TWI443132B - Optical film - Google Patents

Description

Optical film

The invention relates to optical films.

A flat display device (FPD) includes a member using an optical film such as a polarizing plate and a phase difference plate. The optical film is obtained by coating a solution obtained by dissolving a polymerizable compound in a solvent on a support substrate, followed by polymerization.

On the other hand, it is known that the phase difference (Re(λ)) of the optical film that imparts light having a wavelength of λ nm is determined by the product of the birefringence 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 Re(λ) of a certain wavelength λnm by the phase difference Re (550) of 550 nm, and it is known that Re(λ)/Re(550)) is a wavelength region close to 1, and shows the reverse wavelength dispersion of [Re(450)/Re(550)]<1 and [Re(650)/Re(550)]>1 In the wavelength region, the same polarization conversion can be performed.

In SID Symposium Digest of Technical Papers, Vol. 37, p. 1673, 2006, a compound (LC242) represented by the following formula is disclosed as a polymerizable compound.

The present invention provides the following, etc.:

[1] An optical film obtained by polymerizing a compound containing a group represented by the formula (A) and at least one polymerizable group:

(wherein Ar represents a divalent group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and the total number of π electrons of the aromatic ring contained in the divalent group is N _π 12 or more; D _a and D _b independently represent a single bond, -CO-O-, -O-CO-, -C(=S)-O-, .-OC(=S)-, -CR ¹ R ² -, -CR ¹ R ² -CR ³ R ⁴ -, -O-CR ¹ R ² -, -CR ¹ R ² -O-, -CR ¹ R ² -O-CR ³ R ⁴ -, -CR ¹ R ² -O-CO-, -O-CO-CR ¹ R ² -, -CR ¹ R ² -O-CO-CR ³ R ⁴ -, -CR ¹ R ² -CO-O-CR ³ R ⁴ - ^{, -NR 1 -CR 2 R 3 -} , - CR 2 R 3 -NR 1 -, - CO-NR 1 - or ^{-NR 1 -CO-; R 1, R} 2, R 3 and R ⁴ each independently represents a hydrogen atom, a fluorine atom or an alkyl group having a carbon number of 1 to 4; G _a and G _b each independently represent a divalent alicyclic hydrocarbon group, the alicyclic hydrocarbon-based may be selected from halogen atoms, having a carbon number of 1 to 4, At least one of an alkyl group, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group and a nitro group, and at least one of the alicyclic hydrocarbon groups The methylene group may be substituted by -O-, -S- or -NH-);

[2] The optical film according to [1], wherein the compound having a group represented by the formula (A) and at least one polymerizable group contains a group represented by the formula (B) and at least one polymerizable group. Compound:

Wherein Ar, D _a , D _b , G _a and G _b represent the same meaning as defined in [1]; E ¹ and E ² independently represent -CR ⁵ R ⁶ -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC (=S)-O-, -CO-NR ⁵ -, -NR ⁵ -CO-, -O-CH ₂ -, -CH ₂ -O-, -S-CH ₂ -, -CH ₂ -S- or a single bond; R ⁵ and R ⁶ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms;

[3] The optical film according to [2], wherein the compound having a group represented by the formula (B) and at least one polymerizable group contains a group represented by the formula (C) and at least one polymerizable group. Compound:

Wherein Ar, D _a , D _b , G _a , G _b , E ¹ and E ² represent the same meanings as defined in [1] and [2]; B ¹ and B ² independently represent -CR ⁵ R ⁶ -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR ⁵ -, -NR ⁵ -CO-, -O-CH ₂ -, -CH ₂ -O-, -S-CH ₂ -, -CH ₂ -S- or a single bond; R ⁵ and R ⁶ represent the same meaning as defined in [2]; A ¹ and A ² each independently represent a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group The alicyclic hydrocarbon group and the aromatic hydrocarbon group may be selected from 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, and a carbon number. Substituting at least one of a group of 1 to 4 fluoroalkoxy, cyano and nitro; k and 1 each independently represent an integer from 0 to 3;

[4] The optical film according to [3], wherein the compound represented by the formula (C) and the at least one polymerizable group are compounds represented by the formula (D):

(wherein Ar, D _a , D _b , G _a , G _b , E ¹ , E ² , B ¹ , B ² , k and 1 represent the same as defined in [1], [2] and [3] Meaning; F ¹ and F ² each independently represent an alkylene group having 1 to 12 carbon atoms, and the alkylene group may be selected from an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen. At least one of the groups of atoms is substituted, and at least one methylene group constituting the alkylene group may be substituted by -O- or -CO-; and any of P ¹ and P ² represents polymerization. a base, the other represents a hydrogen atom or a polymerizable group);

[5] The optical film according to [3] or [4], which satisfies the formula (2) and the formula (3):

(N _π -4)/3<k+1+4 (2)

12≦N _π ≦22 (3) ;

[6] The optical film according to [4], wherein the compound represented by the formula (D) is a compound represented by the formula (1):

(wherein Ar, E ¹ , E ² , B ¹ , B ² , F ¹ , F ² , P ¹ , P ² , k and 1 represent and [1], [2], [3] and [4] The definition has the same meaning; D ¹ and D ² independently represent *-O-CO- (* indicates the part combined with Ar), -C(=S)-O-, -OC(=S)-, - CR ¹ R ² -, -CR ¹ R ² -CR ³ R ⁴ -, -O-CR ¹ R ² -, -CR ¹ R ² -O-, -CR ¹ R ² -O-CR ³ R ⁴ -, ^{-CR 1 R 2 -O-CO -} , - O-CO-CR 1 R 2 -, - CR 1 R 2 -O-CO-CR 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 represents The same meaning as defined in [1]; G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group which may be selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, and a carbon number. At least one of a group consisting of a fluoroalkyl group of 1 to 4, an alkoxy group having 1 to 4 carbon atoms, a cyano group, and a nitro group, and at least one methylene group constituting the alicyclic hydrocarbon group may be Substituted by -O-, -S- or -NH-);

[7] The optical film according to any one of [1] to [6], wherein any one of the bases of the Ar system (Ar-1) to the formula (Ar-13):

(wherein Z ¹ represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, a carboxyl group, a fluoroalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, an N-alkylamino group having 1 to 6 carbon atoms, and 2 to 12 carbon atoms N,N-dialkylamino group, N-alkylsulfamoyl having 1 to 6 carbon atoms, or N,N-dialkylamine sulfonyl group having 2 to 12 carbons; Q ¹ and Q ³ each independently represent -CR ⁷ R ⁸ -, -S-, -NR ⁷ -, -CO- or -O-; R ⁷ and R ⁸ each independently represent a hydrogen atom or a carbon number of 1 to 4 The alkyl group; Y ¹ , Y ² and Y ³ each independently represent a substituted aromatic hydrocarbon group or a substituted aromatic heterocyclic group; W ¹ and W ² each independently represent a hydrogen atom, a cyano group, and a a base or a halogen atom; m represents an integer from 0 to 6, and n represents an integer from 0 to 2;

[8] The optical film according to [1], [2], [3], [4], [5] or [7], wherein D _a and D _b each independently represent *-O-CO-, *-OC(=S)-, *-O-CR ¹ R ² -, *-NR ¹ -CR ² R ³ - or *-NR ¹ -CO- (* indicates a site to which Ar is bonded);

[9] The optical film according to [1], [2], [3], [4], [5], [7] or [8], wherein G _a and G _b are 1,4-extension rings Hexyl

[10] The optical film according to [6], wherein D ¹ and D ² each independently represent *-O-CO-, *-OC(=S)-, *-O-CR ¹ R ² -, * -NR ¹ -CR ² R ³ - or *-NR ¹ -CO- (* indicates a site to which Ar is bonded);

[11] The optical film of [6] or [10] wherein G ¹ and G ² are 1,4-cyclohexylene;

[12] The optical film according to any one of [1] to [11] wherein the phase difference (Re (550)) at a wavelength of 550 nm is 113 to 163 nm;

[13] The optical film according to any one of [1] to [11] wherein the phase difference (Re (550)) at a wavelength of 550 nm is 250 to 300 nm;

[14] A composition comprising: a compound containing a group represented by the formula (A) and at least one polymerizable group, and a compound represented by the formula (4):

(wherein Ar represents a divalent group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and the total number of π electrons of the aromatic ring contained in the divalent group is N _π 12 or more; D _a and D _b each independently represent a single bond, -CO-O-, -O-CO-, -C(=S)-O-, -OC(=S)-, -CR ¹ R ² -, -CR ¹ R ² -CR ³ R ⁴ -, -O-CR ¹ R ² -, -CR ¹ R ² -O-, -CR ¹ R ² -O-CR ³ R ⁴ -, -CR ¹ R ² -O-CO-, -O-CO-CR ¹ R ² -, -CR ¹ R ² -O-CO-CR ³ R ⁴ -, -CR ¹ R ² -CO-O-CR ³ R ⁴ -, ^{-NR 1 -CR 2 R 3 -,} - CR 2 R 3 -NR 1 -, - CO-NR 1 - or ^{-NR 1 -CO-; R 1, R} 2, R 3 and R ⁴ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having a carbon number of 1 to 4; G _a and G _b each independently represent a divalent alicyclic hydrocarbon group, the alicyclic hydrocarbon-based may be selected from halogen atoms, alkoxy having a carbon number of 1 to 4 by Substituting at least one of a group of a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group and a nitro group, and constituting at least one of the alicyclic hydrocarbon groups The methyl group can be replaced by -O-, -S- or -NH-)

(wherein A ¹¹ represents an aromatic hydrocarbon group, an alicyclic hydrocarbon group or a heterocyclic group, and the aromatic hydrocarbon group, the alicyclic hydrocarbon group and the heterocyclic group may be selected from a halogen atom, an alkyl group having 1 to 6 carbon atoms, Substituting at least one of a group of alkoxy groups having 1 to 6 carbon atoms, an N-alkylamino group having 1 to 6 carbon atoms, a nitro group, a cyano group and a fluorenyl group; B ¹¹ and B ¹² are each independently represented -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 a single bond; R ¹⁴ and R ¹⁵ are independent The ground represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms, and R ¹⁴ and R ¹⁵ may be bonded to form an alkylene group having 4 to 7 carbon atoms; and E ¹¹ represents an alkylene group having 1 to 12 carbon atoms. the system may be selected from alkylene groups having 1 to 6 carbon atoms, the group at least one of the carbon atoms substituted by an alkoxy group and a halogen atom of from 1 to 6 formed by; P ¹¹ represents a polymerizable group; G is Hydrogen atom, halogen atom, alkyl group having 1 to 13 carbon atoms, carbon An alkoxy group of 1 to 13, a fluoroalkyl group having 1 to 13 carbon atoms, an N-alkylamino group having 1 to 13 carbon atoms, a cyano group or a nitro group, or an alkylene group having 1 to 12 carbon atoms; The alkylene group may be substituted with at least one selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a halogen atom; t represents 1 To the integer of 5);

[15] The composition according to [14], wherein the compound represented by the formula (A) and the at least one polymerizable group are compounds represented by the formula (1):

(wherein Ar represents the same meaning as defined in [14]; D ¹ and D ² each independently represent *-O-CO- (* indicates a site bonded to Ar), -C(=S)-O- , -OC(=S)-, -CR ¹ R ² -, -CR ¹ R ² -CR ³ R ⁴ -, -O-CR ¹ R ² -, -CR ¹ R ² -O-, -CR ₁ R ₂ -O-CR ³ R ⁴ -, -CR ¹ R ² -O-CO-, -O-CO-CR ¹ R ² -, -CR ¹ R ² -O-CO-CR 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 And R ² , R ³ and R ⁴ represent the same meanings as defined in [14]; G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group which may be selected from a halogen atom, carbon Substituting at least one of an alkyl group of 1 to 4, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group and a nitro group, and constituting the alicyclic ring At least one methylene group of the group hydrocarbon group may be substituted by -O-, -S- or -NH-; E ¹ and E ² each independently represent -CR ⁵ R ⁶ -, -CH ₂ -CH ₂ -, - O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S )-O-, -CO-NR ⁵ -, -NR ⁵ -CO-, -O-CH ₂ -, -CH ₂ -O-, -S-CH ₂ -, -CH ₂ -S- or a single bond; R ⁵ and R ⁶ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms; and B ¹ and B ² each independently represent -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 single a bond; A ¹ and A ² each independently represent a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group, and the alicyclic hydrocarbon group and the aromatic hydrocarbon group may be selected from a halogen atom and an alkyl group having 1 to 4 carbon atoms. And replacing at least one of a group consisting of a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a fluoroalkoxy group having 1 to 4 carbon atoms, a cyano group and a nitro group; 1 independently represents an integer of 0 to 3; respectively, F ¹ and F ² each independently represent an alkylene group having 1 to 12 carbon atoms, and the alkylene group may be selected from an alkyl group having 1 to 5 carbon atoms and a carbon number. At least one of a group of 1 to 5 alkoxy groups and a halogen atom is substituted, and at least one methylene group constituting the alkylene group may be substituted by -0- or -C0-; P ¹ and Any one of P ² represents a polymerizable group, and the other represents a hydrogen atom or a polymerizable group);

[16] The composition according to [14] or [15], which further comprises a photopolymerization initiator;

[17] A polarizing plate comprising: the optical film according to any one of [1] to [13], and a polarizing film;

[18] A color filter in which a color filter layer, an alignment film, and an optical film according to any one of [1] to [13] are sequentially laminated;

[19] A liquid crystal display device comprising the color filter according to [18];

[20] A flat display device comprising: the polarizing plate according to [17]; and a liquid crystal panel;

[21] An organic electroluminescence (EL) display device comprising: an organic EL panel comprising the polarizing plate according to [17];

[22] A compound of the formula (1):

(wherein Ar represents a divalent group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and the total number of π electrons of the aromatic ring contained in the divalent group is N _π 12 or more; D ¹ and D ² independently represent *-O-CO- (* indicates a portion bonded to Ar), -C(=S)-O-, -OC(=S)-, -CR ¹ R ² -, -CR ¹ R ² -CR ³ R ⁴ -, -O-CR ¹ R ² -, -CR ¹ R ² -O-, -CR ¹ R ² -O-CR ³ R ⁴ -, -CR ¹ R ² -O-CO-, -O-CO-CR ¹ R ² -, -CR ¹ R ² -O-CO-CR ³ R ⁴ -, -CR ¹ R2-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 each independently represent a hydrogen An atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms; and G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group which may be selected from a halogen atom and a carbon number of 1 to 4 Substituting at least one of a group of a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group and a nitro group, and constituting at least one of the alicyclic hydrocarbon groups The methyl group may be substituted by -O-, -S- or -NH-; E ¹ and E ² each independently represent -CR ⁵ R ⁶ -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -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 And R ⁵ and R ⁶ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms; and B ¹ and B ² each independently represent -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; A ¹ and A ² each independently represent a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group, and the alicyclic hydrocarbon group and the aromatic hydrocarbon group may be selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, and carbon. Substituting at least one of a group of 1 to 4 fluoroalkyl groups, 1 to 4 carbon atoms alkoxy groups, a carbon number 1 to 4 fluoroalkoxy group, a cyano group, and a nitro group; k and 1 respectively Independently representing an integer of 0 to 3; F ¹ and F ² each independently represent a C 1 to 12 alkyl group which may be selected from an alkyl group having 1 to 5 carbon atoms and a carbon number of 1 to Substituting at least one of a group of 5 alkoxy groups and halogen atoms, and constituting the extension At least one methylene group of the alkyl group may be substituted by -O- or -CO-; any of P ¹ and P ² represents a polymerizable group, and the other represents a hydrogen atom or a polymerizable group);

[23] The compound according to [22], which satisfies the formula (2) and the formula (3):

(N _π -4)/3<k+1+4 (2)

12≦N _π ≦22 (3) ;

[24] The compound according to [22] or [23], wherein any one of the groups represented by the formula (Ar-1) to the formula (Ar-13):

(wherein Z ¹ represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, a carboxyl group, a fluoroalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, an N-alkylamino group having 1 to 6 carbon atoms, and 2 to 12 carbon atoms N,N-dialkylamino group, N-alkylamine sulfonyl group having 1 to 6 carbon atoms, or N,N-dialkylamine sulfonyl group having 2 to 12 carbons; Q ¹ and Q ³ Respectively 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; ¹ , Y ² and Y ³ each independently represent a substituted aromatic hydrocarbon group or a substituted aromatic heterocyclic group; and W ¹ and W ² each independently represent a hydrogen atom, a cyano group, a methyl group or a halogen atom; m represents an integer from 0 to 6, and n represents an integer from 0 to 2);

[25] [22] a compound according to any of [24], wherein, D ¹ and D ² each independently represent a * -O-CO -, * - OC (= S) -, * - O- CR ¹ R ² -, *-NR ¹ -CR ² R ³ - or *-NR ¹ -CO- (* indicates a site to which Ar is bonded);

[26] [22] according to any one of the compound [25], wherein, G ¹ and G ² is 1,4-phenylene;

[27] A method for producing an unpolymerized film, which comprises applying a solution containing the compound according to any one of [22] to [26] onto a support substrate or an alignment formed on a support substrate. On the film and drying it to form an unpolymerized film;

[28] A method for producing an optical film, which comprises polymerizing an unpolymerized film obtained by the production method according to [27] to form an optical film.

The optical film of the present invention is obtained by polymerizing a compound containing a group represented by the following formula (A) and at least one polymerizable group (hereinafter abbreviated as compound (A)):

(wherein Ar represents a divalent group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and the total number of π electrons of the aromatic ring contained in the divalent group is N _π Is 12 or more; D _a and D _b independently represent a single bond, -CO-O-, -O-CO-, -C(=S)-O-, -OC(=S)-, -CR ¹ R ² -, -CR ¹ R ² -CR ³ R ⁴ -, -O-CR ¹ R ² -, -CR ¹ R ² -O-, -CR ¹ R ² -O-CR ³ R ⁴ -, -CR ¹ R ² -O-CO-, -O-CO-CR ¹ R ² -, -CR ¹ R ² -O-CO-CR ³ R ⁴ -, -CR ¹ R ² -CO-O-CR ³ R ⁴ - ^{, -NR 1 -CR 2 R 3 -} , - CR 2 R 3 -NR 1 -, - CO-NR 1 - or ^{-NR 1 -CO-; R 1, R} 2, R 3 and R ⁴ each independently represents a hydrogen atom, a fluorine atom or an alkyl group having a carbon number of 1 to 4; G _a and G _b each independently represent a divalent alicyclic hydrocarbon group, the alicyclic hydrocarbon-based may be selected from halogen atoms, having a carbon number of 1 to 4, At least one of an alkyl group, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group and a nitro group, and at least one of the alicyclic hydrocarbon groups The methylene group may be substituted by -O-, -S- or -NH-).

In the present invention, the "optical film" is a film which can penetrate light, and means a film having optical function. Optical function means refraction, birefringence, and the like. A retardation film belonging to one of the optical films is used to convert linearly polarized light into circularly polarized or elliptically polarized light, or conversely convert circularly polarized or elliptically polarized light into linearly polarized light.

The optical film of the present invention has the group represented by the above formula (A), and the same polarization conversion can be performed in a wide wavelength region. Further, the wavelength dispersion characteristics of the optical film can be adjusted by adjusting the content of the group represented by the formula (A) in the optical film.

Ar is selected from an aromatic hydrocarbon ring system having aromatic and heterocyclic groups formed by at least one divalent group of an aromatic ring, the divalent radical of an aromatic ring contained in [pi] N _π electrons of the total number of 12 or more, more It is preferably 12 or more and 22 or less, more preferably 13 or more and 22 or less.

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

Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthroline ring. Examples of the aromatic heterocyclic ring include a furan ring, a pyrrole ring, a thiophene ring, a pyridine ring, a thiazole ring, and a benzothiazole ring. Wait. Among them, a benzene ring, a thiazole ring, and a benzothiazole ring are preferred.

Any of Ar is a group represented by the following formula (Ar-1) to formula (Ar-13).

(wherein Z ¹ represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, a carboxyl group, a fluoroalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, an N-alkylamino group having 1 to 6 carbon atoms, and 2 to 12 carbon atoms N,N-dialkylamino group, N-alkylamine sulfonyl group having 1 to 6 carbon atoms, or N,N-dialkylamine sulfonyl group having 2 to 12 carbons; Q ¹ and Q ³ Respectively 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; ¹ , Y ² and Y ³ each independently represent a substituted aromatic hydrocarbon group or a substituted aromatic heterocyclic group; and W ¹ and W ² each independently represent a hydrogen atom, a cyano group, a methyl group or a halogen atom; m represents an integer from 0 to 6, and n represents an integer from 0 to 2.)

The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and a fluorine atom, a chlorine atom or a bromine atom is preferred.

The alkyl group having 1 to 6 carbon atoms may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, a third butyl group, a pentyl group or a hexyl group, and the like. An alkyl group of 1 to 4 is preferred, and an alkyl group having 1 to 2 carbon atoms is more preferred, and a methyl group is particularly preferred.

The alkylsulfinyl group having 1 to 6 carbon atoms may, for example, be a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group or a butylsulfinyl group. , isobutylsulfinyl, t-butylsulfinyl, tert-butylsulfinyl, pentylsulfinyl, hexylsulfinyl, etc., having an alkyl group of 1 to 4 carbon atoms The sulfinyl group is preferred, and the alkylsulfinyl group having 1 to 2 carbon atoms is more preferred, and the methylsulfinyl group is particularly preferred.

The alkylsulfonyl group having 1 to 6 carbon atoms may, for example, be methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl or isobutylsulfonate. a base, a second butyl sulfonyl group, a tert-butylsulfonyl group, a pentylsulfonyl group, a hexylsulfonyl group, etc., preferably an alkylsulfonyl group having 1 to 4 carbon atoms, and having a carbon number of 1 to The alkylsulfonyl group of 2 is more preferred, and the methylsulfonyl group is particularly preferred.

The fluoroalkyl group having 1 to 6 carbon atoms may, for example, be a fluoromethyl group, a trifluoromethyl group, a fluoroethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group or the like, and a fluorocarbon having 1 to 4 carbon atoms. The base is preferably a fluoroalkyl group having 1 to 2 carbon atoms, more preferably a trifluoromethyl group.

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 second butoxy group, and a third butoxy group. The pentyloxy group, the hexyloxy group and the like are preferably an alkoxy group having 1 to 4 carbon atoms, more preferably an alkoxy group having 1 to 2 carbon atoms, particularly preferably a methoxy group.

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 second butylthio group, a third butylthio group, The pentylthio group, the hexylthio group and the like are preferably an alkylthio group having 1 to 4 carbon atoms, more preferably an alkylthio group having 1 to 2 carbon atoms, and particularly preferably a methylthio group.

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, and N-butylamino group. , N-isobutylamino group, N-second butylamino group, N-tert-butylamino group, N-pentylamino group, N-hexylamino group, etc., with N to 1 to 4 carbon atoms The alkylamine group is preferred, and the N-alkylamine group having 1 to 2 carbon atoms is more preferred, and the N-methylamino group is particularly preferred.

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, N,N-diisopropylamino, N,N-dibutylamino, N,N-diisobutylamino, N,N-dipentylamine a N,N-dihexylamino group, etc., preferably a N,N-dialkylamino group having 2 to 8 carbon atoms, more preferably an N,N-dialkylamine group having 2 to 4 carbon atoms. It is particularly preferred to use N,N-dimethylamine.

The N-alkylamine sulfonyl group having 1 to 6 carbon atoms may, for example, be N-methylaminesulfonyl, N-ethylaminesulfonyl, N-propylaminesulfonyl, N-isopropylamine. Sulfonyl, N-butylamine sulfonyl, N-isobutylamine sulfonyl, N-butylbutylsulfonyl, N-t-butylamine sulfonyl, N-pentylamine Sulfhydryl group, N-hexylamine sulfonyl group, etc., preferably N-alkylamine sulfonyl group having 1 to 4 carbon atoms, more preferably N-alkylamine sulfonyl group having 1 to 2 carbon atoms, It is particularly preferred to use N-methylamine sulfonyl.

The N,N-dialkylamine sulfonyl group having 2 to 12 carbon atoms may, for example, be N,N-dimethylaminesulfonyl, N-methyl-N-ethylaminesulfonyl, N,N- Diethylamine sulfonyl, N,N-dipropylamine sulfonyl, N,N-diisopropylamine sulfonyl, N,N-dibutylamine sulfonyl, N,N-di Isobutylamine sulfonyl, N,N-dipentylamine sulfonyl, N,N-dihexylamine sulfonyl, etc., N,N-dialkylamine sulfonyl group having 2 to 8 carbon atoms More preferably, N,N-dialkylamine sulfonyl group having 2 to 4 carbon atoms is more preferred, and N,N-dimethylamine sulfonyl group is 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, and an N,N-dimethyl group. The amino group, N-methylamine sulfonyl group or N,N-dimethylamine sulfonyl group is preferred.

