KR20190090760A - Optical film - Google Patents

Abstract

The present invention relates to an optical film obtained by polymerizing a compound including at least one polymerizable group and a group represented by formula (A): -G_a-D_a-Ar-D_b-G_b-. In the formula, Ar represents a bivalent group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and the sum number (N_π) of π electrons of the aromatic ring included in the bivalent group is 12 or higher. D_a and D_b independently represent a single bond, -CO-O-, -O-CO-, -C(=S)-O-, -O-C(=S)-, -CR^1R^2-, -CR^1R^2-CR^3R^4-, -O-CR^1R^2-, -CR^1R^2-O-, -CR^1R^2-O-CR^3R^4-, -CR^1R^2-O-CO-, -O-CO-CR^1R^2-, -CR^1R^2-O-CO-CR^3R^4-, -CR^1R^2-CO-O-CR^3R^4-, -NR^1-CR^2R^3-, -CR^2R^3-NR^1-, -CO-NR^1-, or NR^1-CO-. G_a and G_b independently represent a bivalent alicyclic hydrocarbon group. A regular polarization conversion is possible in a wide wavelength region.

Description

Optical film {OPTICAL FILM}

The present invention relates to an optical film.

The flat panel display apparatus (FPD) contains the member using optical films, such as a polarizing plate and retardation plate. As an optical film, the optical film obtained by superposing | polymerizing after apply | coating the solution obtained by melt | dissolving a polymeric compound in a solvent to a support base material is mentioned.

On the other hand, it is known that the phase difference Re (λ) of the optical film imparted by the light having a wavelength λ nm is determined by the product of the birefringence Δn and the film thickness d (Re (λ) = Δn × d ). In addition, the wavelength dispersion characteristic is a value (Re (λ) / Re (550) obtained by dividing the phase difference value Re (λ) at a certain wavelength λ nm by the phase difference value Re (550) at 550 nm. )), Where (Re (λ) / Re (550)) is close to 1, or [Re (450) / Re (550)] <1 and [Re (650) / Re (550)]> In the wavelength range which shows reverse wavelength dispersion of 1, it is known that a fixed polarization conversion is possible.

SID Symposium Digest of Technical Filters, 2006, Volume 37, p. 1673 discloses a compound (LC242) represented by the following formula as a polymerizable compound.

According to the present invention,

[1] Formula (A)

(In the formula, Ar represents a divalent group having at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic hetero rings, and the total number of π electrons in the aromatic ring contained in the divalent group (N _π ). Is at least 12. D _a and D _b are each independently a single bond,

R <^1> , R <^2> , R <^3> and R <^4> represent a hydrogen atom, a fluorine atom, or a C1-C4 alkyl group each independently. G _a and G _b each independently represent a divalent alicyclic hydrocarbon group, the alicyclic hydrocarbon group being 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 A group represented by at least one selected from the group consisting of a no group and a nitro group, and at least one methylene group constituting the alicyclic hydrocarbon group may be substituted with -O-, -S- or -NH-) and at least Optical film obtained by superposing | polymerizing the compound containing one polymeric group;

[2] A compound containing a group represented by formula (A) and at least one polymerizable group is formula (B)

Wherein Ar, D _a , D _b , G _a and G _b have the same meanings as defined in [1], and E ¹ and E ² are each independently —CR ⁵ R ⁶ —, —CH ₂ —CH _2- , -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C (= S) -O-, -OC (= S)-,- OC (= S) -O-, -CO-NR ^5- , -NR ⁵ -CO-, -O-CH _2- , -CH ₂ -O-, -S-CH _2- , -CH ₂ -S- Or a single bond, R ⁵ and R ⁶ independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms) and an optical film according to [1], which is a compound containing at least one polymerizable group. ;

[3] A compound containing a group represented by formula (B) and at least one polymerizable group is formula (C)

(Wherein Ar, D _a , D _b , G _a , G _b , E ¹ and E ² have the same meanings as defined in [1] and [2], and B ¹ and B ² are each independently

Or a single bond, and R ⁵ and R ⁶ have the same meanings 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 having a halogen atom, an alkyl group having 1 to 4 carbon atoms, and a fluoro having 1 to 4 carbon atoms. It may be substituted by at least one selected from the group consisting of an alkyl group, 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. k and l each independently represent the integer of 0-3), The optical film as described in [2] which is a compound containing group and at least 1 polymeric group;

[4] A compound containing a group represented by formula (C) and at least one polymerizable group is represented by formula (D)

Wherein Ar, D _a , D _b , G _a , G _b , E ¹ , E ² , B ¹ , B ² , k and l have the same meanings as defined in [1], [2] and [3] F ¹ and F ² each independently represent an alkylene group having 1 to 12 carbon atoms, and the alkylene group is 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; At least one methylene group constituting the alkylene group may be substituted or may be substituted with -O- or -CO- One of P ¹ and P ² represents a polymerizable group, and the other is a hydrogen atom or polymerization. Optical film as described in [3] which is a compound represented by the following:

[5] The optical film according to [3] or [4], which satisfies Formula (2) and Formula (3);

[6] The compound represented by formula (D) is formula (1)

Wherein Ar, E ¹ , E ² , B ¹ , B ² , F ¹ , F ² , P ¹ , P ² , k and l are in [1], [2], [3] and [4] Have the same meaning as defined, D ¹ and D ² are each independently * -O-CO- (* represents a binding site 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- represents and R ¹ , R ² , R ³ and R ⁴ represent the same meaning as defined in [1], G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group, and the alicyclic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, and a carbon number 1 Even if substituted with at least one selected from the group consisting of a fluoroalkyl group having 4 to 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 substituted with -O-, -S- or -NH-); an optical film according to claim 4;

[7] The optical film according to any one of [1] to [6], wherein Ar is any of the groups represented by formulas (Ar-1) to (Ar-13);

(In formula, Z <^1> is a halogen atom, a C1-C6 alkyl group, a cyano group, a nitro group, a C1-C6 alkylsulfinyl group, a C1-C6 alkylsulfonyl group, a carboxyl group, a C1-C6 fluoro. Alkyl group, C1-C6 alkoxy group, C1-C6 alkylthio group, C1-C6 N-alkylamino group, C2-C12 N, N- dialkylamino group, C1-C6 N-alkyl Sulfamoyl group or N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms, Q ¹ and Q ³ each independently represent -CR ⁷ R ^8- , -S-, -NR ^7- , -CO- or Represents -O- and R ⁷ and R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 4. Y ¹ , Y ² and Y ³ may each independently be substituted with an aromatic hydrocarbon group or substituted. which represents an aromatic heterocyclic ring. W ¹ and W ² are each independently a hydrogen atom, methyl Or a halogen atom. M represents an integer of 0 to 6, n represents an integer of 0 to 2)

[8] D _a and D _b are each independently * -O-CO-, * -OC (= S)-, * -O-CR ¹ R ^2- , * -NR ¹ -CR ² R ³ -or * The optical film as described in [1], [2], [3], [4], [5], or [7], which is -NR ¹ -CO- (* represents a bonding site with Ar);

[9] the optical film according to [1], [2], [3], [4], [5], [7], or [8], wherein G _a and G _b are 1,4-cyclohexylene groups;

[10] D ¹ and D ² are each independently * -O-CO-, * -OC (= S)-, * -O-CR ¹ R ^2- , * -NR ¹ -CR ² R ³ -or * -NR ¹ -CO- (* represents a binding site with Ar) the optical film according to [6];

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

[12] The optical film according to any one of [1] to [11], wherein the retardation value (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 retardation value (Re (550)) at a wavelength of 550 nm is 250 to 300 nm;

[14] Formula (A)

(In the formula, Ar represents a divalent group having at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic hetero rings, and the total number of π electrons in the aromatic ring contained in the divalent group (N _π ). Is at least 12. D _a and D _b are each independently a single bond,

R <^1> , R <^2> , R <^3> and R <^4> represent a hydrogen atom, a fluorine atom, or a C1-C4 alkyl group each independently. G _a and G _b each independently represent a divalent alicyclic hydrocarbon group, the alicyclic hydrocarbon group being 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 A group represented by at least one selected from the group consisting of a no group and a nitro group, and at least one methylene group constituting the alicyclic hydrocarbon group may be substituted with -O-, -S- or -NH-) and at least Compound comprising one polymerizable group and formula (4)

(In formula, A <^11> represents an aromatic hydrocarbon group, an alicyclic hydrocarbon group, or a heterocyclic group, and this aromatic hydrocarbon group, an alicyclic hydrocarbon group, and a heterocyclic group are a halogen atom, a C1-C6 alkyl group, and a C1-C6 alkoxy. group, having 1 to 6 carbon atoms in the N- alkylamino group, a nitro group, a cyano group and mercapto group may be substituted by at least one selected from the group consisting of. B ¹¹ and B ¹² are each independently

Alternatively, a single bond may be represented, and R ¹⁴ and R ¹⁵ may each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms, and R ¹⁴ and R ¹⁵ may be bonded to each other to form an alkylene group having 4 to 7 carbon atoms. E ¹¹ represents an alkylene group having 1 to 12 carbon atoms, and 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. P ¹¹ represents a polymerizable group. G is a hydrogen atom, a halogen atom, a C1-C13 alkyl group, a C1-C13 alkoxy group, a C1-C13 fluoroalkyl group, a C1-C13 N-alkylamino group, a cyano group, or a nitro group, or The polymeric group couple | bonded through a C1-C12 alkylene group is shown, and this alkylene group may be substituted by at least 1 chosen from the group which consists of a C1-C6 alkyl group, a C1-C6 alkoxy group, and a halogen atom. a composition containing the compound represented by t represents an integer of 1-5;

[15] A compound containing a group represented by formula (A) and at least one polymerizable group is formula (1)

(In the formula, Ar represents the same meaning as defined in [14]. D ¹ and D ² each independently represent * -O-CO- (* represents a binding site to Ar),

R ¹ , R ² , R ³ and R ⁴ represent the same meaning as defined in [14], G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group, and the alicyclic hydrocarbon group is a halogen atom. May be substituted with at least one selected from the group consisting of 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 constituting the alicyclic hydrocarbon group. One methylene group may be substituted with -O-, -S-, or -NH-. E ¹ and E ² are each independently

Or a single bond is represented, R <^5> and R <^6> respectively independently represents a hydrogen atom, a fluorine atom, or a C1-C4 alkyl group. B ¹ and B ² are each independently

Or a single bond. 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 having a halogen atom, an alkyl group having 1 to 4 carbon atoms, and a fluoro having 1 to 4 carbon atoms. It may be substituted by at least one selected from the group consisting of an alkyl group, 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. k and l respectively independently represent the integer of 0-3. F ¹ and F ² each independently represent an alkylene group having 1 to 12 carbon atoms, and the alkylene group 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; At least one methylene group constituting the alkylene group may be substituted with -O- or -CO-. Either one of P ¹ and P ² represents a polymerizable group, and the other represents a hydrogen atom or a polymerizable group), the composition according to [14];

[16] the composition according to [14] or [15], further containing 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 the optical film according to any one of [1] to [13] are laminated in this order;

[19] a liquid crystal display device comprising the color filter described in [18];

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

[21] an organic EL display device comprising an organic electroluminescent panel comprising the polarizing plate according to [17];

[22] Formula (1)

(In the formula, Ar represents a divalent group having at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic hetero rings, and the total number of π electrons in the aromatic ring contained in the divalent group (N _π ). Is at least 12. D ¹ and D ² are each independently * -O-CO- (* represents a binding site to Ar),

R <^1> , R <^2> , R <^3> and R <^4> represent a hydrogen atom, a fluorine atom, or a C1-C4 alkyl group each independently. G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group, the alicyclic hydrocarbon group being 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 cyan It may be substituted by at least one chosen from the group which consists of a furnace group and a nitro group, and the at least 1 methylene group which comprises the alicyclic hydrocarbon group may be substituted by -O-, -S-, or -NH-. E ¹ and E ² are each independently

Or a single bond is represented, R <^5> and R <^6> respectively independently represents a hydrogen atom, a fluorine atom, or a C1-C4 alkyl group. B ¹ and B ² are each independently

Or a single bond. 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 having a halogen atom, an alkyl group having 1 to 4 carbon atoms, and a fluoro having 1 to 4 carbon atoms. It may be substituted by at least one selected from the group consisting of an alkyl group, 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. k and l respectively independently represent the integer of 0-3. F ¹ and F ² each independently represent an alkylene group having 1 to 12 carbon atoms, and the alkylene group 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; At least one methylene group constituting the alkylene group may be substituted with -O- or -CO-. Either one 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 Formula (2) and Formula (3);

[24] The compound according to [22] or [23], wherein Ar is any of a group represented by formula (Ar-1) to formula (Ar-13);

(In formula, Z <^1> is a halogen atom, a C1-C6 alkyl group, a cyano group, a nitro group, a C1-C6 alkylsulfinyl group, a C1-C6 alkylsulfonyl group, a carboxyl group, a C1-C6 fluoro. Alkyl group, C1-C6 alkoxy group, C1-C6 alkylthio group, C1-C6 N-alkylamino group, C2-C12 N, N- dialkylamino group, C1-C6 N-alkyl Sulfamoyl group or N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms, Q ¹ and Q ³ each independently represent -CR ⁷ R ^8- , -S-, -NR ^7- , -CO- or Represents -O- and R ⁷ and R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 4. Y ¹ , Y ² and Y ³ may each independently be substituted with an aromatic hydrocarbon group or substituted. which represents an aromatic heterocyclic ring. W ¹ and W ² are each independently a hydrogen atom, methyl Or a halogen atom. M represents an integer of 0 to 6, n represents an integer of 0 to 2)

[25] D ¹ and D ² are each independently * -O-CO-, * -OC (= S)-, * -O-CR ¹ R ^2- , * -NR ¹ -CR ² R ³ -or The compound according to any one of [22] to [24], wherein * -NR ¹ -CO- (* represents a binding site to Ar);

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

[27] A method for producing an unpolymerized film, wherein the solution containing the compound according to any one of [22] to [26] is applied onto a support substrate or an alignment film formed on the support substrate and dried.

[28] a method for producing an optical film comprising polymerizing the unpolymerized film obtained by the production method described in [27]; And so on.

