JP7047028B2 - Compounds, optical films and methods for manufacturing optical films - Google Patents

Description

The present invention relates to compounds, optical films and methods for producing optical films.

The 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 applying a solution obtained by dissolving a polymerizable compound in a solvent to a supporting substrate and then polymerizing the film. It is known that the phase difference (Re (λ)) of the optical film given by light having a wavelength of λ nm is determined by the product of the birefringence index Δn and the film thickness d (Re (λ) = Δn). × d). Further, the wavelength dispersion characteristic is usually expressed by a value (Re (λ) / Re (550)) obtained by dividing the phase difference value Re (λ) at a certain wavelength λ by the phase difference value Re (550) at 550 nm, and (Re). The wavelength range in which (λ) / Re (550)) is close to 1, and the inverse 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 indicated wavelength range.
For example, as the polymerizable compound, LC242 (manufactured by BASF) is commercially available (Non-Patent Document 1).

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

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

The present invention is a compound represented by the formula (1).
P ¹ -F ^1- (B ¹ -A ¹ ) _k -E ¹ -G ¹ -D ¹ -Ar-D ² -G ² -E ^2- (A ² -B ² ) _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 π electrons contained in the aromatic ring in the Ar group. The number N _π of is 12 or more.
D ¹ and D ² are independently * -O-CO- (* represents the position to be bound to Ar), -C (= S) -O-, -OC (= S)-, respectively. -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 -NR ¹ -CO-. R ¹ , R ² , R ³ and R ⁴ 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 may be 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 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 -,- Represents NR ⁵ -CO-, -O-CH _2- , -CH ₂ -O-, -S-CH _2- , -CH ₂ -S- or a single bond. R ⁵ and R ⁶ independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
A ¹ and A ² independently represent a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group, respectively. 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. 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). ]

According to the compound of the present invention, it is possible to provide an optical film capable of uniform polarization conversion in a wide wavelength range.

The compound of the present invention (hereinafter, may be referred to as “compound (1)”) is represented by the formula (1).
P ¹ -F ^1- (B ¹ -A ¹ ) _k -E ¹ -G ¹ -D ¹ -Ar-D ² -G ² -E ^2- (A ² -B ² ) _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 π electrons contained in the aromatic ring in the Ar group. The number N _π of is 12 or more.
D ¹ and D ² are independently * -O-CO- (* represents the position to be bound to Ar), -C (= S) -O-, -OC (= S)-, respectively. -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 -NR ¹ -CO-. R ¹ , R ² , R ³ and R ⁴ 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 may be 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 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 -,- Represents NR ⁵ -CO-, -O-CH _2- , -CH ₂ -O-, -S-CH _2- , -CH ₂ -S- or a single bond. R ⁵ and R ⁶ independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
A ¹ and A ² independently represent a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group, respectively. 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. 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 formulas (2) and (3).
(N _π -4) / 3 <k + l + 4 (2)
12 ≤ N _π ≤ 22 (3)
[In equations (2) and (3), N _π , k and l have the same meanings as above. ]

Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthroline ring and the like, 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. Rings and the like can be mentioned. Of these, a benzene ring, a thiazole ring, and a benzothiazole ring are preferable.

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

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

In the formula (1), it is preferable that Ar is any divalent group represented by the formulas (Ar-1) to (Ar-13).

[In the formulas (Ar-1) to (Ar-13), Z ¹ is a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 6 carbon atoms, and a carbon number of carbon atoms. Alkylsulfonyl group of 1 to 6, carboxyl group, fluoroalkyl group of 1 to 6 carbon atoms, alkoxy group of 1 to 6 carbon atoms, alkylthio group of 1 to 6 carbon atoms, N-alkylamino group of 1 to 6 carbon atoms , N, N-dialkylamino group having 2 to 12 carbon atoms, N-alkylsulfamoyl group having 1 to 6 carbon atoms or N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms.
^Q1 and ^Q3 independently represent -CR ⁷ R ^8- , -S-, -NR ^7- , -CO- or -O-, respectively.
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 aromatic hydrocarbon group or an aromatic heterocyclic group which may be substituted.
W ¹ and W ² independently represent a hydrogen atom, a cyano group, a methyl group or a halogen atom, respectively.
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 a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group and the like, and carbon. Alkyl groups having a number of 1 to 4 are preferable, alkyl groups having 1 to 2 carbon atoms are more preferable, and methyl groups are particularly preferable.

Examples of the alkylsulfinyl group having 1 to 6 carbon atoms include a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group, a butylsulfinyl group, an isobutylsulfinyl group, a sec-butylsulfinyl group, a tert-butylsulfinyl group, and a pentylsulfinyl group. Examples thereof include a 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 a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl group, an isobutylsulfonyl group, a sec-butylsulfonyl group, a tert-butylsulfonyl group, and a pentylsulfonyl group. Examples thereof include a group and a hexyl sulfonyl group, and an alkyl sulfonyl group having 1 to 4 carbon atoms is preferable, an alkyl sulfonyl group having 1 to 2 carbon atoms is more preferable, and a methyl sulfonyl 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, a nonafluorobutyl group and the like, and have 1 to 4 carbon atoms. 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 a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group and a hexyloxy group. Therefore, 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 a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, a butylthio group, an isobutylthio group, a sec-butylthio group, a tert-butylthio group, a pentylthio group and a 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 and N-isobutylamino group. Examples thereof include N-sec-butylamino group, N-tert-butylamino group, N-pentylamino group, N-hexylamino group, and N-alkylamino group having 1 to 4 carbon atoms is preferable, and N-alkylamino group having 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, and the like. Examples thereof include N, N-diisopropylamino group, N, N-dibutylamino group, N, N-diisobutylamino group, N, N-dipentylamino group, N, N-dihexylamino group, and have 2 to 8 carbon atoms. The N, N-dialkylamino group is preferable, the N, N-dialkylamino group having 2 to 4 carbon atoms is more preferable, and the 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-. Butyl sulfamoyl group, N-isobutyl sulfamoyl group, N-sec-butyl sulfamoyl group, N-tert-butyl sulfamoyl group, N-pentyl sulfamoyl group, N-hexyl sulfamoyl group, etc. The N-alkylsulfamoyl group having 1 to 4 carbon atoms is preferable, the N-alkylsulfamoyl group having 1 to 2 carbon atoms is more preferable, and the N-methylsulfamoyl group is particularly preferable.

Examples of the N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms include an N, N-dimethylsulfamoyl group, an N-methyl-N-ethylsulfamoyl group, and an N, N-diethylsulfamoyl group. N, N-dipropylsulfamoyl group, N, N-diisopropylsulfamoyl group, N, N-dibutylsulfamoyl group, N, N-diisobutylsulfamoyl group, N, N-dipentylsulfamoyl group, Examples thereof include an N, N-dihexyl sulfamoyl group, preferably an N, N-dialkyl sulfamoyl group having 2 to 8 carbon atoms, and more preferably an N, N-dialkyl sulfamoyl group having 2 to 4 carbon atoms. , N, N-dimethylsulfamoyl groups are particularly preferred.

Z ¹ is a halogen atom, a methyl group, a cyano group, a nitro group, a carboxyl group, a methylsulfonyl group, a trifluoromethyl group, a methoxy group, a methylthio group, an N-methylamino group, an 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, a tert-butyl group and the like, and have 1 to 2 carbon atoms. Alkyl groups are preferred, and methyl groups are more preferred.
Q ¹ is preferably -S-, -CO-, -NH-, -N (CH ₃ )-, and Q ³ is preferably -S-, -CO-.

Examples of the aromatic hydrocarbon group in 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 heteroatom such as a nitrogen atom such as a frill group, a pyrrolyl group, a thienyl group, a pyridinyl group, a thiazolyl group and a benzothiazolyl group, an oxygen atom and a sulfur atom, and has 4 to 20 carbon atoms. Examples thereof include the aromatic heterocyclic group of, and a frill group, a pyrrolyl group, a thienyl group, a pyridinyl group and a thiazolyl group are preferable.

The aromatic hydrocarbon group and the aromatic heterocyclic group may have at least one substituent, and the substituents include a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, and a nitro group. Alkyl sulfinyl group with 1 to 6 carbon atoms, alkylsulfonyl group with 1 to 6 carbon atoms, carboxyl group, fluoroalkyl group with 1 to 6 carbon atoms, alkoxy group with 1 to 6 carbon atoms, alkylthio group with 1 to 6 carbon atoms , N-alkylamino group with 1 to 6 carbon atoms, N, N-dialkylamino group with 2 to 12 carbon atoms, N-alkylsulfamoyl group with 1 to 6 carbon atoms, N, N with 2 to 12 carbon atoms -Dialkylsulfamoyl group and the like include 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, and carbon. An alkoxy group having 1 to 2 carbon atoms, an alkylthio group having 1 to 2 carbon atoms, an N-alkylamino group having 1 to 2 carbon atoms, an N, N-dialkylamino group having 2 to 4 carbon atoms, and an alkyl having 1 to 2 carbon atoms. Sulfamoyl groups are preferred.

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

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

[In the formulas (Y-1) to (Y-6), Z ² is a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 6 carbon atoms, and a carbon number of carbon atoms. Alkylsulfonyl group of 1 to 6, carboxyl group, fluoroalkyl group of 1 to 6 carbon atoms, alkoxy group of 1 to 6 carbon atoms, thioalkyl group of 1 to 6 carbon atoms, N-alkylamino group of 1 to 6 carbon atoms , N, N-dialkylamino group having 2 to 12 carbon atoms, N-alkylsulfamoyl group having 1 to 6 carbon atoms or 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. .. ]

As Z ² , 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 is preferable.

Further, the fact that Y ¹ , Y ² and Y ³ are independently represented by the formula (Y-1) or the formula (Y-3) in terms of the manufacturing process and cost of the compound (1). Especially preferable.

It is preferable that W ¹ and W ² are independently hydrogen atoms, cyano groups or methyl groups, and it is particularly preferable that they are hydrogen atoms.
m is preferably 0 or 1. n is preferably 0.

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

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

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

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

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

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

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

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

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

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

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

D ¹ and D ² are * -O-CO-, * -OC (= S)-, * -O-CR ¹ R ^2- , * -NR ¹ -CR ² R ^3- or * -NR ¹ -CO- (* represents the binding site with Ar.
) Is preferable. It is more preferable that D ¹ and D ² are * -O-CO-, * -OC (= S)-or * -NR ¹ -CO- (* represents a binding site with Ar). .. R ¹ , R ² , R ³ and R ⁴ are each independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom, a methyl group or an ethyl group.

Examples of G ¹ and G ² include an alicyclic hydrocarbon group which may contain a heteroatom represented by the formulas (g-1) to (g-10), and a 5-membered ring or a 6-membered alicyclic ring. It is preferably a hydrocarbon group.

The groups represented by the above formulas (g-1) to (g-10) are alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, isopropyl group and tert-butyl group; methoxy group, 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. , Chlorine atom, bromine atom and the like may be substituted with a halogen atom.

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

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

In addition, as A ¹ and A ² , a part of the hydrogen atom of the above-exemplified group 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. It is substituted with 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. May be good.

As A ¹ and A ² , it is particularly preferable that both of them are groups of the same type 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 in particular, a 1,4-phenylene group because the compound (1) can be easily produced. Is preferable.

It is preferable that B ¹ and B ² are divalent groups of the same type because the compound (1) can be easily produced. Further, since the production of the compound (1) is easier, of B ¹ and B ² , B ¹ and B ² bound only to A ¹ and A ² are independently -CH ₂ -CH ₂ respectively. -, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-, -O-CH _2- , _-CH2 -O- or a single bond is preferable, and 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 bound to E ¹ or E ² are independently -O-, -CO-O-, -O-CO-, and -O-CO-, respectively. More preferably, it is O-, -CO-NH-, -NH-CO- or a single bond.

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

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

-D ¹ -G ¹ -E ^1- (A ¹ -B ¹ ) _k -F ¹ -P ¹ , -D ² -G ² -E ^2- (A ² -B ² ) _l -F ² -P ² Specific examples include groups represented by the formulas (R-1) to (R-134). * (Asterisk) indicates the bond position with Ar. Further, n in the equations (R-1) to (R-134) represents an integer of 2 to 12.