Examples of the alkyl group having 1 to 4 carbon atoms in R ⁷ and R ⁸ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group and the like, and a carbon number of 1. The alkyl group to 2 is preferred, and the methyl group is more preferred.

Q ¹ to Department -S -, - CO -, - NH -, - N (CH 3) - preferably, Q ³ to line -S -, - CO- preferred.

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 anthracenyl group, a phenanthryl group or a biphenyl group, and a phenyl group or a naphthyl group. Preferably, phenyl is preferred. Examples of the aromatic heterocyclic group include a 4 to 20 carbon aromatic group having at least one hetero atom such as a nitrogen atom, an oxygen atom or a sulfur atom, such as a furyl group, a pyrrolyl group, a thienyl group, a pyridyl group, a thiazolyl group or a benzothiazolyl group. The heterocyclic group is preferably a furyl group, a pyrrolyl group, a thienyl group, a pyridyl group or a thiazolyl group.

The aromatic hydrocarbon group and the aromatic heterocyclic group may have at least one substituent, and examples of the substituent include a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, and an alkyl group having 1 to 6 carbon atoms. Sulfonyl group, alkylsulfonyl group having 1 to 6 carbon atoms, carboxyl group, fluoroalkyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, alkylthio group having 1 to 6 carbon atoms, carbon number An N-alkylamino group of 1 to 6, an N,N-dialkylamino group having 2 to 12 carbon atoms, an N-alkylamine sulfonyl group having 1 to 6 carbon atoms, and a carbon number of 2 to 12, N-dialkylamine sulfonyl and the like, a halogen atom, an alkyl group having 1 to 2 carbon atoms, a cyano group, a nitro group, an alkylsulfonyl group having 1 to 2 carbon atoms, and a fluorocarbon having 1 to 2 carbon atoms. Alkoxy group having 1 to 2 carbon atoms, alkylthio group having 1 to 2 carbon atoms, N-alkylamino group having 1 to 2 carbon atoms, N,N-dialkylamino group having 2 to 4 carbon atoms An N-alkylamine sulfonyl group having 1 to 2 carbon atoms is preferred.

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, an alkylsulfonyl group having 1 to 6 carbon atoms, a carboxyl group, and a carbon number of 1 to 6 Fluoroalkyl group, alkoxy group having 1 to 6 carbon atoms, alkylthio group having 1 to 6 carbon atoms, N-alkylamino group having 1 to 6 carbon atoms, N,N-dioxane having 2 to 12 carbon atoms The amino group, the N-alkylamine sulfonyl group having 1 to 6 carbon atoms, and the N,N-dialkylamine sulfonyl group having 2 to 12 carbon atoms are as described above.

Y ¹ , Y ² and Y ³ are each independently a group represented by the following formulas (Y-1) to (Y-6).

(wherein Z ² represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, a carboxyl group, a fluoroalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, an N-alkylamino group having 1 to 6 carbon atoms, and 2 to 12 carbon atoms N,N-dialkylamino group, N-alkylamine sulfonyl group having 1 to 6 carbon atoms, or N,N-dialkylamine sulfonyl group having 2 to 12 carbon atoms; R represents a hydrogen atom or Methyl; a ₁ represents an integer from 0 to 5, a ₂ represents an integer from 0 to 4, b ₁ represents an integer from 0 to 3, and b ₂ represents an integer from 0 to 2.

From the viewpoint of easy production of the compound (A), Y ¹ , Y ² and Y ³ are each independently a group represented by the formula (Y-1) or (Y-3).

The W ^z and W ² systems are each independently preferably a hydrogen atom, a cyano group or a methyl group, and more preferably a hydrogen atom.

The m system is preferably 0 or 1. The n system is preferably 0.

Ar is more preferably a group represented by the following formula (Ar-6a), formula (Ar-6b), formula (Ar-6c), formula (Ar-10a) or formula (Ar-10b).

(wherein, Z ¹ , n, Q ¹ , Z ² , a ₁ and b ₁ have the same meaning as the above.)

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

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

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

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

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

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

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

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

D _a and D _b are each independently, and represent a single bond, -CO-O-, -O-CO-, -C(=S)-O-, -OC(=S)-, -CR ¹ R ² -, - CR ¹ R ² -CR ³ R ⁴ -, -O-CR ¹ R ² -, -CR ¹ R ² -O-, -CR ¹ R ² -O-CR ³ R ⁴ -, -CR ¹ R ² -O -CO-, -O-CO-CR ¹ R ² -, -CR ¹ R ² -O-CO-CR ³ R ⁴ -, -CR ¹ R ² -CO-O-CR ³ R ⁴ -, -NR ^{1 -CR 2 R 3 -, - CR} 2 R 3 -NR 1 -, - CO-NR 1 - or -NR ¹ -CO-; ^{wherein, R 1, R 2, R} 3 and R ⁴ each independently represent a hydrogen atom a fluorine atom or an alkyl group having 1 to 4 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group (second butyl group), tert-butyl group, etc.).

D _a and D _b are each independently, with *-O-CO-, *-OC(=S)-, *-O-CR ¹ R ² -, *-NR ¹ -CR ² R ³ - or *-NR ¹ -CO- (* indicates a bonding site with Ar) is preferred. D _a and D _b are each independently, preferably *-O-CO-, *-OC(=S)- or *-NR ¹ -CO- (* indicates a bonding site with Ar). R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group.

G _a and G _b are each independently and represent a divalent alicyclic hydrocarbon group, and the alicyclic hydrocarbon group may be selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, and carbon. At least one of a group of alkoxy groups, cyano groups and nitro groups of 1 to 4 is substituted.

The divalent alicyclic hydrocarbon group may, for example, be an alicyclic hydrocarbon group which may contain a hetero atom represented by the following formulas (g-1) to (g-10), and may be a bivalent 5-membered ring or a 6-membered ring. The alicyclic hydrocarbon group is preferred, and the 1,4-cyclohexylene group is more preferred, and the trans-1,4-cyclohexylene group is particularly preferred.

The group represented by the above formula (g-1) to (g-10) may be an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an isopropyl group or a third butyl group; a methoxy group and an ethoxy group; An alkoxy group having 1 to 4 carbon atoms; a fluoroalkyl group having 1 to 4 carbon atoms such as a trifluoromethyl group; a fluoroalkoxy group having 1 to 4 carbon atoms such as a trifluoromethoxy group; a cyano group; a nitro group; Substituted by a halogen atom such as an atom, a chlorine atom or a bromine atom.

The compound (A) contains at least one polymerizable group in addition to the group represented by the above formula (A). The compound (A) preferably has 2 to 4 polymerizable groups, and in view of the film hardness of the obtained optical film, it is preferred to have two polymerizable groups.

The polymerizable group may be a group which can participate in the polymerization reaction of the compound (A), and specifically, for example, a vinyl group, a p-stilbene group, an acryloyl group, a methacryl fluorenyl group, a propylene fluorenyl group, or a group Alkyl methoxy group, carboxyl group, ethyl hydrazino group, hydroxy group, amine carbenyl group, N-alkylamino group having 1 to 4 carbon atoms, amine group, epoxy group, oxetanyl group, methyl group, -N =C=O, -N=C=S, etc. Among them, a point which is suitable for photopolymerization is preferably a radical polymerizable group or a cationic polymerizable group, and is easy to handle and the compound (A) is easy to manufacture, and is a propylene fluorenyl group or a methacryl fluorenyl group. For better, it is especially good for acrylonitrile.

The polymerizable group may be directly bonded to the terminal of the group represented by the formula (A), and preferably bonded to one or more divalent linking groups.

The compound (A) is preferably a compound containing a group represented by the following formula (B); more preferably a compound having a group represented by the following formula (C); and further containing the following formula (D) The compounds shown are particularly preferred.

(wherein Ar, D _a , D _b , G _a and G _b have the same meanings as described above, and E ¹ and E ² are each independently, and represent -CR ⁵ R ⁶ -, -CH ₂ -CH ₂ -, -O -, -S-, -CO-O-,, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S -O-, -CO-NR ⁵ -, -NR ⁵ -CO-, -O-CH ₂ -, -CH ₂ -O-, -S-CH ₂ -, -CH ₂ -S- or a single bond; R ⁵ and R ⁶ are each independently and represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.);

(wherein, Ar, D _a , D _b , G _a , G _b , E ¹ and E ² have the same meanings as described above, and B ¹ and B ² are each independently, and represent -CR ⁵ R ⁶ -, -CH ₂ - CH ₂ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR ⁵ -, -NR ⁵ -CO-, -O-CH ₂ -, -CH ₂ -O-, -S-CH ₂ -, -CH ₂ -S Or a single bond; R ⁵ and R ⁶ have the same meanings as defined above. A ¹ and A ² are each independently and represent a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group, and the alicyclic hydrocarbon group and the aromatic 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 fluoroalkoxy group having 1 to 4 carbon atoms, a cyano group and a nitro group Substituted by at least one of the groups. K and 1 are each independent, representing an integer from 0 to 3.);

(wherein Ar, D _a , D _b , G _a , G _b , E ¹ , E ² , B ¹ and B ² have the same meanings as described above, and F ¹ and F ² are each independently, and represent a carbon number of 1 to 12; An alkyl group which may be substituted with at least one selected from the group consisting of an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen atom, and the alkyl group may be at least one methylene .P ¹ and wherein P represents a polymerizable group one of the -O- or -CO- ² substituted, and the other represents a hydrogen atom or a polymerizable group).

E ¹ and E ² are each independent, preferably -O-, -S-, -CO-O- or -O-CO-, and E ¹ is -CO-O-, and E ² is -O-CO - Better.

Examples of the divalent alicyclic hydrocarbon group or the divalent aromatic hydrocarbon group represented by A ¹ and A ² include a group represented by the above formula (g-1) to the above formula (g-10), and the following formula (a- 1) to the group represented by the formula (a-8), preferably a group represented by the formula (a-1) or the formula (g-1), 1,4-phenylene or 1,4-cyclohexylene Better.

The group represented by the above formula (a-1) to the formula (a-10) may be an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an isopropyl group or a third butyl group; a methoxy group and an ethoxy group; 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 halogen atom such as a fluorine atom, a chlorine atom or a bromine atom is substituted.

From the viewpoint of easily producing a compound having a group represented by the formula (C) or a compound represented by the formula (D), it is preferred that the bases of A ¹ and A ² are the same, and 1,4-phenylene is present. Or 1,4-cyclohexylene is more preferred, and 1,4-phenylene is particularly preferred.

From the viewpoint of easily producing a compound having a group represented by the formula (C) or a compound represented by the formula (D), it is preferred that B ¹ and B ² are the same. Only B ¹ and B ^{2 which} are bonded to A ¹ or A ² are independent, and are -CH ₂ -CH ₂ -, -CO-O-, -O-CO-, -CO-NH-, -NH-CO -, -O-CH ₂ -, -CH ₂ -O- or a single bond; in terms of the liquid crystallinity of the compound represented by the formula (C) or the compound of the formula (D), It is preferred to use -CO-O- or -O-CO-. The B ¹ and B ² systems bonded to E ¹ or E ² are each independently, and are -O-, -CO-O-, -O-CO-, -O-CO-O-, -CO-NH-, - NH-CO- or single-button is preferred.

K is preferably an integer from 0 to 2. 1 is preferably an integer from 0 to 2. The sum of K and 1 is preferably an integer of 5 or less, more preferably an integer of 4 or less, and particularly preferably the following formulas (2) and (3).

(N _π -4)/3<k+1+4 (2)

12≦N _π ≦22 (3)

The compound represented by the formula (D) is preferably a compound represented by the following formula (1).

(wherein, Ar, E ¹ , E ² , B ¹ , B ² , F ¹ , F ² , P ¹ , P ² , k and 1 represent the same meaning as described above, and D ¹ and D ² are each independently, indicating * -0-CO-(* indicates a site bonded to Ar), -C(=S)-O-, -OC(=S)-, CR ¹ R ² -, CR ¹ R ² -CR ³ R ⁴ - , -O-CR ¹ R ² -, -CR ¹ R ² -O-, -CR ¹ R ² -O-CR ³ R ⁴ -, -CR ¹ R ² -O-CO-, -O-CO-CR ¹ R ² -, -CR ¹ R ² -O-CO-CR 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 are each independently and represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms; G ¹ and G ² are each independently and represent a divalent alicyclic hydrocarbon group, and the alicyclic hydrocarbon group and the aromatic heterocyclic group may be selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, and a carbon number of 1. Substituting at least one of a group consisting of a fluoroalkyl group of 4, an alkoxy group having 1 to 4 carbon atoms, a cyano group and a nitro group, at least one methylene group constituting the alicyclic hydrocarbon group may be subjected to -O- , -S- or -NH- replaced.)

D ¹ and D ² are each independently, and are *-O-CO-, *-OC(=S)-, *-O-CR ¹ R ² -, *-NR ¹ -CR ² R ³ - or *-NR ¹ -CO- (* indicates a site bonded to Ar) is preferred. D ¹ and D ² are each independently, and more preferably *-O-CO-, *-OC(=S)- or *-NR ¹ -CO- (* indicates a site bonded to Ar). R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; more preferably a hydrogen atom, a methyl group or an ethyl group.

Specific examples of G ¹ and G ² include a group represented by the above formulas (g-1) to (g-10), preferably a group represented by the formula (g-1), and a 1,4-stretched ring. The hexyl group is more preferred, and the trans-1,4-cyclohexyl group is particularly preferred.

Specific examples of the group represented by the following formula (1-A) and formula (1-B) include the groups represented by the following formulas (R-1) to (R-134). Further, n in the formulae (R-1) to (R-134) represents an integer of 2 to 12.

Specific examples of the compound (1) include the compounds described in the following [Table 1] and [Table 2].

Further, in the compound (xxx) and the compound (xxxi), the group represented by the formula (1-A) and the group represented by the formula (1-B) are (R-57) to (R-120). ) either.

In the above Table 1, the compound (xvii) means a compound wherein the group represented by Ar is a group represented by the formula (ar-78), and the compound represented by Ar is a group represented by the formula (ar-79), or The group represented by Ar is any one of a mixture of a compound represented by the formula (ar-78) and a compound of the formula represented by the formula (ar-79).

In the above Table 2, the compound (xxx) means a compound represented by the formula (ar-120), or a compound represented by the formula (ar-121), or Any one of the mixture of the compound represented by the formula (ar-120) and the compound represented by the formula (ar-121) of the group represented by Ar, the compound (xxxi) means The compound represented by Ar is a compound represented by the formula (ar-122), the compound represented by Ar is a compound represented by the formula (ar-123), or the group represented by Ar is a formula (ar-122) Any of a mixture of a compound of the group shown and a compound of the formula (ar-123) represented by Ar.

Representative examples of the compounds described in Table 1 are as follows.

The method for producing the compound (A) is as follows, taking the compound (1) as an example.

The compound (1) can be suitably combined with conventional organic synthesis reactions (for example, condensation reaction) described in Methoden der Organischen Chemie, Organic Reactions, Organic Syntheses, Comprehensive Organic Synthesis, New Experimental Chemistry Lecture, etc. depending on the structure thereof. , esterification reaction, Williamson synthesis (Williamson synthesis), Ullmann reaction, Wittig reaction, Schiff base reaction, benzylation reaction, taro coupling Reaction (Sonogashira coupling reaction), Suzuki-Miyaura reaction, root-bank reaction, Xiongtian reaction, Lushan reaction, Buchwald-Hartwig Cross Coupling Reaction, Fried-Krafts reaction (Friedel-crafts reaction), Heck reaction, Aldol reaction, etc. can be obtained.

For example, when the compound (1) is D ¹ and D ² -O-CO-, it can be obtained by reacting a compound represented by the formula (1-1) with a compound represented by the formula (1-2). A compound represented by the formula (1-3), which is obtained by reacting the obtained compound represented by the formula (1-3) with a compound represented by the formula (1-4).

(wherein Ar represents the same meaning as the above.)

(wherein R ¹ , R ² , G ¹ , E ¹ , A ¹ , B ¹ , F ¹ , P ¹ and k represent the same meaning as described above.)

(wherein Ar, R ¹ , R ² , G ¹ , E ¹ , A ¹ , B ¹ , F ¹ , P ¹ and k represent the same meaning as the above.)

(wherein R ¹ , R ² , G ² , E ² , A ² , B ² , F ² , P ² and 1 have the same meanings as described above.)

The reaction of the compound of the formula (1-1) with the compound of the formula (1-2) and the reaction of the compound of the formula (1-3) with the compound of the formula (1-4) are preferably carried out at the ester. Implemented in the presence of a chemical.

Specific examples of the esterifying agent include, for example, 1-cyclohexyl-3-(2-N-morpholinoethyl)carbodiimide p-toluenesulfonate, dicyclohexylcarbodiimide, 1-B. 3-(3-dimethylaminopropyl)carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, bis(2,6- a carbodiimide compound such as diisopropylphenyl)carbodiimide, bis(trimethyldecyl)carbodiimide or diisopropylcarbodiimide; 2-methyl-6-nitrobenzene Formate; 2,2'-carbonylbis-1H-imidazole; 1,1'-oxadiazolidine; diphenylphosphonium azide; 1-(4-nitrophenylsulfonyl)-1H-1 , 2,4-triazole; 1H-benzotriazol-1-yloxytripyrrolidinylphosphonium hexafluorophosphate; 1H-benzotriazol-1-yloxytris(dimethylamino)phosphonium Hexafluorophosphate; N,N,N',N'-tetramethyl-O-(N-succinimide)urea ruthenium tetrafluoroborate; N-(1,2,2,2-tetrachloroethane Oxycarbonyloxy) succinimide; N-benzyloxycarbonyl succinimide; O-(6-chlorobenzotriazol-1-yl)-N,N,N',N'-tetramethyl Urea 鎓 tetrafluoroborate, O-(6-chlorobenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate; 2-bromo-1-B Pyridinium tetrafluoroborate; 2-chloro-1,3-dimethylimidazolium chloride; 2-chloro-1,3-dimethylimidazolium hexafluorophosphate; 2-chloro-1-methylpyridinium iodide; 2-chloro 1-methylpyridinium p-toluenesulfonate; 2-fluoro-1-methylpyridinium p-toluenesulfonate; pentachlorophenyl trichloroacetate.

Further, the compound represented by the formula (1-2) and the compound represented by the formula (1-4) can be converted into the corresponding mercapto chloride and then reacted.

The optical film of the present invention can be obtained by polymerizing the compound (A). One type of the compound (A) may be polymerized, or two or more kinds of the compound (A) may be polymerized. Further, the compound (A) and the liquid crystal compound having a polymerizable group other than the compound (A) (hereinafter simply referred to as a liquid crystal compound) may be polymerized.

Examples of the liquid crystal compound are as follows: 3.2 in the liquid crystal manual (Edited by the Liquid Crystal Manual Editorial Board, Japan Maruzen Publishing Co., Ltd.; published on October 30, 2000) Chapter 3 "Molecular Structure and Liquid Crystallinity" 3.2 "Non-pair A compound having a polymerizable group among the compounds described in "Characteristic rod-like liquid crystal molecules" and 3.3 "Planar rod-like liquid crystal molecules".

A liquid crystal compound may be used, or two or more liquid crystal compounds may be used.

Specific examples of the liquid crystal compound include a compound represented by the following formula (4) (hereinafter simply referred to as the compound (4)).

(wherein A ¹¹ represents an aromatic hydrocarbon group, an alicyclic hydrocarbon group or a heterocyclic group, and the aromatic hydrocarbon group, the alicyclic hydrocarbon group and the heterocyclic group may be selected from a halogen atom, an alkyl group having 1 to 6 carbon atoms, and carbon. Substituting at least one of a group of 1 to 6 alkoxy groups, 1 to 6 carbon N-alkylamino groups, a nitro group, a cyano group and a fluorenyl group. B ¹¹ and B ¹² are each independently represented by -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 a single bond; R ¹⁴ and R ¹⁵ are each independently represented a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms; R ¹⁴ and R ¹⁵ may be bonded to form an alkylene group having 4 to 7 carbon atoms; and E ¹¹ represents an alkylene group having 1 to 12 carbon atoms; The group may be substituted with at least one selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a halogen atom; P ¹¹ represents a polymerizable group; and G is a hydrogen atom or a halogen. Atom, an alkyl group having 1 to 13 carbon atoms, and an alkyl group having 1 to 13 carbon atoms a fluoroalkyl group having 1 to 13 carbon atoms, an N-alkylamino group having 1 to 13 carbon atoms, a cyano group or a nitro group, or a polymerizable group bonded via an alkyl group having 1 to 12 carbon atoms, Wherein the alkylene group may be substituted with at least one selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a halogen atom; t represents an integer of 1 to 5.

The polymerizable group in the formula (4) may be a group which can be polymerized with the compound (A), and examples thereof include a vinyl group, a vinyloxy group, a p-stilbene group, an acrylonitrile group, and an acrylonitrile group. Oxygen, methacryl oxime, methacryloxy group, carboxyl group, ethyl hydrazino group, hydroxyl group, amine carbaryl group, amine group, alkyl group having 1 to 4 carbon atoms, epoxy group, oxetane Base, formazan, -N=C=O or -N=C=S, etc. Among them, a point which is suitable for photopolymerization is preferably a radical polymerizable group or a cationic polymerizable group, and is easy to handle and the compound (A) is easily produced, and is propylene fluorenyl group, methacryl fluorenyl group or A vinyloxy group is preferred.

The carbon number of the aromatic hydrocarbon group, the alicyclic hydrocarbon group and the heterocyclic group of A ¹¹ is preferably from 3 to 18, more preferably from 5 to 12, particularly preferably from 5 or 6.

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

(wherein, P ¹¹ , E ¹¹ , B ¹¹ , A ¹¹ , B ¹² and t represent the same meaning as defined above; E ¹² represents an alkylene group having 1 to 12 carbon atoms, and the alkylene group may be selected from carbon atoms At least one selected from the group consisting of an alkyl group of 1 to 6 and an alkoxy group having 1 to 6 carbon atoms and a halogen atom; P ¹² represents a polymerizable group; and F ¹¹ represents a hydrogen atom, a halogen atom, and a carbon number of 1 to An alkyl group of 13, an alkoxy group having 1 to 13 carbon atoms, a fluoroalkyl group having 1 to 13 carbon atoms, an N-alkylamino group having 1 to 13 carbon atoms, a cyano group or a nitro group.

The compound represented by the compound (4-1) and the formula (4-2) can be exemplified by the following formula

(wherein A ¹² to A ¹⁵ are each independently and represent an aromatic hydrocarbon group, an alicyclic hydrocarbon group or a heterocyclic group, and the aromatic hydrocarbon group, the alicyclic hydrocarbon group and the heterocyclic group may be selected from a halogen atom, a carbon number of 1 to Substituting at least one of an alkyl group of 6 , an alkoxy group having 1 to 6 carbon atoms, an N-alkylamino group having 1 to 6 carbon atoms, a nitro group, a cyano group and a fluorenyl group; B ¹³ to B ¹⁶ Respectively independent, representing -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 a single bond; R ¹⁴ and R ¹⁵ means the same meaning as the above.)

The compounds represented by the above formula (4-1), formula (4-2), formula (I), formula (II), formula (III), formula (IV) and formula (V) are preferably such that P ¹¹ and E The bonding between the ¹¹ and the bonding between P ¹² and E ¹² are the conditions of the ether bond or the ester bond, and P ¹¹ , E ¹¹ , P ¹² and E ^{12 are selected} .

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

When the compound (A) and the liquid crystal compound are polymerized, when the total amount of the compound (A) and the liquid crystal compound is 100 parts by weight, the liquid crystal compound is usually used in an amount of 90 parts by weight.

The polymerization is usually carried out in the presence of a polymerization initiator.

The polymerization initiator is preferably a photopolymerization initiator. The photopolymerization initiator may, for example, be a benzoin compound, a benzophenone compound, a benzyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an iodonium salt or a phosphonium salt. Wait. Specific examples of the photopolymerization initiator include, for example, IRGACURE 907 (manufactured by Nippon Ciba), IRGACURE 184 (manufactured by Ciba (Japan), IRGACURE 651 (manufactured by Ciba), and IRGACURE 819 (made by Japan Ciba (share)), IRGACURE 250 (made by Japan Ciba (share)), IRGACURE 369 (made by Japan Ciba (share)), SEIKUOL BZ (made by Seiko Chemical Co., Ltd.), SEIKUOL Z (Seiko Chemical (stock) manufacturing), SEIKUOL BEE (manufactured by Seiko Chemical Co., Ltd.), KAYACURE BP100 (manufactured by Nippon Chemical Co., Ltd.), KAYACURE UVI-6992 (manufactured by Dow Chemical Co., Ltd.), ADEKA OPTOMER SP-152 ( ADEKA OPTOMER SP-170 (made by Eddie Co.).