The optical film of this invention is a following formula (A)

(In the formula, Ar represents a divalent group having at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic hetero rings, and the total number of π electrons in the aromatic ring contained in the divalent group (N _π ). Is at least 12. D _a and D _b are each independently a single bond,

R <^1> , R <^2> , R <^3> and R <^4> represent a hydrogen atom, a fluorine atom, or a C1-C4 alkyl group each independently. G _a and G _b each independently represent a divalent alicyclic hydrocarbon group, the alicyclic hydrocarbon group being 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 A group represented by at least one selected from the group consisting of a no group and a nitro group, and at least one methylene group constituting the alicyclic hydrocarbon group may be substituted with -O-, -S- or -NH-) and at least It is obtained by polymerizing the compound (hereinafter abbreviated as compound (A)) containing one polymerizable group.

In the present invention, the term "optical film" refers to a film having optical function as a film which can transmit light. Optical function means refraction, birefringence, etc. A retardation film, which is a kind of optical film, is used for converting linearly polarized light into circularly polarized light or elliptically polarized light, or conversely converting circularly polarized light or elliptically polarized light into linearly polarized light.

By having the group represented by said formula (A), the optical film of this invention becomes constant polarization conversion in a wide wavelength range. Moreover, the wavelength dispersion characteristic of an optical film can be adjusted by adjusting content of the group represented by Formula (A) in an optical film.

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

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

Examples of the aromatic hydrocarbon ring include benzene ring, naphthalene ring, anthracene ring, and phenanthroline ring, and examples of the aromatic hetero ring include furan ring, pyrrole ring, thiophene ring, pyridine ring, thiazole ring and benzothia A sol ring etc. are mentioned. Especially, a benzene ring, a thiazole ring, and a benzothiazole ring are preferable.

Ar is preferably any group among the groups represented by the following formulas (Ar-1) to (Ar-13).

(In formula, Z <^1> is a halogen atom, a C1-C6 alkyl group, a cyano group, a nitro group, a C1-C6 alkylsulfinyl group, a C1-C6 alkylsulfonyl group, a carboxyl group, a C1-C6 fluoro. Alkyl group, C1-C6 alkoxy group, C1-C6 alkylthio group, C1-C6 N-alkylamino group, C2-C12 N, N- dialkylamino group, C1-C6 N-alkyl Sulfamoyl group or N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms, Q ¹ and Q ³ each independently represent -CR ⁷ R ^8- , -S-, -NR ^7- , -CO- or Represents -O- and R ⁷ and R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 4. Y ¹ , Y ² and Y ³ may each independently be substituted with an aromatic hydrocarbon group or substituted. which represents an aromatic heterocyclic ring. W ¹ and W ² are each independently a hydrogen atom, methyl Or a halogen atom. M represents an integer of 0 to 6, n represents an integer of 0 to 2)

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom, a chlorine atom, a bromine atom is preferable.

Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group and hexyl group. The alkyl group of -4 is preferable, a C1-C2 alkyl group is more preferable, and a methyl group is especially preferable.

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

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

Examples of the fluoroalkyl group having 1 to 6 carbon atoms include fluoromethyl group, trifluoromethyl group, fluoroethyl group, pentafluoroethyl group, heptafluoropropyl group and nonafluorobutyl group, and the like. Fluoroalkyl group is preferable, a C1-C2 fluoroalkyl group is more preferable, and trifluoromethyl group is especially preferable.

Examples of the alkoxy group having 1 to 6 carbon atoms include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group and hexyloxy group. A C1-C4 alkoxy group is preferable, A C1-C2 alkoxy group is more preferable, A methoxy group is especially preferable.

Examples of the alkylthio group having 1 to 6 carbon atoms include methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, sec-butylthio group, tert-butylthio group and pentyl tea. A group, a hexylthio group, etc. are mentioned, A C1-C4 alkylthio group is preferable, A C1-C2 alkylthio group is more preferable, A methylthio group is especially preferable.

Examples of the N-alkylamino group having 1 to 6 carbon atoms include N-methylamino group, N-ethylamino group, N-propylamino group, N-isopropylamino group, N-butylamino group, N-isobutylamino group, and N-sec-butylamino group , N-tert-butylamino group, N-pentylamino group, N-hexylamino group, etc. are mentioned, A C1-C4 N-alkylamino group is preferable, A C1-C2 N-alkylamino group is more preferable, 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 group, N, N -Diisopropylamino group, N, N-dibutylamino group, N, N-diisobutylamino group, N, N-dipentylamino group, N, N-dihexylamino group, etc. are mentioned, N of C2-C8 is mentioned. , N-dialkylamino group is preferable, N, N-dialkylamino group having 2 to 4 carbon atoms is more preferable, and N, N-dimethylamino group is particularly preferable.

As a C1-C6 N-alkyl sulfamoyl group, N-methyl sulfamoyl group, N-ethyl sulfamoyl group, N-propyl sulfamoyl group, N-isopropyl sulfamoyl group, N-butyl sulfamoyl group, N -Isobutyl sulfamoyl group, N-sec-butyl sulfamoyl group, N-tert-butyl sulfamoyl group, N-pentyl sulfamoyl group, N-hexyl sulfamoyl group, etc. are mentioned, N-C1-C4 is mentioned. An alkyl sulfamoyl group is preferable, a C1-C2 N-alkyl sulfamoyl group is more preferable, and an N-methyl sulfamoyl group is especially preferable.

As a C2-C12 N, N- dialkyl sulfamoyl group, N, N- dimethyl sulfamoyl group, N-methyl-N-ethyl sulfamoyl group, N, N- diethyl sulfamoyl group, N, N- Dipropylsulfamoyl group, N, N-diisopropylsulfamoyl group, N, N-dibutylsulfamoyl group, N, N-diisobutylsulfamoyl group, N, N-dipentylsulfamoyl group, N, N -Dihexyl sulfamoyl group etc. are mentioned, A C2-C8 N, N- dialkyl sulfamoyl group is preferable, A C2-C4 N, N- dialkyl sulfamoyl group is more preferable, N, N-dimethylsulfamoyl group is particularly preferred.

Z ¹ is a halogen atom, methyl group, cyano group, nitro group, carboxyl group, methylsulfonyl group, trifluoromethyl group, methoxy group, methylthio group, N-methylamino group, N, N-dimethylamino group, N-methylsulfamoyl group Or N, N-dimethylsulfamoyl group.

Examples of the alkyl group having 1 to 4 carbon atoms in R ⁷ and R ⁸ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, and the like. An alkyl group is preferable and a methyl group is more preferable.

Q ¹ is -S-, -CO-, -NH-, -N ( CH 3) - and should preferably, Q ³ is preferably -S-, -CO-.

As an aromatic hydrocarbon group in Y <^1> , Y <^2> and Y <^3> , C6-C20 aromatic hydrocarbon groups, such as a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and a biphenyl group, are mentioned, A phenyl group and a naphthyl group It is preferable and a phenyl group is more preferable. The aromatic heterocyclic group includes at least one hetero atom such as nitrogen atom, oxygen atom, sulfur atom, such as furyl group, pyrrolyl group, thienyl group, pyridinyl group, thiazolyl group, benzothiazolyl group, and has 4 to 4 carbon atoms. 20 aromatic heterocyclic groups are mentioned, and a furyl group, a pyrrolyl group, a thienyl group, a pyridinyl group, and a thiazolyl group is preferable.

Such an aromatic hydrocarbon group and an aromatic heterocyclic group may have at least one substituent, As a substituent, a halogen atom, a C1-C6 alkyl group, a cyano group, a nitro group, a C1-C6 alkylsulfinyl group, C1-C1 An alkylsulfonyl group having 6 to 6, 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 having 2 to 12 carbon atoms N, N-dialkylamino group, C1-C6 N-alkylsulfamoyl group, C2-C12 N, N- dialkylsulfamoyl group, etc. are mentioned, A halogen atom, a C1-C2 alkyl group, Cyano group, nitro group, alkylsulfonyl group of 1 to 2 carbon atoms, fluoroalkyl group of 1 to 2 carbon atoms, alkoxy group of 1 to 2 carbon atoms, alkylthio group of 1 to 2 carbon atoms, N-alkylamino group of 1 to 2 carbon atoms , A C 2-4 N, N-dialkylamino group, Alkyl sulfamoyl group a small number of 1-2 is preferable.

Halogen atom, C1-C6 alkyl group, cyano group, nitro group, C1-C6 alkylsulfinyl group, C1-C6 alkylsulfonyl group, carboxyl group, C1-C6 fluoroalkyl group, C1-C6 Alkoxy group, C1-C6 alkylthio group, C1-C6 N-alkylamino group, C2-C12 N, N- dialkylamino group, C1-C6 N-alkylsulfamoyl group, and C2-C6 Examples of the N, N-dialkylsulfamoyl group for 12 include the same as those described above.

As Y <^1> , Y <^2> and Y <^3> , it is preferable to independently represent the group represented by following formula (Y-1)-(Y-6).

(In formula, Z <^2> is a halogen atom, a C1-C6 alkyl group, a cyano group, a nitro group, a C1-C6 alkylsulfinyl group, a C1-C6 alkylsulfonyl group, a carboxyl group, a C1-C6 fluoro. Alkyl group, C1-C6 alkoxy group, C1-C6 thioalkyl group, C1-C6 N-alkylamino group, C2-C12 N, N-dialkylamino group, C1-C6 N-alkylsulphate Represents a pamoyl group or an N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms, R represents a hydrogen atom or a methyl group, a ₁ represents an integer of 0 to 5, and a ₂ represents an integer of 0 to 4; , b ₁ represents an integer of 0 to 3, b ₂ represents an integer of 0 to 2)

It is more preferable that Y <^1> , Y <^2> and Y <^3> are group represented independently by Formula (Y-1) or Formula (Y-3) from the point which manufacture of a compound (A) is easy.

It is preferable that W <^1> and W <^2> are a hydrogen atom, a cyano group, or a methyl group independently, and it is more preferable that it is a hydrogen atom.

It is preferable that m is 0 or 1. n 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 (Ar-10b).

(Wherein Z ¹ , n, Q ¹ , Z ² , a ₁ and b ₁ represent the same meanings as above)

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

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

As a specific example of group represented by Formula (Ar-6) and Formula (Ar-7), group represented by Formula (ar-40)-formula (ar-119) is mentioned.

As a specific example of group represented by a formula (Ar-8) and a formula (Ar-9), the group represented by Formula (ar-120)-a formula (ar-129) is mentioned.

As a specific example of group represented by Formula (Ar-10), group represented by Formula (ar-130)-a formula (ar-149) is mentioned.

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

As a specific example of group represented by Formula (Ar-12), group represented by Formula (ar-160)-a formula (ar-179) is mentioned.

As a specific example of group represented by Formula (Ar-13), group represented by Formula (ar-180)-a formula (ar-189) is mentioned.

D _a and D _b are each independently a single bond,

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 (eg, methyl group, ethyl group, propyl group, isopropyl group, butyl group, iso Butyl group, tert-butyl group).

D _a and D _b are each independently * -O-CO-, * -OC (= S)-, * -O-CR ¹ R ^2- , * -NR ¹ -CR ² R ³ -or * -NR It is preferable that it is ^1- CO- (* represents a coupling | bonding site with Ar). It is more preferable that D _a and D _b are each independently * -O-CO-, * -OC (= S)-or * -NR ¹ -CO- (* represents a binding site with Ar). It is preferable that R <^1> , R <^2> , R <^3> and R <^4> are a hydrogen atom or a C1-C4 alkyl group each independently, and it is more preferable that they are a hydrogen atom, a methyl group, or an ethyl group.

G _a and G _b each independently represent a divalent alicyclic hydrocarbon group, the alicyclic hydrocarbon group being 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 It may be substituted by at least one selected from the group consisting of a furnace group and a nitro group.

As a bivalent alicyclic hydrocarbon group, the alicyclic hydrocarbon group which may contain the hetero atom represented by following formula (g-1)-(g-10) is mentioned, A bivalent 5-membered ring or 6-membered ring alicyclic hydrocarbon is mentioned. It is preferable that it is group, 1, 4- cyclohexylene group is more preferable, and a trans-1, 4- cyclohexylene group is especially preferable.

The group represented by said formula (g-1)-(g-10) is a C1-C4 alkyl group, such as a methyl group, an ethyl group, an isopropyl group, and a tert- butyl group; C1-C4 alkoxy groups, such as a methoxy group and an ethoxy group; C1-C4 fluoroalkyl groups, such as a trifluoromethyl group; Fluoroalkoxy groups having 1 to 4 carbon atoms such as trifluoromethoxy group; Cyano; A nitro group; It may be substituted by halogen atoms, such as a fluorine atom, a chlorine atom, and a bromine atom.

In addition to the group represented by said formula (A), a compound (A) has at least 1 polymeric group. It is preferable that a compound (A) has 2-4 polymeric groups, and it is preferable to have two polymeric groups from a viewpoint of the film hardness of the optical film obtained.

The polymerizable group may be any group that can participate in the polymerization reaction of the compound (A), and specifically, a vinyl group, p-stilbene group, acryloyl group, methacroyl group, acryloyloxy group, methacroyloxy group , Carboxyl group, acetyl group, hydroxyl group, carbamoyl group, N-alkylamino group having 1 to 4 carbon atoms, amino group, epoxy group, oxetanyl group, formyl group, -N = C = O, -N = C = S and the like. have. Especially, a radically polymerizable group or a cation polymeric group is preferable at the point which is suitable for photopolymerization, Acryloyl group or a methacroyl group is more preferable at the point which is easy to handle, and also manufacture of a compound (A), Acryl Loyl groups are particularly preferred.

Although a polymeric group may couple | bond directly with the terminal of the group represented by Formula (A), it is preferable to couple | bond with one or more bivalent coupling groups.

As such a compound (A), following formula (B)

(Wherein Ar, D _a , D _b , G _a and G _b represent the same meaning as described above, and E ¹ and E ² are each independently

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 preferably a compound containing a group represented by the following formula (C)

(Wherein Ar, D _a , D _b , G _a , G _b , E ¹ and E ² have the same meanings as above, and B ¹ and B ² are each independently

Or a single bond, and R ⁵ and R ⁶ have the same meaning as described above. A ¹ and A ² each independently represent a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group, the alicyclic hydrocarbon group and the aromatic hydrocarbon group having a halogen atom, an alkyl group having 1 to 4 carbon atoms, and a fluoro having 1 to 4 carbon atoms. It may be substituted by at least one selected from the group consisting of an alkyl group, 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. k and l each independently represent an integer of 0 to 3), and more preferably a compound containing a group represented by the following formula (D)

(In the formula, Ar, D _a , D _b , G _a , G _b , E ¹ , E ² , B ¹ and B ² have the same meaning as above, and F ¹ and F ² are each independently 1 to 12 carbon atoms. An alkylene group, wherein the alkylene group 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 at least one methylene constituting the alkylene group The group may be substituted with -O- or -CO- It is particularly preferable that either of P ¹ and P ² represents a polymerizable group, and the other represents a hydrogen atom or a polymerizable group).