Further, examples of the compound (1) include compounds (i) to (xxxviv). In the table, R1 is -D ¹ -G ¹ -E ^1- (A ¹ -B ¹ ) _k -F ¹ -P ¹ , and R 2 is -D ² -G ² -E ^2- (A ² -B. ² ) Represents _l ^- F2 ^- P2.

In addition, in compound (xxx) and compound (xxxi), any one of the group represented by the formula (1-A) and the group represented by the formula (1-B) is (R-57) to ( It is one of 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 in which the group represented by Ar is a group represented by the formula (ar-79). Alternatively, it means that the group represented by Ar is either a mixture of a compound represented by the formula (ar-78) and a 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 in which the group represented by Ar is a group represented by the formula (ar-121). Alternatively, it means that the group represented by Ar is any one of a mixture of a compound which is a group represented by the formula (ar-120) and a compound which is a group represented by the formula (ar-121), and the compound (xxxxi). ) Shall be a compound in which the group represented by Ar is a group represented by the formula (ar-122), a compound in which the group represented by Ar is a group represented by the formula (ar-123), or a group represented by Ar. It means that it is one of 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).

Further, the compound (i), the compound (ii), the compound (iv), the compound (v), the compound (vi), the compound (ix), the compound (x), the compound (xi), the compound (xvi), and the compound in Table 1 are shown. (Xviii), compound (xix), compound (xx), compound (xxi), compound (xxiii), compound (xxiv), compound (xxv), compound (xxvi), compound (xxvii) ,, compound (xxviii), In addition, typical structural formulas of the compound (xxix) are represented by the formula (ii-1), the formula (iv-1), the formula (v-1), the formula (v-2), the formula (v-3), and the formula ( v-4), formula (v-5), formula (vi-1), formula (ix-1), formula (x-1), formula (xi-1), formula (xvi-1), formula (xix). -1), formula (xx-1), formula (xxi-1), formula (xxiii-1), formula (xxiv-1), formula (xxv-1), formula (xxvi-1), formula (xxvii-). 1), the formula (xxviii-1), the formula (xxix-1), the formula (xxxxi-1), and the formula (xxxvi-1) are exemplified. In the optical film of the present invention, a plurality of different types of compounds (1) may be used.

Further, as the compound (1), for example, the following are exemplified. However, n1 and n2 in the equation independently represent integers of 2 to 12, respectively.

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 synthesis reaction (for example, condensation reaction, esterification reaction, Williamson reaction, etc.) described in Methoden der Organischen Chemie, Organic Reactions, Organic Syntheses, Comprehensive Organic Synthesis, New Experimental Chemistry Course, etc. Ulmann reaction, Wittich reaction, Schiff base formation reaction, benzylation reaction, Sonoh reaction, Suzuki-Miyaura reaction, Negishi reaction, Kumada reaction, Hiyama reaction, Buchwald-Heartwig reaction, Friedelcraft reaction, Heck reaction, Aldor reaction, etc. ) Can be produced by appropriately combining them according to their structure.

For example, in the case of the compound (1) in which D ¹ and D ² are * -O-CO-, 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 has the same meaning as above.)
Compound represented by and 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 above.)
By reacting with the compound represented by, the formula (1-3)

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

(In the formula, Ar, R ¹ , R ² , G ¹ , E ¹ , A ¹ , B ¹ , F ¹ , P ¹ and k have the same meanings as above.)
The compound represented by the above formula (1-3) was obtained, and the obtained compound represented by the formula (1-3) and the formula (1-4) were 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 above.)
It can be produced by reacting with the compound shown by.
The reaction between the compound represented by the formula (1-1) and the compound represented by the formula (1-2) and the reaction between the compound represented by the formula (1-3) and the compound represented by the formula (1-4) , It is preferable to carry out in the presence of an ester agent.

Examples of the esterifying agent (condensing agent) include 1-cyclohexyl-3- (2-morpholinoethyl) carbodiimidemeth-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, Carbodiimides such as 2-methyl-6-nitrobenzoic acid anhydride, 2,2'-carbonylbis-1H-imidazole, 1,1'-oxalyldiimidazole, diphenylphosphoryl azide, 1 (4-nitrobenzenesulfonyl) -1H-1, 2,4-triazole, 1H-benzotriazole-1-yloxytripyrrolidinophosphonium hexafluorophosphate, 1H-benzotriazole-1-yloxytris (dimethylamino) phosphonium hexafluorophosphate, N, N , N', N'-tetramethyl-O- (N-succinimidyl) uronium tetrafluoroborate, N- (1,2,2,2-tetrachloroethoxycarbonyloxy) succinimide, N-carbodibenzoxis succinimide, O -(6-Chlorobenzotriazole-1-yl) -N, N, N', N'-tetramethyluronium tetrafluoroborate, O- (6-chlorobenzotriazole-1-yl) -N, N, N ', N'-Tetramethyluronium hexafluorophosphate, 2-bromo-1-ethylpyridinium tetrafluoroborate, 2-chloro-1,3-dimethylimidazolinium chloride, 2-chloro-1,3-dimethylimidazole Examples thereof include nium hexafluorophosphate, 2-chloro-1-methylpyridinium iodide, 2-chloro-1-methylpyridinium paraltoluenesulfonate, 2-fluoro-1-methylpyridinium paraltoluenesulfonate, and trichloroacetic acid pentachlorophenyl ester. Dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride as condensing agents in terms of reactivity, cost, and usable solvent. , Bis (2,6-diisopropylphenyl) carbodiimide, bis (trimethylsilyl) carbodiimide, bisisopropylcarbodiimide, 2,2'-carbonylbis-1H-imidazole are more preferred.

The composition of the present invention includes a compound containing a group represented by the formula (A) and a polymerizable group (hereinafter, may be referred to as “compound (A)”) and a liquid crystal compound (however, the compound (A)). It is a composition containing (different) and.
-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 contained 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 independently single-bonded, -CO-O-, -O-CO-, -C (= S) -O-, -OC (= S)-, -CR ¹ R, respectively. ^2- , -CR ¹ R ² -CR ³ R ^4- , -O-CR ¹ R ^2- , -CR ¹ R ² -O-, -CR ¹ R ² -O-CR ³ R ^4- , -CR ¹ R ² -O-CO-, -O-CO-CR ¹ R ^2- , -CR ¹ R ² -O-CO-CR ³ R ^4- , -CR ¹ R ² -CO-O-CR ³ R ^4- , -NR ¹ -CR ² R ^3- , -CR ¹ R ² -NR ^3- , -CO-NR ^1- , or -NR ¹ -CO-. R ¹ , R ² , R ³ and R ⁴ independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.
^{Ga and G b each} independently represent a divalent alicyclic hydrocarbon group. The hydrogen atom contained in the alicyclic hydrocarbon group may be 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 liquid crystal compounds include Chapter 3 of the Liquid Crystal Handbook (edited by the Liquid Crystal Handbook Editorial Committee, published on October 30, 2000 by Maruzen Co., Ltd.), 3.2 non-chiral rod-shaped liquid crystal molecules with molecular structure and liquid crystal properties, 3. .3 Among the compounds described in the chiral rod-shaped liquid crystal molecule, a compound having a polymerizable group can be mentioned.
As the liquid crystal compound, a plurality of different compounds may be used in combination.

Examples of the liquid crystal compound include a compound represented by the formula (4) (hereinafter, may be 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), A11 represents an aromatic hydrocarbon group, an alicyclic hydrocarbon group or a heterocyclic group, and is included in the aromatic hydrocarbon group, an alicyclic hydrocarbon group and a 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 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-, -OC (= 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-, -OC ( = 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 even if R ¹⁴ and R ¹⁵ are linked to form an alkylene group having 4 to 7 carbon atoms. good.
E ¹¹ represents an alkylene group having 1 to 12 carbon atoms. The hydrogen atom contained in the alkylene group may be substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogen atom.
^P11 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, and the like. It is a nitro group or represents a polymerizable group 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 and 1 to 6 carbon atoms. It may be substituted with an alkoxy group or a halogen atom.
t represents an integer from 1 to 5. ]

In particular, the polymerizable group in P11 and G may be any group that can be polymerized with the compound (A), and a vinyl group, a vinyloxy group, a p- ^stylben group, an acryloyl group, an acryloyloxy group, a metachloroyl group, and the like. Metachlorooxy group, carboxyl group, acetyl group, hydroxyl group, carbamoyl group, amino group, alkylamino group with 1 to 4 carbon atoms, epoxy group, oxetanyl group, formyl group, -N = C = O or -N = C = S and the like can be mentioned. Among them, a radical polymerizable group or a cationically polymerizable group is preferable in terms of being suitable for photopolymerization, and an acryloyloxy group, a metachloroyloxy group or a vinyloxy group is preferable in that it is easy to handle and the liquid crystal compound can be easily produced. Radicals are preferred.

Further, the carbon number of the aromatic hydrocarbon group, the alicyclic hydrocarbon group and the heterocyclic group of A11 is, for example, ³ to 18, preferably 5 to 12, and 5 or 6, respectively. Is particularly preferable.

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

P ¹¹ -E ^{11-(B 11 -A 11 ) t1} _-B ¹² -E ¹² -P ¹² (4-1)
P ¹¹ -E ^11- (B ¹¹ -A ¹¹ ) _t2 -B ¹² -F ¹¹ (4-2)
[In the formula (4-1) and the formula (4-2), P ¹¹ , E ¹¹ , B ¹¹ , A ¹¹ , and B ¹² have the same meanings as 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, and a nitrile group. , Represents a nitro group.
E ¹² is synonymous with E ¹¹ .
P ¹² is synonymous with P ¹¹ .
t ¹ and t ² are synonymous with t. ]

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

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

In addition, in the compound represented by the formula (4-1), the formula (4-2), the formula (I), the formula (II), the formula (III), the formula (IV) and the formula (V), P ¹¹ It is preferable that both are bonded via an ether bond or an ester bond by appropriately selecting a combination of ^P12 and ^E11 and further appropriately selecting a combination of ^P12 and E12.

Specific examples of the compound (4) include the following formulas (I-1) to (I-5), formulas (II-1) to formulas (II-6), and formulas (III-1) to formulas (III-1) to (forms). III-19), compounds represented by formulas (IV-1) to formulas (IV-14), formulas (V-1) to formulas (V-5), and the like can be mentioned. However, k in the formula represents an integer of 1 to 11. These liquid crystal compounds are preferable because they are easy to synthesize and are easily available on the market.

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

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, benzylketals, α-hydroxyketones, α-aminoketones, iodonium salts, sulfonium salts and the like, and more specifically, Irgacure 907. , Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369 (all manufactured by Ciba Japan Co., Ltd.), Sakeol BZ, Sakeol Z, Sakeol BEE (all manufactured by Seiko Kagaku Co., Ltd.), kayacure. BP100 (manufactured by Nippon Kayaku Co., Ltd.), KayaCure UVI-6992 (manufactured by Dow), ADEKA PTOMER SP-152 or ADEKA PTOMER SP-170 (all manufactured by ADEKA Corporation) and the like can be mentioned.

The amount of the polymerization initiator used is, for example, 0.1 part by weight to 30 parts by weight, preferably 0.5 part by weight to 10 parts by weight, based on 100 parts by weight of the total of the liquid crystal compound and the compound (A). 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 having an optical function. The optical function means refraction, birefringence, and the like. A retardation film, which is a kind of optical film, is used for converting linearly polarized light into circularly polarized light or elliptically polarized light, and conversely, converting circularly polarized light or elliptically polarized light to linearly polarized light.

The optical film of the present invention is formed by polymerizing a compound containing a group represented by the formula (A) and a polymerizable group. The group represented by the formula (A) is preferably a group represented by the formula (B), more preferably a group represented by the formula (C), and is represented by the formula (1). It is particularly preferable to be a group.