The polymerization initiator is used in an amount of usually 0.1 part by weight to 30 parts by weight, based on 100 parts by weight of the total of the liquid crystal compound and the compound (A), preferably from 0.5 part by weight to 10 parts by weight. When it is in the above range, the compound (A) can be polymerized without disturbing the orientation of the liquid crystal compound.

The wavelength dispersion property of the optical film of the present invention can be arbitrarily determined by adjusting the content of the structural unit derived from the compound (A) in the optical film. When the content of the structural unit derived from the compound (A) in the optical film is increased, the obtained optical film exhibits a more planar wavelength dispersion property and exhibits reverse wavelength dispersion characteristics.

In order to obtain an optical film exhibiting the required wavelength dispersion characteristics, it can be carried out in the following manner. First, a composition containing a liquid crystal compound having a different content of the structural unit derived from the compound (A) and a compound (A) is prepared in an amount of about 2 to 5 types, and an optical film having the same film thickness is produced using each composition. The phase difference of the obtained optical film was measured, and the correlation between the content derived from the structural unit of the compound (A) and the phase difference of the optical film was determined. Based on the obtained correlation, the content of the structural unit derived from the compound (A) necessary for the desired phase difference of the optical film having the above film thickness is determined so as to modulate the liquid crystal compound and the compound in such a manner as to be the content. The composition of (A) is polymerized.

The method for producing the optical film of the present invention will be described below.

First, the compound (A), the above liquid crystal compound, and the above polymerization initiator are mixed to prepare a composition containing the compound (A). When the obtained composition is formed into a film, it is preferred to prepare a solution containing the compound (A) by using an organic solvent at the point where the composition can be easily formed. Further, additives such as a polymerization inhibitor, a photosensitizer, and a leveling agent may be used if necessary.

Examples of the polymerization inhibitor include hydroquinone or a hydroquinone compound having a substituent such as an alkyl ether, a catechol compound having a substituent such as an alkyl ether such as butyl catechol, and a pyrogallol compound, and 2 , a free radical scavenger such as 2,6,6-tetramethyl-1-piperidinyloxy radical, a thiophenol compound, a β-naphthylamine compound, a β-naphthol compound, or the like.

The stability of the resulting optical film can be improved by the use of a polymerization inhibitor, that is, the polymerization reaction can be easily controlled. The polymerization inhibitor is used in an amount of usually from 0.1 part by weight to 30 parts by weight, based on 100 parts by weight of the total of the liquid crystal compound and the compound (A), preferably from 0.5 part by weight to 10 parts by weight. When it is in the above range, the compound (A) can be polymerized without disturbing the orientation of the liquid crystal compound.

The photosensitizer may, for example, be an onion ketone compound such as xanthonone or thioxanthone, an anthracene compound having a substituent such as an alkyl ether, phenothiazine or red fluorene.

The polymerization reaction can be carried out with high sensitivity by the use of a photosensitizer. The photosensitizer is usually used in an amount of from 0.1 part by weight to 30 parts by weight, based on 100 parts by weight of the total of the liquid crystal compound and the compound (A), preferably from 0.5 part by weight to 10 parts by weight. When it is in the above range, the compound (A) can be polymerized without disturbing the orientation of the liquid crystal compound.

The leveling agent may, for example, be an additive for radiation hardening paint (manufactured by BYK Chemical Co., Ltd.; BYK-352, BYK-353, BYK-361N), a coating additive (manufactured by Toray Dow Corning Co., Ltd.); SH28PA, DC11PA , ST80PA), coating additives (manufactured by Shin-Etsu Chemical Co., Ltd.; KP321, KP323, X22-161A, KF6001), fluorine-containing additives (manufactured by Dainippon Ink Chemical Industry Co., Ltd.; F-445, F-470, F- 479) and so on.

The optical film can be smoothed by using a leveling agent. Further, in the production process of the optical film, the fluidity of the composition containing the compound (A) can be controlled, and the crosslinking density of the obtained optical film can be adjusted. The leveling agent is usually used in an amount of from 0.1 part by weight to 30 parts by weight, based on 100 parts by weight of the total of the liquid crystal compound and the compound (A), preferably from 0.5 part by weight to 10 parts by weight. When it is in the above range, the compound (A) can be polymerized without disturbing the orientation of the liquid crystal compound.

The organic solvent is an organic solvent which can dissolve the compound (A), a liquid crystal compound or the like, and is, for example, an inert solvent in the polymerization reaction, and specifically, for example, methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, methyl Alcohol solvent such as cellosolve or butyl cellosolve; ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, ethyl lactate and the like a solvent; a ketone solvent such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone or methyl isobutyl ketone; an aliphatic hydrocarbon solvent such as pentane, hexane or heptane; An aromatic hydrocarbon solvent such as toluene, xylene or chlorobenzene; a nitrile solvent such as acetonitrile; an ether solvent such as propylene glycol monomethyl ether, tetrahydrofuran or dimethoxyethane; a halogenated hydrocarbon solvent such as chloroform; phenol Wait. These organic solvents may be used singly or in combination of two or more. In particular, the composition containing the compound (A) and the liquid crystal compound is excellent in compatibility, and is soluble in an alcohol solvent, an ester solvent, a ketone solvent, a non-chlorinated aliphatic hydrocarbon solvent, and a non-chlorinated aromatic component. In the hydrocarbon solvent, it can be formed into a film without using a halogenated hydrocarbon solvent.

The viscosity of the solution containing the compound (A) is preferably adjusted to 10 Pa‧s or less, and preferably about 0.1 to 7 Pa‧s, in consideration of the coatability of the composition.

The solid content concentration in the solution containing the compound (A) is usually from 5 to 50% by weight. When the solid content concentration is 5% by weight or more, the optical film is not too thin, and there is a tendency to impart a birefringence required for the liquid crystal panel to adjust the optical optics (Adaptive Optics). Further, when the solid content concentration is 50% by weight or less, the viscosity of the composition is not too small, and the optical film is less likely to have a tendency to form uneven thickness.

The solution containing the compound (A) is applied onto a support substrate, dried, and polymerized, whereby an optical film can be obtained.

The solution containing the compound (A) is applied onto a support substrate and dried to obtain an unpolymerized film. When the unpolymerized film exhibits a liquid crystal phase such as a nematic type, the resulting optical film exhibits birefringence oriented by a single domain (Monodomain). Since the unpolymerized film is usually oriented at a temperature of from about 0 ° C to about 120 ° C, preferably from 25 ° C to 80 ° C, a support substrate which does not necessarily have sufficient heat resistance can be used. Further, the unpolymerized film does not crystallize even after cooling to about 10 to 30 ° C after the orientation, and thus is easy to handle.

The film thickness can be adjusted by appropriately adjusting the concentration of the compound (A) in the solution containing the compound (A) or the coating amount of the solution to the supporting substrate. When the compound (A) is a fixed amount of a solution, the phase difference (retardation value: Re(λ)) of the obtained optical film is determined according to the formula (7), so that the desired Re(λ) is obtained. Simply adjust the film thickness d.

Re(λ)=d×Δn(λ) (7)

(wherein, Re(λ) represents a phase difference of a wavelength λnm; d represents a film thickness; and Δn(λ) represents a birefringence of a wavelength λnm.)

Examples of the coating method of the support substrate include extrusion coating, gravure direct printing, gravure reverse printing, CAP coating, and die coating. A coating method of an applicator such as a dipper, a bar coater, or a spin coater can also be used.

Examples of the supporting substrate include glass, plastic sheets, plastic films, and translucent films. Examples of the light-transmitting film include polyolefin films such as polyethylene, polypropylene, and norbornene-based polymers; polyvinyl alcohol film; polyethylene terephthalate film; polymethacrylate film; polyacrylic acid. Ester film; cellulose ester film; polyethylene naphthalate film; polycarbonate film; polyfluorene film; polyether film; polyether ketone film; polyphenylene sulfide film; polyphenylene ether film.

Even in the step of requiring the optical film strength such as the bonding step, the transporting step, and the storage step of the optical film, by using the supporting substrate, the optical film can be prevented from being damaged and easy to handle.

After the alignment film is formed on the support substrate, a solution containing the compound (A) is preferably applied to the alignment film. When the solution containing the compound (A) is applied, the alignment film is preferably one having a solvent resistance insoluble in the solution. Further, in the heat treatment for removing the solvent or for orienting the liquid crystal molecules, the alignment film is preferably one having heat resistance. Further, in the case of rubbing, an oriented film which does not cause peeling or the like by rubbing or the like is preferable. The alignment film is preferably composed of a polymer or a composition containing a polymer.

The above-mentioned polymer may, for example, be a polyamine or a gelatin compound having a guanamine bond in the molecule, a polyamidimide having a quinone imine bond in the molecule, and a polylysine, a polyvinyl alcohol, an alkyl group of a hydrolyzate thereof. Polymers such as polyvinyl alcohol, polypropylene decylamine, polyoxazole, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid or polyacrylate. These polymers may be used singly or in combination of two or more. Further, it may be a copolymer of the polymers. These polymers can be easily obtained by chain polymerization such as polycondensation polycondensation, deamination polycondensation, radical polymerization, anionic polymerization, cationic polymerization or the like, coordination polymerization, ring-opening polymerization, or the like.

These polymers are generally used as a solution dissolved in a solvent. The solvent is not limited, and specific examples thereof include alcohol solvents such as methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, methyl cellosolve, and butyl cellosolve; ethyl acetate, butyl acetate, and ethylene glycol An ester solvent such as an ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate or ethyl lactate; acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone, a ketone solvent such as methyl isobutyl ketone; an aliphatic hydrocarbon solvent such as pentane, hexane or heptane; an aromatic hydrocarbon solvent such as toluene, xylene or chlorobenzene; a nitrile solvent such as acetonitrile; An ether solvent such as ether, tetrahydrofuran or dimethoxyethane; or a halogenated hydrocarbon solvent such as chloroform. These organic solvents may be used singly or in combination of two or more.

The oriented film can be formed directly using a commercially available oriented film material. The commercially available oriented film material may, for example, be Sunever (registered trademark; manufactured by Nissan Chemical Industries Co., Ltd.), Optmer (registered trademark; manufactured by JSR).

When such an alignment film is used, since the refractive index is controlled without stretching, the in-plane unevenness of birefringence becomes small, and large optics corresponding to the enlargement of a flat display device (FPD) on a supporting substrate can be provided. membrane.

The method of forming the alignment film on the support substrate is, for example, a method of applying a commercially available alignment film material or a compound as an alignment film material to a support substrate, followed by annealing treatment.

The thickness of the alignment film is generally from 10 nm to 10,000 nm, preferably from 10 nm to 1000 nm. As in the above range, the compound (A) or the like can be oriented on the oriented film at a desired angle. If necessary, the oriented film may be subjected to brushing treatment, or UV polarized light may be applied to the oriented film.

The method of brushing the oriented film is, for example, a method in which a rotating roller having a brushed cloth is brought into contact with an oriented film placed on a stage.

The method of laminating an unpolymerized film on an alignment film laminated on the support substrate can reduce the production cost and can be on the roll film as compared with the method of producing a liquid crystal cell and injecting the liquid crystal compound into the liquid crystal cell. Production of membranes.

The removal of the solvent can be carried out in parallel with the polymerization, however, in terms of film formability, it is preferred to remove most of the solvent before the polymerization.

Examples of the method for removing the solvent include natural drying, air drying, and vacuum drying. The temperature at which the solvent is removed by heating is preferably from 10 to 120 ° C, more preferably from 25 to 80 ° C. The heating time is preferably from 10 seconds to 60 minutes, more preferably from 30 seconds to 30 minutes. When the heating temperature and the heating time are within the above ranges, the supporting substrate used does not necessarily require heat resistance.

The obtained unpolymerized film is subjected to polymerization and hardening to obtain a film in which the orientation of the compound (A) is fixed, that is, a polymer film. An optical film having a small refractive index change in the plane direction of the film and a large refractive index change in the normal direction of the film can be obtained.

The method of polymerizing the unpolymerized film can be appropriately determined depending on the type of the liquid crystal compound and the compound (A). The photopolymerization method can be used as the photopolymerizable group in the polymerizable group in the compound (A) and the liquid crystal compound, and a thermal polymerization method can be used as the polymerizable group. For example, by photopolymerization, the unpolymerized film can be polymerized at a low temperature, and a polymerizable group having photopolymerization is used in terms of a wide selection of heat resistance of the substrate and an industrially easy point of manufacture. The compound (A) and the liquid crystal compound are preferred. Further, in terms of film formability, photopolymerization is also preferred. The photopolymerization reaction is carried out by irradiating visible light, ultraviolet light or laser light on the unpolymerized film. In operation, ultraviolet light is particularly preferred. The light irradiation can be carried out at a temperature at which the compound (A) becomes a liquid crystal phase. At this time, the polymer film may be patterned by a mask or the like.

The optical film of the present invention is easy to manufacture because of the adhesion between the support substrate and the optical film and the adhesion between the alignment film and the optical film.

The optical film of the present invention is thinner than a stretched film which imparts a phase difference by extending the polymer.

A film in which an alignment film and an optical film are laminated can be obtained by peeling off the support substrate. The alignment film is peeled off to obtain an optical film.

The optical film thus obtained is excellent in transparency and can be used as a film for various displays. The thickness of the optical film is as described above, and varies depending on the phase difference of the optical film. The thickness is preferably 0.1 μm to 10 μm, and preferably 0.5 μm to 3 μm at the point of reducing photoelasticity.

The phase difference of the optical film exhibiting birefringence is generally about 50 to 500 nm, preferably 100 nm to 300 nm.

An optical film which can be converted into the same polarized light in a wider wavelength range by such a film can be used as an optical compensation film in FPDs of all liquid crystal panels or organic ELs.

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

The optical film of the present invention can also be used as an optical film for a vertical orientation (VA: Vertical Almography) mode. When it is used as an optical film for a VA mode, the content of the structural unit derived from the compound (A) in the optical film may be appropriately selected. The film thickness is adjusted so that the Re (550) of the obtained optical film is preferably from 40 nm to 100 nm, more preferably from about 60 nm to 80 nm.

The optical film of the present invention can also be used in an antireflection film such as an anti-reflection (AR) film, a polarizing film, a retardation film, an elliptically polarizing film, a Wide View Film, or a transmissive liquid crystal display. An optical compensation film for viewing angle compensation or the like.

The optical film of the present invention exhibits excellent optical characteristics as long as one piece, and a plurality of laminated layers can also be used. Can be combined with other diaphragms. Specific examples of the combination with the other film include an elliptically polarizing plate in which the optical film of the present invention is bonded to a polarizing film, and the optical film of the present invention is further bonded to the ellipsic polarizing plate as a wide-band λ/4 plate. Broadband circular polarizer, etc.

The optical film of the present invention can be formed by coating and polymerization on a support substrate or an alignment film, whereby as shown in Fig. 1, a wide frequency can be formed on the filter more easily than in the past, such as λ/4. , λ/2 optical film.

Fig. 1 is a schematic view showing the color filter 1 of the present invention.

The filter 1 is formed by sequentially laminating the filter layer 4, the alignment film 3, and the optical film 2 of the present invention.

An example of the method of manufacturing the optical filter 1 is as follows. First, an oriented polymer is formed by laminating a polymer of orientation on the filter layer 4 and performing an orientation brushing process. The oriented polymer can be laminated using an inkjet method.

Next, the solution containing the compound (A) is applied to the obtained alignment film 3 to have a desired phase difference to form the optical film 2, and the solution is adjusted so that the content of the compound (A) is such that the obtained optical film has Modulated by the desired wavelength dispersion characteristics.

A thinner liquid crystal display device can be manufactured by using the filter 1. As an example, the schematic view of the liquid crystal display device 5 of the present invention is as shown in Fig. 2.

In the liquid crystal display device 5 shown in FIG. 2, the substrate 7 opposed to the backlight such as a glass substrate is fixed to the polarizing plate 6 via an adhesive. The optical film 2' is formed on the filter layer 4' formed on the substrate 7 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. The substrate 11 such as a backlight-side glass substrate is fixed to the polarizing plate 10 via an adhesive. Forming a thin film transistor (TFT) and an insulating layer 12 for actively driving the liquid crystal layer on the substrate 11, and forming a transparent electrode 13 and/or a reflective electrode by using Ag, Al or ITO (Indium Tin Oxide) in the TFT. 13'. The structure of the liquid crystal display device 5 shown in Fig. 2 is a structure in which the number of optical films is smaller than that of the conventional liquid crystal display device, and thus a thinner liquid crystal display device can be manufactured.

The filter layer 1' is a method of manufacturing the liquid crystal display device 5 formed on the liquid crystal layer side of one substrate, and one of them is described below. On the substrate on the backlight side, after depositing and patterning the gate electrode, the gate insulating film and the amorphous germanium formed of Mo and MoW on the borosilicate glass, the amorphous germanium is annealed by excimer laser to crystallize. A semiconductor film is formed, and then P, B, or the like is doped in the fields on both sides of the gate electrode to form an n-channel, p-channel TFT. Further, a substrate on the backlight side can be obtained by forming the insulating layer 12 made of SiO ₂ . Further, ITO is sprayed on the backlight-side substrate 11, whereby the transparent electrode 13 for the full-transmission type display device can be laminated on the backlight-side substrate. Further, in the same manner, by using Ag, Al or the like instead of ITO, the reflective electrode 13' for a total reflection type display device can be obtained. Further, by appropriately combining the reflective electrode and the transparent electrode, a backlight-side electrode for a transflective liquid crystal display device can be obtained.

On the one hand, the filter layer 4' is formed on the opposite substrate 7. A full-color liquid crystal display device can also be obtained by using the filters of R, G, and B in combination. Next, an orientation film 3' is formed on the filter layer 4' by coating a directional polymer and brushing it. The composition containing the compound (A) of the present invention is applied onto the alignment film 3', and heated to a temperature range of the liquid crystal phase, and polymerized to form an optical film 2' by ultraviolet light irradiation. After the optical film is formed, the counter electrode 8 can be formed by sputtering ITO. Further, an alignment film is formed on the counter electrode to form a liquid crystal phase 9. Finally, the liquid crystal display device 5 can be fabricated by being assembled in combination with the substrate on the backlight side.

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

Next, the polarizing plate of the present invention and the FPD including the polarizing plate will be described.

The polarizing plate of the present invention comprises the optical film and the polarizing film of the present invention, and is usually obtained by laminating the optical film and the polarizing film of the present invention. Specifically, it is obtained by a film having a polarizing function, that is, a film which is bonded to the optical film of the present invention directly or on both sides of the polarizing film. In the present specification, "adhesive" means both an adhesive and an adhesive. Hereinafter, the polarizing plate of the present invention will be described using Figs. 3 to 5 .

3(a) to 3(e) are schematic views of the polarizing plate 1 of the present invention.

The polarizing plate 30a shown in Fig. 3(a) directly bonds the laminated body 14 and the polarizing film 15, and the laminated body 14 is formed of the supporting substrate 16, the alignment film 17, and the optical film 18. The polarizing plate 30a is formed by laminating the support substrate 16, the alignment film 17, the optical film 18, and the polarizing film 15 in this order.

The polarizing plate 30b shown in Fig. 3(b) is formed by bonding the laminated body 14 and the polarizing film 15 via the adhesive layer 19.

The polarizing plate 30c shown in Fig. 3(c) directly bonds the laminated body 14 and the laminated body 14', and directly bonds the laminated body 14' and the polarizing film 15.

In the polarizing plate 30d shown in Fig. 3(d), the laminated body 14 and the laminated body 14' are bonded together via the adhesive layer 19, and the polarizing film 15 is directly bonded to the laminated body 14'.

The polarizing plate 30e shown in Fig. 3(e) has the laminated body 14 and the laminated body 14' bonded via the adhesive layer 19, and the laminated body 14' and the polarizing film 15 are interposed via the adhesive layer 19'. And the structure of the fit.

As the material for replacing the laminated body 14, the optical film 18 from which the support substrate 16 and the alignment film 17 are peeled off from the laminated body 14, or the film formed by the alignment film 17 and the optical film 18 from which the support substrate 16 is peeled off from the laminated body 14 can be used. . As the place of the laminated body 14', the optical film 18' which peels the support substrate 16' and the orientation film 17' from the laminated body 14', or the orientation film 17' which peels the support substrate 16' from the laminated body 14' can be used. And a film formed by the optical film 18'.

The polarizing plate of the present invention may be laminated with a plurality of layers, and the laminated bodies of the plurality of layers may be the same or different.

The polarizing film 15 may be a film having a polarizing function, and specifically, a film obtained by adsorbing iodine or a dichroic dye to a polyvinyl alcohol film, and extending the polyvinyl alcohol film to adsorb iodine or two colors Film of sexual pigments, etc.

The adhesive used in the adhesive layer 19 and the adhesive layer 19' is preferably an adhesive having high transparency and excellent heat resistance. Examples of the adhesive include an acrylic adhesive, an epoxy adhesive, and a urethane adhesive.

The flat display device of the present invention includes the optical film of the present invention, and specific examples thereof include a liquid crystal display device including a laminate in which a polarizing plate of the present invention is bonded to a liquid crystal panel, and a polarizing plate comprising the present invention. An organic EL display device of an organic EL panel in which a light-emitting layer is bonded.

The embodiment of the flat display device of the present invention is exemplified by a liquid crystal display device and an organic EL display device, and will be described below.

Fig. 4 is a schematic view showing a laminate 21 of a liquid crystal panel 20 and a polarizing plate 30 of a liquid crystal display device of the present invention. The laminate 21 is obtained by laminating the polarizing plate 30 of the present invention and the liquid crystal panel 20 via the adhesive layer 22. A voltage is applied to the liquid crystal panel 20 by using an electrode (not shown), thereby driving liquid crystal molecules to display in black and white.

Fig. 5 is a schematic view showing an organic EL panel 23 of the organic EL display device of the present invention. The organic EL panel 23 is obtained by bonding the polarizing plate 30 of the present invention and the light-emitting layer 24 via the adhesive layer 25.

In the above organic EL panel, the polarizing film 30 has a function of a wide-band circular polarizing plate. The light-emitting layer 24 is at least one layer made of a conductive organic compound.

[Examples]

The present invention will be described in more detail below by way of examples, but the examples are not limited to the examples.

Example 1-1

(1) A compound represented by the above formula (a) is obtained by reacting hydroquinone with dihydropyran according to the method described in JP-A-2004-262884.

(2) 100.1 g of the obtained compound of the formula (a), 97.1 g of potassium carbonate, 64 g of 6-bromohexanol and 200 mL of N,N-dimethylacetamide were mixed. The resulting mixture was reacted under a nitrogen atmosphere at 90 ° C, and then reacted at 100 ° C. The resulting reaction mixture was allowed to cool to room temperature. Methyl isobutyl ketone was added to the reaction mixture, and the mixture was separated into an organic layer and an aqueous layer. The obtained organic layer was washed first with pure water, an aqueous sodium hydroxide solution, and then with pure water. Anhydrous sodium sulfate was added to the organic layer after washing to carry out dehydration treatment. After the sodium sulfate was removed by filtration, the filtrate was concentrated under reduced pressure. Methanol was added to the obtained residue, and the precipitate was precipitated by filtration, and the precipitate obtained was dried in vacuo to give 126 g of the compound of the formula (b). The yield was 91% (based on 6-bromohexanol).

(3) 126 g of the compound represented by the formula (b), 1.40 g of 3,5-di-t-butyl-4-hydroxytoluene, 116.7 g of dimethylaniline, and 1,3-dimethyl-2-imidazole 1.00 g of linone was dissolved in chloroform. The resulting solution was ice-cooled, and 58.1 g of acrylonitrile chloride was added dropwise under a nitrogen atmosphere and reacted at room temperature. Pure water was added to the obtained reaction mixture and stirred. The organic layer was separated from the aqueous layer, and the obtained organic layer was washed with aqueous hydrochloric acid, saturated aqueous sodium carbonate and then purified water. Anhydrous sodium sulfate was added to the organic layer after washing to dry it. After sodium sulfate was removed by filtration, 1 g of 3,5-di-t-butyl-4-hydroxytoluene was added to the obtained filtrate, and the mixture was concentrated under reduced pressure to give the compound of the formula (c).

(4) After adding 200 mL of tetrahydrofuran to the obtained compound of the formula (c), 200 mL of tetrahydrofuran was further added. After hydrochloric acid was added to the obtained solution, it was reacted under a nitrogen atmosphere at 60 °C. Saturated brine was added to the obtained reaction mixture and stirred, and the mixture was separated into an organic layer and an aqueous layer. Anhydrous sodium sulfate was added to the obtained organic layer and subjected to dehydration treatment. After the sodium sulfate was removed by filtration, the obtained filtrate was concentrated under reduced pressure. Hexane was added to the obtained concentrate and stirred under ice cooling. The precipitated solid was taken out by filtration. The solid which was taken out was vacuum dried to obtain 90 g of the compound represented by the above formula (d). The yield was 79% (based on the compound represented by the formula (c)).