It is preferable that E <^1> and E <^2> are respectively independently -O-, -S-, -CO-O-, or -O-CO-. It is more preferable that E <^1> is -CO-O- and E <^2> is -O-CO-.

As a bivalent alicyclic hydrocarbon group or bivalent aromatic hydrocarbon group represented by A <^1> and A <^2> , group represented by said formula (g-1)-formula (g-10), following formula (a-1)-formula (a -8) is mentioned, group represented by a formula (a-1) or a formula (g-1) is preferable, and a 1, 4- phenylene group or a 1, 4- cyclohexylene group is more preferable.

Groups represented by said formula (a-1)-formula (a-8) are C1-C4 alkyl groups, such as a methyl group, an ethyl group, an isopropyl group, and a tert- butyl group; C1-C4 alkoxy groups, such as a methoxy group and an ethoxy group; C1-C4 fluoroalkyl groups, such as a trifluoromethyl group; Fluoroalkoxy groups having 1 to 4 carbon atoms such as trifluoromethoxy group; Cyano; A nitro group; It may be substituted by halogen atoms, such as a fluorine atom, a chlorine atom, and a bromine atom.

It is preferable that A <^1> and A <^2> are the same group from the point which is easy to manufacture the compound containing group represented by Formula (C), or the compound represented by Formula (D), and is a ¹ , 4- phenylene group or 1, 4- cyclo It is more preferable that it is a hexylene group, and it is especially preferable that it is a 1, 4- phenylene group.

Type in that they are easy to manufacture of a compound represented by the formula or a compound (D) comprising a group represented by (C), it is preferably the same group are B ¹ and B ^2. B ¹ and B ² , each bonded only to A ¹ or A ^2, are each independently —CH ₂ —CH ₂ —, —CO—O—, —O—CO—, —CO—NH—, —NH—CO—, _{-O-CH 2 -, -CH 2} -O- , or from the viewpoint of the liquid crystal compound and a compound represented by the formula (D) comprising a preferably single bond, and represented by the formula (D), -CO-O- Or -O-CO-. B ¹ and B ² bonded to E ¹ or E ² are each independently -O-, -CO-O-, -O-CO-, -O-CO-O-, -CO-NH-, -NH It is preferable that it is -CO- or a single bond.

It is preferable that k is an integer of 0-2. It is preferable that l is an integer of 0-2. It is preferable that the sum total of k and l is an integer of 5 or less, It is more preferable that it is an integer of 4 or less, It is especially preferable to satisfy following formula (2) and (3).

As a compound represented by Formula (D), it is following formula (1).

(Wherein Ar, E ¹ , E ² , B ¹ , B ² , F ¹ , F ² , P ¹ , P ² , k and l have the same meanings as above, and D ¹ and D ² are each independently * -O-CO- (* represents a binding site with Ar),

R <^1> , R <^2> , R <^3> and R <^4> represent a hydrogen atom, a fluorine atom, or a C1-C4 alkyl group each independently. G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group, the alicyclic hydrocarbon group and the aromatic heterocyclic group each having a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, and a carbon atom having 1 to 4 carbon atoms. At least one methylene group constituting the alicyclic hydrocarbon group may be substituted with at least one selected from the group consisting of an alkoxy group, a cyano group and a nitro group of 4, and may be substituted with -O-, -S- or -NH-. The compound represented by) is preferable.

D ¹ and D ² are each independently * -O-CO-, * -OC (= S)-, * -O-CR ¹ R ^2- , * -NR ¹ -CR ² R ³ -or * -NR ¹ It is preferable that -CO- (* represents a coupling | bonding site with Ar). It is more preferable that D ¹ and D ² are each independently * -O-CO-, * -OC (= S)-or * -NR ¹ -CO- (* represents a binding site with Ar). It is preferable that R <^1> , R <^2> , R <^3> and R <^4> are a hydrogen atom or a C1-C4 alkyl group each independently, and it is more preferable that they are a hydrogen atom, a methyl group, or an ethyl group.

As a specific example of G <^1> and G <^2> , group represented by said formula (g-1)-(g-10) is mentioned, The group represented by a formula (g-1) is preferable, 1, 4- cyclohexylene The group is more preferable, and a trans-1,4-cyclohexylene group is especially preferable.

Formula (1-A) and Formula (1-B)

As a specific example of group represented by, the group represented by following formula (R-1)-formula (R-134) is mentioned. In addition, n in Formula (R-1)-Formula (R-134) represents the integer of 2-12.

As a specific example of a compound (1), the compound of the following Table 1-Table 2 is mentioned.

In addition, in the compound (xxx) and the compound (xxxi), any one of the group represented by the formula (1-A) and the group represented by the formula (1-B) is in (R-57) to (R-120). Which one.

In the said Table 1, the compound (x ') is a group represented by the compound represented by the group represented by Ar (78), the group represented by Ar, the group represented by Ar (79), or the group represented by Ar (a-78) Or a mixture of a compound represented by formula (I) and a group represented by formula (ar-79).

In the said Table 2, a compound (xxx) is a group represented by the compound represented by the group (ar-120) represented by Ar, the group represented by the formula (ar-121) represented by Ar, or group represented by Ar (ar-120) It means any of a mixture of the compound represented by the group) and the group represented by the formula (ar-121), the compound (xxxi) is a compound represented by the group represented by the formula (ar-122), Ar represented by Ar, The group is either a compound represented by the formula (ar-123) or a group represented by Ar is a mixture of a compound represented by the formula (ar-122) and a compound represented by the formula (ar-123).

Representative examples of the compound of Table 1 are shown below.

The manufacturing method of a compound (A) is demonstrated below using a compound (1) as an example.

Compound (1) is a known organic synthesis reaction described in Methoden der Organischen Chemie, Organic Reactions, Organic Syntheses, Comprehensive Organic Synthesis, New Experimental Chemistry, etc. (eg, condensation reaction, esterification reaction, Williamson reaction, Ulman) Reaction, Wittig reaction, Schiff base reaction, benzylation reaction, Sonogashira reaction, Suzuki-Miyaura reaction, Negishi reaction, Kumada reaction, Hiyama reaction, Buchwald-Heartwig reaction, Plidel craft reaction, Heck reaction, Aldol reaction, etc.) can be manufactured by combining suitably according to the structure.

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

(Wherein Ar represents the same meaning as above) and the compound represented by the formula (1-2)

In the formula, R ¹ , R ² , G ¹ , E ¹ , A ¹ , B ¹ , F ¹ , P ¹ and k represent the same meaning as above.

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

In the formula, R ¹ , R ² , G ² , E ² , A ² , B ² , F ² , P ² and l represent the same meanings as described above.

The reaction between the compound represented by the formula (1-1) and the compound represented by the formula (1-2) and the compound represented by the formula (1-3) and the compound represented by the formula (1-4) are in the presence of an ester agent. It is preferable to carry out.

Specific examples of the esterifying agent include 1-cyclohexyl-3- (2-morpholinoethyl) carbodiimide, meto-p-toluenesulfonate, dicyclohexylcarbodiimide, 1-ethyl-3- (3 -Dimethylaminopropyl) carbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, bis (2,6-diisopropylphenyl) carbodiimide, bis (trimethylsilyl) carbodiimide , Carbodiimide compounds such as bisisopropylcarbodiimide, 2-methyl-6-nitrobenzoic anhydride, 2,2'-carbonylbis-1H-imidazole, 1,1'-oxalyldiimidazole, di Phenylphosphoryl azide, 1 (4-nitrobenzenesulfonyl) -1H-1,2,4-triazole, 1H-benzotriazol-1-yloxytripyrrolidinophosphonium hexafluorophosphate, 1H-benzo Triazol-1-yloxytris (dimethylamino) phosphonium hexafluorophosphate, N, N, N ', N'-tetramethyl-O- (N-succinimidyl) uroniumtetrafluoro Late, N- (1,2,2,2-tetrachloroethoxycarbonyloxy) succinimide, N-carbenzoxysuccinimide, O- (6-chlorobenzotriazol-1-yl)- N, N, N ', N'-tetramethyluroniumtetrafluoroborate, O- (6-chlorobenzotriazol-1-yl) -N, N, N', N'-tetramethyluroniumhexafluoro Lophosphate, 2-bromo-1-ethylpyridiniumtetrafluoroborate, 2-chloro-1,3-dimethylimidazolinium chloride, 2-chloro-1,3-dimethylimidazolinium hexafluorophosphate , 2-chloro-1-methylpyridinium iodide, 2-chloro-1-methylpyridinium p-toluenesulfonate, 2-fluoro-1-methylpyridinium p-toluenesulfonate, trichloroacetatepentachloro Phenyl ester etc. are mentioned.

You may make it react after converting the compound represented by Formula (1-2) and the compound represented by Formula (1-4) to the corresponding acid chloride.

The optical film of this invention is obtained by superposing | polymerizing a compound (A). One type of compound (A) may be polymerized and two or more types of compound (A) may be polymerized. Moreover, you may superpose | polymerize the liquid crystal compound (henceforth a liquid crystal compound hereafter) which has polymeric groups other than a compound (A) and a compound (A).

As a liquid crystal compound, three "molecular structure and liquid crystalline", 3.2 "non-chiral rod-shaped liquid crystal molecule" and 3.3 "chiral" of a liquid crystal handbook (Liquid Crystal Handicap Editing Committee edited, Maruzen, October 30, 2000 issuance) The compound which has a polymeric group can be mentioned in the compound of "rod-shaped liquid crystal molecule."

One type of liquid crystal compound may be used and two or more types of liquid crystal compounds may be used.

As a specific example of such a liquid crystal compound, Formula (4)

(In formula, A <^11> represents an aromatic hydrocarbon group, an alicyclic hydrocarbon group, or a heterocyclic group, and this aromatic hydrocarbon group, an alicyclic hydrocarbon group, and a heterocyclic group are a halogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy. group, having 1 to 6 carbon atoms in the N- alkylamino group, a nitro group, a cyano group and mercapto group may be substituted by at least one selected from the group consisting of. B ¹¹ and B ¹² are each independently

Alternatively, a single bond may be represented, and R ¹⁴ and R ¹⁵ may each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms, and R ¹⁴ and R ¹⁵ may be bonded to each other to form an alkylene group having 4 to 7 carbon atoms. E ¹¹ represents an alkylene group having 1 to 12 carbon atoms, and 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. P ¹¹ represents a polymerizable group. G is a hydrogen atom, a halogen atom, a C1-C13 alkyl group, a C1-C13 alkoxy group, a C1-C13 fluoroalkyl group, a C1-C13 N-alkylamino group, a cyano group, or a nitro group, or The polymeric group couple | bonded through a C1-C12 alkylene group is shown, and this alkylene group may be substituted by at least 1 chosen from the group which consists of a C1-C6 alkyl group, a C1-C6 alkoxy group, and a halogen atom. t shows the integer of 1-5) (Hereinafter, abbreviate as a compound (4).), etc. are mentioned.

As a polymeric group in Formula (4), what is necessary is just a group which can superpose | polymerize with a compound (A), and a vinyl group, vinyloxy group, p-stilbene group, acryloyl group, acryloyloxy group, methacroyl group, Methacroyloxy group, carboxyl group, acetyl group, hydroxyl group, carbamoyl group, amino group, C1-C4 alkylamino group, epoxy group, oxetanyl group, formyl group, -N = C = O or -N = C = S and the like Can be mentioned. Especially, a radically polymerizable group or a cation polymeric group is preferable at the point which is suitable for photopolymerization, and an acryloyloxy group, a methacroyloxy group, or a vinyloxy group is preferable at the point which is easy to handle and manufacture of a liquid crystal compound is also easy. .

It is preferable that carbon number of the aromatic hydrocarbon group, alicyclic hydrocarbon group, and heterocyclic group of A <^11> is 3-18, It is more preferable that it is 5-12, It is especially preferable that it is 5 or 6.

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

(In formula, P <^11> , E <^11> , B <^11> , A <^11> , B <^12> and t represent the same meaning as the above, E <^12> represents a C1-C12 alkylene group and this alkylene group is C1-C6 It may be substituted by at least one selected from the group consisting of an alkyl group, an alkoxy group having 1 to 6 carbon atoms and a halogen atom, P ¹² represents a polymerizable group, F ¹¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 13 carbon atoms, and 1 carbon atom. An alkoxy group having 13 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)

As a compound represented by Formula (4-1) and Formula (4-2), the compound represented by following formula (I), formula (II), formula (III), formula (IV), or formula (V) is mentioned. have.

(In formula, A <^12> -A <^15> represents an aromatic hydrocarbon group, an alicyclic hydrocarbon group, or a heterocyclic group each independently, The aromatic hydrocarbon group, an alicyclic hydrocarbon group, and a heterocyclic group are a halogen atom, a C1-C6 alkyl group, at least one is C 1 -C 6 alkoxy group, selected from N- alkylamino group, the group consisting of a nitro group, a cyano group and a mercapto group of a carbon number of 1 to 6 may be substituted. B ¹³ ~ B ¹⁶ are each independently

Or a single bond, and R ¹⁴ and R ¹⁵ represent the same meaning as above).

Examples of the compound represented by the formula (4-1), formula (4-2), formula (I), formula (II), formula (III), formula (IV) and formula (V) include P ¹¹ and E ^11. P ¹¹ , E ¹¹ , P ¹² and E ¹² are preferably selected such that the bond between and the bond between P ¹² and E ¹² is an ether bond or an ester bond.

As a specific example of a compound (4), following formula (I-1)-formula (I-5), formula (II-1)-formula (II-6), formula (III-1)-formula (III- 19), the compound represented by Formula (IV-1)-Formula (IV-14), Formula (V-1)-Formula (V-5), etc. are mentioned. In the following formula, k represents the integer of 1-11. The following liquid crystal compound is preferable from a viewpoint of the commercialization etc. which are easy to synthesize | combine.

When superposing | polymerizing a compound (A) and a liquid crystal compound, the usage-amount of a liquid crystal compound is 90 weight part or less normally when the sum total of a compound (A) and a liquid crystal compound is 100 weight part.