-E ¹ -Ga-D a-Ar ^a -D ^b -G ^{b -E 2- ( B} )
[In the formula (B), Ar ^a , D ^a , D ^b , ^{Ga and G b have} the same meanings as above, and E ¹ and E ² are independently -CR ⁵ R ^6- , -CH ₂ respectively. -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 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 -Ga-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 , ^{Ga, G b ,} E ¹ and E ² have the same meanings as described above.
B ¹ and B ² are independently of -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. R5 and ^R6 have the ^same meanings as above.
A ¹ and A ² independently represent a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group, respectively. 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. 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 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 π electrons contained in the aromatic ring in the Ar group. The number N _π of is 12 or more.
D ¹ and D ² are independently * -O-CO- (* represents the position to be bound to Ar), -C (= S) -O-, -OC (= S)-, respectively. -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 -NR ¹ -CO-. R ¹ , R ² , R ³ and R ⁴ 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 may be 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 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 -,- Represents NR ⁵ -CO-, -O-CH _2- , -CH ₂ -O-, -S-CH _2- , -CH ₂ -S- or a single bond. R ⁵ and R ⁶ independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
A ¹ and A ² independently represent a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group, respectively. 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. 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 characteristic 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. Increasing the content of the structural unit derived from the compound (A) among the structural units in the optical film exhibits a flatter wavelength dispersion characteristic and further a reverse wavelength dispersion characteristic.

Specifically, with respect to the composition containing the liquid crystal compound and the compound (A), about 2 to 5 kinds of compositions having different contents of structural units derived from the compound (A) are prepared, and each composition will be described later. As described above, the phase difference value of the optical film obtained by manufacturing the optical film having the same film thickness is obtained, and from the result, the content of the structural unit derived from the compound (A) and the phase difference value of the optical film are obtained. The correlation may be obtained, and the content of the structural unit derived from the compound (A) necessary for giving a desired retardation value to the optical film at 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, to the compound (A), if necessary, an organic solvent, the above-mentioned liquid crystal compound as a host, the above-mentioned polymerization initiator, a polymerization inhibitor, a photosensitizer, a leveling agent and other additives are added and mixed. Prepare the solution. In particular, it is preferable to contain an organic solvent so that the film can be easily formed at the time of film formation, and it is preferable to contain 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 with respect to 100 parts by weight of the total of the liquid crystal compound and the compound (A).

The amount of the polymerization initiator used is, for example, 0.1 part by weight to 30 parts by weight, preferably 0.5 part by weight to 10 parts by weight, based on 100 parts by weight of the total of the liquid crystal compound and the compound (A). 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 in preparing the optical film of the present invention. Examples of the polymerization inhibitor include hydroquinones having a substituent such as hydroquinone or an alkyl ether, catechols having a substituent such as an alkyl ether such as butyl catechol, pyrogallols, 2,2,6,6-tetramethyl-1. -Radical catching agents such as piperidinyloxy radicals, thiophenols, β-naphthylamines, β-naphthols and the like can be mentioned.

By using a 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 part by weight to 30 parts by weight, preferably 0.5 part by weight to 10 parts by weight, based on 100 parts by weight of the total of the liquid crystal compound and the compound (A). 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 or thioxanthone, anthracene having a substituent such as anthracene or alkyl ether, phenothiazine or rubrene.

By using a photosensitizer, the polymerization of the liquid crystal compound or the compound (A) can be made highly sensitive. The amount of the photosensitizer used is, for example, 0.1 part by weight to 30 parts by weight, preferably 0.5 part by weight to 10 parts by weight, based on 100 parts by weight of the total of the liquid crystal compound and the compound (A). It is a part 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. Examples of the leveling agent include additives for radiation-curable paints (manufactured by Big Chemie Japan: BYK-352, BYK-353, BYK-361N), paint additives (manufactured by Toray Dow Corning Co., Ltd .: SH28PA, DC11PA, ST80PA). Paint additives (manufactured by Shin-Etsu Chemical Co., Ltd .: KP321, KP323, X22-161A, KF6001) or fluorine-based additives (manufactured by Dainippon Ink and Chemicals Co., Ltd .: F-445, F-470, F-479), etc. Can be mentioned.

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

〔Organic solvent〕
The organic solvent used for preparing the mixed solution containing the compound (A) and the liquid crystal compound is an organic solvent capable of dissolving the compound (A) and the liquid crystal compound, and may be any solvent that is inert to the polymerization reaction. , Specifically alcohols such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl cellosolve or butyl cellosolve; esters such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, gamma butyrolactone or propylene glycol methyl ether acetate. Solvents; Ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methylamylketone or methylisobutylketone; aliphatic hydrocarbon solvents such as pentane, hexane or heptane; aromatic hydrocarbons such as toluene, xylene or chlorobenzene Examples thereof include solvents, acetonitrile, propylene glycol monomethyl ether, tetrahydrofuran, dimethoxyethane, ethyl lactate, chloroform, phenol and the like. 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-based solvents, ketone-based solvents, non-chlorine-based aliphatic hydrocarbon solvents, non-chlorine-based aromatic hydrocarbon solvents, etc. It can be dissolved and coated without using the halogenated hydrocarbon of.

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, preferably about 0.1 to 7 Pa · s, so that it can be easily applied.

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

Subsequently, the mixed solution can be applied to the supporting base material, dried and polymerized to obtain the desired optical film on the supporting base material.

[Unpolymerized film preparation process]
A mixed solution containing the compound (A) is applied onto the supporting substrate and dried to obtain an unpolymerized film. When the unpolymerized film exhibits a liquid crystal phase such as a nematic phase, the obtained 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., a supporting base material that is not always sufficient in terms of heat resistance as exemplified above can be used as the alignment film. Further, it is easy to handle because it does not crystallize even if it is further cooled to about 30 to 10 ° C. after orientation.

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

Re (λ) = d × Δn (λ) (7)
(In the equation, Re (λ) represents the phase difference value at the wavelength λ nm, d represents the film thickness, and Δn (λ) represents the birefringence index at the wavelength λ nm.)

Examples of the coating method on 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. Further, a method of applying using a coater such as a dip coater, a bar coater or a spin coater can be mentioned.

Examples of the supporting base material include glass, a plastic sheet, a plastic film, and a translucent film. Examples of the translucent film include polyolefin films such as polyethylene, polypropylene, and norbornene-based polymers, polyvinyl alcohol films, polyethylene terephthalate films, polymethacrylic acid ester films, polyacrylic acid ester films, cellulose ester films, and polyethylene naphthalate films. , Polycarbonate film, polysulfone film, polyether sulfone film, polyether ketone film, polyphenylene sulfide film, polyphenylene oxide film and the like.

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

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

Examples of the polymer include polyamides and gelatins having an amide bond in the molecule, polyimide having an imide bond in the molecule and its hydrolyzate polyamic acid, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, and polyoxazole. Polymers such as polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid or polyacrylic acid esters can be mentioned. These polymers may be used alone, may be mixed in two or more kinds, or may be copolymerized. 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, but 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, methylamylketone or methylisobutylketone; 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.

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

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

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

The thickness of the alignment film thus obtained is, for example, 10 nm to 10000 nm, preferably 10 nm to 1000 nm. Within the above range, compound (A) and the like can be oriented at a desired angle on the alignment film.

Further, these alignment films can be rubbed or irradiated with polarized UV, if necessary. As a result, 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 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 base material. 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. Furthermore, it is possible to produce films as roll films.

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

Examples of the solvent drying method include natural drying, ventilation drying, vacuum 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. As long as the heating temperature and the heating time are within the above ranges, a support base material having insufficient heat resistance can be used as the support base material.

[Unpolymerized film polymerization step]
In the unpolymerized film polymerization step, the unpolymerized film obtained in the above unpolymerized film preparation step is polymerized and cured. As a result, a film in which the orientation of the compound (A) is fixed, that is, a polymerized film is obtained. Therefore, it is possible to produce a polymerized 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 for polymerizing the unpolymerized film is determined according to the type of the liquid crystal compound and the compound (A). If the polymerizable group contained in the compound (A) is P ¹ and / or P ² , and the polymerizable group contained in the liquid crystal compound is photopolymerizable, the above is carried out by photopolymerization, and if the polymerizable group is thermally polymerizable, the above is carried out. The unpolymerized film can be polymerized. In the present invention, it is particularly preferable to polymerize the unpolymerized film by photopolymerization. Since the unpolymerized film can be polymerized at a low temperature by photopolymerization, the range of heat resistance of the supporting substrate is widened. It also facilitates industrial production. 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 light irradiation in which ultraviolet light is particularly preferable may be performed while heating the compound (A) to a temperature at which the liquid crystal phase is formed. At this time, the polymerized film can be patterned by masking or the like.

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

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

In the method for producing an optical film of the present invention, a step of peeling off a supporting base material may be included following the above steps. With such a configuration, the obtained laminate becomes a film composed of an alignment film and an optical film. Further, in addition to the step of peeling off the supporting base material, the step of peeling off 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 various display films. As described above, the thickness of the formed layer varies depending on the retardation value of the obtained optical film. In the present invention, the thickness is preferably 0.1 to 10 μm, and more preferably 0.5 to 3 μm in terms of reducing photoelasticity.

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

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

In order to use the optical film of the present invention as a wideband λ / 4 plate or λ / 2 plate, the content of the structural unit derived from the compound (A) is appropriately selected. In the case of a λ / 4 plate, the film thickness of the obtained optical film Re (550) may be adjusted to 113 to 163 nm, preferably 135 to 140 nm, particularly preferably about 137.5 nm, and the λ / 2 plate may be used. 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 Alingment) mode, the content of the structural unit derived from the compound (A) is appropriately selected. The film thickness may be adjusted so that Re (550) is preferably about 40 to 100 nm, more preferably about 60 to 80 nm.

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

The optical film of the present invention is used as an antireflection film such as an antireflection (AR) film, a polarizing film, a retardation film, an elliptical polarizing film, a viewing angle expansion film, an optical compensation film for viewing angle compensation of a transmissive liquid crystal display, and the like. can do. Further, although one optical film of the present invention exhibits excellent optical characteristics, a plurality of optical films may be laminated.

It may also be combined with other films. Specific examples thereof include an elliptical polarizing plate in which the optical film of the present invention is bonded to a polarizing film, and a broadband circular polarizing plate in which the optical film of the present invention is further bonded to the elliptical polarizing plate as a broadband λ / 4 plate. Be done.

Since the optical film of the present invention can be formed by applying it on an alignment film and polymerizing it by irradiation with ultraviolet rays, as shown in FIG. 1, it is easier than before to apply a wide band, for example, λ / 4, λ on a color filter. A 2/2 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 the manufacturing method of the color filter 1 having the above configuration will be described. First, an oriented polymer is printed on the color filter layer 4 and subjected to a rubbing treatment to form an oriented film 3.
Next, a mixed solution containing the compound (A) was prepared on the obtained alignment film 3 so as to have a desired wavelength dispersion characteristic, and the mixture was applied while adjusting the thickness so as to obtain a desired retardation value, and optically. Form film 2.

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

FIG. 2 is a schematic view showing a liquid crystal display device 5 according to the present invention.
In the liquid crystal display device 5 shown in FIG. 2, a substrate 7 facing a backlight such as a glass substrate is fixed on the polarizing plate 6 via an adhesive, and a color filter layer 4'created on the substrate 7 is provided. An optical film 2'is formed on the alignment film 3'via 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 the polarizing plate 10 via an adhesive, and a thin film transistor (TFT) and an insulating layer 12 for actively driving a liquid crystal layer are formed on the substrate 11. Further, a transparent electrode 13 and / or a reflecting electrode 13'by 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 makes it possible to manufacture a thinner liquid crystal display device.

An example of a manufacturing method of the liquid crystal display device 5 in which the color filter 1'is formed on the liquid crystal layer side of one of the substrates will be described below. A gate electrode made of Mo, MoW, etc., a gate insulating film, and amorphous silicon are deposited and patterned on a borosilicate glass on a substrate on the backlight side, and the amorphous silicon is crystallized by annealing with an excimer laser. A semiconductor thin film can be formed, and then P, B, etc. can be doped in the regions on both sides of the gate electrode to form n-channel and p-channel TFTs. Further, by forming an insulating film made of SiO ₂ , a substrate on the backlight side can be obtained. Further, by spattering ITO on the backlight side substrate 11, the transparent electrode 13 for the fully transmissive display device can be laminated on the backlight side substrate. Similarly, by using Ag, Al, or the like instead of ITO, a reflective electrode 13'for a total internal reflection type display device can be obtained. Further, by appropriately combining a reflective electrode and a transparent electrode, a backlight-side electrode for a semi-transmissive liquid crystal display device can be obtained.