(5) 24.68 g of trans-cyclohexanedicarboxylic acid and toluene were mixed. 74.91 g of grass chlorobenzene and 0.5 mL of N,N-dimethylformamide were added to the resulting mixture, and the resulting mixture was stirred under a nitrogen atmosphere to cause a reaction. After completion of the reaction, the mixture was concentrated under reduced pressure. To the resulting residue, chloroform was added to obtain a solution 1.

12 g of the compound of the formula (d) obtained in the above (4) was dissolved in chloroform. Further, the obtained solution and 12.6 g of pyridine were mixed to obtain a solution 2.

Solution 2 was added dropwise to solution 1 under ice cooling. The resulting solution was stirred under a nitrogen atmosphere to cause a reaction. After the reaction mixture was filtered, the obtained filtrate was concentrated under reduced pressure. The obtained concentrate was dropped into a water/methanol mixed solution (volume ratio: 1/1), and the resulting precipitate was taken out by filtration. The precipitate was pulverized, washed with pure water, and vacuum dried. The obtained powder was pulverized, heptane was added, and toluene was further added. The resulting mixture was filtered to remove insoluble components. After the obtained filtrate was concentrated under reduced pressure, heptane was added to the obtained residue. The resulting precipitate was taken out by filtration and dried under vacuum to give 7.8 g of the compound of the above formula (e). The yield was 40% (based on the compound represented by the formula (d)).

(6) 56.8 g of the compound of the formula (d) obtained in the above (4), 2.65 g of dimethylaminopyridine, 50 g of trans-1,4-cyclohexanedicarboxylic acid monoethoxymethyl ester, and chloroform. Mix 300mL. The resulting mixture was ice-cooled, and a solution of 48.79 g of dicyclohexylcarbodiimide and 50 mL of chloroform was added dropwise thereto. After the completion of the dropwise addition, the resulting mixture was stirred at room temperature to cause a reaction. After completion of the reaction, 200 mL of chloroform and 200 mL of heptane were added to the reaction mixture. The resulting mixture was filtered and the insoluble ingredients were removed. The filtrate obtained was washed with 2N hydrochloric acid. The resulting mixture was filtered and the insoluble components were removed, and then dried over anhydrous sodium sulfate. After removing sodium sulfate by filtration, the obtained filtrate was concentrated. Further, the obtained solid was vacuum dried to obtain 100 g of the compound of the above formula (e').

100 g of the obtained compound of the formula (e'), 3.64 g of pure water, 3.84 g of p-toluenesulfonic acid monohydrate and 200 mL of tetrahydrofuran were mixed. The resulting mixture was stirred under a nitrogen atmosphere at 50 ° C to cause a reaction. After the reaction was over, the reaction mixture was allowed to cool to room temperature. The reaction mixture was concentrated under reduced pressure and dichloromethane was evaporated. The precipitate precipitated was taken out by filtration. The removed precipitate was washed with pure water and then vacuum dried. The obtained powder was dissolved in chloroform, and the resulting solution was filtered through a silica gel. The filtrate was mixed with 400 mL of chloroform, and the resulting solution was concentrated. After toluene was added to the obtained residue, the resulting solution was concentrated under reduced pressure. Heptane was added to the residue, and the precipitated solid was taken out by filtration. Further, the taken solid was vacuum dried to obtain 64.1 g of the compound represented by the above formula (e). The yield was 76% (based on the compound represented by the formula (d)).

Example 1-2

(1) 4,7-Dimethoxy-2-phenylbenzothiazole was synthesized according to the method described in J. Chem. Soc., Perkin Trans. 1, 205-210 (2000).

(2) 10.8 g of 4,7-dimethoxy-2-phenylbenzothiazole and 54.0 g of pyridine chloride were mixed, and the resulting mixture was stirred at 220 ° C to cause a reaction. After the reaction was completed, the reaction mixture was cooled and water was added. The precipitate precipitated was taken out by filtration. The precipitate thus obtained was washed with water and hexane to obtain 8.7 g of the compound of the above formula (ii-a). The yield was 89% (based on 4,7-dimethoxy-2-phenylbenzothiazole).

Example 1--3

(1) 2.55 g of the compound represented by the formula (ii-a), 9.67 g of the compound represented by the formula (e), 0.28 g of dimethylaminopyridine and 50 mL of chloroform were mixed. To the resulting mixture, 40 mL of a chloroform solution containing 5.31 g of dicyclohexylcarbodiimide was added dropwise under ice cooling. The resulting mixture was stirred to cause a reaction. After the reaction was over, the reaction mixture was filtered. The obtained filtrate was dried over anhydrous sodium sulfate and concentrated under reduced pressure. Ethyl acetate was added to the resulting residue. After the obtained solution was concentrated under reduced pressure, 200 mL of methanol was added to the obtained concentrated residue and ice-cooled. The precipitate which precipitated was taken out by filtration, washed with heptane, and dried in vacuo to give 6.1 g of the compound of the formula (ii-1). Yield: 56% (based on the compound represented by the formula (ii-a)).

¹ H-NMR (d ₆ -dimethyl fluorene): 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 to 6.36 (m, 2H), 6.91 to 7.03 (m, 8H), 7.36 (s, 2H), 7.60 ( m, 3H), 8.06 (m, 2H)

The phase transition temperature of the obtained compound of the formula (ii-1) was observed by a polarizing microscope, and it was found that the compound represented by the formula (ii-1) exhibited at 96 ° C to 115 ° C when the temperature was raised. The smectic phase exhibits a nematic phase at 115 ° C to 226 ° C and a nematic phase at 226 ° C to 50 ° C when cooled.

Example 2

(1) After mixing 100 g of trans-cyclohexanedicarboxylic acid and 500 mL of N,N-dimethylacetamide, the resulting mixture was heated to 60 °C. After adding 48.2 g of potassium carbonate to the obtained solution, it was stirred at 80 °C. Further, 94.4 g of bromotoluene was added and stirred to cause a reaction. The resulting reaction mixture was allowed to cool and then poured into ice. The precipitate precipitated was taken out by filtration. The taken-out precipitate was washed with a water/methanol mixed solution (volume ratio = 1/1), and dried under vacuum. The obtained powder was dissolved in toluene, and the resulting solution was concentrated on a silica gel while being concentrated under reduced pressure. After the silicone rubber was placed in a gel column, it was eluted with 500 mL of a chloroform/heptane mixed solution (volume ratio = 1/4). Next, the compound represented by the above formula (f) was eluted with a mixed solution of chloroform/heptane (volume ratio = 1/2). The solution containing the obtained compound of the formula (f) is concentrated to obtain 63 g of the compound represented by the formula (f). The yield was 42% (based on trans-cyclohexanedicarboxylic acid).

(2) 4.87 g of the compound represented by the formula (ii-a), 11.54 g of the compound represented by the formula (f), 0.54 g of dimethylaminopyridine and 50 mL of chloroform were mixed. To the resulting mixture, 60 mL of a chloroform solution containing 10.89 g of dicyclohexylcarbodiimide was added dropwise under ice cooling. The resulting mixture was stirred to cause a reaction. The reaction mixture was filtered. The obtained filtrate was dried and concentrated under reduced pressure. After ethyl acetate was added to the residue obtained, the obtained solution was concentrated under reduced pressure. Methanol was added to the resulting residue and ice-cooled. The precipitate which precipitated was taken out by filtration, and dried in vacuo to give 11.4 g of the compound of formula (ii-b). Yield: 78% (based on the compound represented by the formula (ii-a)).

(3) 11.4 g of the compound represented by the formula (ii-b), 1.14 g of 10% palladium-carbon (55% by weight), 0.1 mL of acetic acid and 200 mL of tetrahydrofuran were mixed. After removing oxygen from the resulting mixture using nitrogen gas, the pressure was reduced, and the reaction was stirred under a hydrogen atmosphere. The resulting reaction mixture was filtered. After the obtained filtrate was concentrated under reduced pressure, heptane was added to a concentrated residue. The precipitated solid was taken out by filtration, and dried in vacuo to give 4.7 g of the compound of formula (ii-c). Yield: 55% (based on the compound represented by the formula (ii-b)).

(4) 4.41 g of the compound represented by the formula (ii-c), 4.65 g of the compound represented by the formula (d), 0.22 g of dimethylaminopyridine, and 30 mL of chloroform were mixed. To the resulting mixture, 20 mL of a chloroform solution containing 4.36 g of dicyclohexylcarbodiimide was added dropwise under ice cooling. The resulting mixture was stirred to cause a reaction. After the reaction was over, the reaction mixture was filtered. The obtained filtrate was dried and concentrated under reduced pressure. Ethyl acetate was added to the concentrated residue and dissolved. The resulting solution was concentrated under reduced pressure. Methanol was added to the concentrated residue and then ice-cooled. The precipitate which precipitated was taken out by filtration, and dried in vacuo to give 4.80 g of the compound of formula (ii-1). Yield: 58% (based on the compound represented by the formula (ii-c)).

Example 3-1

(1) 69.4 g of 2,5-dimethoxyaniline, 91.7 g of triethylamine, and 994.3 g of dehydrated chloroform were mixed. To the resulting mixture, 99.4 g of 4-bromobenzylammonium chloride was added. The resulting mixture was stirred at 60 ° C to cause a reaction. The resulting reaction mixture was cooled to room temperature and placed in water. The resulting mixture was separated to give an organic layer. The organic layer was washed with water and hydrochloric acid, and then concentrated under reduced pressure. The obtained solid was washed with hexane to give 139.6 g of the compound of formula (vi-d).

(2) 90.0 g of the compound represented by the formula (vi-d), 2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphane heterocycle 65.0 g of butane-2,4-disulfide (2,4-bis(4-methoxypheny1)-1,3-dithia-2,4-diphosphetane-2,4-disulfide) and 3132 g of toluene were mixed. The resulting mixture was stirred at 80 ° C to cause a reaction. After completion of the reaction, the resulting reaction mixture was cooled and concentrated. After adding methanol to the concentrated residue, the resulting precipitate was taken out by filtration. The precipitate was washed with ethanol to give 93.8 g of a compound of formula (vi-e). Yield: 99.5% (based on the compound represented by the formula (vi-d)).

(3) 93.8 g of the compound represented by the formula (vi-e), 315 g of sodium hydroxide and 5250 g of water were mixed. After the resulting mixture was stirred under ice cooling, an aqueous solution containing 174.3 g of potassium ferricyanide was added under ice cooling. The resulting mixture was stirred to cause a reaction. After the reaction was completed, the precipitated solid was taken out by filtration. The solid which was taken out was washed with cold water and hexane to give 88.2 g of the compound of formula (vi-f). The yield was 95% (based on the compound represented by the formula (vi-e)).

(4) After 11.2 g of the compound represented by the formula (vi-f) and 56.0 g of pyridine chloride were mixed, the resulting mixture was stirred at 180 ° C to cause a reaction. After the resulting reaction mixture was cooled, water was added. The precipitate which precipitated was washed with water, hexane and chloroform to obtain 7.7 g of the compound of the formula (vi-a). The yield was 74% (based on the compound represented by the formula (vi-f)).

Example 3-2

Except that the compound represented by the formula (vi-a) obtained in the above Example 3-1 was used instead of the compound represented by the formula (ii-a) in Example 2, the same procedure as in Example 2 was carried out, and the following formula was obtained. The compound shown in (vi-1).

Example 4-1

10.0 g of the compound represented by the formula (vi-a), 5.56 g of copper (I) cyanide and 100 g of N-methylpyrrolidone were mixed. The resulting mixture was stirred at 200 ° C under a nitrogen atmosphere to cause a reaction. After completion of the reaction, the reaction mixture was cooled, and water was added. The deposited precipitate was taken out by filtration, and then sufficiently washed with water to obtain 6.6 g of the compound of the formula (iv-a). The yield was 79% (based on the compound represented by the formula (vi-a)).

Example 4-2

The same as Example 1-3 except that the compound of the formula (iv-a) obtained in the above Example 4-1 was used instead of the compound represented by the formula (ii-a) in Example 1-3. A compound represented by the following formula (iv-1) is obtained.

₁ H-NMR (CDCl ₃ ): 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 ～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 of the formula (iv-1) is observed by a structure observation by a polarizing microscope, and the compound represented by the formula (iv-1) exhibits a stratification at 142 ° C to 159 ° C at a temperature rise. The phase exhibits a nematic phase at 159 ° C to 190 ° C, and when cooled, it exhibits a nematic phase and crystallizes up to 136 ° C.

Example 5-1

(1) The same procedure as in Example 3-1 (1) was carried out except that 4-nitrobenzhydryl chloride was used instead of 4-bromobenzylidene chloride in Example 3-1 (1). A compound represented by the formula (vb). Yield: 98% (based on 2,5-dimethoxyaniline).

(2) In addition to using the formula obtained in (1) above

The compound represented by the formula (vb) was subjected to the same procedure as in the example 3-1 (2) except for the compound of the formula (vi-d) in Example 3-1 (2), and the following formula (vc) was obtained. The compound shown. Yield: 89% (based on the compound represented by the formula (v-b)).

(3) Except that the compound represented by the formula (vc) obtained in the above (2) is used instead of the compound represented by the formula (vi-e) in the embodiment 3-1 (3), and the same as in the example 3-1 ( 3) In the same manner, a compound represented by the following formula (vd) was obtained. Yield: 52% (based on the compound represented by the formula (v-c)).

(4) 21.0 g of the compound of the formula (v-d) obtained and 441 g of dehydrated toluene were mixed. After the resulting mixture was ice-cooled, 100 g of boron tribromide was added. The resulting mixture was stirred at 70 ° C to cause a reaction. After the reaction was completed, the reaction mixture was cooled to room temperature. After the reaction mixture was ice-cooled, 1588 g of water was added. The precipitate which precipitated was taken out by filtration, and washed with water and chloroform to obtain 16.5 g of the compound represented by the above formula (v-a). Yield: 86% (based on the compound represented by the formula (v-d)).

Example 5-2

2.88 g of the compound of the formula (v-a) obtained in the above Example 5-1, 8.37 g of the compound represented by the above formula (e), 0.24 g of dimethylaminopyridine and 75 mL of chloroform were mixed. To the resulting mixture, 40 mL of a chloroform solution containing 4.95 g of dicyclohexylcarbodiimide was added dropwise under ice cooling. The resulting mixture was stirred to cause a reaction. After the reaction was over, the reaction mixture was filtered. After the filtrate was dried, it was concentrated under reduced pressure. After ethyl acetate was added to a concentrated residue and dissolved, the resulting solution was concentrated under reduced pressure. 200 mL of methanol was added to the concentrated residue and ice-cooled. The precipitate which precipitated was taken out by filtration, washed with methanol, and dried in vacuo to give 10.3 g of the compound of the formula (v-1). Yield: 94% (based on the compound represented by the formula (v-a)).

¹ H-NMR (CDCl ₃ ): δ (ppm) 1.45 to 1.86 (m, 24H), 2.35 to 2.83 (m, 12H), 3.93 to 3.97 (t, 4H), 4.15 to 4.20 (t, 4H), 5.80 ～5.84 (dd, 2H), 6.07 to 6.18 (m, 2H), 6.37 to 6.44 (m, 2H), 6.87 to 7.02 (m, 8H), 7.27 (d, 2H), 8.19 to 8.23 (d, 2H) 8.34 to 8.38 (d, 2H)

The phase transition temperature of the obtained compound of the formula (v-1) is observed by a structure observation by a polarizing microscope, and the compound represented by the formula (v-1) exhibits a stratification at 160 ° C to 169 ° C when the temperature is raised. The phase exhibits a nematic phase at 169 ° C to 224 ° C and a nematic phase at 224 ° C to 154 ° C upon cooling.

Example 6-1

(1) 43.0 g of 2,5-dimethoxyaniline, 59.7 g of triethylamine, and 499.7 g of dehydrated chloroform were mixed. To the resulting mixture was added 50.0 g of isonicotine hydrazine hydrochloride. The resulting mixture was stirred at 60 ° C to cause a reaction. After the reaction was completed, the reaction mixture was cooled and placed in water. The resulting mixture was separated to give an organic layer and an aqueous layer. After the aqueous layer was extracted with chloroform, the obtained chloroform layer was mixed with the previously obtained organic layer. The organic layer after mixing was washed with water, and then concentrated under reduced pressure to give 71.5 g of the compound of the formula (ix-b). Yield: 99% (based on 2,5-dimethoxyaniline).

(2) 70.0 g of the compound represented by the formula (ix-b), 2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphane heterocycle 65.8 g of butane-2,4-disulfide and 2436 g of toluene were mixed. The resulting mixture was stirred at 80 ° C to cause a reaction. After completion of the reaction, the obtained reaction mixture is cooled and concentrated to give a compound represented by the above formula (ix-c).

(3) The obtained compound of the formula (ix-c), 333 g of sodium hydroxide and 5550 g of water were mixed, and the resulting mixture was stirred under ice cooling. An aqueous solution containing 184.3 g of potassium ferricyanide was added to the mixture under ice cooling and stirred to cause a reaction. After completion of the reaction, the precipitated solid was taken out by filtration, and then washed with cold water and hexane to obtain 25.9 g of the compound of the formula (ix-d). The yield was 35% (based on the compound represented by the formula (ix-b)).

(4) After mixing 5.6 g of the compound represented by the formula (ix-d) and 28.0 g of pyridine chloride, the resulting mixture was stirred at 180 ° C to cause a reaction. After the reaction was completed, the reaction mixture was cooled. Water was added to the reaction mixture, and the precipitate which precipitated was taken out by filtration. The precipitate thus obtained was washed with water and chloroform to obtain 3.4 g of the compound of the above formula (ix-a). The yield was 68% (based on the compound represented by the formula (ix-d)).

Example 6-2

2.24 g of the compound represented by the formula (ix-a) obtained in the above Example 6-1, 8.37 g of the compound represented by the formula (e), 0.24 g of dimethylaminopyridine and 50 mL of chloroform were mixed. To the resulting mixture, 30 mL of a chloroform solution containing 4.95 g of dicyclohexylcarbodiimide was added dropwise under ice cooling. The resulting mixture was stirred to cause a reaction. After the reaction was over, the reaction mixture was filtered. After the filtrate was dried, it was concentrated under reduced pressure. Ethyl acetate was added to the concentrated residue and dissolved. After the obtained solution was concentrated under reduced pressure, 200 mL of methanol was added to the concentrated residue and ice-cooled. The precipitate which precipitated was taken out by filtration, washed with heptane, and dried in vacuo to give 4.4 g of the compound of the above formula (ix-1). Yield: 43% (based on the compound represented by the formula (ix-a)).

¹ H-NMR (CDCl ₃ ): δ (ppm) 1.43 to 1.84 (m, 24H), 2.29 to 2.83 (m, 12H), 3.93 to 3.97 (t, 4H), 4.15 to 4.18 (t, 4H), 5.80 ～5.84 (dd, 2H), 6.07 to 6.18 (m, 2H), 6.37 to 6.44 (m, 2H), 6.86 to 7.02 (m, 8H), 7.22 (m, 1H), 7.28 (d, 2H), 7.78 ~7.81(br,2H), 8.14~8.17(br,1H)

Example 7-1

(1) 170.0 g of 3-methyl-4-nitrobenzoic acid, 238.7 g of oxalic acid chloride, 2.2 g of 1,3-dimethyl-2-imidazolidinone, and 1703 g of dehydrated chloroform were mixed. The resulting mixture was thoroughly stirred at room temperature. After the mixture was concentrated under reduced pressure, 608 g of dehydrated chloroform was added to the obtained solid. To the resulting solution, a mixed solution of 120.0 g of 2,5-dimethoxyaniline, 158.5 g of triethylamine, and 840 g of dehydrated chloroform was added. The resulting mixture was stirred at room temperature to cause a reaction. After the reaction was completed, the reaction mixture was poured into 973 g of water. The resulting mixture was separated to give an organic layer. The organic layer was washed with 973 g of 1N hydrochloric acid, and concentrated under reduced pressure to give 107.8 g of the compound of formula (v'-b). Yield: 44% (based on 2,5-dimethoxyaniline).

(2) The same procedure as in Example 5-1 was carried out except that the compound represented by the formula (v'-b) obtained in the above (1) was used instead of the compound represented by the formula (vb) in the above Example 5-1. Thus, a compound represented by the above formula (v'-a) is obtained.

Example 7-2

Except that the compound represented by the formula (v'-a) obtained in the above (2) was used instead of the compound represented by the formula (va) in the above Example 5-2, the same procedure as in Example 5-2 was carried out, and the obtained A compound represented by the formula (v'-1). Yield: 73% (based on the compound represented by the formula (v'-a)).

¹ H-NMR (CDCl ₃ ): δ (ppm) 1.45 to 1.90 (m, 24H), 2.29 to 2.83 (m, 15H), 3.92 to 3.97 (t, 4H), 4.15 to 4.20 (t, 4H), 5.80 ～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 of the formula (v'-1) is observed by a structure observation by a polarizing microscope, and the compound represented by the formula (v'-1) is present at 127 ° C to 154 ° C when the temperature is raised. The smectic phase exhibits a nematic phase at 154 ° C to 217 ° C and a nematic phase at 217 ° C to 113 ° C upon cooling.

Example 8

Except that the compound of the formula (vi-a) was used instead of the compound of the formula (V) in the above Example 5-2, the same procedure as in Example 5-2 was carried out, and the following formula (vi-1) was obtained. The compound shown. Yield: 84% (based on the compound of the formula (vi-a)).

Example 9

(1) The same procedure as in Example 5-1 was carried out except that 2-thienylmethane chloride was used instead of 4-nitrobenzylidene chloride in the above Example 5-1, and the following formula (xa) was obtained. The compound shown.

(2) The following formula was obtained in the same manner as in Example 5-2 except that the compound of the formula (xa) obtained above was used instead of the compound of the formula (V) in the above Example 5-2. X-1) the compound shown. Yield: 84% (based on the compound represented by the formula (x-a)).

¹ H-NMR (CDCl ₃ ): 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 ～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),

The phase transition temperature of the obtained compound represented by the formula (x-1) is observed by a structure observation by a polarizing microscope, and the compound represented by the formula (x-1) exhibits a stratification at 101 ° C to 106 ° C when the temperature is raised. The phase exhibits a nematic phase at 106 ° C to 180 ° C, and when cooled, it exhibits a nematic phase and crystallizes up to 81 ° C.

Example 10-1

(1) 52.3 g of 2,5-dimethoxyaniline, 69.0 g of triethylamine, and 200 g of dehydrated chloroform were mixed. To the resulting mixture, 50.0 g of 3-thienylguanidinium chloride was added dropwise under ice cooling. The resulting mixture was stirred at room temperature for 1 hour to cause a reaction. The reaction mixture was poured into water. The resulting mixture was separated to give an organic layer. The organic layer was washed with water and hydrochloric acid, and then concentrated under reduced pressure. The obtained solid was washed with hexane to obtain 82.1 g of the compound of the above formula (xi-b). Yield: 91% (based on 2,5-dimethoxyaniline).

(2) 81 g of the compound represented by the formula (xi-b), 2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphazene 64.7 g of alkane-2,4-disulfide and 500 g of toluene were mixed. The resulting mixture was stirred at 80 ° C to cause a reaction. After completion of the reaction, the reaction mixture was cooled and concentrated to give a red viscous liquid containing the compound of the above formula (xi-c).

(3) The obtained red viscous liquid containing the compound of the formula (xi-c), 73.8 g of sodium hydroxide and 750 g of water were mixed, and the resulting mixture was stirred under ice cooling. An aqueous solution containing 257.8 g of potassium ferricyanide was added to the mixture under ice cooling. The resulting mixture was stirred to cause a reaction. After the reaction was completed, the precipitated solid was taken out from the reaction mixture by filtration. The solid which was taken out was washed with cold water and hexane, and then recrystallized from ethanol to obtain 49.1 g of the compound of the above formula (xi-d). The yield was 58% (based on the compound represented by the formula (xi-b)).

(4) After mixing 40.0 g of the compound represented by the formula (xi-d) and 200.0 g of pyridine chloride, the resulting mixture was stirred at 180 ° C for 2 hours to cause a reaction. After the resulting reaction mixture was cooled, water was added. The precipitate which precipitated was taken out by filtration, and washed with water and hexane to obtain 36.4 g of the compound of the above formula (xi-a).

Example 10-2

The same procedure as in Example 5-2 was carried out except that the compound of the formula (xi-a) obtained in the above Example 10-1 was used instead of the compound of the formula (V) in the above Example 5-2. A compound represented by the following formula (xi-1). Yield: 55% (based on the compound represented by the formula (xi-a)).