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

As a polymerization initiator, a photoinitiator is preferable. As a photoinitiator, a benzoin compound, a benzophenone compound, a benzyl ketal compound, the (alpha)-hydroxy ketone compound, the (alpha)-amino ketone compound, an iodonium salt, a sulfonium salt, etc. are mentioned. As a specific example of such a photoinitiator, Irgacure 907 (IRGACURE 907; Chiba Japan Co., Ltd.), Irgacure 184 (IRGACURE 184; Chiba Japan Co., Ltd.), Irgacure 651 (IRGACURE 651; Chiba Japan) Co., Ltd.), Irgacure 819 (manufactured by Chiba Japan), Irgacure 250 (manufactured by Chiba Japan), Irgacure 369 (manufactured by Chiba Japan), Say Kuol BZ (SEIKUOL BZ; manufactured by Seiko Chemical Co., Ltd.), Seikool Z (SEIKUOL Z; manufactured by Seiko Chemical Co., Ltd.), Seikool BEE (SEIKUOL BEE; manufactured by Seiko Chemical Co., Ltd.), Kayakure BP100 (KAYACURE BP100; manufactured by Nippon Gunpowder Co., Ltd.) , Kayakure UVI-6992 (KAYACURE UVI-6992; manufactured by Dow), Adeka OPTOMER SP-152 (ADEKA OPTOMER SP-152; ADEKA Co., Ltd.), Adeka OPTOMER SP-170 (ADEKA OPTOMER SP-170; ADEKA Co., Ltd.) There.

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

The wavelength dispersion characteristic of the optical film of this invention can be arbitrarily determined by adjusting content of the structural unit derived from the compound (A) in an optical film. When content of the structural unit derived from the compound (A) in an optical film increases, the optical film obtained shows a more flat wavelength dispersion characteristic, and also reverse wavelength dispersion characteristic.

In order to obtain the optical film which shows the required wavelength dispersion characteristic, it is good to, for example as follows. First, about 2-5 types of compositions containing the liquid crystal compound from which content of the structural unit derived from a compound (A) differ, and a compound (A) are prepared, and the optical film of the same film thickness is manufactured using each composition. . The phase difference value of the obtained optical film is measured, and the correlation between the content of the structural unit derived from a compound (A) and the phase difference value of an optical film is calculated | required. Based on the obtained correlation, content of the structural unit derived from the compound (A) required for the optical film in the said film thickness to show a desired retardation value is calculated | required, and a liquid crystal compound and a compound (A) so that it may become said content. A composition containing is prepared and polymerized.

The manufacturing method of the optical film of this invention is demonstrated below.

First, a compound (A), the said liquid crystal compound, and the said polymerization initiator are mixed, and the composition containing a compound (A) is prepared. When forming the obtained composition, since it can form easily, it is preferable to prepare the solution containing a compound (A) using an organic solvent, when preparing the composition. Moreover, you may use additives, such as a polymerization inhibitor, a photosensitizer, and a leveling agent, as needed.

As a polymerization inhibitor, the catechol compound which has substituents, such as a hydroquinone compound which has substituents, such as a hydroquinone or an alkyl ether, alkyl ethers, such as butyl catechol, a pyrogallol compound, 2,2,6,6- tetramethyl- Radical supplements such as 1-piperidinyloxy radicals, thiophenol compounds, β-naphthylamine compounds, β-naphthol compounds and the like.

By using a polymerization inhibitor, control of a polymerization reaction becomes easy and the stability of the optical film obtained can be improved. The usage-amount of a polymerization inhibitor is 0.1 weight part-30 weight part normally with respect to 100 weight part of total liquid crystal compounds and a compound (A), Preferably they are 0.5 weight part-10 weight part. If it is in the said range, a compound (A) can be polymerized without disturbing the orientation of a liquid crystal compound.

Examples of the photosensitizer include xanthone compounds such as xanthone and thioxanthone, anthracene compounds having substituents such as anthracene or alkyl ether, phenothiazine, rubrene and the like.

By using a photosensitizer, a polymerization reaction can be performed with high sensitivity. The usage-amount of a photosensitizer is 0.1 weight part-30 weight part normally with respect to a total of 100 weight part of a liquid crystal compound and a compound (A), Preferably they are 0.5 weight part-10 weight part. If it is in the said range, a compound (A) can be polymerized without disturbing the orientation of a liquid crystal compound.

As a leveling agent, additives for radiation-hardening paints (BIC Chemie Japan make: BYK-352, BYK-353, BYK-361N), paint additives (Toray Dow Corning Corporation make: SH28PA, DC11PA, ST80PA), paint additives (Shin-Etsu) Chemical Industry Co., Ltd. make: KP321, KP323, X22-161A, KF6001), a fluorine additive (Deinippon Ink Chemical Co., Ltd. make: F-445, F-470, F-479), etc. are mentioned.

By using a leveling agent, an optical film can be smoothed. Moreover, in the manufacturing process of an optical film, you may control the fluidity | liquidity of the composition containing a compound (A), or adjust the crosslinking density of the optical film obtained. The usage-amount of a leveling agent is 0.1 weight part-30 weight part normally with respect to a total of 100 weight part of a liquid crystal compound and a compound (A), Preferably they are 0.5 weight part-10 weight part. If it is in the said range, a compound (A) can be polymerized without disturbing the orientation of a liquid crystal compound.

The organic solvent is an organic solvent capable of dissolving a compound (A), a liquid crystal compound, or the like, and may be a solvent inert to the polymerization reaction. Specifically, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl Alcohol solvents such as cellosolve and butyl cellosolve; Ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, and ethyl lactate; Ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone, and methyl isobutyl ketone; Aliphatic hydrocarbon solvents such as pentane, hexane and heptane; Aromatic hydrocarbon solvents such as toluene, xylene and chlorobenzene; Nitrile solvents such as acetonitrile; Ether solvents such as propylene glycol monomethyl ether, tetrahydrofuran and dimethoxyethane; Halogenated hydrocarbon solvents such as chloroform; Phenol; And the like. These organic solvents may be used independently and may be used in combination of 2 or more type. In particular, the composition containing the compound (A) and the liquid crystal compound is excellent in compatibility and can be dissolved in an alcohol solvent, an ester solvent, a ketone solvent, a non-chlorinated aliphatic hydrocarbon solvent and a non-chlorinated aromatic hydrocarbon solvent. The film can be formed without using a solvent.

The viscosity of the solution containing the compound (A) is usually adjusted to 10 Pa · s or less, preferably 0.1 to 7 Pa · s, in consideration of the applicability of the composition.

In addition, the density | concentration of solid content in the solution containing a compound (A) is 5-50 weight% normally. When the concentration of the solid content is 5% or more, the optical film does not become too thin, and there is a tendency for the birefringence required for optical compensation of the liquid crystal panel to be provided. Moreover, since the viscosity of a composition does not become small too much and there exists a tendency for the nonuniformity to generate | occur | produce easily in the film thickness of an optical film, when concentration of solid content is 50% or less, it is preferable.

An optical film can be obtained by apply | coating the solution containing such a compound (A) on a support base material, and drying and superposing | polymerizing.

The unpolymerized film is obtained when apply | coating and drying the solution containing compound (A) on a support base material. When an unpolymerized film shows liquid crystal phases, such as a nematic phase, the optical film obtained shows birefringence by monodomain orientation. Since an unpolymerized film is orientated normally at about 0-120 degreeC, Preferably it is 25-80 degreeC, the support base material which heat resistance is not necessarily sufficient can be used. Moreover, since an unpolymerized film does not crystallize even if it cools to about 10-30 degreeC after orientation, handling is easy.

The film thickness can be prepared by suitably adjusting the density | concentration of the compound (A) in the solution containing a compound (A), and the application amount of this solution on a support base material. In the case of the solution where the quantity of a compound (A) is constant, the phase difference value (retardation value, Re ((lambda))) of the optical film obtained is Formula (7)

Re (λ) = d × Δn (λ) (7)

In the formula, Re (λ) represents the phase difference value at the wavelength λ nm, d represents the film thickness, and Δn (λ) represents the birefringence index at the wavelength λ nm. In order to obtain Re (λ), the film thickness d may be adjusted.

As a coating method to a support base material, an extrusion coating method, the direct gravure coating method, the reverse gravure coating method, the CAP coating method, the die coating method, etc. are mentioned. The method of apply | coating using coaters, such as a dip coater, a bar coater, and a spin coater, is also mentioned.

Glass, a plastic sheet, a plastic film, a light transmissive film, etc. are mentioned as a support base material. As a translucent film, Polyolefin films, such as polyethylene, a polypropylene, and norbornene-type polymer; Polyvinyl alcohol film; Polyethylene terephthalate film; Polymethacrylic acid ester film; Polyacrylic acid ester film; Cellulose ester film; Polyethylene naphthalate film; Polycarbonate film; Polysulfone film; Polyether sulfone film; Polyether ketone film; Polyphenylene sulfide film; Polyphenylene oxide film; And the like.

Also in the process which requires the intensity | strength of the optical film, such as an adhesion process, a conveyance process, and a storage process of an optical film, when a support base material is used, there is no damage of an optical film, etc., and it can handle easily.

After forming an orientation film on a support base material, it is preferable to apply | coat the solution containing a compound (A) on this orientation film. It is preferable that an oriented film has solvent tolerance which does not melt | dissolve in the solution at the time of application | coating of the solution containing a compound (A). Moreover, it is preferable that an orientation film has heat resistance in heat processing for removal of a solvent and the orientation of a liquid crystal molecule. Moreover, it is preferable that it is an orientation film which does not generate | occur | produce peeling by friction etc. at the time of rubbing. As such an oriented film, what consists of a polymer or a composition containing a polymer is preferable.

The polymer may be a polyamide or gelatin compound having an amide bond in a molecule, a polyimide having an imide bond in a molecule, and a polyamic acid, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, or polyoxa which is a hydrolyzate thereof. And polymers such as sol, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid or polyacrylic acid ester. These polymers may be used independently or may be used in mixture of 2 or more types. Moreover, the copolymer of these polymers may be sufficient. These polymers can be easily obtained by polycondensation such as dehydration polycondensation and deamine polycondensation, radical polymerization, anion polymerization, chain polymerization such as cationic polymerization, coordination polymerization, ring-opening polymerization and the like.

These polymers are usually used as a solution dissolved in a solvent. Solvents are not limited. Specifically, water; Alcohol solvents such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl cellosolve and butyl cellosolve; Ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, and ethyl lactate; Ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone, and methyl isobutyl ketone; Aliphatic hydrocarbon solvents such as pentane, hexane and heptane; Nitrile solvents, such as aromatic hydrocarbon solvents, such as toluene, xylene, and chlorobenzene, and acetonitrile; Ether solvents such as propylene glycol monomethyl ether, tetrahydrofuran and dimethoxyethane; Halogenated hydrocarbon solvents such as chloroform; And the like. These organic solvents may be used independently and may be used in combination of 2 or more type.

An oriented film may be formed using a commercially available aligning film material as it is. Examples of commercially available alignment film materials include Sun Ever (registered trademark; manufactured by Nissan Chemical Industries, Ltd.), Optimer (registered trademark; manufactured by JSR Corporation), and the like.

When such an alignment film is used, it is not necessary to perform refractive index control by stretching, so that in-plane nonuniformity of birefringence is reduced, and a large optical film that can cope with the enlargement of a flat panel display device (FPD) can be provided on a supporting substrate. Can be.

As a method of forming an oriented film on a support base material, the method of apply | coating as a solution the compound used as the oriented film material or material of an oriented film marketed on a support base material, and apply | coats an annealing after that is mentioned.

The thickness of the alignment film is usually 10 nm to 10000 nm, preferably 10 nm to 1000 nm. When it is in the said range, a compound (A) etc. can be orientated at a desired angle on the alignment film. As needed, you may rub the orientation film, and you may irradiate polarization UV to an orientation film.

As a method of rubbing an oriented film, the method of making the rubbing roll wound around the rotating rubbing cloth contact with the oriented film mounted and conveyed on a stage is mentioned.

The method of laminating | stacking an unpolymerized film on the orientation film laminated | stacked on such a support base material can reduce a production cost compared with the method of manufacturing a liquid crystal cell and inject | pouring a liquid crystal compound into the liquid crystal cell, and also by roll film Film production is also possible.

Although removal of a solvent may be performed in parallel with a polymerization reaction, it is preferable from a viewpoint of film formability to remove most solvents before performing a polymerization reaction.

As a removal method of a solvent, methods, such as natural drying, ventilation drying, and vacuum drying, are mentioned. It is preferable that it is 10-120 degreeC, and, as for the temperature at the time of heating and removing a solvent, it is more preferable that it is 25-80 degreeC. It is preferable that it is for 10 seconds-60 minutes, and, as for a heat time, it is more preferable that it is for 30 seconds-30 minutes. If heating temperature and a heat time exist in the said range, the support base material in which heat resistance is not necessarily enough can be used as a support base material.

By superposing | polymerizing and hardening the obtained unpolymerized film, the film by which the orientation of the compound (A) was fixed, ie, a polymeric film, is obtained. An optical film with a small refractive index change in the planar direction of the film and a large refractive index change in the normal direction of the film is obtained.

What is necessary is just to determine suitably the method of superposing | polymerizing an unpolymerized film according to the kind of liquid crystal compound and a compound (A). The photopolymerization method is used if the polymerizable group in the compound (A) and the liquid crystal compound is a photopolymerizable group, and the thermal polymerization method is used if the polymerizable group is a thermopolymerizable group. According to the photopolymerization method, a compound (A) having a photopolymerizable polymerizable group and a liquid crystal can be polymerized at a low temperature, and the range of selection of heat resistance of the supporting substrate is wide and industrial production is easy. Preference is given to using compounds. In addition, the photopolymerization method is also preferable from the viewpoint of film forming properties. The photopolymerization reaction is carried out by irradiating the unpolymerized film with visible light, ultraviolet light or laser light. In view of handling, ultraviolet light is particularly preferred. You may perform light irradiation at the temperature at which a compound (A) takes a liquid crystal phase. At this time, a polymeric film can also be patterned by masking etc.

The optical film of this invention has favorable adhesiveness of a support base material and an optical film, and adhesiveness of an oriented film and an optical film, and its manufacture is easy.

The optical film of this invention is a thin film compared with the stretched film which gives retardation by extending a polymer.

By peeling a support base material, the film in which an oriented film and an optical film were laminated | stacked is obtained. Moreover, an oriented film can be peeled and an optical film can be obtained.