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 the R, G, and B color filters together. Next, the alignment polymer is applied onto the color filter layer 4'and rubbed to form the alignment film 3'. A composition containing the compound (A) according to the present invention is applied onto the alignment film 3', and the film is polymerized by ultraviolet irradiation to form an optical film 2'while being heated to a temperature range in which a liquid crystal phase is obtained.
After forming the optical film, the counter electrode 8 can be formed by sputtering ITO. Further, the liquid crystal display device 5 can be created by forming an alignment film on the counter electrode, forming the liquid crystal phase 9, and finally assembling the liquid crystal phase 9 together with the substrate on the backlight side. 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. Since the desired wavelength dispersion characteristic can be obtained and the phase difference value can be controlled from the film thickness, the lamination of the optical film can be omitted.

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

As described above, the film according to the present invention can be used in a wide range of applications. For example, among these, a polarizing plate formed by laminating an optical film and a polarizing film according to the present invention and an FPD provided with the polarizing plate will be described below. The polarizing plate according to the present invention will be described below. Alternatively, it can be obtained by directly laminating the optical film on both sides or by using an adhesive or a pressure-sensitive adhesive. In the following description of FIGS. 3 to 5, the adhesive and the pressure-sensitive adhesive may be collectively referred to as an adhesive.

3 (a) to 3 (e) 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 bonded to each other, and the laminated body 14 is composed of a support base material 16, an alignment film 17, and an optical film 18.
The polarizing plate 30a is laminated in the order of the supporting base material 16, the alignment film 17, the optical film 18, and the polarizing film 15.

In the polarizing plate 30b shown in FIG. 3B, the laminated body 14 and the polarizing film 15 are bonded to each other 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 to each other, and further, the laminated body 14'and the polarizing film 15 are directly bonded to each other.

In the polarizing plate 30d shown in FIG. 3D, the laminated body 14 and the laminated body 14'are bonded to each other via the adhesive layer 19, and the polarizing film 15 is directly bonded to 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 to each other via the adhesive layer 19, and the laminated body 14'and the polarizing film 15 are further bonded to each other via the adhesive layer 19'. The configuration of the pasted together is shown.

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

In the polarizing plate of the present invention, a plurality of laminated bodies may be laminated, and the plurality of laminated bodies may 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 on a polyvinyl alcohol-based film and stretching the film, or a polyvinyl alcohol-based film stretched to obtain iodine or a dichroic dye. Examples thereof include an adsorbed film.

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, a urethane adhesive, or the like is used.

The flat panel display device of the present invention includes the optical film of the present invention, for example, a liquid crystal display device including a bonded product in which the polarizing film of the present invention and a liquid crystal panel are bonded together, or the polarizing film of the present invention. , An organic EL display device including an organic EL panel to which a light emitting layer is bonded can be mentioned.

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 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.

Examples of the liquid crystal display device include a liquid crystal display device including a bonded product 21 of a liquid crystal panel 20 and a polarizing plate 30 as shown in FIG. The bonded product 21 is formed 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 an electrode (not shown), the liquid crystal molecules are driven and an optical shutter effect is exhibited.

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

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

In the organic EL panel, the polarizing film 30 functions as a broadband circular polarizing plate.
Further, 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 by way of examples. Unless otherwise specified, "%" and "part" in the example are% by weight and parts by weight.

The compounds were synthesized by the following scheme. The raw material monotetrahydropyranyl-protected hydroquinone (a) was synthesized by the method described in Patent Document (Japanese Patent Laid-Open No. 2004-262884).

(First route)

(Second route)

(Example of synthesis 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 and dispersed in dimethylacetamide. The mixture was stirred at 90 ° C. and then at 100 ° C. under a nitrogen atmosphere. Then, the mixture was cooled to room temperature, pure water and methyl isobutyl ketone were added, and the recovered organic layer was washed with an aqueous sodium hydroxide solution and pure water, dehydrated, filtered, and concentrated under reduced pressure. Methanol was added to the residue, and the resulting precipitate was filtered and dried under vacuum to obtain 126 g (428 mmol) of compound (b). The yield was 91% based on 6-bromohexanol.

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

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

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

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

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

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

(Production example of compound (ii-a))
Compound (ii-a) was synthesized by the following scheme. The raw material, 4,7-dimethoxy-2-phenylbenzothiazole, was prepared by J. Mol. Chem. Soc. , Perkin Trans. It was synthesized by the method described in 1 magazine, pp. 205-210 (2000).

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

(Production example of compound (vi-a))
Compound (vi-a) was synthesized by the following scheme.

[Example of synthesis of compound (vi-d)]
69.4 g (453 mmol) of 2,5-dimethoxyaniline, 91.7 g (906 mmol) of triethylamine and 994.3 g of dehydrated chloroform were mixed and stirred, and 99.4 g (453 mmol) of 4-bromobenzoyl chloride was added to the obtained mixed solution. Was added. Then, the temperature was raised to 60 ° C., the mixture was stirred, cooled to room temperature, and the mixed solution was put 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 (vid) as a main component. The yield was 102% based on 2,5-dimethoxyaniline.

[Example of synthesis of compound (vi-e)]
90.0 g (268.0 mmol) of compound (vi-d), 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetan-2,4-disulfide (Lawesson's reagent) 65 9.0 g (160.0 mmol) and 3132 g of toluene were mixed, and the obtained mixed solution 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% on a compound (vid) basis.

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

[Example of synthesis of compound (vi-a)]
11.2 g (32.0 mmol) of compound (vi-f) and 56.0 g (5-fold mass) of pyridinium chloride were mixed, heated to 180 ° C., and stirred. After cooling the obtained mixed solution, 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% on a compound (vi-f) basis.

(Example of synthesis of compound (va))
After benzothiazole was synthesized by the same method as that for compound (vi-a), compound (va) was synthesized by a 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.

(Example of synthesis of compound (vb))
In the synthesis example of the compound (vi-d), a solid containing the compound (vb) as a main component was obtained by the same method except that the raw material 4-bromobenzoyl chloride was changed to 4-nitrobenzoyl chloride. The yield was 98% based on 2,5-dimethoxyaniline.

(Example of synthesis of compound (vc))
In the synthesis example of the compound (vi-e), a solid containing the compound (vic) as a main component was obtained by the same method except that the raw material compound (vid) was changed to the compound (vb). .. The yield was 89% on a compound (vb) basis.

(Example of synthesis of compound (vd))
In the synthesis example of the compound (vi-f), a solid containing the compound (vd) as a main component was obtained by the same method except that the raw material compound (vi-e) was changed to the compound (vic). .. The yield was 52% on a compound (vc) basis.

(Example of synthesis of compound (va))
21.0 g (66.0 mmol) of compound (vd) and 441 g of dehydrated toluene were mixed and stirred. The obtained mixture was ice-cooled, 100 g (398 mmol) of boron tribromide was added, the temperature was raised to 70 ° C., and the mixture was stirred. After cooling to room temperature, the mixture was further 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 compound (va) as a main component. rice field. The yield was 86% on a compound (vd) basis.

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

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

[Example of synthesis of compound (ix-c)]
70.0 g (272.0 mmol) of compound (ix-b), 2,4-bis (4-methoxyphenyl) -1,3-dithear 2,4-diphosphetane-2,4-disulfide (Lawesson's reagent) 65.8 g (162.0 mmol) and 2436 g of toluene were mixed, heated to 80 ° C., and stirred. The obtained mixed solution was cooled and then concentrated to obtain a solid containing the compound (ix-c) as a main component. The compound (ix-c) was not purified and the whole amount was used as it was in the next step.

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

[Example of synthesis of compound (ix-a)]
5.6 g (21.0 mmol) of compound (ix-d) and 28.0 g (5-fold mass) of pyridinium chloride were mixed, heated to 180 ° C. and stirred. After cooling the obtained mixed solution, 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% on a compound (ix-d) basis.

(Production example of compound (iv-a))
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 solution, water was added, the obtained precipitate was taken out, and the mixture was thoroughly washed with water to obtain 6.6 g of a solid containing the compound (iv-a) as a main component. The yield was 79% on a compound (vi-a) basis.

<Example of synthesis of compound (ii-1) in the first pathway>
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. To the obtained mixed solution, 40 mL of a chloroform solution of 5.31 g (28 mmol) of dicyclohexylcarbodiimide was added dropwise under ice-cooling. The obtained reaction solution was stirred and filtered, and then the separated organic layer was recovered. The organic layer was dried and then concentrated under reduced pressure. Ethyl acetate was added to the residue to dissolve it, and after concentration under reduced pressure, 200 mL of methanol was added and reprecipitation was performed under ice-cooling. The precipitate was collected by filtration, washed with n-heptane, filtered, and the obtained solid was vacuum dried to obtain 6.1 g of compound (ii-1). The yield was 56% based on 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. Compound (ii-1) exhibited a smectic phase from 96 ° C. to 115 ° C. when the temperature was raised, a nematic phase from 115 ° C. to 226 ° C., and a nematic phase from 226 ° C. to 50 ° C. when the temperature was lowered. ..

<Example of synthesis of compound (v-1) in the first pathway>
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. To the obtained mixed solution, 40 mL of a chloroform solution of 4.95 g (24 mmol) of dicyclohexylcarbodiimide was added dropwise under ice-cooling. The obtained reaction solution was stirred and filtered, and then the separated organic layer was recovered. The organic layer was dried and then concentrated under reduced pressure. Ethyl acetate was added to the residue to dissolve it, and after concentration under reduced pressure, 200 mL of methanol was added and reprecipitation was performed under ice-cooling. The precipitate was collected by filtration, washed with methanol, filtered, and the obtained solid was vacuum-dried to obtain 10.3 g of compound (v-1). The yield was 94% based on 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), 4.15-4.20 (t, 4H), 5.80-5.84 (dd, 2H), 6.07-6.18 (m, 2H), 6. 37 to 6.44 (m, 2H), 6.87 to 7.02 (m, 8H), 7.27 (d, 2H), 8.19 to 8.23 (d, 2H), 8.34 to 8.38 (d, 2H)

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

<Example of synthesis of compound (ix-1) in the first pathway>
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, and after concentration 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, filtered, and the obtained solid was vacuum dried to obtain 4.4 g of compound (ix-1). The yield was 43% based on 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), 4.15-4.18 (t, 4H), 5.80-5.84 (dd, 2H), 6.07-6.18 (m, 2H), 6. 37 to 6.44 (m, 2H), 6.86 to 7.02 (m, 8H), 7.22 (m, 1H), 7.28 (d, 2H), 7.78 to 7.81 ( br, 2H), 8.14-8.17 (br, 1H)

<Example of synthesis of compound (iv-1) in the first pathway>
The compound (iv-a) is used as a starting material in the same manner as shown in the above-mentioned example of synthesis of compound (ii-1) in the first pathway and the example of synthesis of compound (ix-1) in the first pathway. For example, 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., a nematic phase from 159 ° C. to 190 ° C. or higher when the temperature was raised, and a nematic phase up to 136 ° C. when the temperature was lowered, and crystallized. ..

<Example of synthesis of compound (ii-1) by the second pathway>
(Example of synthesis of compound (f))
100 g (581 mmol) of transcyclohexanedicarboxylic acid and 500 mL of dimethylacetamide were mixed, and the obtained mixed solution was heated to 60 ° C. and dissolved. 48.2 g (349 mmol) of potassium carbonate was added to the obtained mixed solution, 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 mixed water / methanol solution (volume ratio 1/1), and vacuum dried. The obtained powder was dissolved in toluene and adsorbed on silica gel while being concentrated 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 recovered solution was vacuum dried to obtain 63 g of compound (f). The yield was 42% based on the transcyclohexanedicarboxylic acid.

(Example of synthesis of compound (ii-b))
Compound (ii-a) 4.87 g (20 mmol), compound (f) 11.54 g (44 mmol) and dimethylaminopyridine 0.54 g (4 mmol) were mixed with 50 mL of chloroform. 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, and after concentration under reduced pressure, methanol was added and reprecipitation was performed under ice-cooling. The precipitate was collected by filtration and vacuum dried to obtain 11.4 g of compound (ii-b). The yield was 78% based on compound (ii-a).

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

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

<Example of synthesis of compound (vi-1) by the second pathway>
The compound (iv-1) was obtained by using the compound (vi-a) as a starting material by the same method shown in the above-mentioned synthesis example of the compound (ii-1) in the second route.

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

(Production example of compound (xa))
Compound (x-a) was synthesized by the following scheme.

In the synthesis example of the compound (vb), the compound (x-b) compound was obtained by the same method except that the raw material 4-nitrobenzoyl chloride was changed to the thiophenecarbonyl chloride, and the compound (vic) was obtained. 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))
Compound (v'-a) was synthesized by the following scheme.