¹ H-NMR (CDCl ₃ ): 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 ～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 compound represented by the formula (xi-1) obtained is observed by a structure observation by a polarizing microscope, and the compound represented by the formula (xi-1) exhibits a stratification at 111 ° C to 125 ° C when the temperature is raised. The phase exhibits a nematic phase at 125 ° C to 242 ° C and a nematic phase at 242 ° C to 82 ° C upon cooling.

Example 11

(1) The same procedure as in Example 5-1 was carried out except that 3,5-dimethylbenzimidyl chloride was used instead of 4-nitrobenzhydryl chloride in the above Example 5-1, and the following was obtained. a compound of the formula (xvi-a).

(2) The same procedure as in Example 5-2 was carried out except that the compound of the formula (xvi-a) obtained above was used instead of the compound of the formula (V) in the above Example 5-2, and the following was obtained. a compound of the formula (xvi-1). Yield: 78% (based on the compound represented by the formula (xvi-a)).

¹ H-NMR (CDCl ₃ ): δ (ppm) 1.45 to 1.86 (m, 24H), 2.35 to 2.83 (m, 18H), 3.92 to 3.97 (t, 4H), 4.15 to 4.19 (t, 4H), 5.80 ～5.84 (dd, 2H), 6.07 to 6.18 (m, 2H), 6.37 to 6.44 (m, 2H), 6.86 to 7.01 (m, 8H), 7.13 (s, 1H), 7.20 (s, 2H), 7.66 (s, 2H)

The phase transition temperature of the compound represented by the formula (xvi-1) obtained is observed by a structure observation by a polarizing microscope, and the compound represented by the formula (xvi-1) exhibits a stratification at a temperature of from 91 ° C to 100 ° C at a temperature rise. The phase exhibits a nematic phase at 100 ° C to 210 ° C and is thermally polymerized.

Example 12-1

(1) 11.0 g of 4,7-dimethoxy-2-phenylbenzothiophene and 288 g of glacial acetic acid were mixed. A solution obtained by mixing 4.0 g of concentrated nitric acid and 14.4 g of glacial acetic acid was added dropwise to the resulting mixture. The resulting mixture was stirred at room temperature to cause a reaction. After the reaction was completed, the reaction mixture was poured into 1154 g of ice water. The precipitated solid was taken out by filtration to obtain 11.8 g of the compound of the above formula (xvii-d). The compound of the formula (xvii-d) is a mixture of two isomers having different substitution positions of the nitro group. Yield: 92% (based on 4,7-dimethoxy-2-phenylbenzothiazole).

(2) The same procedure as in Example 5-1 was carried out except that the compound represented by the formula (xvii-d) obtained in the above (1) was used instead of the compound represented by the formula (vd) in the above Example 5-1. The compound represented by the above formula (xvii-a) is obtained. The compound represented by the formula (xvii-a) is a mixture of two isomers having different substitution positions of a nitro group.

Example 12-2

The same procedure as in Example 5-2 was carried out except that the compound of the formula (xvii-a) obtained in the above Example 12-1 was used instead of the compound of the formula (V) in the above Example 5-2. A compound represented by the following formula (Xvii-1). Yield: 53% (based on the compound of the formula (xvii-a)).

1H-NMR (CDCl ₃ ): δ (ppm) 1.45 to 1.86 (m, 24H), 2.35 to 2.83 (m, 12H), 3.93 to 3.97 (t, 4H), 4.15 to 4.20 (t, 4H), 5.80 5.84 (dd, 2H), 6.07 to 6.18 (m, 2H), 6.37 to 6.44 (m, 2H), 6.87 to 7.00 (m, 8H), 7.44 (2s, 1H), 7.50 (m, 3H), 8.02 8.06 (m,

The phase transition temperature of the compound represented by the formula (xvii-1) obtained is observed by a structure observation by a polarizing microscope, and the compound represented by the formula (xvii-1) exhibits a stratification at 129 ° C to 148 ° C when the temperature is raised. The phase exhibits a nematic phase at 148 ° C to 186 ° C and a nematic phase at 186 ° C to 105 ° C upon cooling.

Example 13

(1) The same procedure as in Example 5-1 was carried out except that the pentafluorobenzhydryl chloride was used instead of the 4-nitrobenzimid chloride in the above Example 5-1, and the following formula (xviii-a) was obtained. ) the compound shown.

(2) The same procedure as in Example 5-2 was carried out except that the compound represented by the formula (xviii-a) obtained above was used instead of the compound represented by the formula (V) in the above Example 5-2, A compound represented by the formula (xviii-1). Yield: 82% (based on the compound represented by the formula (xviii-a)).

¹ H-NMR (CDCl ₃ ): δ (ppm) 1.45 to 1.86 (m, 24H), 2.35 to 2.87 (m, 18H), 3.92 to 3.97 (t, 4H), 4.15 to 4.20 (t, 4H), 5.80 ～5.84 (dd, 2H), 6.07 to 6.18 (m, 2H), 6.37 to 6.44 (m, 2H), 6.86 to 7.00 (m, 8H), 7.32 to 7.35 (d, 2H)

The phase transition temperature of the compound represented by the formula (xviii-1) obtained is observed by a structure observation by a polarizing microscope, and the compound represented by the formula (xviii-1) exhibits a stratification at 124 ° C to 166 ° C when the temperature is raised. The phase exhibits a nematic phase at 166 ° C to 199 ° C and a nematic phase at 199 ° C to 79 ° C upon cooling.

Example 14-1

(1) 58.7 g of 2,5-dimethoxyaniline, 77.5 g of triethylamine, and 400 g of dehydrated chloroform were mixed. To the resulting mixture, 50.0 g of 2-furopyryl chloride was added under ice cooling. The resulting mixture was stirred at room temperature for 1 hour to cause a reaction. After the obtained reaction mixture was poured into water, the resulting mixture was separated, and the organic layer was separated. The organic layer was washed with water and hydrochloric acid, and then concentrated under reduced pressure. Hexane was added to the residue to be crystallized, and 86.3 g of the compound represented by the above formula (xix-b) was obtained. Yield: 91% (based on 2,5-dimethoxyaniline).

(2) 40 g of the compound represented by the formula (xix-b), 2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphazene 34.0 g of alkane-2,4-disulfide and 120 g of toluene were mixed. The resulting mixture was stirred at 80 ° C for 8 hours to cause a reaction. The reaction mixture was cooled and concentrated to give a red viscous liquid containing the compound of the above formula (xix-c).

(3) The obtained red viscous liquid containing the compound of the formula (xix-c), 38.8 g of sodium hydroxide and 700 g of water were mixed, and the resulting mixture was stirred under ice cooling. An aqueous solution containing 145.3 g of potassium ferricyanide was added to the mixture under ice cooling. The resulting mixture was stirred to cause a reaction. The solid precipitated in the reaction mixture was filtered off, washed with cold water and hexane, and then washed with methanol. The obtained solid was recrystallized using ethanol to obtain 19.5 g of the compound represented by the above formula (xix-d). The yield was 46% (based on the compound represented by the formula (xix-b)).

(4) After mixing 9.00 g of the compound represented by the formula (xix-d) and 45.0 g of pyridine chloride, the resulting mixture was stirred at 180 ° C to cause a reaction. After the reaction was completed, the reaction mixture was cooled, and water was added. The precipitate which precipitated was taken out by filtration, washed with water and hexane, and washed with toluene to obtain 7.68 g of the compound represented by the above formula (xix-a). The yield was 96% (based on the compound represented by the formula (xix-d)).

Example 14-2

The same procedure as in Example 5-2 was carried out except that the compound of the formula (xix-a) obtained in the above Example 14-1 was used instead of the compound of the formula (V) in the above Example 5-2. A compound represented by the following formula (xix-1). Yield: 78% (based on the compound represented by the formula (xix-a)).

¹ H-NMR (CDCl ₃ ): δ (ppm) 1.45 to 1.82 (m, 24H), 2.34 to 2.83 (m, 12H), 3.92 to 3.97 (t, 4H), 4.15 to 4.20 (t, 4H), 5.80 ～5.84 (dd, 2H), 6.07 to 6.18 (m, 2H), 6.37 to 6.44 (m, 2H), 6.59 (brm, 1H), 6.86 to 7.00 (m, 8H), 7.20 (2s, 3H), 7.59 (s, 1H)

The phase transition temperature of the compound represented by the formula (xix-1) obtained is observed by a structure observation by a polarizing microscope, and the compound represented by the formula (xix-1) exhibits a stratification at a temperature of 91 ° C to 130 ° C when the temperature is raised. The phase exhibits a nematic phase at 130 ° C to 180 ° C, and when cooled, it exhibits a nematic phase and crystallization until 62 ° C.

Example 15

(1) The same formula as in Example 5-1 was carried out except that 5-chloro-2-thiophenemethyl chlorobenzene was used instead of 4-nitrobenzhydryl chloride in the above Example 5-1, and the following formula was obtained. The compound shown in (xx-a).

(2) The same procedure as in Example 5-2 was carried out except that the compound of the formula (xx-a) obtained above was used instead of the compound of the formula (V) in the above Example 5-2, and the same was obtained. A compound represented by the formula (xx-1). Yield: 40% (based on the compound represented by the formula (xx-a)).

¹ H-NMR (CDCl ₃ ): δ (ppm) 1.45 to 1.86 (m, 24H), 2.35 to 2.80 (m, 12H), 3.92 to 3.97 (t, 4H), 4.15 to 4.20 (t, 4H), 5.80 ～5.84 (dd, 2H), 6.07 to 6.18 (m, 2H), 6.37 to 6.44 (m, 2H), 6.86 to 7.02 (m, 8H), 7.19 (s, 2H), 7.40 (d, 2H)

The phase transition temperature of the compound represented by the formula (xx-1) obtained is observed by a structure observation by a polarizing microscope, and the compound represented by the formula (xx-1) exhibits a smectic phase at 110 to 114 ° C when the temperature is raised. The nematic phase is present at 114 ° C to 160 ° C, and when it is cooled, a nematic phase is formed up to 69 ° C and crystallized.

Example 16-1

(1) 59.3 g of 2,5-dimethoxyaniline, 78.4 g of triethylamine, and 500 g of dehydrated chloroform were mixed. To the resulting mixture, 57.1 g of 3-thiazolylguanidine chloride was added dropwise under ice cooling. The resulting mixture was stirred at room temperature to cause a reaction. After the reaction was completed, the reaction mixture was poured into water. The resulting mixture was separated to give an organic layer. The organic layer was washed with water and hydrochloric acid, and then concentrated under reduced pressure. The obtained solid was washed with hexane, and then crystallized from heptane / ethyl acetate (volume ratio = 3 / 1). The obtained solid was washed with heptane / ethyl acetate (volume ratio = 4 / 1) to obtain 77.2 g of the compound of the above formula (xxi-b). Yield: 75% (based on 2,5-dimethoxyaniline).

(2) 77g of the compound represented by the formula (xxi-b), 2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphazene 61.3 g of alkane-2,4-disulfide and 500 g of toluene were mixed. The resulting mixture was stirred at 80 ° C to cause a reaction. After completion of the reaction, the reaction mixture was cooled, followed by concentration to obtain an orange viscous liquid containing the compound of the above formula (xxi-c).

(3) The obtained orange viscous liquid containing the compound of the formula (xxi-c), 70.0 g of sodium hydroxide and 750 g of water were mixed, and the resulting mixture was stirred under ice cooling. An aqueous solution containing 245.0 g of potassium ferricyanide was added to the mixture under ice cooling. The resulting mixture was stirred to cause a reaction. After completion of the reaction, the solid precipitated in the reaction mixture was filtered out, washed with cold water and hexane, and then washed with hot ethanol to obtain 45.9 g of the compound of the formula (xxi-d). The yield was 57% (based on the compound represented by the formula (xxi-b)).

(4) After mixing 45.0 g of the compound represented by the formula (xxi-d) and 225.0 g of pyridine chloride, the resulting mixture was stirred at 180 ° C for 2 hours to cause a reaction. After the resulting reaction mixture was cooled, water was added. The precipitate which precipitated was taken out by filtration, and washed with water, hexane and toluene to obtain 39.9 g of the compound represented by the above formula (xxi-a). The yield was 100% (based on the compound represented by the formula (xxi-d)).

Example 16-2

The same procedure as in Example 5-2 was carried out except that the compound of the formula (xxi-a) obtained in the above Example 16-1 was used instead of the compound of the formula (V) in the above Example 5-2. A compound represented by the following formula (xxi-1). Yield: 71% (based on the compound represented by the formula (xxi-a)).

¹ H-NMR (CDCl ₃ ): δ (ppm) 1.43 to 1.86 (m, 24H), 2.35 to 2.84 (m, 12H), 3.90 to 3.97 (t, 4H), 4.15 to 4.19 (t, 4H), 5.80 ～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 represented by the formula (xxi-1) is observed by a structure observation by a polarizing microscope, and the compound represented by the formula (xxi-1) exhibits a nematic at 162 ° C to 246 ° C when the temperature is raised. The phase exhibits a nematic phase at 246 ° C to 120 ° C during cooling.

Example 17-1

(1) 38.3 g of 2,5-dimethoxyaniline, 50.5 g of triethylamine, and 200 g of dehydrated chloroform were mixed. To the resulting mixture, 54.6 g of 4-methanesulfonyl benzhydryl chloride was added under ice cooling. The resulting mixture was stirred at room temperature to cause a reaction. After the reaction was completed, the reaction mixture was poured into water. The resulting mixture was separated to give an organic layer. The organic layer was washed with water and hydrochloric acid, and then concentrated under reduced pressure. The obtained solid was washed with hexane, and then crystallized from heptane / ethyl acetate (volume ratio = 3 / 1). Further, it was washed with heptane/ethyl acetate (volume ratio = 3/1) to obtain 52.2 g of the compound of the above formula (xxiii-b) as white crystals. Yield: 62% (based on 2,5-dimethoxyaniline).

(2) 54.5 g of the compound represented by the formula (xxiii-b), 2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphane heterocycle Butane-2,4-disulfide 64.7 g and toluene 500 g were mixed. The resulting mixture was stirred at 80 ° C to cause a reaction. After completion of the reaction, the reaction mixture was cooled and concentrated to obtain a red viscous liquid containing the compound of the above formula (xxiii-c).

(3) The obtained red viscous liquid containing the compound of the formula (xxiii-c), 37.2 g of sodium hydroxide and 380 g of water were mixed, and the resulting mixture was stirred under ice cooling. An aqueous solution containing 163.5 g of potassium ferricyanide was added to the mixture under ice cooling. The resulting mixture was stirred to cause a reaction. After completion of the reaction, the solid precipitated in the reaction mixture was taken out by filtration, washed with cold water and hexane, washed with hot ethanol, and recrystallized using toluene to obtain the above formula (xxiii-d). Compound 25.2 g. The yield was 47% (based on the compound represented by the formula (xxiii-b)).

(4) After mixing 10.0 g of the compound represented by the formula (xxiii-d) and 100.0 g of pyridine chloride, the resulting mixture was stirred at 180 ° C for 2 hours to cause a reaction. After the reaction mixture was cooled, water was added. The precipitate thus precipitated was washed with water, hexane and toluene to obtain 7.8 g of the compound of the above formula (xxiii-a). The yield was 85% (based on the compound represented by the formula (xxiii-d)).

Example 17-2

The same procedure as in Example 5-2 was carried out except that the compound of the formula (xxiii-a) obtained in the above Example 17-1 was used instead of the compound of the formula (V) in the above Example 5-2. A compound represented by the following formula (xxiii-1). Yield: 46% (based on the compound represented by formula (xxiii-a)).

¹ H-NMR (CDCl ₃ ): δ (ppm) 1.44 to 1.86 (m, 24H), 2.35 to 2.84 (m, 12H), 3.11 (s, 3H), 3.92 to 3.97 (t, 4H), 4.15 to 4.20 (t, 4H), 5, 80 to 5.84 (dd, 2H), 6.07 to 6.15 (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 compound represented by the formula (xxiii-1) obtained is observed by a structure observation by a polarizing microscope, and the compound represented by the formula (xxiii-1) exhibits a smectic phase at 137 to 146 ° C when the temperature is raised. The nematic phase is present at 146 ° C to 170 ° C, and when cooled, a nematic phase is formed up to 78 ° C and crystallized.

Example 18

(1) The same procedure as in Example 3-1 was carried out except that 4-fluorobenzhydryl chloride was used instead of 4-bromobensyl chloride in the above Example 3-1, and the following formula (xxiv-a) was obtained. ) the compound shown.

(2) The same procedure as in Example 5-2 was carried out except that the compound represented by the formula (xxiv-a) obtained in the above (1) was used instead of the compound represented by the formula (va) in the above Example 5-2. A compound represented by the following formula (xxiv-1) is obtained. Yield: 54% (based on the compound represented by the formula (xxiv-a)).

¹ H-NMR (CDCl ₃ ): 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 ～5.84 (m, 2H), 6.07 to 6.18 (m, 2H), 6.36 to 6.44 (m, 2H), 6.86 to 7.02 (m, 8H), 7.14 to 7.21 (m, 4H), 8.00 to 8.07 (m, 2H)

The phase transition temperature of the compound represented by the formula (xxiv-1) obtained is observed by a structure observation by a polarizing microscope, and the compound represented by the formula (xxiv-1) exhibits a nematic phase at 95 to 212 ° C when the temperature is raised. When cooling, the nematic phase is present at 212 ° C to 86 ° C.

Example 19

(1) The same procedure as in Example 3-1 was carried out except that 4-trifluoromethylbenzimidium chloride was used instead of 4-bromobenzhydryl chloride in the above Example 3-1, and the following formula was obtained ( Compound shown in xxv-a).

(2) The same procedure as in Example 5-2 was carried out except that the compound represented by the formula (xxv-a) obtained in the above (1) was used instead of the compound represented by the formula (va) in the above Example 5-2. A compound represented by the following formula (xxv-1) is obtained. Yield: 77% (based on the compound represented by the formula (xxv-a)).

¹ H-NMR (CDCl ₃ ): δ (ppm) 1.44 to 1.90 (m, 24H), 2.35 to 2.82 (m, 12H), 3.92 to 3.98 (t, 4H), 4.15 to 4.21 (t, 4H), 5.79 ～5.84 (m, 2H), 6.07 to 6.18 (m, 2H), 6.36 to 6.44 (m, 2H), 6.86 to 7.02 (m, 8H), 7.21 to 7.29 (m, 2H), 7.74 to 7.78 (d, 2H), 8.13 to 8.17 (d, 2H)

The phase transition temperature of the compound represented by the obtained formula (xxv-1) is observed by a structure observation by a polarizing microscope, and the compound represented by the formula (xxv-1) exhibits a nematic phase at 135 to 193 ° C when the temperature is raised. When cooling, the nematic phase is present at 193 ° C to 114 ° C.

Example 20

(1) 10.0 g of 2,3-dicyanohydroquinone, 35.0 g of potassium hydroxide, and 70.0 g of water were mixed. The resulting mixture was heated while stirring at 100 °C. After the mixture was cooled to room temperature, 40.0 g of sulfuric acid was added and stirred. The resulting mixture was extracted with ethyl acetate. The obtained organic layer was concentrated under reduced pressure, and the obtained solid was dried in vacuo to give 8.5 g of the compound of formula (xxvi-b). Yield: 68% (based on 2,3-dicyanohydroquinone).

(2) 2.5 g of the compound represented by the formula (xxvi-b), 2.5 g of aniline, and 50.0 g of tetrahydrofuran were mixed. The resulting mixture was heated while stirring at 100 °C. After the mixture was cooled to room temperature, a solution obtained by dissolving 3.1 g of dicyclohexylcarbodiimide in 9.4 g of tetrahydrofuran was added dropwise at room temperature. The resulting mixture was heated at 60 °C. After the obtained reaction mixture was filtered, the obtained filtrate was concentrated under reduced pressure. Methanol was added to the concentrated residue and stirred. The precipitate was taken out by filtration, and dried in vacuo to give 0.4 g of the compound of formula (xxvi-a). Yield: 12% (based on the compound represented by the formula (xxvi-b)).

(3) 0.3 g of the compound represented by the formula (xxvi-a), 0.03 g of 4-dimethylaminopyridine, 1.2 g of the compound represented by the formula (e), and 24 g of chloroform were mixed. A solution obtained by dissolving 0.9 g of dicyclohexylcarbodiimide in 4.7 g of chloroform was added dropwise to the resulting mixture at room temperature. The resulting mixture was stirred. After the mixture was filtered, 12 g of 2N hydrochloric acid was added and partitioned to give an organic layer. After the organic layer was concentrated, methanol was added to a concentrated residue and stirred. The precipitate was taken out by filtration, and dried under vacuum to give 0.7 g of the compound of the formula (xxvi-1). Yield: 54% (based on the compound of the formula (xxvi-a)).

¹ H-NMR (CDCl ₃ ): 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)

Example 21

(1) 2.5 g of the compound represented by the formula (xxvi-b), 2.7 g of 2-aminothiazole, and 50.0 g of tetrahydrofuran were mixed. The resulting mixture was heated while stirring at 100 °C. After the obtained mixture was cooled to room temperature, a solution obtained by dissolving 3.1 g of dicyclohexylcarbodiimide in 9.4 g of tetrahydrofuran was added dropwise at room temperature. The resulting mixture was stirred. After the obtained reaction mixture was filtered, the obtained filtrate was concentrated under reduced pressure. Methanol was added to the concentrated residue and stirred. The precipitate was taken out by filtration, and dried in vacuo to give 0.4 g of the compound of formula (xxvii-a). Yield: 13% (based on the compound represented by the formula (xxvi-b)).

(2) 0.3 g of the compound represented by the formula (xxvii-a), 0.03 g of 4-dimethylaminopyridine, 1.2 g of the compound represented by the formula (e), and 23 g of chloroform were mixed. A solution obtained by dissolving 0.9 g of dicyclohexylcarbodiimide in 4.6 g of chloroform was added dropwise to the resulting mixture at room temperature. The resulting mixture was stirred. After the obtained reaction mixture was filtered, 12 g of 2N hydrochloric acid was added to the obtained filtrate. The resulting mixture was separated to give an organic layer. After the organic layer was concentrated, methanol was added to a concentrated residue and stirred. After the precipitate was taken out by filtration, it was dried in vacuo to give the compound of the formula (xxvii-1), 0, 3 g. Yield: 25% (based on the compound represented by the formula (xxvii-a)).

¹ H-NMR (CDCl ₃ ): 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 compound represented by the obtained formula (xxvii-1) is observed by a structure observation by a polarizing microscope, and the compound represented by the formula (xxvii-1) exhibits a smectic phase at 143 to 152 ° C when the temperature is raised. The nematic phase is present at 152 ° C to 186 ° C, and when it is cooled, a nematic phase is formed up to 99 ° C and crystallized.

Example 22

Except that 1,4-dihydroxyindole was used instead of the compound of the formula (V) in the above Example 5-2, the same procedure as in Example 5-2 was carried out, and the following formula (i-1) was obtained. Compound. Yield: 34% (based on 1,4-dihydroxyindole).

¹ H-NMR (CDCl ₃ ): 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 ～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 of the formula (i-1) is observed by a structure observation by a polarizing microscope, and the compound represented by the formula (i-1) exhibits a smectic phase at 125 to 128 ° C when the temperature is raised. The nematic phase is present at 128 ° C to 200 ° C, and when cooled, a nematic phase is formed up to 106 ° C and crystallized.

Example 23

12.5 g of the compound represented by the formula (e), 0.4 g of 4-dimethylaminopyridine, 2.9 g of 1,5-dihydroxyindole, and 100 g of chloroform were mixed. A solution obtained by dissolving 9.3 g of dicyclohexylcarbodiimide in 25 g of chloroform was added dropwise to the resulting mixture at room temperature. The resulting mixture was stirred to cause a reaction. To the resulting reaction mixture, 124 g of 1N hydrochloric acid was added and stirred. After the obtained mixture was filtered, the obtained filtrate was separated to give an organic layer. After the organic layer was concentrated, methanol was added to the residue. The resulting mixture was filtered to remove the solid. The obtained solid matter was dried to obtain 10.5 g of a compound represented by the following formula (xxviii-1). Yield: 84% (based on 1,5-dihydroxyindole).

¹ H-NMR (CDCl ₃ ): δ (ppm) 1.44 to 1.89 (m, 24H), 2.31 to 2.81 (m, 12H), 3.92 to 3.97 (m, 4H), 4.15 to 4.21 (m, 4H), 5.79 ～5.85 (m, 2H), 6.07 to 6.18 (m, 2H), 6.36 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 ~ 8.22 (m, 2H)

Example 24

12.5 g of the compound represented by the formula (e), 0.4 g of 4-dimethylaminopyridine, 2.9 g of 1,2-dihydroxyindole, and 100 g of chloroform were mixed. A solution obtained by dissolving 9.3 g of dicyclohexylcarbodiimide in 25 g of chloroform was added dropwise to the resulting mixture at room temperature. The resulting mixture was stirred to cause a reaction. To the resulting reaction mixture, 124 g of 1N hydrochloric acid was added and stirred. After the obtained mixture was filtered, the obtained filtrate was separated to give an organic layer. After the organic layer was concentrated, methanol was added to the residue. The resulting mixture was filtered to remove the solid. The obtained solid matter was dried to obtain 10.3 g of a compound represented by the following formula (xxix-1). Yield: 82% (based on 1,2-dihydroxyindole). The obtained compound was heated to confirm the phase transition temperature, and as a result, no liquid crystal phase was observed but dissolved at 105 °C.