The optical film obtained in this way is excellent in transparency, and is used as various display films. Although the thickness of an optical film differs according to the phase difference value of an optical film as mentioned above, it is preferable that it is 0.1-10 micrometers, and it is more preferable that it is 0.5-3 micrometers at the point which makes optical elasticity small.

The phase difference value of the optical film which shows birefringence is about 50-500 nm normally, Preferably it is 100-300 nm.

By such a thin film, the optical film which can carry out constant polarization conversion in a wider wavelength range can be used as an optical compensation film in FPDs, such as all liquid crystal panels and organic EL.

The optical film of the present invention can be used as a wideband [lambda] / 4 plate or [lambda] / 2 plate. When using as a broadband (lambda) / 4 plate or (lambda) / 2 plate, what is necessary is just to select suitably content of the structural unit derived from the compound (A) in an optical film, and the film thickness of an optical film. When using as a (lambda) / 4 plate, what is necessary is just to adjust a film thickness so that Re (550) of the optical film obtained will be 113-163 nm normally, Preferably it is 135-140 nm, Especially preferably, it is about 137.5 nm. . When using as a (lambda) / 2 plate, what is necessary is just to adjust a film thickness so that Re (550) of the optical film obtained is 250-300 nm normally, Preferably it is 273-277 nm, Especially preferably, it is about 275 nm. .

The optical film of the present invention can also be used as an optical film for VA (Vertical Alingment) mode. When using as an optical film for VA modes, what is necessary is just to select content of the structural unit derived from the compound (A) in an optical film suitably. What is necessary is just to adjust a film thickness so that Re (550) of the optical film obtained becomes 40-100 nm, More preferably, it is about 60-80 nm.

The optical film of this invention can also be used for antireflection films, such as an anti-reflection (AR) film, a polarizing film, retardation film, an elliptical polarizing film, a viewing angle expansion film, or the optical compensation film for viewing angle compensation of a transmissive liquid crystal display.

Although the optical film of this invention shows the outstanding optical characteristic even if one sheet is used, you may laminate | stack and use multiple sheets. Moreover, you may use in combination with another film. As an example combined with another film, the elliptical polarizing plate which adhere | attached the optical film of this invention to the polarizing film, and the broadband circular polarizing plate etc. which bonded the optical film of this invention as a broadband (lambda) / 4 plate further to the elliptically polarizing plate are mentioned. Can be.

Since the optical film of this invention can be formed by apply | coating and superposing | polymerizing on a support base material or an oriented film, as shown in FIG. 1, broadband, for example, (lambda) / 4, (lambda) / 2, is made on a color filter more easily than before, An optical film can be formed.

1 is a schematic view showing a color filter 1 according to the present invention.

As for the color filter 1, the color filter layer 4, the oriented film 3, and the optical film 2 of this invention are laminated | stacked in this order.

An example of the manufacturing method of such a color filter 1 is described below. First, an orientation polymer is laminated on the color filter layer 4, and a rubbing treatment is performed to form an alignment film 3. The alignment polymer may be laminated using the inkjet method.

Subsequently, on the obtained orientation film 3, the solution containing the compound (A) whose content of the compound (A) was adjusted so that the optical film obtained may have desired wavelength dispersion characteristic, and the thickness which becomes a desired phase difference value The solution is apply | coated so that the optical film 2 may be formed.

By using such a color filter 1, a thinner liquid crystal display device can be manufactured. As an example, the schematic diagram which shows the liquid crystal display device 5 which concerns on this invention was shown in FIG.

In the liquid crystal display device 5 shown in FIG. 2, the board | substrate 7 which opposes backlight, such as a glass substrate, is fixed on the polarizing plate 6 via an adhesive agent. The optical film 2 'is formed on the color filter layer 4' manufactured on the board | substrate 7 through the alignment film 3 '. Moreover, the counter electrode 8 is formed on the optical film 2 ', and the liquid crystal phase 9 is formed on the counter electrode 8. As for the backlight side, the board | substrate 11, such as a glass substrate, is being fixed to the polarizing plate 10 via an adhesive agent. Further, a thin film transistor (TFT) and an insulating layer 12 for active driving of the liquid crystal layer are formed on the substrate 11, and the transparent electrode 13 made of Ag, Al, or ITO (Indium Tin Oxide) is further formed on the TFT. And / or a reflective electrode 13 'is formed. The structure of the liquid crystal display device 5 shown in FIG. 2 is a structure with few sheets of an optical film compared with the conventional liquid crystal display device, and manufacture of a thinner liquid crystal display device becomes possible.

An example of the manufacturing method of the liquid crystal display device 5 in which the color filter 1 'was formed in the liquid crystal layer side of one board | substrate is described below. On the substrate on the backlight side, a semiconductor thin film is formed on borosilicate glass by depositing and patterning a gate electrode, a gate insulating film, and amorphous silicon made of Mo, MoW, or the like, and annealing the amorphous silicon with an excimer laser. P, B and the like can be doped in regions adjacent to the gate electrode to form n-channel and p-channel TFTs. In addition, the substrate on the backlight side is obtained by forming the insulating layer 12 made of SiO ₂ . In addition, by sputtering ITO on the backlight side substrate 11, the transparent electrode 13 for the all-transmissive display device can be laminated on the backlight side substrate. Similarly, by using Ag, Al or the like instead of ITO, the reflective electrode 13 'for the total reflection type display device is obtained. Moreover, by combining suitably a reflective electrode and a transparent electrode, the electrode of the backlight side for semi-transmissive liquid crystal display devices is also obtained.

On the other hand, the color filter layer 4 'is formed in the board | substrate 7 which opposes. By using together the color filter of R, G, and B, the full color liquid crystal display device is also obtained. Next, the alignment film 3 'is formed by apply | coating and rubbing an orientation polymer on the color filter layer 4'. Polymerization and the optical film 2 'are formed by ultraviolet irradiation, apply | coating the composition containing the compound (A) which concerns on this invention on this alignment film 3', and heating to the temperature range which takes a liquid crystal phase. After the optical film is formed, the counter electrode 8 can be formed by sputtering ITO. Moreover, the liquid crystal display device 5 can be manufactured by forming an alignment film on the counter electrode, forming the liquid crystal phase 9, and finally assembling together with the substrate on the backlight side.

Moreover, the optical film of this invention can be used also for the retardation plate of a reflection type liquid crystal display and an organic electroluminescent display, the retardation plate, and the FPD provided with the said optical film. The said FPD is not specifically limited, For example, a liquid crystal display device (LCD) and organic EL are mentioned.

Then, the FPD provided with the polarizing plate of this invention and this polarizing plate is demonstrated.

The polarizing plate of this invention contains the optical film and polarizing film of this invention, and is usually obtained by laminating | stacking the optical film and polarizing film of this invention. Specifically, it is obtained by adhering the optical film of the present invention directly to one or both surfaces of a film having a polarizing function, that is, a polarizing film, or using an adhesive. In this specification, "adhesive" means both an adhesive and an adhesive. Hereinafter, the polarizing plate of this invention is demonstrated using FIGS.

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

As for the polarizing plate 30a shown to FIG. 3 (a), the laminated body 14 and the polarizing film 15 are directly bonded, and the laminated body 14 is the support base material 16, the orientation film 17, and the optical film ( 18). The polarizing plate 30a is laminated | stacked in the order of the support base material 16, the orientation film 17, the optical film 18, and the polarizing film 15. As shown in FIG.

The laminated body 14 and the polarizing film 15 are adhere | attached through the adhesive bond layer 19 in the polarizing plate 30b shown to FIG. 3 (b).

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

In the polarizing plate 30d shown in FIG. 3 (d), the laminate 14 and the laminate 14 ′ are bonded to each other through the adhesive layer 19, and the polarizing film 15 is placed on the laminate 14 ′. Is directly bonded.

The polarizing plate 30e shown in FIG. 3 (e) bonds the laminate 14 and the laminate 14 ′ through the adhesive layer 19, and further laminates the laminate 14 ′ and the polarizing film 15. It has a structure bonded through the adhesive bond layer 19 '.

Instead of the laminated body 14, you may use the optical film 18 which peeled the support base material 16 and the orientation film 17 from the laminated body 14, and peels off the support base material 16 from the laminated body 14. You may use the film which consists of one alignment film 17 and the optical film 18. Instead of the laminated body 14 ', you may use the optical film 18' which peeled the support base material 16 'and the orientation film 17' from the laminated body 14 ', and supports it from the laminated body 14'. You may use the film which consists of the orientation film 17 'which peeled the base material 16', and the optical film 18 '.

The polarizing plate of this invention may laminate | stack two or more laminated bodies, and these some laminated bodies may all be the same, or may differ.

The polarizing film 15 should just be a film which has a polarizing function, and specifically, the film and polyvinyl alcohol-type film which extended | stretched and made the polyvinyl alcohol-type film adsorb | suck an iodine or a dichroic dye, and extended | stretched iodine or a dichroic dye The film which adsorbed is mentioned.

It is preferable that the adhesive agents used for the adhesive bond layer 19 and the adhesive bond layer 19 'are adhesives with high transparency and excellent heat resistance. As such an adhesive, an acrylic adhesive, an epoxy adhesive, a urethane adhesive, etc. are mentioned.

The flat panel display device of this invention is equipped with the optical film of this invention, Specifically, the liquid crystal display device provided with the adhesive goods which the polarizing plate of this invention and the liquid crystal panel adhere | attached, and the polarizing plate and light emitting layer of this invention are The organic electroluminescence display provided with the bonded organic electroluminescent panel is mentioned.

As an embodiment of the flat panel display device of the present invention, a liquid crystal display device and an organic EL display device will be described below as an example.

4 is a schematic view showing the adhesive product 21 of the liquid crystal panel 20 and the polarizing plate 30 of the liquid crystal display device of the present invention. The adhesive article 21 is obtained by bonding the polarizing plate 30 and the liquid crystal panel 20 of the present invention through the adhesive layer 22. By applying a voltage to the liquid crystal panel 20 using an electrode (not shown), the liquid crystal molecules can be driven to perform monochrome display.

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 film 30 and the light emitting layer 24 of the present invention through the adhesive layer 25.

In the organic EL panel, the polarizing film 30 functions as a broadband circular polarizing plate. Moreover, the said light emitting layer 24 is a layer of at least 1 layer which consists of electroconductive organic compounds.

The optical film of this invention is possible for constant polarization conversion in a wide wavelength range.

1 is a schematic view showing a color filter 1 of the present invention.
2 is a schematic view showing a liquid crystal display device 5 of the present invention.
3 is a schematic view showing the polarizing plate 30 of the present invention.
4 is a schematic view showing the adhesive product 21 of the liquid crystal panel 20 and the polarizing plate 30 of the liquid crystal display device of the present invention.
5 is a schematic view showing an organic EL panel 23 of the organic EL display device of the present invention.
DESCRIPTION OF THE REFERENCE NUMERALS
1, 1 ': color filter
2, 2 ': optical film
3, 3 ': alignment film
4, 4 ': color filter layer
5: liquid crystal display
6, 10: polarizer
7, 11: substrate
8: counter electrode
9: liquid crystal layer
12: TFT, insulation layer
13: transparent electrode
13 ': reflective electrode
30, 30a, 30b, 30c, 30d, 30e: polarizer
14, 14 ': laminate
15: polarizing film
16, 16 ': support substrate
17, 17 ': alignment film
18, 18 ': optical film
19, 19 ', 22, 25: adhesive layer
20: liquid crystal panel
21: adhesive
23: organic EL panel
24: light emitting layer

Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples.

Example 1-1

(1) According to the method of Unexamined-Japanese-Patent No. 2004-262884, hydroxyquinone and dihydropyran were made to react and the compound represented by said formula (a) was obtained.

(2) 100.1 g of the compound represented by the obtained Formula (a), 97.1 g of potassium carbonate, 64 g of 6-bromohexanol and 200 ml of N, N-dimethylacetamide were mixed. The obtained mixture was reacted at 90 ° C. under a nitrogen atmosphere, and then further reacted at 100 ° C. The reaction mixture obtained was left to cool to room temperature. Methyl isobutyl ketone was added to the reaction mixture, followed by stirring. The mixture was separated into an organic layer and an aqueous layer. The obtained organic layer was washed with pure water, aqueous sodium hydroxide solution and pure water again. Anhydrous sodium sulfate was added to the organic layer after washing | cleaning, and it dehydrated. After sodium sulfate was removed by filtration, the obtained filtrate was concentrated under reduced pressure. Methanol was added to the obtained residue, and the precipitate which precipitated was taken out by filtration. The precipitate taken out was dried in vacuo to give 126 g of the compound represented by the formula (b). Yield 91% (based on 6-bromohexanol).

(3) 126 g of the compound represented by obtained formula (b), 1.40 g of 3,5-di-tert-butyl-4-hydroxytoluene, 116.7 g of dimethylaniline and 1.00 g of 1,3-dimethyl-2-imidazolidinone Was dissolved in chloroform. The obtained solution was ice-cooled, 58.1 g of acryloyl chloride was added dropwise under nitrogen atmosphere, and the mixture was reacted at room temperature. Pure water was added and stirred to the obtained reaction mixture. The organic layer and the aqueous layer were separated, and the obtained organic layer was washed with aqueous hydrochloric acid, saturated aqueous sodium carbonate solution and further pure water. Anhydrous sodium sulfate was added to the organic layer after washing | cleaning, and it dried. After sodium sulfate was removed by filtration, 1 g of 3,5-di-tert-butyl-4-hydroxytoluene was added to the obtained filtrate and concentrated under reduced pressure to obtain a compound represented by the formula (c).

(4) After adding 200 ml of tetrahydrofuran to the compound represented by obtained formula (c), 200 ml of tetrahydrofuran was further added. After adding hydrochloric acid to the obtained solution, it was made to react at 60 degreeC by nitrogen atmosphere. Saturated brine was added to the obtained reaction mixture, followed by stirring, and the mixture was separated into an organic layer and an aqueous layer. Anhydrous sodium sulfate was added to the obtained organic layer, and it dehydrated. After 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 taken out was dried in vacuo to obtain 90 g of the compound represented by the formula (d). Yield: 79% (based on the compound represented by formula (c)).

(5) 24.68 g of trans-cyclohexanedicarboxylic acid and toluene were mixed. 74.91 g of oxalyl chloride and 0.5 ml of N, N-dimethylformamide were added to the obtained mixture. The obtained mixture was reacted by stirring in a nitrogen atmosphere. After the reaction was completed, the mixture was concentrated under reduced pressure. Chloroform was added to the obtained residue to obtain solution 1.