[Example of synthesis 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. Mixed, well stirred at room temperature. The pressure of the obtained mixed solution 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 was stirred at room temperature. The reaction solution was put into 973 g of water and separated to remove an organic layer. Further, this organic layer was washed with 973 g of 1N hydrochloric acid. The solvent was distilled off from the obtained organic layer under reduced pressure to obtain 107.8 g of a solid containing the compound (v'-b) as a main component. The yield was 44% based on 2,5-dimethoxyaniline.

[Example of synthesis of compound (v'-a)]
In the example of synthesizing the compound (vc), the compound (v'-c) is obtained by the same method except that the raw material compound (vb) is changed to the compound (v'-b), and the compound (v'-c) is obtained. Compounds (v'-d) and (v'-a) were obtained in the same manner as in the synthetic examples of vd) and (va), respectively.

(Production example of compound (xa))
Compound (x-a) was synthesized by the following scheme.

In the synthesis example of the compound (vb), the compound (x-b) compound was obtained by the same method except that the raw material 4-nitrobenzoyl chloride was changed to the thiophenecarbonyl chloride, and the compound (vic) was obtained. 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))
Compound (xi-a) was synthesized by the following scheme.

[Example of synthesis 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-tenoyl acid chloride was added to the obtained mixture. Dropped under ice-cooling. Then, the temperature was raised to room temperature, the mixture was stirred for 1 hour, and then the mixed solution was put into water. The separated organic layer was washed with water and hydrochloric acid. The solvent was distilled off from the obtained organic layer under reduced pressure, and the obtained solid was washed with hexane 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.

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

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

[Example of synthesis of compound (xi-a)]
40.0 g (144.2 mmol) of compound (xi-f) and 200.0 g (5-fold mass) of pyridinium chloride were mixed, heated to 180 ° C., and stirred for 2 hours. After cooling the obtained mixed solution, 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% on a compound (xid) basis.

(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 raw material 4-nitrobenzoyl chloride was changed to 3,5-dimethylbenzoyl chloride, and the compound (v) was obtained. The compounds (xvi-c), (xvi-d), and (xvi-a) were obtained in the same manner as in the synthetic examples of (c), (vd), and (va), respectively.

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

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

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

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

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

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

[Example of synthesis of compound (xix-b)]
58.7 g (383 mmol) of 2,5-dimethoxyaniline, 77.5 g (766 mmol) of triethylamine, and 400 g of dehydrated chloroform were mixed and stirred, and 50.0 g (383 mmol) of 2-furancarboxylic acid chloride was added to the obtained mixed solution. Was added under ice-cooling. Then, the mixture was heated to room temperature, stirred for 1 hour, and then put 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.

[Example of synthesis of compound (xix-c)]
Compound (xix-b) 40 g (162.0 mmol), 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosfetan-2,4-disulfide (Lawesson's reagent) 34.0 g ( 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 obtained mixed solution was cooled and then concentrated to obtain a red viscous liquid containing a decomposition product of Lawesson's reagent and a partially white crystal containing a compound (xix-c) as a main component.

[Example of synthesis 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 is added to the obtained mixed solution under ice-cooling, and the mixture is stirred. The precipitated solid is washed with cold water and hexane, washed with methanol, and recrystallized from ethanol. As a result, 19.5 g of the compound (xix-d) was obtained. The yield was 46% on a compound (xix-b) basis.

[Example of synthesis of compound (xix-a)]
9.00 g (34.4 mmol) of compound (xix-d) and 45.0 g (5-fold mass) of pyridinium chloride were mixed, heated to 180 ° C. and stirred. After cooling the obtained mixed solution, 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% on a compound (xix-d) basis.

(Example of synthesis of compound (xx-a))
After benzothiazole was synthesized by the same method as that for compound (xx-a), compound (xx-a) was synthesized by a 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.

[Example of synthesis 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-thiazole carboxylic acid chloride was added to the obtained mixed solution with ice. Dropped in cold. Then, the mixture was heated to room temperature, stirred, and then put into water. The separated organic layer was washed with water and hydrochloric acid. The solvent was distilled off from the obtained organic layer under reduced pressure, and the obtained solid was washed with hexane and crystallized with heptane-ethyl acetate 3/1 (v / v). Further washing with heptane-ethyl acetate 4/1 (v / v) gave 77.2 g of a solid containing the compound (xxi-b) as a main component. The yield was 75% based on 2,5-dimethoxyaniline.

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

[Example of synthesis of compound (xxi-d)]
A mixture containing the compound (xxi-c) obtained in the previous 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 the mixture was stirred. The precipitated solid was washed with cold water and hexane, and the compound (xxi-) was washed with hot ethanol. d) 45.9 g was obtained. The yield was 57% on a compound (xxb-d) basis.

[Example of synthesis of compound (xxi-a)]
45.0 g (144.2 mmol) of compound (xxi-d) and 225.0 g (5-fold 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 (xxii-a) as a main component. The yield was 100% on a compound (xxi-d) basis.

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

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

[Example of synthesis 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 (Lawesson's reagent) 64 .7 g (160.0 mmol) and 500 g of toluene were mixed, heated to 80 ° C., and stirred. The obtained mixed solution was cooled and then concentrated to obtain a red viscous liquid containing a decomposition product of Lawesson's reagent and a compound (xxiii-c) as main components.

[Example of synthesis 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 is added to the obtained mixed solution under ice-cooling, and the mixture is stirred. The precipitated solid is washed with cold water and hexane, washed with hot ethanol, and recrystallized from toluene. As a result, 25.2 g of the compound (xxiii-d) was obtained. The yield was 47% on a compound (xxiii-b) basis.

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

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

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

<Example of synthesis of compound (v'-1) in the first pathway>
The compound (v'-1) was obtained in the same manner as in the synthesis example of the compound (v-1) except that the raw material compound (va) was changed to the compound (v'-a). The yield was 73% based on 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 to 4.20 (t, 4H), 5.80 to 5.84 (dd, 2H), 6.07 to 6.18 (m, 2H), 6 .37 to 6.44 (m, 2H), 6.86 to 7.01 (m, 8H), 7.23 (m, 2H), 7.98 to 8.11 (m, 3H)

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

<Example of synthesis of compound (vi-1) in the first pathway>
The compound (vi-1) was obtained in the same manner as in the synthesis example of the compound (v-1) except that the raw material compound (va) was changed to the compound (vi-a). The yield was 84% on a compound (vi-a) basis.

<Example of synthesis of compound (x-1) in the first pathway>
The compound (x-1) was obtained in the same manner as in the synthesis example of the compound (v-1) except that the raw material compound (va) was changed to the compound (xa). The yield was 84% based on 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) exhibited a smectic phase from 101 ° C. to 106 ° C., a nematic phase from 106 ° C. to 180 ° C. or higher when the temperature was raised, and a nematic phase up to 81 ° C. when the temperature was lowered, and crystallized. ..

<Example of synthesis of compound (xi-1) in the first pathway>
The compound (xi-1) was obtained in the same manner as in the synthesis example of the compound (v-1) except that the raw material compound (va) was changed to the compound (xi-a). The yield was 55% based on 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 observed by texture observation with a polarizing microscope. The compound (xi-1) exhibited a smectic phase from 111 ° C. to 125 ° C., a nematic phase from 125 ° C. to 242 ° C. when the temperature was raised, and a nematic phase from 242 ° C. to 82 ° C. when the temperature was lowered. ..

<Example of synthesis of compound (xvi-1) in the first pathway>
The compound (xvi-1) was obtained in the same manner as in the synthesis example of the compound (v-1) except that the raw material compound (va) was changed to the compound (xvi-a). The yield was 78% on a compound (xvi-a) basis.

¹ H-NMR (CDCl ₃ ) of compound (xvi-1): δ (ppm) 1.45 to 1.86 (m, 24H), 2.35 to 2.83 (m, 18H), 3.92 to 3.97 (t, 4H), 4.15-4.19 (t, 4H), 5.80-5.84 (dd, 2H), 6.07-6.18 (m, 2H), 6. 37 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 temperature rise, and was thermally polymerized.

<Example of synthesis of compound (xvii-1) in the first pathway>
The compound (xvii-1) was obtained in the same manner as in the synthesis example of the compound (v-1) except that the raw material compound (va) was changed to the compound (xvii-a). The yield was 53% on a compound (xvii-a) basis.

¹ H-NMR (CDCl ₃ ) of compound (xvii-1): δ (ppm) 1.45 to 1.86 (m, 24H), 2.35-2.83 (m, 12H), 3.93 to 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), 6.87 to 7.00 (m, 8H), 7.44 (2s, 1H), 7.50 (m, 3H), 8.02 to 8.06 (m, 3H). m, 2H)

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

<Example of synthesis of compound (xviii-1) in the first pathway>
The compound (xviii-1) was obtained in the same manner as in the synthesis example of the compound (v-1) except that the raw material compound (va) was changed to the compound (xviiii-a). The yield was 82% on a compound (xviii-a) basis.

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

The phase transition temperature of the obtained compound (xvii-1) was observed 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. when the temperature was raised, and a nematic phase from 199 ° C. to 79 ° C. when the temperature was lowered. ..

<Example of synthesis of compound (xix-1) in the first pathway>
The compound (xix-1) was obtained in the same manner as in the synthesis example of the compound (v-1) except that the raw material compound (va) was changed to the compound (xix-a). The yield was 78% on a compound (xix-a) basis.

¹ H-NMR (CDCl ₃ ) of compound (xix-1): δ (ppm) 1.45 to 1.82 (m, 24H), 2.34 to 2.83 (m, 12H), 3.92 to 3.97 (t, 4H), 4.15 to 4.20 (t, 4H), 5.80 to 5.84 (dd, 2H), 6.07 to 6.18 (m, 2H), 6. 37 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., a nematic phase from 130 ° C. to 180 ° C. or higher when the temperature was raised, and a nematic phase up to 62 ° C. when the temperature was lowered, and crystallized. ..

<Example of synthesis of compound (xx-1) in the first pathway>
The compound (xx-1) was obtained in the same manner as in the synthesis example of the compound (v-1) except that the raw material compound (va) was changed to the compound (xx-a). The yield was 40% on a compound (xx-a) basis.

¹ H-NMR (CDCl ₃ ) of compound (xx-1): δ (ppm) 1.45 to 1.86 (m, 24H), 2.35 to 2.80 (m, 12H), 3.92 to 3.97 (t, 4H), 4.15-4.20 (t, 4H), 5.80-5.84 (dd, 2H), 6.07-6.18 (m, 2H), 6. 37 to 6.44 (m, 2H), 6.86 to 7.02 (m, 8H), 7.19 (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) exhibited a smectic phase from 110 ° C. to 114 ° C., a nematic phase from 114 ° C. to 160 ° C. or higher when the temperature was raised, and a nematic phase up to 69 ° C. when the temperature was lowered, and crystallized. ..

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

¹ H-NMR (CDCl ₃ ) of compound (xxi-1): δ (ppm) 1.43 to 1.86 (m, 24H), 2.35 to 2.84 (m, 12H), 3.90 to 3.97 (t, 4H), 4.15 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) in the first pathway>
The compound (xxiii-1) was obtained in the same manner as in the synthesis example of the compound (v-1) except that the raw material compound (va) was changed to the compound (xxiii-a). The yield was 46% on a compound (xxiii-a) basis.

¹ H-NMR (CDCl ₃ ) of compound (xxiii-1): δ (ppm) 1.44 to 1.86 (m, 24H), 2.35-2.84 (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 observed by texture observation with a polarizing microscope. The compound (xxiii-1) exhibited a smectic phase from 137 ° C. to 146 ° C., a nematic phase from 146 ° C. to 170 ° C. or higher when the temperature was raised, and a nematic phase up to 78 ° C. when the temperature was lowered, and crystallized. ..

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

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

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

<Example of synthesis of compound (xxv-1) in the first pathway>
<Example of synthesis of compound (xxv-1) in the first pathway>
The compound (xxv-1) was obtained in the same manner as in the synthesis example of the compound (v-1) except that the raw material compound (va) was changed to the compound (xxv-a). The yield was 77% on a compound (xxv-a) basis.