¹ H-NMR (CDCl ₃ ): δ (ppm) 1.44 to 1.83 (m, 24H), 2.29 to 2.82 (m, 12H), 3.91 to 3.97 (m, 4H), 4.14 to 4.20 (m, 4H), 5.79 ～5.84 (m, 2H), 6.07 to 6.18 (m, 2H), 6.36-6.44 (m, 2H), 6.85 to 7.02 (m, 8H), 7.59 to 7.64 (d, 1H), 7.75 to 7.83 (m, 2H) 8.20 to 8.34 (m, 3H)

Example 25

(1) 23 g of trans-cinnamic acid, 75.5 g of 1H-benzotriazol-1-yloxytripyrrolidinium hexafluorophosphate, 15.7 g of triethylamine, and 1.9 g of dimethylaminopyridine Dehydrated N,N-dimethylacetamide 200g was mixed. The resulting mixture was stirred under light-shielding while being chilled. After 24.6 g of 2,5-dimethoxyaniline was added to the resulting mixture, the resulting mixture was stirred at 0 ° C for 8 hours and stirred at room temperature overnight. The resulting reaction mixture was extracted with methyl isobutyl ketone to give an organic layer. The obtained organic layer was washed three times with a saturated aqueous sodium carbonate solution. After the organic layer was concentrated under reduced pressure, methanol was added to the residue to crystallize. The crystals were taken out by filtration and dried under vacuum. The filtrate was allowed to stand at room temperature overnight. The precipitated crystals were taken out by filtration and dried under vacuum. The obtained crystals were mixed, washed again with cold methanol and dried to give 38.6 g of the compound of the above formula (xxxii-b) as a pale gray powder. Yield: 88% (based on 2,5-dimethoxyaniline).

(2) 30 g of the compound represented by the formula (xxxii-b), 2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphazene 22.27 g of alkane-2,4-disulfide and 500 g of toluene were mixed. The resulting mixture was stirred at 80 ° C to cause a reaction. The obtained reaction mixture was cooled and concentrated to give a red viscous solid containing the compound of the above formula (xxxii-c).

(3) The obtained red viscous solid containing the compound of the formula (xxxii-c), 25.4 g of sodium hydroxide and 750 g of water were mixed, and the resulting mixture was stirred under ice cooling. An aqueous solution containing 95.1 g of potassium ferricyanide was added to the mixture under ice cooling. The resulting mixture was stirred. The precipitated solid was taken out, washed with cold water and hexane, and then washed with hot methanol to obtain 17.7 g of the compound of the above formula (xxxii-d) as a yellow powder. The yield was 56% (based on the compound represented by the formula (xxxii-b)).

(4) After 10.6 g of the compound represented by the formula (xxxii-d) and 106.0 g of pyridine chloride were mixed, the resulting mixture was stirred at 180 ° C to cause a reaction. After the resulting reaction mixture was cooled, water was added. The precipitate which precipitated was taken out, and washed with water and hexane to obtain 10.8 g of the compound represented by the above formula (xxxii-a).

(5) 0.54 g of the compound represented by the formula (xxxii-a), 0.02 g of 4-dimethylaminopyridine, 1.76 g of the compound represented by the formula (e), and 30 g of chloroform were mixed. To the resulting mixture, 0.92 g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride was added and stirred. After the obtained mixture was filtered through celite, the filtrate was concentrated under reduced pressure. The residue was developed by using a column chromatography apparatus using chloroform as a solvent, and then chloroform/acetone (volume ratio = 95/5) was used as a solution. After recovering the orange adsorption layer, the resulting solution was concentrated under reduced pressure. The residue was crystallized with ethanol. The crystals were taken out by filtration, washed with heptane and dried in vacuo to give 1.21 g of the compound of formula (xxxii-1). Yield: 56% (based on the compound represented by formula (xxxii-a)).

¹ H-NMR (CDCl ₃ ): δ (ppm) 1.44 to 1.83 (m, 24H), 2.34 to 2.84 (m, 12H), 3.92 to 3.97 (t, 4H), 4.15 to 4.20 (t, 4H), 5.79 ～5.84 (dd, 2H), 6.07 to 6.1.8 (m, 2H), 6.37 to 6.43 (m, 2H), 6.87 to 7.01 (m, 8H), 7.19 (s, 2H), 7.34 to 7.59 (m, 7H)

The phase transition temperature of the compound represented by the obtained formula (xxxii-1) is observed by a structure observation by a polarizing microscope, and the compound represented by the formula (xxxii-1) exhibits a nematic at 125 ° C to 180 ° C when the temperature is raised. The phase exhibits a nematic phase and crystallizes up to 55 ° C when the temperature is lowered.

Example 26

(1) A compound represented by the following formula (e") was obtained in the same manner as in Example 1-1 except that 4-bromobutanol was used instead of 6-bromohexanol in the above Example 1-1. .

(2) The same formula as in Example 5-2 was carried out except that the compound of the formula (e'') was used instead of the compound of the formula (V) in the above Example 5-2, and the following formula (v) was obtained. -2) The compound shown. Yield: 72% (based on the compound represented by the formula (e'')).

¹ H-NMR (CDCl ₃ ): 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 ～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 27-1

(1) 59.5 g of the compound represented by the formula (a), 70 g of sodium hydroxide 21.7 g of '11-bromoundecyl alcohol, and 280 g of N,N-dimethylacetamide were mixed. The obtained mixture was stirred at 90 ° C under a nitrogen atmosphere, and then stirred at 110 ° C to cause a reaction. After the resulting reaction mixture was cooled to room temperature, it was poured into 1680 g of pure water. The precipitate precipitated was taken out by filtration. The precipitate was washed with 400 mL of a 6N aqueous sodium hydroxide solution, washed with heptane, and dried in vacuo to give 83 g of the compound of formula (b''). Yield: 82% (based on 11-bromoundecyl alcohol).

(2) 80 g of the compound represented by the formula (b'''), 1.40 g of 3,5-di(t-butyl)-4-hydroxytoluene, 61.2 g of dimethylaniline, and 1,3-di Methyl-2-imidazolidinone 1.00 g and chloroform were mixed. Under a nitrogen atmosphere, 29.8 g of acrylonitrile chloride was added dropwise to the resulting mixture under ice cooling. The resulting mixture was stirred at room temperature to cause a reaction. After completion of the reaction, the reaction mixture was washed with 2N aqueous hydrochloric acid and saturated aqueous sodium carbonate and concentrated. 700 mL of methanol was added to the obtained concentrate, and 3.34 g of p-toluenesulfonic acid and 3 g of water were further added. The resulting solution was stirred at 60 ° C for 3 hours to cause a reaction. After the completion of the reaction, 1400 g of pure water was added to the obtained reaction mixture. After the precipitated solid was taken out, it was washed with a water/methanol mixed solution (volume ratio = 2/1), washed with heptane, and dried under vacuum to obtain 62 g of the compound of the above formula (d'''). . Yield: 84% (based on the compound represented by the formula (b''').

(3) 40.3 g of the compound represented by the formula (d'''), 1.49 g of dimethylaminopyridine, 28 g of trans-1,4-cyclohexanedicarboxylic acid monoethoxymethyl ester, and Mix 150 mL of chloroform. The resulting mixture was stirred under ice cooling under ice. To the mixture, a solution of 27.3 g of dicyclohexylcarbodiimide in 50 mL of chloroform was added dropwise. After the completion of the dropwise addition, the mixture was stirred at room temperature to cause a reaction. To the resulting reaction mixture were added 200 mL of chloroform and 200 mL of heptane. The precipitate which precipitated was filtered. The obtained filtrate was washed with 2N hydrochloric acid, and then filtered to remove insoluble components. The obtained filtrate was dried over anhydrous sodium sulfate, filtered and evaporated.

The obtained concentrate, 2.34 g of pure water, 1.40 g of 3,5-di(t-butyl)-4-hydroxytoluene, 3.95 g of p-toluenesulfonic acid monohydrate, and 200 mL of tetrahydrofuran were mixed. The resulting mixture was stirred at 70 ° C for 3 hours under a nitrogen atmosphere to cause a reaction. After the reaction mixture was allowed to stand to cool to room temperature, the precipitate which precipitated was removed by filtration. The resulting filtrate was concentrated under reduced pressure at room temperature. 200 mL of heptane was added to the residue. The deposited precipitate was taken out by filtration, washed with pure water, and dried in vacuo. After the obtained powder was dissolved in chloroform, it was filtered through silica gel. 400 mL of chloroform and heptane were added to the filtrate to cause crystallization. The obtained powder was taken out by filtration, and dried in vacuo to give 44.4 g of the compound of formula (e'''). Yield: 82% (based on the compound represented by the formula (d''').

Example 27-2

The same procedure as in Example 5-2 was carried out except that the compound of the formula (e''') obtained in the above Example 27-1 was used instead of the compound of the formula (V) in the above Example 5-2. A compound represented by the following formula (v-3) is obtained. Yield: 82% (based on the compound represented by the formula (e''').

¹ H-NMR (CDC1 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 ～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 of the formula (v-3) is observed by a polarizing microscope. The compound represented by the formula (v-3) exhibits a stratification at 164 to 174 ° C when the temperature is raised. The phase exhibits a nematic phase at 174 ° C to 195 ° C, and exhibits a nematic phase at 195 ° C to 167 ° C and a smectic phase at 167 ° C to 151 ° C and crystallizes upon cooling.

Example 28-1

(1) 88.5 g of the compound represented by the formula (a), 35.5 g of sodium hydroxide, 75 g of 8-chlorooctanol, and 300 g of N,N-dimethylacetamide were mixed. The obtained mixture was stirred at 90 ° C under a nitrogen atmosphere, and then stirred at 100 ° C for 2 hours to cause a reaction. After cooling the obtained reaction mixture to room temperature, it was poured into 600 g of pure water. The precipitate precipitated was taken out by filtration. The precipitate was washed with 400 mL of a 6N aqueous sodium hydroxide solution, washed with heptane, and dried in vacuo to give 132 g of the compound of formula (b. Yield: 90% (based on 8-chlorooctanol).

(2) 100 g of the compound represented by the formula (b''''), 1.40 g of 3,5-di(t-butyl)-4-hydroxytoluene, and 86.4 g of dimethylaniline, 1,3- Dimethyl-2-imidazolidinone 1.00 g and chloroform were mixed. Under a nitrogen atmosphere, 42.11 g of acrylonitrile chloride was added dropwise to the resulting mixture under ice cooling. The resulting mixture was stirred at room temperature for 2 hours to cause a reaction. After completion of the reaction, the reaction mixture was washed with 2N aqueous hydrochloric acid and saturated aqueous sodium carbonate and concentrated. 300 mL of methanol was added to the obtained concentrate, and 3.34 g of p-toluenesulfonic acid and 3 g of water were further added. The resulting solution was stirred at 60 ° C for 3 hours to cause a reaction. After the completion of the reaction, 1400 g of pure water was added to the obtained reaction mixture. After the precipitated solid was taken out, it was washed with a water/methanol mixed solution (volume ratio = 2/1), washed with heptane, and dried under vacuum to obtain a compound represented by the above formula (d'''). 72g. Yield: 79% (based on the compound represented by the formula (b'''').

(3) 25.1 g of the compound represented by the formula (d''''), 1.06 g of dimethylaminopyridine, and 20 g of trans-1,4-cyclohexanedicarboxylic acid monoethoxymethyl ester. Mix with 70 mL of chloroform. The resulting mixture was stirred under ice cooling under ice. To the mixture, 19.5 g of dicyclohexylcarbodiimide was added dropwise to a 50 mL chloroform solution. After the completion of the dropwise addition, the mixture was stirred at room temperature to cause a reaction. To the resulting reaction mixture were added 200 mL of chloroform and 200 mL of heptane. The precipitate precipitated was filtered. The obtained filtrate was washed with 2N hydrochloric acid, and the insoluble matter was removed by filtration. The obtained filtrate was dried over anhydrous sodium sulfate, filtered and evaporated.

The obtained concentrate, 1.46 g of pure water, 1.40 g of 3,5-di(t-butyl)-4-hydroxytoluene, 2.46 g of p-toluenesulfonic acid monohydrate, and 200 mL of tetrahydrofuran were mixed. The resulting mixture was stirred at 70 ° C for 2 hours under a nitrogen atmosphere to cause a reaction. After the reaction mixture was allowed to stand to cool to room temperature, the precipitate which precipitated was removed by filtration. The resulting filtrate was concentrated under reduced pressure at room temperature. 800 mL of pure water was added to the residue. The deposited precipitate was taken out by filtration, washed with pure water, and dried in vacuo. The obtained powder was washed with ethanol/water (volume ratio = 2/3), and then washed with heptane. The obtained powder was vacuum dried to obtain 30.1 g of the compound of the above formula (e''''). Yield: 84% (based on the compound represented by the formula (d'''').

Example 28-2

The same procedure as in Example 5-2 was carried out except that the compound of the formula (e'''') obtained in the above Example 28-1 was used instead of the compound of the formula (V) in the above Example 5-2. Thus, a compound represented by the following formula (v-4) is obtained. Yield: 69% (based on the compound represented by the formula (e'''').

¹ H-NMR (CDCl ₃ ): 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 ～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 of the formula (v-4) is observed by a structure observation by a polarizing microscope, and the compound represented by the formula (v-4) exhibits a smectic phase at 163 to 167 ° C when the temperature is raised. The nematic phase is present at 167 ° C to 220 ° C, and when cooled, the smectic phase is exhibited at 220 ° C to 156 ° C and crystallized.

Example 29

(1) 12.5 g of the compound represented by the formula (v-a), 1.06 g of 4-dimethylaminopyridine, 20.0 g of the compound represented by the formula (f), and 50 g of chloroform were mixed. Into the obtained mixture, a solution obtained by dissolving 19.7 g of dicyclohexylcarbodiimide in 30 g of chloroform was added dropwise at room temperature, and the resulting mixture was stirred to cause a reaction. The resulting reaction mixture was filtered, and 12 g of 2N hydrochloric acid was added to the obtained filtrate and stirred. The resulting mixture was separated to give an organic layer. The organic layer was concentrated, and tetrahydrofuran was added to the obtained concentrated residue. The precipitate which precipitated was removed by filtration, and the filtrate was concentrated under reduced pressure. Heptane was added to the concentrated residue to cause crystallization. The crystals were taken out by filtration, and dried under vacuum to give a pale yellow powder of the compound of the above formula (g).

(2) The obtained compound represented by the formula (g) is mixed with tetrahydrofuran. The resulting solution was mixed with 1.18 g of pure water, 1.40 g of 3,5-di-t-butyl-4-hydroxytoluene, 1.55 g of p-toluenesulfonic acid monohydrate, and 115 mL of tetrahydrofuran. The resulting mixture was stirred under a nitrogen atmosphere at 70 ° C for 2 hours to cause a reaction. After the reaction mixture is allowed to cool to room temperature, the resulting precipitate is removed by filtration, and the obtained powder is washed with tetrahydrofuran, washed with heptane, and the obtained powder is dried in vacuo to obtain 18 g of the above formula (h). Compound. The yield was 70% (based on the compound represented by the formula (v-a)).

(3) 25.36 g of triphosgene and 125 g of tetrahydrofuran were mixed under ice cooling. To the resulting mixed solution, 37 g of 4-hydroxybutyl acrylate and 28.0 g of dimethylaniline were added dropwise, and the resulting mixture was stirred at room temperature for 2 hours to cause a reaction. To the obtained reaction mixture, 49.9 g of the compound of the formula (a) and 49.9 g of pyridine were dissolved in 50 mL of tetrahydrofuran to obtain a solution. The resulting mixture was stirred at room temperature overnight to cause a reaction. The white precipitate was removed by filtration, and the obtained filtrate was concentrated under reduced pressure. After 120 mL of ethanol was added to the residue, 44 g of p-toluenesulfonic acid monohydrate was added to adjust the pH of the solution to 4. The resulting solution was stirred at room temperature for 1 hour and poured into 1000 g of ice. The upper clarified portion was removed by decantation, and the resulting lower layer was mixed with water/ethanol (volume ratio = 1/3), and the upper clarified portion was removed by decantation. The lower layer obtained was washed with heptane, and after decantation, 50.0 g of the compound of the above formula (i) was obtained. The yield was 70% (based on 4-hydroxybutyl acrylate).

(4) 6.1 g of the compound represented by the formula (h), 6.0 g of the compound represented by the formula (i), 0.26 g of dimethylaminopyridine and 20 mL of chloroform were mixed. To the resulting mixture, 10 mL of a solution of 5.30 g of chloroform of dicyclohexylcarbodiimide was added dropwise under ice cooling. The resulting mixture was stirred to cause a reaction. After the reaction was completed, the reaction mixture was filtered to remove insoluble components. 2N hydrochloric acid was added to the obtained filtrate and liquid-separated. The obtained organic layer was dried, filtered over Celite, and evaporated. Methanol was added to the residue to cause crystallization. The resulting precipitate was taken out and dissolved in chloroform. To the resulting solution, 500 mg of activated carbon was added and allowed to stand overnight, and then filtered through diatomaceous earth. The obtained filtrate was mixed with ethanol, and the resulting precipitate was collected by filtration, washed with heptane, and dried in vacuo to give 2.8 g of the compound of formula (v-5). The yield was 25% (based on the compound represented by the formula (h)).

¹ H-NMR (CDCl ₃ ): 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 9.22 (d, 2H), 8.35 to 8.38 (d, 2H)

The phase transition temperature of the obtained compound of the formula (v-5) was observed by a polarizing microscope, and it was found that the compound represented by the formula (v-5) exhibited a smectic phase at 142 ° C to 163 ° C at a temperature of 163 ° C. The nematic phase was exhibited at 224 ° C, and when it was cooled, a nematic phase was formed up to 108 ° C and crystallized.

Example 30

(1) 30.73 g of benzyl p-hydroxybenzoate, 31 g of trans-1,4-cyclohexanedicarboxylic acid monoethoxymethyl ester, 31.95 g of dicyclohexylcarbodiimide, dimethylamine 1.64 g of pyridine and 200 mL of dehydrated chloroform were mixed, and the mixture was stirred and reacted under a nitrogen atmosphere at room temperature. After completion of the reaction, 100 mL of heptane was added to the reaction mixture, and the resulting precipitate was filtered. The obtained filtrate was washed with 1N hydrochloric acid and dried over anhydrous sodium sulfate. After sodium sulfate was filtered, methanol/water (volume ratio = 50/50) was added to the filtrate, and the obtained crystal was removed by filtration, washed with heptane and pure water, and dried under vacuum to obtain the above formula (j). The compound shown was 58.0 g, and the yield was 98% (based on benzyl p-hydroxybenzoate).

(2) 50.0 g of the compound represented by the formula (j) and 150 mL of tetrahydrofuran were mixed, and 2 g of acetic acid and 7.5 g of palladium carbon were added to the resulting mixture, followed by stirring under a nitrogen atmosphere. The mixture was stirred under reduced pressure under a reduced pressure of hydrogen. At the point of stopping the hydrogen consumption, the atmosphere was changed to a nitrogen atmosphere, and the reaction mixture was filtered through celite, and the filtrate was concentrated with an evaporator. The residue was washed with methanol/water (volume ratio = 50/50), and dried in vacuo to give 32.0 g of the compound of formula (k). The yield was 80% (based on the compound represented by the formula (j)).

(3) 16 g of the compound represented by the formula (k), 6.91 g of (4-hydroxybutyl acrylate), 10.88 g of dicyclohexylcarbodiimide, 0.56 g of dimethylaminopyridine, and 2,6-di- 10 mg of tert-butyl-4-methylphenol and 80 mL of dehydrated chloroform were mixed. The resulting mixture was stirred under a nitrogen atmosphere at room temperature to cause a reaction. 40 mL of heptane was added to the reaction mixture, and the resulting precipitate was filtered. The obtained filtrate was washed with 1N hydrochloric acid and dried over anhydrous sodium sulfate. After removing sodium sulfate and concentrating, 18.5 g of the compound represented by the above formula (1) can be obtained. The yield was 85% (based on the compound represented by the formula (j)).

(4) 18.5 g of the compound represented by the formula (1), 0.87 g of pure water, 0.87 g of p-toluenesulfonic acid monohydrate, and 80 mL of tetrahydrofuran were mixed. The resulting mixture was stirred and reacted under a nitrogen atmosphere at 60 °C. The reaction mixture was allowed to cool to room temperature and then concentrated. To the concentrated residue, 200 mL of heptane was added, and the precipitate was precipitated by filtration, and the precipitate was washed with pure water, and dried under vacuum to give 7.5 g of the compound of the above formula (m). The yield was 40% (based on the compound represented by the formula (1)).

(5) 4.95 g of the compound of the formula (m), 1.70 g of the compound of the formula (va), 2.95 g of dicyclohexylcarbodiimide, 0.29 g of dimethylaminopyridine and 40 mL of dehydrated chloroform were mixed. The resulting mixture was stirred and reacted under a nitrogen atmosphere at room temperature. 20 mL of heptane was added to the reaction mixture, and the resulting precipitate was filtered. The obtained filtrate was washed with 1N hydrochloric acid and dried over anhydrous sodium sulfate. After removing sodium sulfate by filtration, it was concentrated under reduced pressure on an evaporator. Ethyl acetate was added to the residue. 300 mL of methanol cooled in an ice bath was added to the concentrated residue, and the deposited precipitate was taken out, washed with heptane, and dried under vacuum to obtain 2.9 g of the compound of the above formula (v-6). The yield was 45% (based on the compound represented by the formula (m)).

¹ H-NMR (CDCl ₃ ): 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 ～5.86 (dd, 2H), 6.08 to 6.18 (m, 2H), 6.38 to 6.45 (m, 2H), 7.17 to 7.21 (dd, 4H), 7.29 (d, 2H), 8.07 to 8.11 (d, 4H) 8.19 to 8.22 (d, 2H), 8.34 to 8.38 (d, 2H)

When the phase transition temperature of the compound represented by the formula (v-6) is observed by a polarizing microscope, it is understood that the compound represented by the formula (v-6) exhibits a smectic phase at 124 ° C to 135 ° C at a temperature rise. The nematic phase is present at 135 ° C to 220 ° C, and when it is cooled, a nematic phase is formed up to 103 ° C and crystallized.

Example 31

(1) 30 g of the compound represented by the formula (b), 1.40 g of 3,5-di-t-butyl-4-hydroxytoluene, 15.5 g of triethylamine, and 1,3-dimethyl-2-imidazole 1.00 g of pyridine ketone and 300 mL of tetrahydrofuran were mixed, and 16.0 g of methacryl oxime chloride was added dropwise to the obtained solution under a nitrogen atmosphere and ice cooling. The resulting mixture was stirred at room temperature for 3 hours. Upon completion of the reaction, p-toluenesulfonic acid monohydrate was added to the reaction mixture to adjust to pH 2. 1.47 g of pure water was added to the mixture and stirred at room temperature for 3 hours. To the resulting mixture were added 100 mL of heptane and 2N hydrochloric acid. The resulting mixture was separated to give an organic layer. The organic layer was concentrated under reduced pressure, and 1000 g of ice was added to the concentrated residue, and the mixture was stirred for crystallization. The crystals were taken out, washed with water/methanol (volume ratio = 2/1), washed with heptane, pure water, and dried under vacuum. Thus, 12.4 g of the compound represented by the above formula (n) can be obtained. The yield was 44% (based on the compound represented by the formula (b)).