Compound 12g represented by formula (d) obtained in the above (4) was dissolved in chloroform. 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 obtained solution was reacted by stirring in a nitrogen atmosphere. After filtering the reaction mixture, the obtained filtrate was concentrated under reduced pressure. The obtained concentrate was added dropwise to a water / methanol mixed solution (volume ratio: 1/1), and the resulting precipitate was taken out by filtration. The precipitate was triturated, washed with pure water and dried in vacuo. After pulverizing the obtained powder, heptane was added, and toluene was further added. The obtained mixture was filtered to remove insoluble components. The obtained filtrate was concentrated under reduced pressure, and then heptane was added to the obtained residue. The produced precipitate was taken out by filtration and dried in vacuo to obtain 7.8 g of the compound represented by the formula (e). Yield: 40% (based on the compound represented by formula (d)).

(6) 56.8 g of the compound represented by the formula (d) obtained in the above (4), 2.65 g of dimethylaminopyridine, 50 g of trans-1,4-cyclohexanedicarboxylic acid monoethoxymethyl ester, and 300 ml of chloroform were mixed. . The solution which consists of 48.79 g of dicyclohexylcarbodiimide and 50 ml of chloroforms was dripped, while ice-cooling the obtained mixture in nitrogen atmosphere. After completion of the dropwise addition, the obtained mixture was stirred at room temperature and reacted. After the reaction was completed, 200 ml of chloroform and 200 ml of heptane were added to the reaction mixture. The obtained mixture was filtered to remove insolubles. The obtained filtrate was washed with 2N hydrochloric acid. The obtained mixture was filtered to remove insoluble content, and then dried by adding anhydrous sodium sulfate. After sodium sulfate was removed by filtration, the filtrate obtained was concentrated. The obtained solid was dried in vacuo to obtain 100 g of the compound represented by the formula (e ').

 100 g of the compound represented by the obtained formula (e '), 3.64 g of pure water, 3.84 g of p-toluenesulfonic acid monohydrate and 200 ml of tetrahydrofuran were mixed. The obtained mixture was stirred and reacted at 50 ° C. under a nitrogen atmosphere. After the reaction was completed, the reaction mixture was allowed to cool to room temperature. The reaction mixture was concentrated under reduced pressure, and 200 ml of heptane was added to the obtained residue. The precipitate which precipitated was taken out by filtration. The precipitate taken out was washed with pure water and then vacuum dried. The obtained powder was dissolved in chloroform, the obtained solution was passed through silica gel, and then filtered. The filtrate was mixed with 400 ml of chloroform and the resulting solution was concentrated. Toluene was added to the obtained residue, and the obtained solution was concentrated under reduced pressure. Heptane was added to the obtained residue, and the precipitated solid was taken out by filtration. The solid taken out was dried in vacuo to give 64.1 g of the compound represented by the formula (e). Yield: 76% (based on the compound represented by formula (d)).

Examples 1-2

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

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

Example 1-3

(1) 2.55 g of a compound represented by formula (ii-a), 9.67 g of a compound represented by formula (e), 0.28 g of dimethylaminopyridine, and 50 ml of chloroform were mixed. 40 ml of chloroform solutions containing 5.31 g of dicyclohexylcarbodiimide were added dropwise to the obtained mixture under ice cooling. The obtained mixture was stirred and reacted. After the reaction was completed, the reaction mixture was filtered. The obtained filtrate was dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. Ethyl acetate was added to the obtained residue. After concentrating the obtained solution under reduced pressure, 200 ml of methanol was added to the obtained residue, and it was 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 represented by the formula (ii-1). Yield: 56% (based on the compound represented by formula (ii-a)).

As a result of performing the phase transition temperature of the compound represented by obtained Formula (ii-1) by texture observation with a polarization microscope, the compound represented by Formula (ii-1) shows a smectic phase from 96 degreeC to 115 degreeC at the time of temperature rising. It showed that the nematic phase was shown from 115 degreeC to 226 degreeC, and it showed the nematic phase from 226 degreeC to 50 degreeC at the time of temperature drop.

Example 2

(1) 100 g of trans-cyclohexanedicarboxylic acid and 500 ml of N, N-dimethylacetamide were mixed, and the obtained mixture was heated to 60 ° C. 48.2 g of potassium carbonate was added to the obtained solution, and the mixture was stirred at 80 ° C. Further, 94.4 g of benzyl bromide was added and stirred to react. The reaction mixture obtained was left to cool and poured into ice. The precipitate which precipitated was taken out by filtration. The precipitate taken out was washed with a water / methanol mixed solution (volume ratio = 1/1) and then dried in vacuo. The obtained powder was dissolved in toluene, and the obtained solution was adsorbed onto silica gel while concentrating under reduced pressure. The silica gel was placed in a silica gel column and eluted with 500 ml of a chloroform / heptane mixed solution (volume ratio = 1/4). Subsequently, the compound represented by said formula (f) was eluted with the chloroform / heptane mixed solution (volume ratio = 1/2). The solution containing the compound represented by obtained formula (f) was concentrated, and 63 g of compounds represented by formula (f) were obtained. Yield: 42% (based on trans-cyclohexanedicarboxylic acid).

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

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

(4) 4.41 g of the compound represented by obtained Formula (ii-c), 4.65 g of the compound represented by Formula (d), 0.22 g of dimethylaminopyridine, and 30 ml of chloroform were mixed. To the obtained mixture, 20 ml of a chloroform solution containing 4.36 g of dicyclohexylcarbodiimide was added dropwise under ice cooling. The obtained mixture was stirred and reacted. After the reaction was completed, the reaction mixture was filtered. After drying the obtained filtrate, it concentrated under reduced pressure. Ethyl acetate was added to the concentrated residue to dissolve it. The resulting solution was concentrated under reduced pressure. Methanol was added to the concentrated residue, followed by ice cooling. The precipitate which precipitated was taken out by filtration and dried in vacuo to obtain 4.80 g of the compound represented by formula (ii-1). Yield: 58% (based on the compound represented by 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. 99.4 g of 4-bromobenzoyl chloride was added to the obtained mixture. The obtained mixture was stirred at 60 ° C for reaction. The obtained reaction mixture was cooled to room temperature and then poured into water. The obtained mixture was separated to obtain an organic layer. The organic layer was washed with water and hydrochloric acid, and then concentrated under reduced pressure. The obtained solid was wash | cleaned with hexane, and 139.6 g of compounds represented by a formula (VII-d) were obtained.

(2) 90.0 g of compounds represented by obtained formula (VII-d), 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetane-2,4-disulfide 65.0 g and 3132 g of toluene were mixed. The obtained mixture was stirred at 80 ° C for reaction. After the reaction was completed, the obtained reaction mixture was cooled and then concentrated. Ethanol was added to the concentrated residue, and the resulting precipitate was taken out by filtration. The precipitate was washed with ethanol to obtain 93.8 g of the compound represented by formula (VII-e). Yield: 99.5% (based on the compound represented by the formula (VII-d)).

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

(4) 11.2 g of the compound represented by the obtained formula (VII-f) and 56.0 g of pyridinium chloride were mixed, and the obtained mixture was stirred at 180 ° C for reaction. After cooling the obtained reaction mixture, water was added. The precipitate deposited was washed with water, hexane and chloroform to obtain 7.7 g of the compound represented by the formula (VII-a). Yield: 74% (based on the compound represented by the formula (VII-f)).

Example 3-2

In Example 2, it carried out similarly to Example 2 except having used the compound represented by the formula (VII-a) obtained by said Example 3-1 instead of the compound represented by Formula (ii-a), The compound represented by following formula (VII-1) was obtained.

Example 4-1

10.0 g of the compound represented by the formula (VII-a), 5.56 g of copper cyanide (I), and 100 g of N-methylpyrrolidone were mixed. The obtained mixture was stirred and reacted at 200 ° C. under a nitrogen atmosphere. After the reaction was completed, the reaction mixture was cooled and water was added. Precipitated precipitate was taken out by filtration, washed well with water to obtain 6.6 g of the compound represented by the formula (VII-a). Yield: 79% (based on the compound represented by the formula (VII-a)).

Example 4-2

In Example 1-3, except for using the compound represented by the formula (VII-a) obtained in the said Example 4-1 instead of the compound represented by the formula (ii-a), it carried out similarly to Example 1-3. It carried out and obtained the compound represented by following formula (VII-1).

As a result of performing the phase transition temperature of the compound represented by obtained formula (VII-1) by texture observation with a polarization microscope, the compound represented by Formula (VII-1) shows a smectic phase from 142 degreeC to 159 degreeC at the time of temperature rising. It showed that the nematic phase was shown from 159 degreeC to 190 degreeC or more, and it showed that a nematic phase up to 136 degreeC and crystallized at the time of temperature-fall.

Example 5-1

(1) Example 3-1 In the same manner as in Example 3-1 (1), except that 4-nitrobenzoyl chloride was used in place of 4-bromobenzoyl chloride, the formula (1) The compound represented by VIII-b) was obtained. Yield: 98% (based on 2,5-dimethoxyaniline).

(2) Example 3-1 In Example 3-1, except that the compound represented by the formula (VII-b) obtained in the above (1) was used instead of the compound represented by the formula (VII-d). It carried out similarly to 1 (2), and obtained the compound represented by a formula (VII-c). Yield: 89% (based on the compound represented by the formula (VII-b)).

(3) Example 3-1 In Example 3-1, except that the compound represented by the formula (VII-c) obtained in the above (2) was used instead of the compound represented by the formula (VII-e). It carried out similarly to 1 (3), and obtained the compound represented by a formula (VII-d). Yield: 52% (based on the compound represented by the formula (VII-d)).

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

Example 5-2

2.88 g of the compound represented by formula (VII-a) obtained in Example 5-1, 8.37 g of compound represented by formula (e), 0.24 g of dimethylaminopyridine, and 75 ml of chloroform were mixed. 40 ml of chloroform solutions containing 4.95 g of dicyclohexylcarbodiimide were dripped at the obtained mixture under ice cooling. The obtained mixture was stirred and reacted. After the reaction was completed, the reaction mixture was filtered. The filtrate was dried and then concentrated under reduced pressure. Ethyl acetate was added and dissolved in the concentrated residue, and the resulting solution was concentrated under reduced pressure. To the concentrated residue was added 200 ml of methanol and ice-cooled. The precipitate which precipitated was taken out by filtration, washed with methanol, and dried in vacuo to obtain 10.3 g of the compound represented by the formula (VII-1). Yield: 94% (based on the compound represented by the formula (VII-a)).

As a result of performing the phase transition temperature of the compound represented by obtained formula (VII-1) by texture observation with a polarization microscope, the compound represented by Formula (VII-1) shows a smectic phase from 160 degreeC to 169 degreeC at the time of temperature rising. It showed that the nematic phase was shown from 169 degreeC to 224 degreeC, and the nematic phase was shown from 224 degreeC to 154 degreeC at the time of temperature drop.

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. 50.0 g of isicotinoyl chloride hydrochloride was added to the obtained mixture. The obtained mixture was stirred at 60 ° C for reaction. After the reaction was completed, the reaction mixture was cooled down and poured into water. The obtained mixture was separated to obtain an organic layer and an aqueous layer. The aqueous layer was extracted with chloroform and the obtained chloroform layer was mixed with the organic layer obtained above. The organic layer after mixing was washed with water, and then concentrated under reduced pressure to obtain 71.5 g of the compound represented by the formula (VII-b). Yield: 99% (based on 2,5-dimethoxyaniline).

(2) 70.0 g of compounds represented by obtained formula (VII-b), 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetane-2,4-disulfide 65.8 g and 2436 g of toluene were mixed. The obtained mixture was stirred at 80 ° C for reaction. After completion | finish of reaction, after cooling a reaction mixture, it concentrated and obtained the compound represented by said Formula (VII-c).

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

(4) 5.6 g of the compound represented by the obtained formula (VII-d) and 28.0 g of pyridinium chloride were mixed, and the obtained mixture was stirred at 180 ° C to react. After the reaction was completed, the reaction mixture was cooled. Water was added to the reaction mixture, and the precipitated precipitate was taken out by filtration. The precipitate taken out was washed with water and chloroform to obtain 3.4 g of the compound represented by the formula (VII-a). Yield: 68% (based on the compound represented by the formula (VII-d)).

Example 6-2

2.24 g of the compound represented by formula (VII-a) obtained in Example 6-1, 8.37 g of the compound represented by formula (e), 0.24 g of dimethylaminopyridine, and 50 ml of chloroform were mixed. 30 ml of chloroform solutions containing 4.95 g of dicyclohexylcarbodiimide were added dropwise to the obtained mixture under ice cooling. The obtained mixture was stirred and reacted. After the reaction was completed, the reaction mixture was filtered. After drying the obtained filtrate, it concentrated under reduced pressure. Ethyl acetate was added to the concentrated residue to dissolve it. The resulting solution was concentrated under reduced pressure, and then 200 ml of methanol was added to the concentrated residue, followed by ice cooling. The precipitate which precipitated was taken out by filtration, washed with heptane, and dried in vacuo to obtain 4.4 g of the compound represented by the formula (VII-1). Yield: 43% (based on the compound represented by formula (VII-1)).

Example 7-1

(1) 170.0 g of 3-methyl-4-nitrobenzoic acid, 238.7 g of oxalyl chloride, 2.2 g of 1,3-dimethyl-2-imidazolidinone and 1703 g of dehydrated chloroform were mixed. The resulting mixture was sufficiently stirred at room temperature. The mixture was concentrated under reduced pressure, and 608 g of dehydrated chloroform was added to the obtained solid. To the obtained 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 reacted by stirring at room temperature. After the reaction was completed, the reaction mixture was poured into 973 g of water. The obtained mixture was separated to obtain an organic layer. The organic layer was washed with 973 g of 1N hydrochloric acid, and then concentrated under reduced pressure to obtain 107.8 g of the compound represented by the formula (VII'-b). Yield: 44% (based on 2,5-dimethoxyaniline).

(2) Example 5-1 in Example 5-1, except that the compound represented by the formula (VII'-b) obtained in the above (1) was used instead of the compound represented by the formula (VII-b). In the same manner as in the above, the compound represented by the formula (VII'-a) was obtained.

Example 7-2

In the said Example 5-2, it replaces the compound represented by Formula (VII-a), and is similar to Example 5-2 except having used the compound represented by Formula (VII'-a) obtained by said (2). It carried out and obtained the compound shown by following formula (VII'-1). Yield: 73% (based on the compound represented by the formula (VII'-a)).