¹ H-NMR (CDCl ₃ ) of compound (xxv-1): δ (ppm) 1.44 to 1.90 (m, 24H), 2.35 to 2.82 (m, 12H), 3.92 to 3.98 (t, 4H), 4.15-4.21 (t, 4H), 5.79-5.84 (m, 2H), 6.07-6.18 (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 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 raised, 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 crystals at around 114 ° C. That is, it was found that the compound (xxiv-1) exhibited a nematic phase from 135 ° C. to 193 ° C. when the temperature was raised, and a nematic phase from 193 ° C. to 114 ° C. when the temperature was lowered.

Furthermore, it was also possible to synthesize polymerizable liquid crystals other than benzothiazole by the first route.
The method for synthesizing the liquid crystal molecule is shown below.

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

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

(Example of synthesis 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 mixed solution was heated at 100 ° C. with stirring. The obtained mixed solution was cooled to room temperature, 3.1 g (15.1 mmol) of N, N'-dicyclohexylcarbodiimide was dissolved in 9.4 g of tetrahydrofuran, added dropwise at room temperature, and then heated at 60 ° C. with stirring. The obtained mixed solution was filtered, the obtained organic layer was concentrated under reduced pressure, the solvent was removed, and methanol was added and stirred. The resulting precipitate was filtered and then vacuum dried to give 0.4 g (1.6 mmol) of compound (xxvi-a). The yield was 12% on a compound (xxvi-b) basis.

(Example of synthesis of compound (xxvi-1))
Compound (xxvi-a) 0.3 g (1.2 mmol), 4-dimethylaminopyridine 0.03 (0.3 mmol), compound (e) 1.2 g (2.8 mmol), and chloroform 24 g were mixed. Subsequently, a solution 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 the mixture was stirred. After filtering the obtained mixed solution, 12 g of 2N hydrochloric acid was added and stirred, the liquid was separated, and the organic layer was taken out. After distilling off the solvent of this organic layer, methanol was added and the mixture was stirred. The resulting precipitate was filtered and then vacuum dried to give 0.7 g of compound (xxvi-1).
The yield was 54% based on xxvi-a.

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

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

(Example of synthesis 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 obtained 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 methanol was added and stirred. The resulting precipitate was filtered and then vacuum dried to give 0.4 g (1.5 mmol) of compound (xxvii-a). The yield was 13% on a compound (xxvi-b) basis.

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

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

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

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

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

The phase transition temperature of the obtained compound (i-1) was observed by texture observation with a polarizing microscope. Compound (i-1) exhibited a smectic phase from 125 ° C. to 128 ° C., a nematic phase from 128 ° C. to 200 ° C. or higher when the temperature was raised, and a nematic phase up to 106 ° C. when the temperature was lowered, and crystallized. ..

<Example of synthesis of compound (xxviii-1) in the first pathway>
Compound (e) 12.5 g (30 mmol), 4-dimethylaminopyridine 0.4 (3 mmol), 1,5-dihydroxyanthraquinone 2.9 g (12 mmol), and chloroform 100 g were mixed. A solution prepared by dissolving 9.3 g (45 mmol) of N, N'-dicyclohexylcarbodiimide in 25 g of chloroform in the obtained mixed solution was added dropwise at room temperature, and the mixture was stirred. Then, 124 g of 1N hydrochloric acid was added and stirred, and the liquid obtained by filtering to remove the solid substance was separated and the organic layer was taken out. After distilling off the solvent of this organic layer, methanol was added and the mixture was filtered to remove the solid substance. When the obtained solid material was dried, 10.5 g of the compound (xxviii-1) was obtained. The yield was 84% based on 1,5-dihydroxyanthraquinone.

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

<Example of synthesis of compound (xxix-1) in the first pathway>
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 in the obtained mixed solution was added dropwise at room temperature, and the mixture was stirred. Then, 124 g of 1N hydrochloric acid was added and stirred, and the liquid obtained by filtering to remove the solid substance was separated and the organic layer was taken out. After distilling off the solvent of this organic layer, methanol was added and the mixture was filtered to remove the solid substance. When the obtained solid material was dried, 10.3 g of the compound (xxix-1) was obtained. The yield was 82% based on 1,2-dihydroxyanthraquinone. When the phase transition temperature was confirmed by applying heat to this compound, no liquid crystal phase was observed and the compound was dissolved at 105 ° C.

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

<Example of synthesis of compound (xxxxi-1) in the first pathway>
Compound (xxxiii-1) was produced according to the following scheme.

[Example of synthesis of compound (xxxiii-b)]
Trans-Ceramic acid 23 g (155 mmol), 1H-benzotriazole-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 the mixture is stirred under ice-cooling in the dark, and 24.6 g (155 mmol) of 2,5-dimethoxyaniline is added to the obtained mixed solution at 0 ° C. for 8 hours at room temperature. Stirred all night. The obtained solution was extracted with methyl isobutyl ketone and separated into saturated aqueous sodium carbonate solution three times. The organic layer was recovered, concentrated under reduced pressure, and then 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 recovered and vacuum dried.
Both were washed again with cold methanol and dried to obtain 38.6 g of a light gray powder containing the compound (xxxiii-b) as a main component. The yield was 88% based on 2,5-dimethoxyaniline.

[Example of synthesis of compound (xxxiii-c)]
30 g (106.0 mmol) of compound (xxxiii-b), 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetane-2,4-disulfide (Lawesson's reagent) 22.27 g (55.0 mmol) and 500 g of toluene were mixed, heated to 80 ° C., and stirred. The obtained mixed solution was cooled and then concentrated to obtain a red viscous solid containing a decomposition product of Lawesson's reagent and a compound (xxxiii-c) as main components.

[Example of synthesis of compound (xxxiii-d)]
A mixture containing the compound (xxxxii-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 mixture was stirred. The precipitated solid was washed with cold water and hexane, and then washed with hot methanol. To obtain 17.7 g of the compound (xxxxii-d) as a yellow powder. The yield was 56% on a compound (xxxxii-b) basis.

[Example of synthesis of compound (xxxiii-a)]
10.6 g (35.7 mmol) of the compound (xxxxii-d) and 106.0 g (10 times by mass) of pyridinium chloride were mixed, the temperature was raised to 180 ° C., and the mixture was stirred for 2 hours. After cooling the obtained mixed solution, water was added, and the obtained precipitate was washed with water and hexane to obtain 10.8 g of a solid containing the compound (xxxiii-a) as a main component. The yield was 110% on a compound (xxxxii-d) basis.

(Example of synthesis of compound (xxxiii-1))
0.54 g (2.01 mmol) of compound (xxxiii-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. To the obtained mixed solution, 0.92 g (4.81 mmol) of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride was added, and the mixture was stirred. The obtained mixed solution was filtered through cerite and then concentrated under reduced pressure. The crude product was developed by column chromatography using 100% chloroform as an eluent, and then developed with a 95% chloroform and 5% acetone eluent. The orange adsorption band was recovered, concentrated under reduced pressure, and crystallized with ethanol. After recovering the crystals by filtration, the crystals were further washed with heptane and vacuum dried to obtain 1.21 g of the compound (xxxxi-1) as a white powder. The yield was 56% on the basis of xxxiii-a.

¹ H-NMR (CDCl ₃ ) of compound (xxxiii-1): δ (ppm) 1.44 to 1.83 (m, 24H), 2.34 to 2.84 (m, 12H), 3.92 to 3.97 (t, 4H), 4.15-4.20 (t, 4H), 5.79-5.84 (dd, 2H), 6.07-6.18 (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 (xxxxi-1) was observed by texture observation with a polarizing microscope. The compound (xxxiii-1) exhibited a nematic phase from 125 ° C. to 180 ° C. or higher when the temperature was raised, and exhibited a nematic phase up to 55 ° C. when the temperature was lowered, and crystallized.

Further, if the alkyl chain length of the compound (e) is changed in the same manner, the compounds (v-2), (v-3) and (v-4) can be synthesized by the same method as in the first pathway. Examples of synthesis of each compound are shown below.

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

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

(Example of synthesis of compound (d''))
80 g (219 mmol) of compound (b''), 1.40 g (6.42 mmol) of 3,5-ditershallybutyl-4-hydroxytoluene, 61.2 g (505 mmol) of N, N-dimethylaniline, 1,3- 1.00 g of dimethyl-2-imidazolidinone and chloroform were mixed. To the obtained mixed solution, 29.8 g (329 mmol) of aquiloyl chloride was added dropwise under a nitrogen atmosphere and ice cooling, and the mixture was returned to room temperature and then stirred. After confirming the completion of the reaction, the mixture was washed with a 2N hydrochloric acid aqueous solution and a saturated sodium carbonate aqueous solution, and the recovered organic layer was concentrated to obtain an intermediate. 700 ml of methanol was added to the obtained intermediate, and 3.34 g (18 mmol) of p-toluenesulfonic 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 obtained white powder was washed with water-methanol 2/1 (v / v), washed with heptane, and vacuum dried to obtain 62 g of compound (d ″). The yield was 84% based on compound (b'').

(Example of synthesis of compound (e''))
40.3 g (120 mmol) of compound (d''), 1.49 g (12.2 mmol) of dimethylaminopyridine, 28 g (122 mmol) of trans 1,4-cyclohexanedicarboxylic acid monoethoxymethyl ester (compound (f)), and 150 mL of chloroform was mixed. The obtained mixture was 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 the 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 recovered and washed with 2N aqueous hydrochloric acid solution. The organic layer was recovered, the insoluble component was filtered, dried over anhydrous sodium sulfate, filtered, and then the solvent was removed to obtain an intermediate.

The intermediate obtained in the previous section, 2.34 g (130 mmol) of pure water, 1.40 g (6.42 mmol) of 3,5-ditershallybutyl-4-hydroxytoluene, and 3.95 g of p-toluenesulfonic acid monohydrate (. 20.8 mmol) and 200 mL of THF were mixed. The obtained mixture 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 precipitated precipitate was collected by filtration, washed with pure water, and vacuum dried. The resulting powder was redissolved in chloroform and filtered through silica gel. The filtrate was collected and crystallized by adding 400 mL of chloroform and heptane. The obtained powder was collected by filtration and vacuum dried to obtain 44.4 g of compound (e ″). The yield was 82% in two steps based on compound (d ″).

(Example of synthesis of compound (b'''))
Monotetrahydropyranyl protected hydroquinone (a) 88.5 g (455 mmol), sodium hydroxide 35.5 g (888 mmol), 8-chlorooctanol 75 g (455 mmol), and dimethylacetamide 300 g were mixed. The obtained mixture was stirred at 90 ° C. and then at 100 ° C. for 2 hours under a nitrogen atmosphere. Then, the mixture was cooled to room temperature, the mixed solution was poured into 600 g of pure water, and the precipitated precipitate was recovered by filtration. Then, the precipitate was washed with 400 mL of a 6N aqueous sodium hydroxide solution, washed with heptane, and vacuum dried to obtain 132 g of the compound (b''''). The yield was 90% on the basis of 8-chlorooctanol.

(Example of synthesis of compound (d'''))
100 g (310 mmol) of compound (b'''), 1.40 g (6.42 mmol) of 3,5-ditershallybutyl-4-hydroxytoluene, 86.4 g (713 mmol) of N, N-dimethylaniline, 1, 3 -Dimethyl-2-imidazolidinone 1.00 g and chloroform were mixed. 42.11 g (465 mmol) of aquiloyl chloride was added dropwise to the obtained mixed solution under a nitrogen atmosphere and ice cooling, and the mixture was returned to room temperature and then 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 recovered organic layer was concentrated to obtain an intermediate. 300 ml of methanol was added to the obtained intermediate, and 3.34 g (18 mmol) of p-toluenesulfonic 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 for crystallization, and this was recovered. The obtained powder was washed with water-methanol 2/1 (v / v), further washed with heptane, and vacuum dried to obtain 72 g of the compound (d'''). The yield was 79% based on compound (b'''').

(Example of synthesis of compound (e'''))
25.1 g (86 mmol) of compound (d'''), 1.06 g (8.7 mmol) of dimethylaminopyridine, 20 g (86.9 mmol) of trans 1,4-cyclohexanedicarboxylic acid monoethoxymethyl ester (compound (f)). ), And 70 mL of chloroform were mixed. The obtained mixture was 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 the 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 recovered and washed with 2N aqueous hydrochloric acid solution. The organic layer was recovered, the insoluble component was filtered, dried over anhydrous sodium sulfate, filtered, and then the solvent was removed to obtain an intermediate.

