature increase and exhibiting a melting point and showing a nematic phase from 159° C. to 121° C. at the time of temperature decrease.

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

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

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 Big Chemie Japan)

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

(Example 3)
The coating solution (mixed solution) having the composition shown in Table 2 was applied onto the polyvinyl alcohol substrate that had been subjected to the rubbing treatment described in Example 1 by a spin coating method. After drying on a hot plate at 80° C. for 1 minute, it was further dried at 210° C. for 1 minute. The obtained unpolymerized film was cooled to 190° C. and irradiated with ultraviolet rays of 1200 mJ/cm ² while keeping the temperature at the same temperature to prepare 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)
The coating solution (mixed solution) having the composition shown in Table 2 was applied onto the polyvinyl alcohol substrate that had been subjected to the rubbing treatment described in Example 1 by a spin coating method. After drying on a hot plate at 80° C. for 1 minute, 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 prepare an optical film having a thickness of 2.27 μm.

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

(Example 7)
The coating solution (mixed solution) having the composition shown in Table 2 was applied onto the polyvinyl alcohol substrate that had been subjected to the rubbing treatment described in Example 1 by a spin coating method. 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 temperature at the same temperature to prepare 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 liquid (mixed solution) having the composition shown in Table 2 was used.

(Example 9)
The coating solution (mixed solution) having the composition shown in Table 2 was applied onto the polyvinyl alcohol substrate that had been subjected to the rubbing treatment described in Example 1 by a spin coating method. After drying on a hot plate at 80° C. for 1 minute, the temperature was further raised to 170° C. and dried. The resulting unpolymerized film was irradiated with ultraviolet rays 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 liquid (mixed solution) having the composition shown in Table 2 was used.

(Comparative Example 1)
The coating solution (mixed solution) having the composition shown in Table 2 was applied onto the polyvinyl alcohol substrate that had been subjected to the rubbing treatment described in Example 1 by a spin coating method. 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 ultraviolet rays of 1200 mJ/cm ² while keeping the temperature at the same temperature to prepare 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 was measured by using a measuring machine (KOBRA-WR, manufactured by Oji Scientific Instruments Co., Ltd.), and the retardation value Re(450) of the wavelength of 450 nm was measured by a program attached to the apparatus. A retardation value Re (550) at a wavelength of 550 nm and a retardation value Re (650) at a wavelength of 650 nm were calculated. The results are shown in Table 3.

<Production Example of Compound (TM-1)>
The synthetic 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, and 0.21 g (1.7 mmol) of 4-dimethylaminopyridine. , And dehydrated pyridine (392 g) were mixed, and subsequently, a solution of N,N′-dicyclohexylcarbodiimide (DCC) (46.2 g, 224.4 mmol) dissolved in dehydrated pyridine (98 g) was added dropwise, and the resulting mixed liquid was heated at 60° C. The temperature was raised to and stirred.
The precipitated solid was filtered off, the solution was concentrated, and 196 g of chloroform was added to the solution. The chloroform solution was washed with 196 g of 2N hydrochloric acid, and the separated organic layer was taken out. The organic layer was purified with a silica gel column under reduced pressure to obtain 2.8 g of a solid containing the compound (TC-1) as a main component. The yield was 70% based on trans-4-n-pentylcyclohexanecarboxylic acid.

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))
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 in a container. Then, subsequently, a solution of 1.4 g (6.7 mmol) of N,N′-dicyclohexylcarbodiimide (DCC) dissolved in 19 g of chloroform was added dropwise, and the obtained mixed liquid was stirred at room temperature. After separating the precipitated solid by filtration, chloroform was added to the solution.
The chloroform solution was washed with 2N hydrochloric acid (94 g), 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 matter was washed with methanol to obtain 1.2 g of compound (TM-1). The yield was 24% based on the compound (TC-1).

¹ H-NMR (CDCl ₃ ) of compound (TM-1): δ (ppm) 0.9 (3Hy), 1.0 (2Hx), 1.2-2.0 (2Hu+2Hv+2Hw+2Hq+2Hr+2Hp+2Hs+2Hh+2Hm+4Hl+Hk+2Hi), 2.2-2. .5 (2Hh+2Hm+2Hi), 2.6-2.8 (Hg+Hn+Hj), 3.9 (2Ht), 4.2 (2Ho), 5.8 (Hz ₃ ), 6.1 (Hz ₁ ), 6.4. _{(Hz 2), 6.9-7.0 (2He} + 2Hf), 7.3 (Ha + Hb), 8.2-8.4 (2Hc + 2Hd)

The phase transition temperature of the obtained compound (TM-1) was observed by texture observation with a polarizing microscope. As the temperature was 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, it changed to an isotropic phase at around 173°C. When the temperature was lowered from here, it 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., exhibits a nematic phase from 153° C. to 173° C., and exhibits a nematic phase from 170° C. to 102° C. when the temperature is lowered. It turned out to be present.