As a result of performing the phase transition temperature of the compound represented by obtained formula (VII'-1) by texture observation with a polarization microscope, the compound represented by Formula (VII'-1) is smected from 127 degreeC to 154 degreeC at the time of temperature rising. It showed that a tick phase was shown, the nematic phase was shown from 154 degreeC to 217 degreeC, and the nematic phase was shown from 217 degreeC to 113 degreeC at the time of temperature drop.

Example 8

In the said Example 5-2, it carried out similarly to Example 5-2 except having used the compound represented by Formula (VII-a) instead of the compound represented by Formula (VII-a), The compound represented by -1) was obtained. Yield: 84% (based on the compound represented by the formula (VII-a)).

Example 9

(1) In the said Example 5-1, it carries out similarly to Example 5-1 except having used 2-thiophene carbonyl chloride instead of 4-nitrobenzoyl chloride, The following formula (VII-a) The compound shown by was obtained.

(2) In the same manner as in Example 5-2 in Example 5-2, except that the compound represented by formula (VII-a) obtained above was used instead of the compound represented by formula (VII-a). And the compound represented by following formula (VII-1) was obtained. Yield: 84% (based on the compound represented by the formula (VII-a)).

As a result of performing the phase transition temperature of the compound represented by obtained formula (VII-1) by texture observation with a polarization microscope, the compound represented by Formula (VII-1) shows a smectic phase from 101 degreeC to 106 degreeC at the time of temperature rising. It showed that the nematic phase was shown from 106 degreeC to 180 degreeC or more, and it showed that a nematic phase was crystallized to 81 degreeC at the time of temperature drop.

Example 10-1

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

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

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

(4) 40.0 g of the compound represented by the obtained formula (xi-d) and 200.0 g of pyridinium chloride were mixed, and the obtained mixture was stirred at 180 ° C for 2 hours to react. After cooling the obtained reaction mixture, water was added. The precipitate which precipitated was taken out by filtration, washed with water and hexane, and 36.4 g of the compound represented by the formula (xi-a) was obtained.

Example 10-2

In the said Example 5-2, it replaces the compound represented by Formula (VII-a), and is the same as Example 5-2 except having used the compound represented by Formula (xi-a) obtained by the said Example 10-1. The compound represented by the following formula (xi-1) was obtained. Yield: 55% (based on the compound represented by formula (xi-a)).

As a result of performing the phase transition temperature of the compound represented by obtained formula (xi-1) by texture observation with a polarization microscope, the compound represented by Formula (xi-1) shows a smectic phase from 111 degreeC to 125 degreeC at the time of temperature rising. It showed that the nematic phase was shown from 125 degreeC to 242 degreeC, and the nematic phase was shown from 242 degreeC to 82 degreeC at the time of temperature drop.

Example 11

(1) In the said Example 5-1, it carries out similarly to Example 5-1 except having used 3, 5- dimethyl benzoyl chloride instead of 4-nitrobenzoyl chloride, and is a following formula (xvi-a) The compound shown by was obtained.

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

As a result of performing the phase transition temperature of the compound represented by obtained formula (xvi-1) by texture observation with a polarization microscope, the compound represented by Formula (xvi-1) shows a smectic phase from 91 degreeC to 100 degreeC at the time of temperature rising. It showed that the nematic phase was shown from 100 degreeC to 210 degreeC, and it thermopolymerized.

Example 12-1

(1) 11.0 g of 4,7-dimethoxy-2-phenylbenzothiazole and 288 g of glacial acetic acid were mixed. The solution obtained by mixing 4.0 g of concentrated nitric acid and 14.4 g of glacial acetic acid was dripped at the obtained mixture. The resulting mixture was reacted by stirring at room temperature. After the reaction was completed, the reaction mixture was poured into 1154 g of cold water. The precipitated solid was taken out by filtration to obtain 11.8 g of the compound represented by the formula (xvii-d). The compound represented by the formula (xvii-d) was a mixture of two isomers differing in the substitution position of the nitro group. Yield 92% (based on 4,7-dimethoxy-2-phenylbenzothiazole).

(2) In Example 5-1, except that the compound represented by formula (xvii-d) obtained in the above (1) was used instead of the compound represented by the formula (VII-d). It carried out similarly and obtained the compound represented by said formula (xvii-a). The compound represented by Formula (xvii-a) was a mixture of two isomers from which the nitro group substituted position differs.

Example 12-2

In the said Example 5-2, it replaces the compound represented by Formula (VII-a), and is the same as Example 5-2 except having used the compound represented by Formula (xvii-a) obtained by the said Example 12-1. The compound represented by the following formula (xvii-1) was obtained. Yield: 53% (based on the compound represented by formula (xvii-a)).

As a result of performing the phase transition temperature of the compound represented by obtained formula (xvii-1) by texture observation with a polarization microscope, the compound represented by Formula (xvii-1) shows a smectic phase from 129 degreeC to 148 degreeC at the time of temperature rising. It showed that the nematic phase was shown from 148 degreeC to 186 degreeC, and the nematic phase was shown from 186 degreeC to 105 degreeC at the time of temperature drop.

Example 13

(1) In the said Example 5-1, it carries out similarly to Example 5-1 except having used pentafluorobenzoyl chloride instead of 4-nitrobenzoyl chloride, and is represented by following formula (xviii-a) The compound was obtained.

(2) In the same manner as in Example 5-2 in Example 5-2, except that the compound represented by formula (xviii-a) obtained above was used instead of the compound represented by formula (VII-a). Thus, the compound represented by the following formula (xviii-1) was obtained. Yield: 82% (based on the compound represented by the formula (xviii-a)).

As a result of performing the phase transition temperature of the compound represented by obtained formula (xviii-1) by texture observation with a polarization microscope, the compound represented by Formula (xviii-1) shows a smectic phase from 124 degreeC to 166 degreeC at the time of temperature rising. It showed that the nematic phase was shown from 166 degreeC to 199 degreeC, and it showed the nematic phase from 199 degreeC to 79 degreeC at the time of temperature drop.

Example 14-1

(1) 58.7 g of 2,5-dimethoxyaniline, 77.5 g of triethylamine, and 400 g of dehydrated chloroform were mixed. 50.0 g of 2-furancarboxylic acid chloride was added to the obtained mixture under ice cooling. The obtained mixture was stirred at room temperature for 1 hour to react. The obtained reaction mixture was poured into water, the obtained 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 crystallize to obtain 86.3 g of the compound represented by the formula (xix-b). Yield: 91% (based on 2,5-dimethoxyaniline)

(2) 40 g of compounds represented by obtained formula (xix-b), 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetane-2,4-disulfide 34.0 g and toluene 120 g were mixed. The obtained mixture was stirred at 80 ° C. for 8 hours to react. After cooling the obtained reaction mixture, it concentrated and obtained the red viscous liquid containing the compound represented by the said Formula (xix-c).

(3) The red viscous liquid containing the compound represented by obtained formula (xix-c), 38.8 g of sodium hydroxide, and 700 g of water were mixed, and the obtained 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 obtained mixture was stirred and reacted. The solid precipitated in the reaction mixture was taken out by filtration, washed with cold water and hexane, and further washed with methanol. The obtained solid was recrystallized using ethanol to obtain 19.5 g of the compound represented by the formula (xix-d). Yield: 46% (based on the compound represented by formula (xix-b)).

(4) 9.00 g of the compound represented by the obtained formula (xix-d) and 45.0 g of pyridinium chloride were mixed, and the obtained mixture was stirred at 180 ° C for reaction. After the reaction was completed, the reaction mixture was cooled down and water was added. The precipitate which precipitated was taken out by filtration, and it wash | cleaned with water, hexane, and toluene further, and obtained 7.68 g of the compound represented by said Formula (xix-a). Yield: 96% (based on the compound represented by formula (xix-d)).

Example 14-2

In the said Example 5-2, it replaces the compound represented by Formula (VII-a), and is the same as Example 5-2 except having used the compound represented by Formula (xix-a) obtained by the said Example 14-1. The compound was represented by the following formula (xix-1) to obtain a compound. Yield: 78% (based on the compound represented by formula (xix-a)).

As a result of performing the phase transition temperature of the compound represented by obtained formula (xix-1) by texture observation with a polarization microscope, the compound represented by Formula (xix-1) shows a smectic phase from 91 degreeC to 130 degreeC at the time of temperature rising. It showed that the nematic phase was shown from 130 degreeC to 180 degreeC or more, and it showed that the nematic phase was crystallized to 62 degreeC at the time of temperature drop.

Example 15

(1) In Example 5-1, except for using 5-chloro-2-thiophencarbonyl chloride instead of 4-nitrobenzoyl chloride, it was carried out in the same manner as in Example 5-1, the following formula ( The compound represented by xx-a) was obtained.

(2) In the same manner as in Example 5-2 in Example 5-2, except that the compound represented by formula (xx-a) obtained above was used instead of the compound represented by formula (VII-a). And the compound represented by following formula (xx-1) was obtained. Yield: 40% (based on the compound represented by formula (xx-a)).

As a result of performing the phase transition temperature of the compound represented by obtained formula (xx-1) by texture observation with a polarization microscope, the compound represented by Formula (xx-1) shows a smectic phase from 110 degreeC to 114 degreeC at the time of temperature rising. It showed that the nematic phase was shown from 114 degreeC to 160 degreeC or more, and the nematic phase was shown to crystallization to 69 degreeC at the time of temperature drop.

Example 16-1

(1) 59.3 g of 2,5-dimethoxyaniline, 78.4 g of triethylamine, and 500 g of dehydrated chloroform were mixed. 57.1 g of 3-thiazole carboxylic acid chloride was dripped at the obtained mixture under ice cooling. The resulting mixture was reacted by stirring at room temperature. After the reaction was completed, the reaction mixture was poured into water. The obtained mixture was separated to obtain 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 represented by the formula (xxi-b). Yield: 75% (based on 2,5-dimethoxyaniline).

(2) 77 g of the compound represented by obtained formula (xxi-b), 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetane-2,4-disulfide 61.3 g and toluene 500 g were mixed. The obtained mixture was stirred at 80 ° C for reaction. After completion of the reaction, the reaction mixture was cooled and then concentrated to obtain an orange viscous liquid containing the compound represented by the formula (xxi-c).

(3) The orange viscous liquid containing the compound represented by obtained formula (xxi-c), 70.0 g of sodium hydroxide, and 750 g of water were mixed, and the obtained 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 obtained mixture was stirred and reacted. After completion of the reaction, the solid precipitated in the reaction mixture was taken out by filtration, washed with cold water and hexane, and further washed with hot ethanol to obtain 45.9 g of the compound represented by the formula (xxi-d). Yield: 57% (based on the compound represented by the formula (xxi-b)).

(4) 45.0 g of the compound represented by the obtained formula (xxi-d) and 225.0 g of pyridinium chloride were mixed, and the obtained mixture was stirred at 180 ° C. for 2 hours to react. After cooling the reaction mixture, water was added. The precipitate which precipitated was taken out by filtration, and it wash | cleaned with water, hexane, and toluene, and obtained 39.9g of compounds represented by said Formula (xxi-a). Yield: 100% (based on the compound represented by the formula (xxi-d)).

Example 16-2

In the said Example 5-2, it replaces the compound represented by Formula (VII-a), and is the same as Example 5-2 except having used the compound represented by Formula (xxi-a) obtained by the said Example 16-1. The compound represented by the following formula (xxi-1) was obtained. Yield: 71% (based on the compound represented by the formula (xxi-a)).

As a result of performing the phase transition temperature of the compound represented by obtained formula (xxi-1) by texture observation with a polarization microscope, the compound represented by Formula (xxi-1) shows a nematic phase from 162 degreeC to 246 degreeC at the time of temperature rising. It turned out that it shows a nematic phase from 246 degreeC to 120 degreeC at the time of temperature reduction.

Example 17-1

(1) 38.3 g of 2,5-dimethoxyaniline, 50.5 g of triethylamine, and 200 g of dehydrated chloroform were mixed. 54.6 g of 4-methylsulfonylbenzoic acid chloride was added to the obtained mixture under ice cooling. The resulting mixture was reacted by stirring at room temperature. After the reaction was completed, the reaction mixture was poured into water. The obtained mixture was separated to obtain 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 crystallized with a heptane / ethyl acetate mixed solution (volume ratio = 3/1). Furthermore, it wash | cleaned with the heptane / ethyl acetate mixed solution (volume ratio = 3/1), and obtained 52.2g of compounds represented by said Formula (xxiii-b) as white crystals. Yield: 62% (based on 2,5-dimethoxyaniline).

(2) 54.5 g of the compound represented by obtained formula (xxiii-b), 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetane-2,4-disulfide 64.7g and 500g of toluene were mixed, and the obtained mixture was stirred at 80 degreeC and made to react. After the completion of the reaction, the obtained reaction mixture was cooled and concentrated to obtain a red viscous liquid containing the compound represented by the formula (xxiii-c).

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

(4) 10.0 g of the compound represented by the obtained formula (xxiii-d) and 100.0 g of pyridinium chloride were mixed, and the obtained mixture was stirred at 180 ° C. for 2 hours to react. After cooling the reaction mixture, water was added. The precipitate which precipitated was wash | cleaned with water, hexane, and toluene, and the compound 7.8g shown by said Formula (xxiii-a) was obtained. Yield: 85% (based on the compound represented by the formula (xxiii-d)).

Example 17-2

In the said Example 5-2, it replaces the compound represented by Formula (VII-a), and is the same as Example 5-2 except having used the compound represented by Formula (xxiii-a) obtained by the said Example 17-1. The compound represented by the following formula (xxiii-1) was obtained. Yield: 46% (based on the compound represented by formula (xxiii-a)).

As a result of performing the phase transition temperature of the compound represented by obtained formula (xxiii-1) by texture observation with a polarization microscope, the compound represented by Formula (xxiii-1) shows a smectic phase from 137 degreeC to 146 degreeC at the time of temperature rising. It showed that the nematic phase was shown from 146 degreeC to 170 degreeC or more, and it showed that the nematic phase was crystallized to 78 degreeC at the time of temperature drop.

Example 18

(1) In the same manner as in Example 3-1, except that 4-fluorobenzoyl chloride was used instead of 4-bromobenzoyl chloride in Example 3-1, the following formula (xxiv-a) The compound shown by was obtained.

(2) In Example 5-2, 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 (VII-a). It carried out similarly and obtained the compound represented by following formula (xxiv-1). Yield: 54% (based on the compound represented by the formula (xxiv-a)).