The intermediate obtained in the previous section, 1.46 g (81 mmol) of pure water, 1.40 g (6.42 mmol) of 3,5-ditershallybutyl-4-hydroxytoluene, and 2.46 g of p-toluenesulfonic acid monohydrate (. 12.9 mmol) and 200 mL of THF were mixed. The obtained mixture was heated to 70 ° C. under a nitrogen atmosphere and then stirred for 2 hours. After allowing to cool to room temperature, the precipitate was removed by filtration, concentrated under reduced pressure at room temperature, and 800 mL of pure water was added to the residue. The precipitated precipitate was collected by filtration, washed with pure water, and vacuum dried. The obtained powder was washed with ethanol and water 2/3 (v / v), and then 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 compound (d ″).

<Example of synthesis of compound (v-2) in the first pathway>
The compound (v-2) was obtained in the same manner as in the synthesis example of the compound (v-1) except that the raw material compound (e) was changed to the compound (e'). The yield was 72% based on 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 to 6.44 (m, 2H), 6.87 to 7.02 (m, 8H), 7.27 (d, 2H), 8.19 to 8.23 (d, 2H), 8.34 to 8.38 (d, 2H)

<Example of synthesis of compound (v-3) in the first pathway>
The compound (v-3) was obtained in the same manner as in the synthesis example of the compound (v-1) except that the raw material compound (e) was changed to the compound (e''). The yield was 82% based on compound (va).

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

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

<Example of synthesis of compound (v-4) by the first pathway>
The compound (v-4) was obtained in the same manner as in the synthesis example of the compound (v-1) except that the raw material compound (e) was changed to the compound (e'''). The yield was 69% based on 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. Compound (v-4) exhibits a smectic phase from 163 ° C to 167 ° C when the temperature rises, a nematic phase from 167 ° C to 220 ° C, and a nematic phase from 220 ° C to 156 ° C when the temperature drops. Crystallized.

Further application of compound (f) to the second pathway enables the synthesis of compound v-1 derivatives with more diverse linking groups. An example of synthesis of compound v-5 is shown below.

<Example of synthesis of compound (v-5) by the second pathway>
Compound (v-5) was synthesized by the following scheme.

(Example of synthesis 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 in the obtained mixed solution was added dropwise at room temperature, and the mixture was stirred. The obtained mixture was filtered, 12 g of 2N hydrochloric acid was added and stirred, the liquid was separated, and the organic layer was taken out. After distilling off the solvent of this organic layer, tetrahydrofuran was added and stirred. The generated precipitate was removed by filtration, concentrated under reduced pressure, and then crystallized with heptane. This was recovered by filtration and vacuum dried to give compound (g) as a pale yellow powder.

(Example of synthesis of compound (h))
A solution prepared by dissolving the intermediate (g) obtained in the previous section in tetrahydrofuran, 1.18 g (65 mmol) of pure water, 1.40 g (6.42 mmol) of 3,5-ditertiarybutyl-4-hydroxytoluene, and paratoluene. 1.55 g (8.2 mmol) of sulfonic acid monohydrate and 115 mL of tetrahydrofuran were mixed. The obtained mixture 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 and then 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 compound (va).

(Example of synthesis 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 solution. 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 in the intermediate solution was added dropwise. The mixture was stirred overnight at room temperature, the white precipitate was removed by filtration, and the mixture was concentrated under reduced pressure. After adding 120 mL of ethanol to the residue, 44 g of p-toluenesulfonic acid monohydrate was added to adjust the pH of the solution to 4. The mixture was stirred at room temperature for 1 hour and the ethanol solution was poured into 1000 g of ice. The supernatant was removed by decantation, and the underlying liquid was further washed with water-ethanol 1/3, and the supernatant was also removed by decantation. Further, the compound (i) was obtained by washing with heptane and decantation. The yield was 50.0 g, and the yield was 70% based on 4-hydroxybutyl acrylate.

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

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

The phase transition temperature of the obtained compound (v-5) was observed by texture observation with a polarizing microscope. The compound (v-5) exhibited a smectic phase from 142 ° C. to 163 ° C., a nematic phase from 163 ° C. to 224 ° C. at the time of temperature rise, 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 pathway. The structure of compound v-6 and an example of its synthesis are shown below.

<Example of synthesis of compound (v-6) in the first pathway>
Compound (v-6) was synthesized by the following scheme. The structure of compound (v-6) is as follows.

(Example of synthesis 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 mixture was stirred at room temperature under a nitrogen atmosphere. 100 mL of heptane was added to the reaction solution, the resulting precipitate was filtered, and the filtrate was recovered. The filtrate was washed with 1N aqueous hydrochloric acid solution. The recovered organic layer was dried and filtered, and then a 50 vol% aqueous solution of methanol was added to the residue, and the obtained crystals were collected by filtration. The crystals were washed with heptane and pure water and then vacuum dried to obtain 58.0 g of compound (j). The yield was 98% based on the parahydroxybenzoic acid benzyl ester.

(Example of synthesis 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 7.5 g of palladium carbon were added to the obtained mixed solution, and the mixture was stirred under a nitrogen atmosphere. The reaction solution was depressurized and then stirred under a hydrogen atmosphere. When hydrogen consumption stopped, the solution was cerite filtered under a nitrogen atmosphere. After removing the solvent with an evaporator, the residue was washed with a 50 vol% aqueous methanol solution and vacuum dried to obtain 32.0 g of compound (k). The yield was 80% based on compound (j).

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

<Production example of compound (m)>
18.5 g of compound (l), 0.87 g of pure water, 0.87 g (4.6 mmol) of p-toluenesulfonic acid monohydrate, and 80 mL of THF were mixed. The obtained mixture 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 precipitated precipitate was collected by filtration, washed with pure water, and dried under vacuum to obtain 7.5 g of compound (m). The yield was 40% in two steps based on compound (l).

(Example of synthesis 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)), N, N'-dicyclohexylcarbodiimide 2.95 g (14.2 mmol), 0.29 g (2.4 mmol) of N, N-dimethylaminopyridine and 40 ml of dehydrated chloroform were mixed. The obtained mixture was stirred at room temperature under a nitrogen atmosphere. 20 mL of heptane was added to the reaction solution, the resulting precipitate was filtered, and the filtrate was recovered. The filtrate was washed with 1N aqueous hydrochloric acid solution. The organic layer was dried and filtered, concentrated under reduced pressure with an evaporator, ethyl acetate was added, concentrated under reduced pressure again, and then 300 mL of methanol cooled in an ice bath was added for reprecipitation. The obtained powder was washed with heptane and then vacuum dried to obtain 2.9 g of compound (v-6). The yield was 45% based on compound (m).

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

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

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

<Example of synthesis of compound (v-7) in the first pathway>
Compound (v-7) was synthesized by the following scheme.

(Example of synthesis of compound (n))
Compound (b) 30 g (102 mmol), 3,5-ditersally butyl-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. 16.0 g (153 mmol) of metaquilloyl chloride was added dropwise under a nitrogen atmosphere and ice cooling, and the mixture was returned to room temperature and then stirred for 3 hours. After confirming the completion of the reaction, p-toluenesulfonic acid monohydrate was added to adjust the pH to 2. 1.47 g of pure water was added to the reaction solution, and 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 the 2N hydrochloric acid aqueous solution to recover the organic layer. After concentrating the organic layer under reduced pressure, 1000 g of ice was added, and the mixture was vigorously stirred and crystallized, which was recovered. The obtained white powder was washed with water-methanol 2/1 (v / v), further washed with heptane and pure water, and vacuum dried to obtain 12.4 g of compound (n). The yield was 44% based on compound (b).

(Example of synthesis of compound (o))
Take 12.0 g (43 mmol) of compound (n), 0.53 g (4.3 mmol) of dimethylaminopyridine, and 10.0 g (44 mmol) of trans 1,4-cyclohexanedicarboxylic acid monoethoxymethyl ester (compound (f)). , Dissolved in 50 mL of chloroform. The mixture was ice-cooled and stirred under a nitrogen atmosphere, and a 20 mL chloroform solution of 9.8 g (48 mmol) of dicyclohexylcarbodiimide was added dropwise. After completion of the 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 recovered and washed with 2N aqueous hydrochloric acid solution. The organic layer was recovered, the insoluble component was filtered, dried over anhydrous sodium sulfate, filtered, and then the solvent was removed to obtain an intermediate.

The intermediate obtained in the previous section, 0.73 g (40 mmol) of pure water, 1.40 g (6.42 mmol) of 3,5-ditershallybutyl-4-hydroxytoluene, and 1.15 g of p-toluenesulfonic acid monohydrate (1.15 g). 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 precipitated precipitate was collected by filtration, washed with pure water, and vacuum dried. The resulting powder 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 vacuum dried to obtain 12.2 g of compound (o).
The yield was 68% in two steps based on compound (n).

<Example of synthesis of compound (v-7)>
In the synthesis example of compound (v-1), 6.7 g of compound (v-7) was obtained by the same method except that the raw material compound (e) was changed to compound (n). The yield was 55% based on compound (va).

¹ H-NMR (CDCl ₃ ) of compound (v-7): δ (ppm) 1.40 to 1.85 (m, 24H), 1.95 (d, 6H), 2.36 to 2.85 ( m, 12H) 3.93 to 3.97 (t, 4H), 4.14 to 4.19 (t, 4H), 5.46 to 5.55 (t, 2H), 6.10 to 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)

<Example of synthesis of compound (v-8) in the first pathway>
Compound (v-8) was synthesized by the following scheme.

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

(Example of synthesis of compound (q))
39 g (156 mmol) of compound (p), 12.2 g (304 mmol) of sodium hydroxide, 21.3 g (156 mmol) of 6-chlorohexanol, and 86 g of dimethylacetamide were mixed. The obtained mixture was stirred at 100 ° C. for 6 hours under a nitrogen atmosphere. After that, it 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 sunken oily crude purified product was dissolved in methyl isobutyl ketone and separated from pure water. The organic layer was recovered, concentrated and vacuum dried to obtain 42 g of compound (q) as a pale red viscous liquid. The yield was 77% based on compound (p).

(Example of synthesis of compound (r))
40 g (114 mmol) of compound (q), 1.40 g (6.42 mmol) of 3,5-ditershallybutyl-4-hydroxytoluene, 31.8 g (262 mmol) of N, N-dimethylaniline, and chloroform were mixed. To the obtained mixed solution, 15.5 g (171 mmol) of aquiloyl chloride was added dropwise under a nitrogen atmosphere and ice cooling, and the mixture was returned to room temperature and then stirred for 3 hours. After confirming the completion of the reaction, the pH was adjusted to 2 by adding paratoluenesulfonic acid monohydrate. 1.64 g of pure water was added to the reaction solution, and the mixture was stirred at room temperature for 1 hour. After confirming the completion of the reaction, 100 mL of heptane was added, and a 2N hydrochloric acid aqueous solution was added until dimethylaniline was completely removed, and the separated organic layer was recovered. The organic layer was treated with activated carbon, filtered through cerite, 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 compound (q).

(Example of synthesis of compound (s))
15.0 g (47 mmol) of compound (r), 0.58 g (4.7 mmol) of dimethylaminopyridine, 10.9 g (47 mmol) of trans 1,4-cyclohexanedicarboxylic acid monoethoxymethyl ester (compound (f)), and 40 mL of chloroform was mixed. The obtained mixture was 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 the dropping, the mixture was stirred at room temperature. 100 mL of heptane was added to the reaction solution and the resulting precipitate was filtered. The filtrate was recovered and washed with 2N aqueous hydrochloric acid solution. The separated organic layer was recovered, the insoluble component was filtered, dried over anhydrous sodium sulfate, silica gel was filtered, and the solvent was removed to obtain an intermediate.

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

<Example of synthesis of compound (v-7)>
0.7 g of the compound (v-7) was obtained by the same method except that the raw material compound (e) was changed to the compound (s) in the synthesis example of the compound (v-1). The yield was 4.5% based on compound (va).

¹ H-NMR (CDCl ₃ ) of compound (v-8): δ (ppm) 1.38 (s, 18H), 1.47 to 1.85 (m, 24H), 2.36 to 2.83 ( m, 12H) 3.95 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)

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

<Example of synthesis of compound (iv-9) and compound (v-9) by the first pathway>
Compound (iv-9) and compound (v-9) have the following structures.