(2) 12.0 g of the compound represented by the formula (n), 0.53 g of dimethylaminopyridine, 10.0 g of trans-1,4-cyclohexanedicarboxylic acid monoethoxymethyl ester, and 50 mL of chloroform. mixing. The resulting solution was stirred under a nitrogen atmosphere and ice-cooled, and a solution of 9.8 g of dicyclohexylcarbodiimide in 20 mL of chloroform was added dropwise. The resulting mixture was stirred at room temperature to cause a reaction. After the reaction was completed, 200 mL of chloroform and 200 mL of heptane were added to the reaction mixture. The resulting precipitate was removed by filtration, and the obtained filtrate was washed with 2N hydrochloric acid. After the insoluble fraction was removed by filtration, the filtrate was dried over anhydrous sodium sulfate. After removing sodium sulfate by filtration, it was concentrated. The obtained concentrated residue, 0.73 g of pure water, 1.40 g of 3,5-di-t-butyl-4-hydroxytoluene, 1.15 g of p-toluenesulfonic acid monohydrate and 100 mL of tetrahydrofuran were mixed, and the mixture was obtained under a nitrogen atmosphere, 70 The reaction was stirred at ° C for 3 hours. After the reaction mixture was allowed to cool to room temperature, the resulting precipitate was removed by filtration. The resulting filtrate was concentrated under reduced pressure at room temperature. 200 mL of heptane was added to the concentrated residue, and the deposited precipitate was collected by filtration, and the precipitate was washed with pure water and dried under vacuum. The obtained powder was dissolved in chloroform, and the resulting solution was filtered through silica gel. The filtrate was mixed with 400 mL of chloroform, and heptane was added to crystallize. The crystal was taken out by filtration, and dried under vacuum to give 12.2 g of the compound of the above formula (o). The yield was 68% (based on the compound represented by the formula (n)).

(3) Except that the compound represented by the formula (2) obtained in the above (2) is used in place of the compound represented by the formula (e) in the above Example 5-2, the same as in the above Example 5-2, 6.7 g of the compound of the formula (v-7). The yield was 55% (based on the compound represented by the formula (v-a)).

_{^{1 H-NMR (CDCl 3)}} : δ (ppm) 1.40 ~ 1.85 (m, 24H), 1.95 (d, 6H), 2.36 ~ 2.85 (m, 12H), 3.93 ~ 3.97 (t, 4H), 4 14. ~ 4.19 (t, 4H), 5.46 to 5.55 (t, 2H), 6.10 to 6.10 (brt, 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 32

(1) 119 g of 2-tert-butylhydroquinone, 0.23 g of p-toluenesulfonic acid monohydrate, and 480 mL of tetrahydrofuran were mixed. In the resulting mixture, 50 g of dihydropyran was added dropwise under ice cooling. After the mixture was stirred at room temperature, 500 mL of heptane was added, and a saturated aqueous sodium hydroxide solution was added thereto, and the resulting mixture was separated, and the obtained organic layer was stood. The precipitated crystals were taken out by filtration, washed with pure water, and dried in vacuo to obtain 39 g of a pale purple powder of the compound of the above formula (p). The yield was 26% (based on dihydropyran).

(2) 39 g of the compound represented by the formula (p), 12.2 g of sodium hydroxide, 21.3 g of 6-chlorohexanol, and 86 g of N,N-dimethylacetamide were mixed. The resulting mixture was stirred for 6 hours under nitrogen atmosphere at 100 ° C, and the resulting reaction mixture was cooled to room temperature, poured into 580 g of pure water, and the supernatant aqueous solution was removed by decantation. The lower oil was dissolved in methyl isobutyl ketone to remove the separated aqueous layer. The organic layer was concentrated, and dried in vacuo to yield 42 g of pale red viscous liquid containing compound of formula (q). The yield was 77% (based on the compound represented by the above formula (p)).

(3) 40 g of the compound represented by the formula (q), 1.40 g of 3,5-di-t-butyl-4-hydroxytoluene, 31.8 g of dimethylaniline, and chloroform were mixed. Under a nitrogen atmosphere and ice cooling, 15.5 g of acrylonitrile chloride was added dropwise to the resulting mixture. The resulting mixture was stirred at room temperature for 3 hours. After the reaction was completed, p-toluenesulfonic acid monohydrate was added to the reaction mixture to adjust the pH to 2. To the resulting mixture, 1.64 g of pure water was added and stirred at room temperature for 1 hour. 100 mL of heptane was added to the resulting mixture, and 2N hydrochloric acid was added thereto to separate the layers. The obtained organic layer was subjected to activated carbon treatment, and after filtration through celite, the filtrate was concentrated under reduced pressure, and the concentrate was poured into heptane to remove the upper layer of the heptane layer by decantation. The lower redish viscous liquid was vacuum dried over 2 days to obtain 26.0 g of the compound of the above formula (r). The yield was 71% (based on the compound represented by the formula (q)).

(4) 15.0 g of the compound of the formula (r), 0.58 g of dimethylaminopyridine, 10.9 g of trans-1,4-cyclohexanedicarboxylic acid monoethoxymethyl ester, and 40 mL of chloroform. mixing. The resulting mixture was stirred under a nitrogen atmosphere and ice-cooled, and a solution of 10.6 g of dicyclohexylcarbodiimide in 10 mL of chloroform was added dropwise. The resulting mixture was stirred at room temperature to cause a reaction. After the reaction was completed, 100 mL of heptane was added to the reaction mixture, and the resulting precipitate was removed by filtration. The obtained filtrate was washed with 2N hydrochloric acid and filtered to remove the insoluble fraction. The filtrate was dried over anhydrous sodium sulfate, filtered over silica gel, and concentrated to give a concentrate and pure water, 0.79 g, 3,5-di-t-butyl-4-hydroxyl 1.40 g of toluene, 1.25 g of p-toluenesulfonic acid monohydrate and 150 mL of tetrahydrofuran were mixed, and the resulting mixture was stirred and reacted at 70 ° C for 3 hours under a nitrogen atmosphere. After the reaction mixture was allowed to cool to room temperature, the formed precipitate was filtered, and the obtained filtrate was concentrated at room temperature under reduced pressure. 300 g of ice was added to the resulting residue, and the precipitate was precipitated by filtration. The precipitate was washed with heptane, dried under vacuum, and the obtained powder was dissolved in chloroform. The filtrate was mixed with 400 mL of chloroform, and heptane was added to the resulting solution to cause crystallization. The crystal was taken out by filtration, washed with ethanol/water (volume ratio = 2/3), and dried under vacuum to obtain 17.9 g of the compound of the above formula (s). The yield was 86% (based on the compound represented by the formula (r)).

(5) The above formula can be obtained in the same manner as in Example 5-2 except that the compound represented by the formula (s) obtained in the above (4) is substituted for the compound represented by the formula (e) in the above Example 5-2. 0.7 g of the compound shown in (v-8). The yield was 4.5% (based on the compound represented by the formula (v-a)).

¹ H-NMR (CDCl ₃ ): 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)

Example 33-1

(1) 125 g of trans-4-hydroxycyclohexanecarboxylic acid, 143.8 g of potassium carbonate, 140.87 g of benzyl bromide, and 700 mL of N,N-dimethylacetamide were mixed. The resulting mixture was stirred and reacted under a nitrogen atmosphere at 80 °C. After the reaction mixture was allowed to cool to room temperature, a mixture of 1000 g of water and 500 g of methyl isobutyl ketone/heptane (weight ratio = 3/2) was poured, and the resulting mixture was stirred and then separated. The obtained organic layer was washed with pure water, dried over anhydrous sodium sulfate and filtered. After the filtrate was concentrated, heptane was added to the obtained residue, and the precipitated solid was collected by filtration, and the solid was dried in vacuo to give 150 g of the compound of the above formula (u). Yield 75% (based on trans-4-hydroxycyclohexanecarboxylic acid).

(2) 30.5 g of the compound of the formula (u), 1.59 g of dimethylaminopyridine, 30 g of trans-1,4-cyclohexanedicarboxylic acid monoethoxymethyl ester, and 200 mL of chloroform were mixed. The resulting mixture was stirred under a nitrogen atmosphere and ice-cooled, and 29.57 g of dicyclohexylcarbodiimide was added dropwise. After completion of the dropwise addition, the mixture was stirred, and 200 mL of chloroform and 200 mL of heptane were added to the obtained reaction mixture, and the resulting precipitate was removed by filtration. The obtained filtrate was washed three times with pure water, dried over anhydrous sodium sulfate and filtered. The resulting filtrate was concentrated, and methanol was added to the residue and stirred. The precipitated solid was taken out by filtration, mixed with methanol, and filtered. The obtained powder was vacuum dried to obtain 42 g of the compound of the above formula (v). The yield was 90% (based on the compound represented by the formula (u)).

(3) 23 g of the compound of the formula (v) obtained was dissolved in 150 mL of tetrahydrofuran. The resulting solution was added with 1.2% of 10% palladium on carbon (50% aqueous) under a nitrogen atmosphere. The obtained mixture was stirred under reduced pressure at room temperature under normal pressure under a hydrogen atmosphere. After the reaction was completed, the reaction mixture was filtered under a nitrogen atmosphere. Toluene was added to the obtained filtrate, and the insoluble matter was removed by filtration. The obtained filtrate was concentrated, and the residue was concentrated with water/methanol (volume ratio = 1/1), followed by washing with water, and the obtained crystals were taken out, and dried in vacuo to obtain 17.8 g of the compound of the above formula (w). The yield was 97% (based on the compound represented by the formula (v)).

(4) 16 g of the compound represented by the formula (w), 0.55 g of dimethylaminopyridine, 6.47 g of 4-hydroxybutyl acrylate, and 100 mL of chloroform were mixed. The resulting mixture was stirred under a nitrogen atmosphere and ice-cooled, and a solution of &lt;RTI ID=0.0&gt;0&gt; The resulting mixture was stirred and allowed to react. To the obtained reaction mixture, 200 mL of toluene was added and filtered. The obtained filtrate was concentrated under reduced pressure, toluene was added to the residue, and the obtained mixture was washed with 1N hydrochloric acid. The solution was dried over anhydrous sodium sulfate, filtered, and concentrated, and the obtained residue was dried in vacuo to give 18.5 g of the compound of formula (x).

(5) 18.5 g of the compound represented by the formula (x), 0.97 g of pure water, 0.85 g of p-toluenesulfonic acid monohydrate, and 100 mL of tetrahydrofuran were mixed. The resulting mixture was stirred under a nitrogen atmosphere at 50 ° C to cause a reaction. After the reaction was completed, the reaction mixture was allowed to cool to room temperature. Tetrahydrofuran was removed from the reaction mixture, and 200 mL of heptane was added to the obtained residue, and the precipitated solid was taken by filtration. After washing with pure water and drying under vacuum, 15.4 g of the compound of the above formula (t) can be obtained. The yield was 81% (based on the compound represented by the formula (w)).

Example 33-2

1.44 g of the compound represented by the formula (v-a), 4.24 g of the compound of the formula (t) obtained in the above Example 33-1, and 0.12 g of dimethylaminopyridine and chloroform were obtained. To the resulting mixture, a solution of 2.48 g of chloroform of dicyclohexylcarbodiimide was added dropwise under ice cooling. The resulting mixture was stirred to react, and the reaction mixture was filtered. Ethyl acetate was added to the residue and concentrated under reduced pressure. Methanol was added to the obtained concentrated residue. The precipitate which precipitated was taken out by filtration. After washing with ethanol and drying in vacuo, 4.65 g of the compound of the formula (v-9) below can be obtained. The yield was 85% (based on the compound represented by the formula (v-a)).

When the phase transition temperature of the compound represented by the formula (v-9) is observed by a polarizing microscope, it is understood that the compound represented by the formula (v-9) exhibits a smectic phase at 146 ° C to 159 ° C when the temperature is raised. The melting point is shown, and when the temperature is lowered, a nematic phase is formed up to 121 ° C and crystallized.

Example 34

Except that the compound of the formula (iv-a) was used instead of the compound of the formula (va) in the above Example 33-2, the same procedure as in Example 33-2 was carried out, and the following formula (iv-9) was obtained. The compound shown.

Example 35

A 2% aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified, manufactured by Wako Pure Chemical Industries, Ltd.) was applied to the glass substrate, and then dried by heating to obtain a film having a thickness of 89 nm. After the surface of the obtained film was subjected to a brushing treatment, a solution having the composition shown in Table 3 below was applied by spin coating on the surface subjected to the brushing treatment. After drying on a hot plate at 100 ° C for 1 minute, the film was heated at 100 ° C and irradiated with ultraviolet rays of 1200 mJ/cm ² to obtain an optical film having a film thickness of 1.04 μm.

In Table 3, "%" indicates the content in the solution. "L1" indicates LC242 commercially available from BASF, "Irg 907" indicates IRGACURE 907 manufactured by Ciba Japan Co., Ltd., and "Irg 819" indicates IRGACURE 819 manufactured by Ciba Japan Co., Ltd. "L2" means BYK 361N manufactured by BYK CHEMIE Japan.

A 2% aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified, manufactured by Wako Pure Chemical Industries, Ltd.) was applied to the glass substrate, and then dried by heating to obtain a film having a thickness of 89 nm. After the surface of the obtained film was subjected to a brushing treatment, the solution of the composition shown in Table 3 was applied by spin coating on the surface subjected to the brushing treatment. After drying on a hot plate at 100 ° C for 1 minute, an ultraviolet film of 1200 mJ/cm ² was irradiated while being heated at 100 ° C to obtain an optical film having a film thickness of 1.28 μm.

Example 37

A 2% aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified, manufactured by Wako Pure Chemical Industries, Ltd.) was applied to the glass substrate, and then dried by heating to obtain a film having a thickness of 89 nm. After the surface of the obtained film was subjected to a brushing treatment, the solution of the composition shown in Table 3 was applied by spin coating on the surface subjected to the brushing treatment. After drying on a hot plate at 80 ° C for 1 minute, it was dried at 210 ° C for 1 minute. The obtained unpolymerized film was irradiated with ultraviolet rays of 1200 mJ/cm ^{2 while} being heated at 190 ° C to obtain an optical film having a film thickness of 2.43 μm.

Example 38

A 2% aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified, manufactured by Wako Pure Chemical Industries, Ltd.) was applied to the glass substrate, and then dried by heating to obtain a film having a thickness of 89 nm. After the surface of the obtained film was subjected to a brushing treatment, the solution of the composition shown in Table 3 was applied by spin coating on the surface subjected to the brushing treatment. After drying on a hot plate at 80 ° C for 1 minute, it was dried at 210 ° C for 1 minute. The obtained unpolymerized film was irradiated with ultraviolet rays of 1200 mJ/cm ^{2 while} being heated at 190 ° C to obtain an optical film having a film thickness of 1.52 μm.

Example 39

A 2% aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified, manufactured by Wako Pure Chemical Industries, Ltd.) was applied to the glass substrate, and then dried by heating to obtain a film having a thickness of 89 nm. After the surface of the obtained film was subjected to a brushing treatment, the solution of the composition shown in Table 3 was applied by spin coating on the surface subjected to the brushing treatment. After drying on a hot plate at 80 ° C for 1 minute, it was dried at 160 ° C. The obtained unpolymerized film was irradiated with ultraviolet rays of 1200 mJ/cm ^{2 while} being heated at 160 ° C to obtain an optical film having a film thickness of 2.27 μm.

Example 40

A 2% aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified, manufactured by Wako Pure Chemical Industries, Ltd.) was applied to the glass substrate, and then dried by heating to obtain a film having a thickness of 89 nm. After the surface of the obtained film was subjected to a brushing treatment, the solution of the composition shown in Table 3 was applied by spin coating on the surface subjected to the brushing treatment. After drying on a hot plate at 80 ° C for 1 minute, it was dried at 140 ° C. The obtained unpolymerized film was irradiated with ultraviolet rays of 1200 mJ/cm ^{2 while} being heated at 140 ° C to obtain an optical film having a film thickness of 1.59 μm.

Example 41

A 2% aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified, manufactured by Wako Pure Chemical Industries, Ltd.) was applied to the glass substrate, and then dried by heating to obtain a film having a thickness of 89 nm. After the surface of the obtained film was subjected to a brushing treatment, the solution of the composition shown in Table 3 was applied by spin coating on the surface subjected to the brushing treatment. After drying on a hot plate at 80 ° C for 1 minute, it was dried at 150 ° C. The obtained unpolymerized film was irradiated with ultraviolet rays of 1200 mJ/cm ^{2 while} being heated at 190 ° C to obtain an optical film having a film thickness of 2.11 μm.

Example 42

A 2% aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified, manufactured by Wako Pure Chemical Industries, Ltd.) was applied to the glass substrate, and then dried by heating to obtain a film having a thickness of 89 nm. After the surface of the obtained film was subjected to a brushing treatment, the solution of the composition shown in Table 3 was applied by spin coating on the surface subjected to the brushing treatment. After drying on a hot plate at 80 ° C for 1 minute, it was dried at 160 ° C. The obtained unpolymerized film was irradiated with ultraviolet rays of 1200 mJ/cm ^{2 while} being heated at 160 ° C to obtain an optical film having a film thickness of 1.56 μm.

Example 43

A 2% aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified, manufactured by Wako Pure Chemical Industries, Ltd.) was applied to the glass substrate, and then dried by heating to obtain a film having a thickness of 8 g nm. After the surface of the obtained film was subjected to a brushing treatment, the solution of the composition shown in Table 3 was applied by spin coating on the surface subjected to the brushing treatment. After drying on a hot plate at 80 ° C for 1 minute, it was dried at 170 ° C. The obtained unpolymerized film was irradiated with ultraviolet rays of 1200 mJ/cm ^{2 while} being heated at 170 ° C to obtain an optical film having a film thickness of 1.40 μm.

Example 44

A 2% aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified, manufactured by Wako Pure Chemical Industries, Ltd.) was applied to the glass substrate, and then dried by heating to obtain a film having a thickness of 89 nm. After the surface of the obtained film was subjected to a brushing treatment, the solution of the composition shown in Table 3 was applied by spin coating on the surface subjected to the brushing treatment. After drying on a hot plate at 80 ° C for 1 minute, it was dried at 140 ° C. The obtained unpolymerized film was irradiated with ultraviolet rays of 1200 mJ/cm ^{2 while} being heated at 140 ° C to obtain an optical film having a film thickness of 1.50 μm.

Comparative example 1

A 2% aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified, manufactured by Wako Pure Chemical Industries, Ltd.) was applied to the glass substrate, and then dried by heating to obtain a film having a thickness of 89 nm. After the surface of the obtained film was subjected to a brushing treatment, the solution of the composition shown in Table 3 was applied by spin coating on the surface subjected to the brushing treatment. After drying on a hot plate at 80 ° C for 1 minute, it was dried at 150 ° C. The obtained unpolymerized film was irradiated with ultraviolet rays of 1200 mJ/cm ^{2 while} being heated at 100 ° C to obtain 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 of the produced optical film was measured using a measuring machine (KOBRA-WR, manufactured by Oji Scientific Instruments Co., Ltd.), and the phase difference Re of the wavelength of 450 nm was calculated by the program to which the device was attached ( 450), phase difference Re (550) at a wavelength of 550 nm, and phase difference Re (650) at a wavelength of 650 nm. The results are shown in Table 4.

Example 45

(1) 4.9 g of the compound represented by the formula (v-a), 1.7 g of trans-4-n-pentylcyclohexanecarboxylic acid, 0.21 g of 4-dimethylaminopyridine, and 392 g of dehydrated pyridine were mixed. To the resulting mixture, a solution obtained by dissolving 46.2 g of dicyclohexylcarbodiimide in 98 g of dehydrated pyridine was added dropwise. The resulting mixture was stirred at 60 ° C to cause a reaction. The resulting reaction mixture was filtered, and the obtained filtrate was concentrated. 196 g of chloroform was added to the concentrate, and the mixture was washed with 196 g of 2N hydrochloric acid, and the obtained solution was purified by a silica gel column under reduced pressure to obtain 2.8 g of the compound of the formula (TC-1). The yield was 70% (based on trans-4-n-pentylcyclohexanecarboxylic acid).

(2) 2.6 g of the compound represented by the formula (TC-1), 2.3 g of the compound represented by the formula (e), 0.07 g of 4-dimethylaminopyridine, and 75 g of chloroform were mixed. To the resulting mixture, a solution obtained by dissolving 1.4 g of dicyclohexylcarbodiimide in 19 g of chloroform was added dropwise. The resulting mixture was stirred at room temperature to cause a reaction. The reaction mixture was filtered, and chloroform was added to the obtained filtrate, and the mixture was washed with 94 g of 2N hydrochloric acid, and methanol was added to the obtained solution under reduced pressure, and the solid matter was taken out and washed with methanol to obtain the above formula (TM-1). The compound shown is 1.2 g. The yield was 24% (based on the compound represented by the formula (TC-1)).

¹ H-NMR (CDCl ₃ ): δ (ppm) 0.9 (3H), 1.0 (2H), 1.2-2.0 (16H), 2.2-2.5 (6H), 2.6-2.8 (3H), 3.9 (2H), 4.2 (2H), 5.8 (1H), 6.1 (1H), 6.4 (1H), 6.9-7.0 (4H), 7.3 (2H), 8.2-8.4 (4H)

When the phase transition temperature of the compound represented by the formula (TM-1) is observed by a polarizing microscope, it is understood that the compound represented by the formula (TM-1) exhibits a smectic phase at 148 ° C to 153 ° C when the temperature is raised. The nematic phase is present at 153 ° C to 173 ° C, and the nematic phase is present up to 102 ° C when the temperature is lowered.

Example 46

A 2% aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified, manufactured by Wako Pure Chemical Industries, Ltd.) was applied to the glass substrate, and then dried by heating to obtain a film having a thickness of 89 nm. After the surface of the obtained film was subjected to a brushing treatment, a solution having the composition shown in Table 5 below was applied by spin coating on the surface subjected to the brushing treatment. After drying on a hot plate at 170 ° C for 1 minute, an ultraviolet film of 9600 mJ/cm ² was irradiated while being heated at 130 ° C to obtain an optical film having a film thickness of 1.353 μm.

In Table 5, "%" indicates the content in the solution. "L1" indicates LC242 commercially available from BASF Corporation, and "Irg 819" indicates IRGACURE 819 manufactured by Ciba Japan Co., Ltd. "L2" means BYK 361N manufactured by BYK CHEMIE Japan.

Comparative example 2

The optical film was produced in the same manner as in Example 46 except that the solution of the composition shown in the above Table 5 was applied by spin coating, dried on a hot plate at 45 ° C for 1 minute, and irradiated with ultraviolet light at room temperature.

For the optical film to be produced, a phase difference of 547 nm was measured using a measuring machine (KOBRA-WR, manufactured by Oji Scientific Instruments Co., Ltd.), and the film thickness d derived from the polymerizable compound of the optical film was a laser microscope (LEXT). , measured by Olympus Co., Ltd., the birefringence ⊿n was calculated from the phase difference of the wavelength of 547 nm and the film thickness d. At the same time, the phase difference between the wavelengths of 447 nm and 628 nm was measured, and the wavelength dispersion characteristics Re(447)/Re(547) and Re(628)/Re(547) were calculated. The results are shown in Table 6.

Examples 47 to 63 and Comparative Example 3

A 2% aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified, manufactured by Wako Pure Chemical Industries, Ltd.) was applied to the glass substrate, and then dried by heating to obtain a film having a thickness of 89 nm. After the surface of the obtained film was subjected to a brushing treatment, a solution having the composition shown in the following Table 7 was applied onto the surface subjected to the brushing treatment by a spin coating method, and after drying, ultraviolet rays were irradiated to obtain an optical film.

In Table 7, "%" indicates the content in the solution. "L1" indicates LC242 commercially available from BASF, "Irg 907" indicates IRGACURE 907 manufactured by Ciba Japan Co., Ltd., and "Irg 819" indicates IRGACURE 819 manufactured by Ciba Japan Co., Ltd. Also, "L2" means BYK 361N manufactured by BYK CHEMIE Japan.

<Measurement of optical characteristics>

The front phase difference of the produced optical film was measured using a measuring machine (KOBRA-WR, manufactured by Oji Scientific Instruments Co., Ltd.). Since the glass substrate used for the substrate has no birefringence, the film obtained by measuring the glass substrate is measured by a measuring machine, whereby the front phase difference of the optical film produced on the glass substrate can be obtained. The front surface differences of the wavelengths of 447.3 nm, 546.9 nm, and 627.8 nm were measured, and Re (447.3) / Re (546.9) (hereinafter, abbreviated as α) and Re (627.8) / Re (546.9) were calculated (hereinafter, abbreviated as β) ). At the same time, the film thickness d (μm) derived from the optical film portion was measured using a laser microscope (LEXT, manufactured by Olympus Co., Ltd.), and the results are shown in Table 8. The birefringence ⊿n is calculated by dividing the value of Re (546.9) by the film thickness d.

Example 64

(1) 125 g of trans-4-hydroxycyclohexanecarboxylic acid, 143.8 g of potassium carbonate, 140.87 g of benzyl bromide, and N,N-dimethylacetamide were mixed. The resulting mixture was stirred and reacted under a nitrogen atmosphere at 80 °C. After the reaction mixture was allowed to cool, it was poured into a solution of water and methyl isobutyl ketone/heptane (weight ratio = 3/2), and the resulting mixture was stirred and then separated. The obtained organic layer was washed with pure water, dried, and filtered. After the filtrate was concentrated, heptane was added to the obtained concentrated residue, and the precipitated solid was filtered out, and the solid was dried in vacuo to yield 150 g of the compound of the above formula (g'). Yield 75% (based on trans-4-hydroxycyclohexanecarboxylic acid).