<Production example of optical film>
(Example 11)
A glass substrate was coated with a 2% by weight aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified type, manufactured by Wako Pure Chemical Industries, Ltd.), and dried by heating to obtain a film having a thickness of 89 nm. Subsequently, the surface of the obtained film was subjected to rubbing treatment, and then the coating solution having the composition shown in Table 4 was applied to the surface subjected to the rubbing treatment by spin coating. After drying on a 170° C. hot plate for 1 minute, while being heated at 130° C., ultraviolet rays of 9600 mJ/cm ² were irradiated 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 as 100% by weight.

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

(Comparative example 2)
An optical film was prepared in the same manner as in Example 1 except that the coating liquids in Table 4 were applied by spin coating, dried on a 45° C. hot plate 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 machine (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 in wavelength 547nm was measured using the measuring machine (KOBRA-WR, Oji Scientific Instruments company make). Moreover, the film thickness derived from the polymerizable compound of the optical film was measured using a laser microscope (LEXT, manufactured by Olympus Corporation). Δn was calculated from the retardation value and the film thickness at a wavelength of 547 nm. Similarly, the phase difference values at wavelengths of 447 nm and 628 nm were measured and the wavelength dispersion characteristics Re(447)/Re(547) and Re(628)/Re(547) were calculated. The results are shown in Table 5.

Since the optical film obtained in Example 11 contains the compound (TM-1), [Re(447)/Re(547)] and [Re(628)/Re(547) are different from Comparative Example 2. )] is closer to 1 and has excellent wavelength dispersion properties.

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

In Table 6, the weight% in the tables other than the solvent means the weight% when the coating liquid is 100% by weight.

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

<Measurement of optical characteristics>
The front retardation value of the produced optical film was measured using a measuring machine (KOBRA-WR, manufactured by Oji Scientific Instruments). Since the glass substrate used as the base material has no birefringence, the front retardation value of the optical film produced on the glass substrate can be obtained by measuring the film with the glass substrate with a measuring machine. .. The obtained optical measurement front phase difference value was measured at wavelengths 447.3 nm, 546.9 nm, and 627.8 nm, respectively, and [Re(447.3)/Re(546.9)] (denoted as α) And [Re(627.8)/Re(546.9)] (denoted as β) were calculated. Further, the film thickness (μm) of the portion derived from the optical film was measured by 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 in [Re(447.
The value of 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 was 1 or more. That is, since the wavelength dependence of the refractive index is small or the so-called reverse wavelength dispersion is exhibited, it has excellent optical compensation characteristics when used in a liquid crystal panel.

The compound of the present invention can provide an optical film capable of uniform polarization conversion in a wide wavelength range.

It is a schematic diagram showing color filter 1 concerning the present invention. It is a schematic diagram showing liquid crystal display device 5 concerning the present invention. It is a schematic diagram showing polarizing plate 30 concerning the present invention. FIG. 3 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. It is a schematic diagram showing organic EL panel 23 of an organic EL display concerning the present invention.

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

Claims (5)

Cyclopentanone or cyclohexanone, contains represented Ru of compounds with formula (1), an optical film-forming composition.
^{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) l -F 2 -P 2 ( 1)
[In 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 heterocycle, and the number Nπ of π electrons contained in the aromatic ring in the Ar group is 13 or more.
D ¹ and D ² are each independently -CO-O-, -O-CO-, -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-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 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. 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-, -OC(=S)-, -OC(=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.
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 It may be substituted with a nitro group. The hydrogen atom contained in the alkyl group having 1 to 4 carbon atoms and the alkoxy group having 1 to 4 carbon atoms may be substituted with a fluorine atom.
k and l each independently represent an integer of 1 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 with an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom, and the methylene group contained in the alkylene group is -O. -Or-CO- may be substituted.
P ¹ and P ² each independently represent a polymerizable group. ] The composition for forming an optical film according to claim 1, further comprising a polymerization initiator. A method for producing an unpolymerized film, which comprises applying the composition for forming an optical film according to claim 1 or 2 onto an alignment film formed on a supporting substrate and drying the composition. A method for producing an optical film, comprising curing the 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 optical film-forming composition according to claim 1.

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