The compound was synthesized by the following scheme.

(Example of synthesis of compound (t))
Compound (t) was synthesized from trans-4-hydroxycyclohexanecarboxylic acid and monoacrylic acid (4-hydroxybutyl: manufactured by Tokyo Kasei Kogyo Co., Ltd.) by a DCC condensation reaction or the like in the same manner as compound (m). .. The total 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 mixture 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 solution consisting of methyl isobutyl ketone / heptane (weight ratio 3/2). After stirring the obtained solution, the separated organic layer was recovered and washed with pure water. The organic layer was dried over anhydrous sodium sulfate, filtered, and then 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)>
Compound (u) 30.5 g (130 mmol), dimethylaminopyridine 1.59 g (13 mmol), trans 1,4-cyclohexanedicarboxylic acid monoethoxymethyl ester 30 g (130 mmol) and chloroform 200 mL were mixed. The obtained mixture was ice-cooled and stirred under a nitrogen atmosphere, and 29.57 g (143 mol) of dicyclohexylcarbodiimide was added dropwise. After the dropping was completed, the mixture was stirred. 200 mL of chloroform and 200 mL of heptane were added to the obtained reaction solution, and the resulting precipitate was filtered. The filtrate was collected and washed 3 times with pure water. The organic layer was recovered, dried over anhydrous sodium sulfate, filtered, methanol was added to the obtained residue and stirred, and the obtained powder was filtered off, and then methanol was further added and stirred.
The obtained powder was collected by filtration and vacuum dried to obtain 42 g of compound (v). The yield was 90% based on 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. To the obtained mixed solution, 1.2 g of 10% palladium-carbon (50% water content) was added under a nitrogen atmosphere. The obtained mixture was depressurized and then stirred at room temperature, normal pressure and hydrogen atmosphere. It was filtered under a 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) and then with 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 compound (v).

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

<Production example of compound (t)>
18.5 g of compound (x), 0.97 g (53.9 mmol) of pure water, 0.85 g (4.5 mmol) of p-toluenesulfonic acid monohydrate and 100 mL of THF were mixed. The obtained mixture 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 precipitated precipitate was collected by filtration, washed with pure water, and dried under vacuum to obtain 15.4 g of compound (t). The yield was 81% in two steps based on compound (x).

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

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

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

<Manufacturing example of optical film>
(Example 1)
A 2% by weight aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified type, manufactured by Wako Pure Chemical Industries, Ltd.) was applied to a glass substrate, and after heating and drying, a film having a thickness of 89 nm was obtained. Subsequently, the surface of the obtained film was subjected to a rubbing treatment, and then the coating liquid having the composition shown in Table 2 was applied to the surface to which the rubbing treatment was performed by a spin coating method. After drying on a 100 ° C. hot plate for 1 minute, the film was irradiated with ultraviolet rays of 1200 mJ / cm ² while heating at 100 ° C. to prepare an optical film having a film thickness of 1.04 μm.
In Table 2, the weight% in the table 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 Initiators: Irgacure 907, Irgacure 819 (manufactured by Ciba Specialty Chemicals, Inc.)
Leveling agent: BYK361N (manufactured by Big Chemie Japan)

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

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

(Example 5)
The coating liquid (mixed solution) having the composition shown in Table 2 was applied by a spin coating method onto the polyvinyl alcohol substrate subjected to the rubbing treatment described in Example 1. After drying on an 80 ° C. hot plate 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 being kept warm at the same temperature to prepare an optical film having a film thickness of 2.27 μm.

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

(Example 7)
The coating liquid (mixed solution) having the composition shown in Table 2 was applied by a spin coating method onto the polyvinyl alcohol substrate subjected to the rubbing treatment described in Example 1. After drying on an 80 ° C. hot plate 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 being kept warm at the same temperature to prepare an optical film having a film thickness of 2.11 μm.

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

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

(Example 10)
An optical film having a film 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 liquid (mixed solution) having the composition shown in Table 2 was applied by a spin coating method onto the polyvinyl alcohol substrate subjected to the rubbing treatment described in Example 1. After drying on an 80 ° C. hot plate for 1 minute, it was further dried at 150 ° C. for 1 minute. The obtained unpolymerized film was cooled to 100 ° C. and irradiated with ultraviolet rays of 1200 mJ / cm ² while keeping the temperature at the same temperature to prepare an optical film having a film thickness of 0.88 μm.

<Measurement of optical characteristics>
In the wavelength range of 450 nm to 700 nm, the phase difference value of the manufactured optical film is measured using a measuring machine (KOBRA-WR, manufactured by Oji Measuring Instruments Co., Ltd.), and the phase difference value Re (450) with a wavelength of 450 nm is measured by the program attached to the device. , The phase difference value Re (550) having a wavelength of 550 nm and the phase difference value Re (650) having 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.

(Example of synthesis of compound (TC-1))
In a container, 4.9 g (17.0 mmol) of compound (va), 1.7 g (8.5 mmol) of trans-4-n-pentylcyclohexanecarboxylic acid, 0.21 g (1.7 mmol) of 4-dimethylaminopyridine. , And 392 g of dehydrated pyridine were mixed, and then a solution prepared by dissolving 46.2 g (224.4 mmol) of N, N'-dicyclohexylcarbodiimide (DCC) in 98 g of dehydrated pyridine was added dropwise, and the obtained mixed solution was mixed at 60 ° C. The temperature was raised to 3 and the mixture was stirred.
After separating the precipitated solid by filtration, the solution was concentrated and 196 g of chloroform was added to the solution. The chloroform solution was washed with 196 g of 2N hydrochloric acid, and the separated organic layer was taken out. The organic layer was purified by a silica gel column under reduced pressure to obtain 2.8 g of a solid containing 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） (Example of synthesis of compound (TM-1))
In a container, 2.6 g (5.6 mmol) of compound (TC-1), 2.3 g (5.6 mmol) of compound (e), 0.07 g (0.56 mmol) of 4-dimethylaminopyridine, and 75 g of chloroform are mixed. Then, a solution prepared by dissolving 1.4 g (6.7 mmol) of N, N'-dicyclohexylcarbodiimide (DCC) in 19 g of chloroform was added dropwise, and the obtained mixed solution was stirred at room temperature. After separating the precipitated solid by filtration, chloroform was added to the solution.
The chloroform solution was washed with 94 g of 2N hydrochloric acid, and the separated organic layer was taken out. Methanol was added to the organic layer under reduced pressure to obtain a solid substance. The obtained solid substance was washed with methanol to obtain 1.2 g of compound (TM-1). The yield was 24% based on compound (TC-1).

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

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

<Manufacturing example of optical film>
(Example 11)
A 2% by weight aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified type, manufactured by Wako Pure Chemical Industries, Ltd.) was applied to a glass substrate, and after heating and drying, a film having a thickness of 89 nm was obtained. Subsequently, the surface of the obtained film was subjected to a rubbing treatment, and then the coating liquid having the composition shown in Table 4 was applied to the surface to which the rubbing treatment was performed by a spin coating method. After drying on a 170 ° C. hot plate for 1 minute, the film was irradiated with ultraviolet rays of 9600 mJ / cm ² while heating at 130 ° C. to prepare an optical film having a film thickness of 1.353 μm.
The weight% in the table 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 liquid shown in Table 4 was applied by a spin coating method, dried on a hot plate at 45 ° C. for 1 minute, and irradiated with ultraviolet rays at room temperature. With respect to the obtained optical film, the phase difference value was measured in the same manner as in Example 1 using a measuring machine (KOBRA-WR, manufactured by Oji Measuring Instruments Co., Ltd.). The results are shown in Table 5.

<Measurement of optical characteristics>
With respect to the prepared optical film, the phase difference value at a wavelength of 547 nm was measured using a measuring device (KOBRA-WR, manufactured by Oji Measuring Instruments Co., Ltd.). Further, 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 phase difference value and the film thickness at a wavelength of 547 nm. Further, in the same manner, 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.

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

<Manufacturing 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 after drying, a film having a thickness of 89 nm was formed. Subsequently, the surface of the obtained film was subjected to a rubbing treatment, and the coating liquid having the composition shown in Table 6 was applied to the surface subjected to the rubbing treatment by a spin coating method and dried. Then, it was irradiated with ultraviolet rays. This made it possible to create an optical film on a glass substrate.

In Table 6, the weight% in the table other than the solvent means the weight% with the coating liquid as 100% by weight.

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

<Measurement of optical characteristics>
The front phase difference value of the produced optical film was measured using a measuring machine (KOBRA-WR, manufactured by Oji Measuring Instruments Co., Ltd.). Since the glass substrate used as the base material does not have birefringence, the front phase difference 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 values were measured at wavelengths of 447.3 nm, 546.9 nm, and 627.8 nm, respectively, and were measured as [Re (447.3) / Re (546.9)] (referred to as α). And [Re (627.8) / Re (546.9)] (referred to as β) were calculated. Further, the film thickness (μm) of the portion derived from the optical film was measured using a laser microscope (LEXT, manufactured by Olympus Corporation). The results are shown in Table 7. Δn was calculated by dividing the value of Re (546.9) by the film thickness.

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

According to the compound of the present invention, it is possible to provide an optical film capable of uniform polarization conversion in a wide wavelength range.

It is a schematic diagram which shows the color filter 1 which concerns on this invention. It is a schematic diagram which shows the liquid crystal display device 5 which concerns on this invention. It is a schematic diagram which shows the polarizing plate 30 which concerns on this invention. It is a schematic diagram which shows the bonded product 21 of the liquid crystal panel 20 and the polarizing plate 30 of the liquid crystal display device which concerns on this invention. It is a schematic diagram which shows the organic EL panel 23 of the organic EL display device which concerns on this 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 Opposite electrode 9 Liquid crystal layer 12 TFT, Insulation layer 13 Transparent electrode 13'Reflective electrode 30, 30a, 30b, 30c, 30d, 30e Polarizing plate 14, 14' Laminated body 15 Polarizing film 16, 16'Supporting substrate 17, 17'Alignment film 18, 18'Optical film 19, 19'', 22, 25 Adhesive layer 20 Liquid crystal panel 21 Laminated product 23 Organic EL panel 24 Light emitting layer

Claims (10)

An optical film comprising a group represented by the formula (A) and a polymerizable group and polymerized with a compound exhibiting a nematic phase, having a thickness of 0.1 to 10 μm and having a wavelength of 450 nm, a retardation value Re ( 450), the phase difference value Re (550) having a wavelength of 550 nm and the phase difference value Re (650) having a wavelength of 650 nm are
An optical film satisfying Re (450) / Re (550) ≤ 1.009 and 0.992 ≤ Re (650) / Re (550).
-G ^a -D ^a -Ar ^a -D ^b -G ^b- (A)
[In the formula (A), Ar ^a represents a divalent group having an aromatic heterocycle, and the number Nπa of π electrons contained in the aromatic ring in the Ar ^a group is 12 or more.
D ^a and D ^b independently represent —CO— or —O—CO— , respectively.
^{Ga and G b each} independently represent a divalent alicyclic hydrocarbon group. The hydrogen atom contained in the alicyclic hydrocarbon group may be 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—. ] Ar ^a has at least one aromatic ring selected from the group consisting of a benzene ring, a naphthalene ring, an anthracene ring, a phenanthroline ring, a furan ring, a pyrrole ring, a thiophene ring, a pyridine ring, a thiazole ring, and a benzothiazole ring. The optical film according to claim 1, which is a divalent group. The optical film according to claim 1 or 2, wherein ^{Ga and G b are} 1,4-cyclohexylene groups. The optical film according to any one of claims 1 to 3, wherein the phase difference value (Re (550)) at a wavelength of 550 nm is for a λ / 4 plate having a wavelength of 113 to 163 nm. The optical film according to any one of claims 1 to 3 , wherein the phase difference value (Re (550)) at a wavelength of 550 nm is for a λ / 2 plate having a wavelength of 250 to 300 nm. The polarizing plate including the optical film according to any one of claims 1 to 5 and a polarizing film. A color filter in which the optical film according to any one of claims 1 to 5 is formed on an oriented polymer directly applied onto a color filter substrate. A flat panel display device including a liquid crystal panel including the polarizing plate according to claim 6. An organic EL display device including an organic electroluminescence panel including the polarizing plate according to claim 6. A liquid crystal display device including the color filter according to claim 7.

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