(2) 30 g of the compound represented by the formula (g'), 23.6 g of trans-4-butylcyclohexanecarboxylic acid, 29.08 g of dicyclohexylcarbodiimide, and 6.26 g of dimethylaminopyridine. Mix 60 mL of dehydrated chloroform. The resulting mixture was stirred under a nitrogen atmosphere at 40 ° C, and then stirred at room temperature to cause a reaction. Heptane was added to the obtained reaction mixture, and the resulting precipitate was removed by filtration. The obtained filtrate was washed with hydrochloric acid, dried and filtered. The obtained filtrate was concentrated, and methanol was added and the mixture was heated. The obtained solution was allowed to cool, and the precipitated crystal was taken out to obtain 32.0 g of the compound of the above formula (h'). The yield was 62% (based on the compound represented by the formula (g')).

(3) 32.0 g of the compound of the formula (h') and 150 mL of 2-propanol were mixed. To the resulting solution, 0.7 g of acetic acid and 6.40 g of palladium/carbon were added, and the mixture was stirred under a nitrogen atmosphere. The resulting mixture was stirred under reduced pressure in a hydrogen atmosphere to cause a reaction. After completion of the reaction, after replacing with nitrogen, the reaction mixture was filtered through Celite, and the filtrate was concentrated. After the concentrated residue was washed with pure water and dried in vacuo, 24.0 g of the compound of the above formula (j') was obtained. The yield was 97% (based on the compound represented by the formula (h')).

(4) 0.97 g of the compound represented by the formula (ii-a), 2.73 g of the compound represented by the formula (j') obtained in the above (3), 0.11 g of 4-dimethylaminopyridine, and 87 g of chloroform are mixed. To the mixture, 2.0 g of dicyclohexylcarbodiimide was dissolved in a solution obtained by dissolving 22 g of chloroform. The resulting mixture was stirred to cause a reaction. The precipitated solid was removed by filtration. The resulting filtrate was washed with hydrochloric acid. In the obtained solution, methanol was added under reduced pressure, and the solid matter was taken out. The solid matter thus taken out was washed with methanol to obtain 2,7 g of the compound represented by the above formula (ii-2). The yield was 81% (based on the compound represented by the formula (ii-a)).

¹ H-NMR (CDCl ₃ ): δ (ppm) 0.87 to 0.98 (m, 10H), 1.20 to 1.60 (m, 28H), 1.75 to 2.00 (m, 10H), 2.10 to 2.35 (m, 10H), 2.63 ~2.83 (m, 2H), 4.76 to 4.88 (m, 2H), 7.18 (s, 2H), 7.61 to 7.64 (m, 3H), 8.00 to 8.03 (m, 2H)

Example 65

1.87 g of the compound represented by the formula (vi-a), 3.96 g of the compound represented by the formula (j'), 0.16 g of 4-dimethylaminopyridine and 127 g of chloroform were mixed. To the resulting mixture, a solution obtained by dissolving 2.9 g of dicyclohexylcarbodiimide in 32 g of chloroform was added dropwise. The resulting mixture was stirred to react, and the precipitated solid was removed by filtration, and the obtained filtrate was washed with hydrochloric acid. In the obtained solution, methanol was added under reduced pressure, and the solid matter was taken out, and the solid matter which was taken out was washed with methanol to obtain 4.1 g of a compound represented by the following formula (vi-2). The yield was 78% (based on the compound represented by the formula (vi-a)).

¹ H-NMR (CDCl ₃ ): δ (ppm) 0.87 to 0.98 (m, 10H), 1.20 to 1.60 (m, 28H), 1.75 to 2.00 (m, 10H), 2.10 to 2.35 (m, 10H), 2.63 ~2.83 (m, 2H), 4.76 to 4.88 (m, 2H), 7.19 (s, 2H), 7.46 to 7.50 (dd, 2H), 7.86 to 7.89 (dd, 2H)

Example 66

The compound represented by the following formula (v-10) was synthesized in the same manner as in the above Example 65, and the yield was 73%.

¹ H-NMR (CDCl ₃ ): δ (ppm) 0.87 to 1.00 (m, 10H), 1.05 to 1.60 (m, 28H), 1.75 to 2.00 (m, 10H), 2.10 to 2.35 (m, 10H), 2.64 ~2.83 (m, 2H), 4.76 to 4.84 (m, 2H), 7.25 (s, 2H), 8.17 to 8.20 (dd, 2H), 8.34 to 8.38 (dd, 2H)

Examples 67 to 68 and Comparative Example 4

A 2% aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified, manufactured by Wako Pure Chemical Industries, Ltd.) was applied to the glass substrate, and then dried by heating to obtain a film having a thickness of 89 nm. After the surface of the obtained film was subjected to a brushing treatment, a solution having the composition shown in the following Table 9 was applied onto the surface subjected to the brushing treatment by a spin coating method, and after drying, ultraviolet rays were irradiated to obtain an optical film.

In Table 9, "%" indicates the content in the solution. "L1" indicates LC242 commercially available from BASF, and "Irg 819" indicates IRGACURE 819 manufactured by Ciba Japan Co., Ltd. "L2" means BYK 361N manufactured by BYK CHEMIE Japan.

<Measurement of optical characteristics>

The front surface difference of the optical film produced was measured by a measuring machine (KOBRA-WR, manufactured by Oji Scientific Instruments Co., Ltd.), and the glass substrate used for the substrate was subjected to measurement without measuring the birefringence. The film can obtain the frontal phase difference of the optical film produced on the glass substrate. The respective frontal phase differences of the wavelengths of 447.3 nm, 546.9 nm, and 627.8 nm were measured, and Re (447.3) / Re (546.9) (hereinafter, abbreviated as α) and Re (627.8) / Re (546.9) were calculated (hereinafter, abbreviated as β) ). Meanwhile, a part of the film thickness d (μm) derived from the optical film was measured using a laser microscope (LEXT, manufactured by Olympus Co., Ltd.), and the results are shown in Table 10. The birefringence ⊿n is calculated by dividing the value of Re (546.9) by the film thickness d.

Industrial useability

The optical film of the present invention may have the same polarization conversion in a wide frequency region.

1, 1’. . . Color filter

2, 2’. . . Optical film

3, 3’. . . Orientation film

4, 4’. . . Color filter layer

5. . . Liquid crystal display device

6,10. . . Polarizer

7,11. . . Substrate

8. . . Counter electrode

9. . . Liquid crystal layer

12. . . TFT, insulating layer

13. . . Transparent electrode

13’. . . Reflective electrode

30, 30a, 30b, 30c, 30d, 30e. . . Polarizer

14, 14’. . . Laminated body

15. . . Polarizing film

16, 16’. . . Support substrate

17, 17’. . . Orientation film

18, 18’. . . Optical film

19, 19', 22, 25. . . Subsequent layer

20. . . LCD panel

twenty one. . . Fitting

twenty three. . . Organic EL panel

twenty four. . . Luminous layer

Fig. 1 is a schematic view of a color filter 1 of the present invention.

Fig. 2 is a schematic view showing a liquid crystal display device 5 of the present invention.

Fig. 3 (a) to (e) are schematic views of the polarizing plate 30 of the present invention.

Fig. 4 is a schematic view showing a laminate 21 of a liquid crystal panel 20 and a polarizing plate 30 of a liquid crystal display device of the present invention.

Fig. 5 is a schematic view showing an organic EL panel 23 of the organic EL display device of the present invention.

1. . . Color filter

2. . . Optical film

3. . . Orientation film

4. . . Color filter layer

Claims (26)

An optical film obtained by polymerizing a compound containing a group represented by the formula (A) and at least one polymerizable group: -G _a -D _a -Ar-D _b -G _b - (A) Any one of the divalent groups represented by the Ar system (Ar-1) to the formula (Ar-13): (In the formula (Ar-1) to the formula (Ar-13), Z ¹ represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 6 carbon atoms, Alkylsulfonyl group having 1 to 6 carbon atoms, carboxyl group, fluoroalkyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, alkylthio group having 1 to 6 carbon atoms, and carbon number 1 to 6 N-alkylamino group, N,N-dialkylamino group having 2 to 12 carbon atoms, N-alkylamine sulfonyl group having 1 to 6 carbon atoms, or N,N-di 2 to 12 carbon atoms Alkylamine sulfonyl; Q ¹ and Q ³ each independently represent -CR ⁷ R ⁸ -, -S-, -NR ⁷ -, -CO- or -O-, but formula (Ar-1) to formula ( In the case of Ar-4), Q ¹ is -CO-; R ⁷ and R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; and Y ¹ , Y ² and Y ³ each independently represent a substitutable An aromatic hydrocarbon group or a substituted aromatic heterocyclic group; W ¹ and W ² each independently represent a hydrogen atom, a cyano group, a methyl group or a halogen atom; m represents an integer of 0 to 6, and n represents an integer of 0 to 2; ), π-aromatic ring of the total number of _N π electrons contained in the divalent group is 12 or more; D _a and D _b each independently represents a single bond, -CO-O -, - O -CO -, - C ( =S)-O-, -OC(=S)-, -CR ¹ R ² -, -CR ¹ R ² -CR ³ R ⁴ -, -O-CR ¹ R ² -, -CR ¹ R ² -O-, -CR ¹ R ² -O-CR ³ R ⁴ -, -CR ¹ R ² -O-CO-, -O-CO-CR ¹ R ² -, -CR ¹ R ² -O-CO-CR ³ R ⁴ -, -CR ¹ R ² -CO-O-CR ³ R ⁴ -, -NR ¹ -CR ² R ³ -, -CR ² R ³ -NR ¹ -, -CO-NR ¹ - or -NR ¹ -CO-; R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms; G _a and G _b respectively Independently representing a divalent alicyclic hydrocarbon group which may be selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms. At least one of the group consisting of a group, a cyano group and a nitro group is substituted, and at least one methylene group constituting the alicyclic hydrocarbon group may be substituted by -O-, -S- or -NH-]. The optical film according to claim 1, wherein the compound having a group represented by the formula (A) and at least one polymerizable group is a compound having a group represented by the formula (B) and at least one polymerizable group. :-E ¹ -G _a -D _a -Ar-D _b -G _b -E ² - (B) (wherein Ar, D _a , D _b , G _a and G _b represent the first item of the patent application scope The meanings defined are the same; E ¹ and E ² independently represent -CR ⁵ R ⁶ -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO- , -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR ⁵ -, -NR ⁵ -CO- , -O-CH ₂ -, -CH ₂ -O-, -S-CH ₂ -, -CH ₂ -S- or a single bond; R ⁵ and R ⁶ each independently represent a hydrogen atom, a fluorine atom or a carbon number of 1 To 4 alkyl). The optical film according to claim 2, wherein the compound having a group represented by the formula (B) and at least one polymerizable group is a compound containing a group represented by the formula (C) and at least one polymerizable group. : (wherein, Ar, D _a , D _b , G _a , G _b , E ¹ and E ² represent the same meanings as defined in the first and second claims of the patent application; B ¹ and B ² are independently Represents -CR ⁵ R ⁶ -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S) -O-, -OC(=S)-, -OC(=S)-O-, -CO-NR ⁵ -, -NR ⁵ -CO-, -O-CH ₂ -, -CH ₂ -O-, -S-CH ₂ -, -CH ₂ -S- or a single bond; R ⁵ and R ⁶ represent the same meanings as defined in the second claim; A ¹ and A ² independently represent a divalent alicyclic ring a hydrocarbon group or a divalent aromatic hydrocarbon group, the alicyclic hydrocarbon group and the aromatic hydrocarbon group may be selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, and a carbon number of 1 to At least one of the group consisting of 4 alkoxy groups, fluoroalkoxy groups having 1 to 4 carbon atoms, cyano groups and nitro groups; k and l each independently represent an integer of 0 to 3). The optical film of claim 3, wherein the compound having a group represented by the formula (C) and at least one polymerizable group is a compound represented by the formula (D): (wherein Ar, D _a , D _b , G _a , G _b , E ¹ , E ² , B ¹ , B ² , k and l represent the same as defined in the first, second and third paragraphs of the patent application scope. Meaning; F ¹ and F ² each independently represent an alkylene group having 1 to 12 carbon atoms, and the alkylene group may be selected from an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen. At least one of the groups of atoms is substituted, and at least one methylene group constituting the alkylene group may be substituted by -O- or -CO-; and any of P ¹ and P ² represents polymerization. The same, the other represents a hydrogen atom or a polymerizable group). For example, in the optical film of claim 4, which satisfies the formula (2) and the formula (3): (N _π -4) / 3 < k + 1 + 4 (2) 12 ≦ N _π ≦ 22 (3) ). The optical film of claim 4, wherein the compound represented by the above formula (D) is a compound represented by the formula (1): (wherein, Ar, E ¹ , E ² , B ¹ , B ² , F ¹ , F ² , P ¹ , P ² , k and l represent those defined in items ¹ , ² , 3 and 4 of the patent application scope. The same meaning; D ¹ and D ² independently represent *-O-CO- (* indicates the part bonded to Ar), -C(=S)-O-, -OC(=S)-, -CR ¹ R ² -, -CR ¹ R ² -CR ³ R ⁴ -, -O-CR ¹ R ² -, -CR ¹ R ² -O-, -CR ¹ R ² -O-CR ³ R ⁴ -, -CR ¹ R ² -O-CO-, -O-CO-CR ¹ R ² -, -CR ¹ R ² -O-CO-CR 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 represent application The meanings defined in the first item of the patent range are the same; G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group, and the alicyclic hydrocarbon group may be selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, At least one of a group consisting of a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, and a nitro group, and at least one methylene group constituting the alicyclic hydrocarbon group It can be substituted by -O-, -S- or -NH-). The optical film of claim 1, wherein D _a and D _b independently represent *-O-CO-, *-OC(=S)-, *-O-CR ¹ R ² -, *- NR ¹ -CR ² R ³ - or *-NR ¹ -CO- (* indicates a site to which Ar is bonded). The optical film of claim 1, wherein G _a and G _b are 1,4-cyclohexylene. The optical film of claim 6, wherein D ¹ and D ² independently represent *-O-CO-, *-OC(=S)-, *-O-CR ¹ R ² -, *- NR ¹ -CR ² R ³ - or *-NR ¹ -CO- (* indicates a site to which Ar is bonded). The optical film of claim 6, wherein G ¹ and G ² are 1,4-cyclohexylene. The optical film of claim 1 of the invention has a phase difference (Re (550)) at a wavelength of 550 nm of 113 to 163 nm. The optical film of claim 1, wherein the phase difference (Re (550)) at a wavelength of 550 nm is 250 to 300 nm. A composition comprising: a compound containing a group represented by the formula (A) and at least one polymerizable group, and a compound represented by the formula (4): -G _a -D _a -Ar-D _b -G _b - (A) [wherein, any one of the divalent groups represented by the Ar system (Ar-1) to the formula (Ar-13): (In the formula (Ar-1) to the formula (Ar-13), Z ¹ represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 6 carbon atoms, Alkylsulfonyl group having 1 to 6 carbon atoms, carboxyl group, fluoroalkyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, alkylthio group having 1 to 6 carbon atoms, and carbon number 1 to 6 N-alkylamino group, N,N-dialkylamino group having 2 to 12 carbon atoms, N-alkylamine sulfonyl group having 1 to 6 carbon atoms, or N,N-di 2 to 12 carbon atoms Alkylamine sulfonyl; Q ¹ and Q ³ each independently represent -CR ⁷ R ⁸ -, -S-, -NR ⁷ -, -CO- or -O-, but formula (Ar-1) to formula ( In the case of Ar-4), Q ¹ is -CO-; R ⁷ and R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; and Y ¹ , Y ² and Y ³ each independently represent a substitutable An aromatic hydrocarbon group or a substituted aromatic heterocyclic group; W ¹ and W ² each independently represent a hydrogen atom, a cyano group, a methyl group or a halogen atom; m represents an integer of 0 to 6, and n represents an integer of 0 to 2; ), π-aromatic ring of the total number of _N π electrons contained in the divalent group is 12 or more; D _a and D _b each independently represents a single bond, -CO-O -, - O -CO -, - C ( =S)-O-, -OC(=S)-, -CR ¹ R ² -, -CR ¹ R ² -CR ³ R ⁴ -, -O-CR ¹ R ^{2 -, - CR 1 R 2} -O -, - CR 1 R 2 -O-CR 3 R 4 -, -CR 1 R 2 -O-CO -, - O-CO-CR 1 R 2 -, - CR ¹ R ² -O-CO-CR ³ R ⁴ -, -CR ¹ R ² -CO-O-CR ³ R ⁴ -, -NR ¹ -CR ² R ³ -, -CR ² R ³ -NR ¹ -, -CO-NR ¹ - or -NR ¹ -CO-; R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms; G _a and G _b respectively Independently representing a divalent alicyclic hydrocarbon group which may be selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms. At least one of a group consisting of a group, a cyano group and a nitro group is substituted, and at least one methylene group constituting the alicyclic hydrocarbon group may be substituted by -O-, -S- or -NH-] (wherein A ¹¹ represents an aromatic hydrocarbon group, an alicyclic hydrocarbon group or a heterocyclic group, and the aromatic hydrocarbon group, the alicyclic hydrocarbon group and the heterocyclic group may be selected from a halogen atom, an alkyl group having 1 to 6 carbon atoms, Substituting at least one of a group of alkoxy groups having 1 to 6 carbon atoms, an N-alkylamino group having 1 to 6 carbon atoms, a nitro group, a cyano group and a fluorenyl group; B ¹¹ and B ¹² are each independently represented -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 a single bond; R ¹⁴ and R ¹⁵ are independent The ground represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms, and R ¹⁴ and R ¹⁵ may be bonded to form an alkylene group having 4 to 7 carbon atoms; and E ¹¹ represents an alkylene group having 1 to 12 carbon atoms. the system may be selected from alkylene groups having 1 to 6 carbon atoms, the group at least one of the carbon atoms substituted by an alkoxy group and a halogen atom of from 1 to 6 formed by; P ¹¹ represents a polymerizable group; G is Hydrogen atom, halogen atom, alkyl group having 1 to 13 carbon atoms, carbon An alkoxy group of 1 to 13, a fluoroalkyl group having 1 to 13 carbon atoms, an N-alkylamino group having 1 to 13 carbon atoms, a cyano group or a nitro group, or an alkyl group having 1 to 12 carbon atoms; The alkylene group may be substituted with at least one selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a halogen atom; t represents 1 To the integer of 5). The composition of claim 13, wherein the compound having a group represented by the formula (A) and at least one polymerizable group is a compound represented by the formula (1): (wherein, Ar represents the same meaning as defined in claim 13; D ¹ and D ² independently represent *-O-CO- (* indicates a portion bonded to Ar), -C (=S) )-O-, -OC(=S)-, -CR ¹ R ² -, -CR ¹ R ² -CR ³ R ⁴ -, -O-CR ¹ R ² -, -CR ¹ R ² -O-, ^{-CR 1 R 2 -O-CR 3} R 4 -, - CR 1 R 2 -O-CO -, - O-CO-CR 1 R 2 -, - CR 1 R 2 -O-CO-CR 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 represent the same meanings as defined in claim 13; G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group, and the alicyclic hydrocarbon group At least one selected from the group consisting of 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 and a nitro group And, at least one methylene group constituting the alicyclic hydrocarbon group may be substituted by -O-, -S- or -NH-; and E ¹ and E ² each independently represent -CR ⁵ R ⁶ -, - CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S ) -, - OC (= S ) -O -, - CO-NR 5 -, - NR 5 -CO- _{-O-CH 2 -, - CH} 2 -O -, - S-CH 2 -, - CH 2 -S- or a single bond; R ⁵ and R ⁶ each independently represent a hydrogen atom, a fluorine atom or a C 1 to 4 alkyl; B ¹ and B ² independently represent -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; A ¹ and A ² each independently represent a divalent alicyclic hydrocarbon group or a divalent aromatic group a hydrocarbon group, the alicyclic hydrocarbon group and the aromatic hydrocarbon group may be selected from 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, and carbon Substituting at least one of a group of fluoroalkoxy groups, cyano groups and nitro groups of 1 to 4; k and l each independently represent an integer of 0 to 3; and F ¹ and F ² each independently represent a carbon number a alkylene group of 1 to 12, which may be substituted by at least one selected from the group consisting of an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen atom, and , constituting the alkylene group is at least one methylene group is optionally replaced by -O- system or -CO-; P ¹ and P ² of any one represents a polymerizable , And the other represents a hydrogen atom or a polymerizable group). The composition of claim 13 or 14, which further comprises a photopolymerization initiator. A polarizing plate comprising: an optical film according to item 1 of the patent application, and a polarizing film. A color filter that sequentially laminates a color filter layer, an alignment film, and Applicant who applied for the optical film of the first item of the patent scope. A liquid crystal display device comprising the color filter of item 17 of the patent application. A flat display device comprising: a polarizing plate according to claim 16 of the patent application; and a liquid crystal panel. An organic electroluminescence (EL) display device comprising: an organic EL panel comprising a polarizing plate according to claim 16 of the patent application. A compound of the formula (1): [wherein, any one of the divalent groups represented by the Ar system (Ar-1) to the formula (Ar-13): (wherein Z ¹ represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, a carboxyl group, a fluoroalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, an N-alkylamino group having 1 to 6 carbon atoms, and 2 to 12 carbon atoms N,N-dialkylamino group, N-alkylamine sulfonyl group having 1 to 6 carbon atoms, or N,N-dialkylamine sulfonyl group having 2 to 12 carbons; Q ¹ and Q ³ Respectively represent -CR ⁷ R ⁸ -, -S-, -NR ⁷ -, -CO- or -O-, respectively, but in the formula (Ar-1) to (Ar-4), Q ¹ is -CO- R ⁷ and R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; and Y ¹ , Y ² and Y ³ each independently represent a substituted aromatic hydrocarbon group or a substituted aromatic heterocyclic ring; And W ¹ and W ² each independently represent a hydrogen atom, a cyano group, a methyl group or a halogen atom; m represents an integer of 0 to 6, and n represents an integer of 0 to 2), and an aromatic ring contained in the divalent group The total number of π electrons N _π is 12 or more; D ¹ and D ² each independently represent *-O-CO- (* indicates a portion bonded to Ar), -C(=S)-O-, -OC (= S)-, -CR ¹ R ² -, -CR ¹ R ² -CR ³ R ⁴ -, -O-CR ¹ R ² -, -CR ¹ R ² -O-, -CR ¹ R ² -O-CR ³ R ⁴ -, -CR ¹ R ² -O-CO-, -O-CO-CR ¹ R ² -, -CR ¹ R ² -O-CO-CR 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 each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms; G ¹ and G ² are each independently The ground represents a divalent alicyclic hydrocarbon group which may be selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms. , a cyano group and a nitro group formed by at least one of the substituents, and at least one methylene group constituting the alicyclic hydrocarbon-based may be of -O -, - S- or -NH- substituted; E ¹ And E ² independently represent -CR ⁵ R ⁶ -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR ⁵ -, -NR ⁵ -CO-, -O-CH ₂ -,- _{CH 2 -O -, - S-} CH 2 -, - CH 2 -S- or a single bond; R ⁵ and R ⁶ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having a carbon number of 1 to 4; B ¹ and B ² independently represents -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; A ¹ and A ² each independently represent a divalent alicyclic group a hydrocarbon group or a divalent aromatic hydrocarbon group, the alicyclic hydrocarbon group and the aromatic hydrocarbon group may be selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, and a carbon number of 1 to 4 Substituting at least one of the alkoxy group, the fluoroalkoxy group having 1 to 4 carbon atoms, the cyano group and the nitro group; k and l each independently represent an integer of 0 to 3; F ¹ and F ² Each of the alkylene groups having a carbon number of 1 to 12 independently represents at least one group selected from the group consisting of an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen atom. Substituted, and at least one methylene group constituting the alkylene group may be substituted by -O- or -CO-; any of P ¹ and P ² represents a polymerizable group, and the other represents A hydrogen atom or a polymerizable group]. For example, in the compound of claim 21, which satisfies the formula (2) and formula (3): (N _π -4) / 3 < k + 1 + 4 (2) 12 ≦ N _π ≦ 22 (3) . The compound of claim 21, wherein D ¹ and D ² independently represent *-O-CO-, *-OC(=S)-, *-O-CR ¹ R ² -, *-NR ¹ -CR ² R ³ - or *-NR ¹ -CO- (* indicates a site to which Ar is bonded). The compound of claim 21, wherein G ¹ and G ² are 1,4-phenylene. A method for producing an unpolymerized film, characterized by coating a solution containing a compound according to any one of claims 21 to 24 on a support substrate or a support substrate The film was dried and allowed to form an unpolymerized film. A method for producing an optical film, which comprises polymerizing an unpolymerized film obtained by the production method of claim 25, to produce an optical film.