As a result of performing the phase transition temperature of the compound represented by obtained formula (xxiv-1) by texture observation with a polarization microscope, the compound represented by Formula (xxiv-1) shows a nematic phase from 95 degreeC to 212 degreeC at the time of temperature rising. It was found that, at the time of temperature reduction, the nematic phase was exhibited from 212 ° C to 86 ° C.

Example 19

(1) In the same manner as in Example 3-1, except that 4-trifluoromethylbenzoyl chloride was used instead of 4-bromobenzoyl chloride in Example 3-1, the following formula (xxv- The compound represented by a) was obtained.

(2) In Example 5-2, except that the compound represented by formula (xxv-a) obtained in the above (1) was used instead of the compound represented by the formula (VII-a). It carried out similarly and obtained the compound represented by following formula (xxv-1). Yield: 77% (based on the compound represented by the formula (xxv-a)).

As a result of performing the phase transition temperature of the compound represented by obtained formula (xxv-1) by texture observation with a polarization microscope, the compound represented by Formula (xxv-1) shows a nematic phase from 135 degreeC to 193 degreeC at the time of temperature rising. It was found that at the time of temperature reduction, a nematic phase was exhibited from 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 at 100 ° C. while stirring. After the mixture was cooled to room temperature, 40.0 g of sulfuric acid was added and stirred again. The obtained mixture was extracted with ethyl acetate. The obtained organic layer was concentrated under reduced pressure, and the obtained solid was dried in vacuo to obtain 8.5 g of the compound represented by the formula (xxvi-b). Yield: 68% (based on 2,3-dicyanohydroquinone).

(2) 2.5 g of the compound represented by the obtained formula (xxvi-b), 2.5 g of aniline and 50.0 g of tetrahydrofuran were mixed. The resulting mixture was heated at 100 ° C. while stirring. 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 filtering the obtained reaction mixture, the obtained filtrate was concentrated under reduced pressure. To the concentrated residue was added methanol and stirred. The precipitate was taken out by filtration and dried in vacuo to obtain 0.4 g of the compound represented by the formula (xxvi-a). Yield: 12% (based on the compound represented by formula (xxvi-b)).

(3) 0.3 g of the compound represented by the obtained 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. The solution obtained by dissolving dicyclohexylcarbodiimide 0.9g in 4.7 g of chloroform was dripped at the obtained mixture at room temperature. The resulting mixture was stirred. After the mixture was filtered, 12 g of 2N hydrochloric acid was added and the mixture was separated to obtain an organic layer. After the organic layer was concentrated, methanol was added to the concentrated residue and stirred. The precipitate was taken out by filtration and dried in vacuo to obtain 0.7 g of the compound represented by the formula (xxvi-1). Yield: 54% (based on the compound represented by formula (xxvi-a)).

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 at 100 ° C. while stirring. After cooling the obtained mixture to room temperature, the solution obtained by dissolving dicyclohexylcarbodiimide 3.1g in 9.4g of tetrahydrofuran was dripped at room temperature. The resulting mixture was stirred. After filtering the obtained reaction mixture, the obtained filtrate was concentrated under reduced pressure. To the concentrated residue was added methanol and stirred. The precipitate was taken out by filtration, and then dried in vacuo to obtain 0.4 g of the compound represented by the formula (xxvii-a). Yield: 13% (based on the compound represented by formula (xxvi-b)).

(2) 0.3 g of the compound represented by the obtained 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. The solution obtained by dissolving dicyclohexylcarbodiimide 0.9g in 4.6g of chloroform was dripped at the obtained mixture at room temperature. The resulting mixture was stirred. After filtering the obtained reaction mixture, 12 g of 2N hydrochloric acid was added to the obtained filtrate. The obtained mixture was separated to obtain an organic layer. After the organic layer was concentrated, methanol was added to the concentrated residue and stirred. The precipitate was taken out by filtration and dried in vacuo to obtain 0.3 g of the compound represented by the formula (xxvii-1). Yield: 25% (based on the compound represented by formula (xxvii-a)).

As a result of performing the phase transition temperature of the compound represented by obtained formula (xxvii-1) by texture observation with a polarization microscope, the compound represented by Formula (xxvii-1) shows a smectic phase from 143 degreeC to 152 degreeC at the time of temperature rising. It showed that the nematic phase was shown from 152 degreeC to 186 degreeC, and it crystallized by showing a nematic phase up to 99 degreeC at the time of temperature-fall.

Example 22

In the said Example 5-2, it carries out similarly to Example 5-2 except having used 1, 4- dihydroxy anthraquinone instead of the compound represented by a formula (VII-a), The compound represented by -1) was obtained. Yield: 34% (based on 1,4-dihydroxyanthraquinone).

As a result of performing the phase transition temperature of the compound represented by obtained formula (VII-1) by texture observation with a polarization microscope, the compound represented by Formula (VII-1) shows a smectic phase from 125 degreeC to 128 degreeC at the time of temperature rising. It showed that the nematic phase was shown from 128 degreeC to 200 degreeC or more, and it showed that the nematic phase was crystallized to 106 degreeC at the time of temperature drop.

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-dihydroxyanthraquinone and 100 g of chloroform were mixed. The solution obtained by dissolving 9.3 g of dicyclohexylcarbodiimide in 25 g of chloroform was dripped at the obtained mixture at room temperature. The obtained mixture was stirred and reacted. 124 g of 1N hydrochloric acid was added to the obtained reaction mixture, followed by stirring. The obtained mixture was filtrated, the obtained filtrate was liquid-separated and the organic layer was obtained. The organic layer was concentrated and methanol was added to the residue. The obtained mixture was filtered to take out the solid. The obtained solid material was dried to obtain 10.5 g of a compound represented by the following formula (xxviii-1). Yield: 84% (based on 1,5-dihydroxyanthraquinone).

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-dihydroxyanthraquinone and 100 g of chloroform were mixed. The solution obtained by dissolving 9.3 g of dicyclohexylcarbodiimide in 25 g of chloroform was dripped at the obtained mixture at room temperature. The obtained mixture was stirred and reacted. 124 g of 1N hydrochloric acid was added to the obtained reaction mixture, followed by stirring. The obtained mixture was filtrated, the obtained filtrate was liquid-separated and the organic layer was obtained. After concentration of the organic layer, methanol was added to the residue. The obtained mixture was filtered to take out the solid. The obtained solid substance was dried and 10.3 g of compounds represented by the following formula (xxix-1) was obtained. Yield: 82% (based on 1,2-dihydroxyanthraquinone). As a result of heating the obtained mixture and confirming the phase transition temperature, the liquid crystal phase was not observed but was dissolved at 105 ° C.

Example 25

(1) 23 g of trans-cinnamic acid, 75.5 g of 1H-benzotriazol-1-yloxytripyrrolidinophosphonium hexafluorophosphate, 15.7 g of triethylamine, 1.9 g of dimethylaminopyridine and dehydrated N, N-dimethylacetamide 200 g was mixed. The obtained mixture was shielded and stirred while ice-cooling. 24.6 g of 2,5-dimethoxyaniline was added to the obtained mixture, and the obtained mixture was stirred at 0 ° C. for 8 hours and at room temperature overnight. The obtained reaction mixture was extracted with methyl isobutyl ketone to obtain an organic layer. The obtained organic layer was washed three times with saturated aqueous sodium carbonate solution. The organic layer was concentrated under reduced pressure, and then methanol was added to the obtained residue to crystallize. The crystals were taken out by filtration and dried in vacuo. The filtrate was left overnight at room temperature. The precipitated crystals were taken out by filtration and dried in vacuo. The obtained crystals were combined, washed again with cold methanol and dried to obtain 38.6 g of the compound represented by the formula (xxxii-b) as a light gray powder. Yield: 88% (based on 2,5-dimethoxyaniline).

(2) 30 g of compounds represented by obtained formula (xxxii-b), 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetane-2,4-disulfide 22.27 g and toluene 500g were mixed, and the obtained mixture was stirred at 80 ° C for reaction. After cooling the obtained reaction mixture, it concentrated and obtained the red viscous solid containing the compound represented by said Formula (xxxii-c).

(3) The red viscous solid, 25.4 g of sodium hydroxide, and 750 g of water containing the compound represented by obtained formula (xxxii-c) were mixed, and the obtained 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 replacement was taken out, washed with cold water and hexane, and further washed with hot methanol to obtain 17.7 g of the compound represented by the formula (xxxii-d) as a yellow powder. Yield: 56% (based on the compound represented by the formula (xxxii-b)).

(4) 10.6 g of the compound represented by the obtained formula (xxxii-d) and 106.0 g of pyridinium chloride were mixed, and the obtained mixture was stirred at 180 ° C. for 2 hours to react. After cooling the obtained reaction mixture, water was added. The precipitate which precipitated was taken out, and it wash | cleaned with water and hexane, and obtained 10.8 g of compounds represented by said formula (xxxii-a).

(5) 0.54 g of the compound represented by the obtained 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. 0.92 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride was added to the obtained mixture, followed by stirring. The obtained mixture was filtered through Celite, and the obtained filtrate was concentrated under reduced pressure. The residue was developed by column chromatography with chloroform as the eluent and then developed with chloroform / acetone (volume ratio = 95/5) as the eluent. The orange adsorption layer was recovered, and the resulting solution was concentrated under reduced pressure. The residue was crystallized from ethanol. The crystals were taken out by filtration, washed with heptane and dried in vacuo to obtain 1.21 g of a compound represented by the formula (xxxii-1) as a white powder. Yield: 56% (based on the compound represented by the formula (xxxii-a)).

As a result of performing the phase transition temperature of the compound represented by obtained formula (xxxii-1) by texture observation with a polarization microscope, the compound represented by Formula (xxxii-1) is a nematic phase from 125 degreeC to 180 degreeC or more at the time of temperature rising. It showed that the nematic phase was shown to 55 degreeC at the time of temperature reduction, and it crystallized.

Example 26

(1) In the said Example 1-1, it carries out similarly to Example 1-1 except having used 4-bromobutanol instead of 6-bromohexanol, and is represented by a following formula (e "). The compound was obtained.

(2) In the same manner as in Example 5-2, except that the compound represented by the formula (e '') was used instead of the compound represented by the formula (VII-a) in Example 5-2, The compound represented by (vi-2) was obtained. Yield: 72% (based on the compound represented by formula (e '')).

Example 27-1

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

(2) 80 g of compounds represented by obtained formula (b '' '), 1.40 g of 3,5-di-tert-butyl-4-hydroxytoluene, 61.2 g of dimethylaniline, and 1,3-dimethyl-2-imidazoli 1.00 g of dinon and chloroform were mixed. 29.8 g of acryloyl chloride was added dropwise to the obtained mixture under a nitrogen atmosphere and ice cooling. The resulting mixture was reacted by stirring at room temperature. After completion of the reaction, the reaction mixture was washed with 2N hydrochloric acid and saturated aqueous sodium carbonate solution and then concentrated. Methanol 700 ml was added to the obtained concentrate, and 3.34 g of p-toluenesulfonic acid and 3 g of water were further added. The obtained solution was reacted by stirring at 60 ° C for 3 hours. After the reaction was completed, 1400 g of pure water was added to the obtained reaction mixture. The precipitated solid was taken out, washed with a water / methanol mixed solution (volume ratio = 2/1), further washed with heptane, and dried in vacuo to give 62 g of a compound represented by the formula (d '' '). Yield: 84% (based on the compound represented by the formula (b '' ')).

(3) 40.3 g of the compound represented by the obtained formula (d '' '), 1.49 g of dimethylaminopyridine, 28 g of trans-1,4-cyclohexanedicarboxylic acid monoethoxymethyl ester and 150 ml of chloroform were mixed. The resulting mixture was ice-cooled and stirred under a nitrogen atmosphere. A 50 ml chloroform solution of 27.3 g of dicyclohexylcarbodiimide was added dropwise to the mixture. After completion of the dropwise addition, the reaction was stirred at room temperature. 200 ml of chloroform and 200 ml of heptane were added to the obtained reaction mixture. Precipitated precipitate was filtered off. The obtained filtrate was washed with 2N hydrochloric acid, and then insoluble components were removed by filtration. The obtained filtrate was dried over anhydrous sodium sulfate, filtered and concentrated.

The obtained concentrate, 2.34 g of pure water, 1.40 g of 3,5-di-tert-butyl-4-hydroxytoluene, 3.95 g of p-toluenesulfonic acid monohydrate and 200 ml of tetrahydrofuran were mixed. The obtained mixture was stirred for 3 hours at 70 ° C under a nitrogen atmosphere to react. After the reaction mixture was allowed to cool to room temperature, the precipitate precipitate was removed by filtration. The obtained filtrate was concentrated under reduced pressure at room temperature. 200 ml of heptane was added to the residue. The precipitate which precipitated was taken out by filtration, washed with pure water and dried in vacuo. The powder obtained was dissolved in chloroform, filtered through silica gel, and crystallized by adding 400 ml of chloroform and heptane to the filtrate. The obtained powder was taken out by filtration and dried in vacuo to obtain 44.4 g of the compound represented by the formula (e '' '). Yield: 82% (based on the compound represented by the formula (d '' ')).

Example 27-2

In the said Example 5-2, it replaces the compound represented by Formula (VII-a), and is the same as Example 5-2 except having used the compound represented by Formula (e '' ') obtained by the said Example 27-1. The compound was represented by the following formula (VII-3). Yield: 82% (based on the compound represented by the formula (e '' ')).

As a result of performing the phase transition temperature of the compound represented by obtained formula (VII-3) by texture observation with a polarization microscope, the compound represented by Formula (VII-3) shows a smectic phase from 164 degreeC to 174 degreeC at the time of temperature rising. It showed that the nematic phase was shown from 174 degreeC to 195 degreeC, the nematic phase was shown from 195 degreeC to 167 degreeC at the time of temperature drop, and the smectic phase was shown to crystallize from 167 degreeC to 151 degreeC.

Example 28-1

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

(2) 100 g of the compound represented by the obtained formula (b '' ''), 1.40 g of 3,5-di-tert-butyl-4-hydroxytoluene, 86.4 g of dimethylaniline, 1,3-dimethyl-2-imida 1.00 g of zolidinones and chloroform were mixed. 42.11 g of acryloyl chloride was dripped at the obtained mixture under nitrogen atmosphere and ice-cooling. The obtained mixture was reacted by stirring at room temperature for 2 hours. After completion of the reaction, the reaction mixture was washed with 2N hydrochloric acid and saturated aqueous sodium carbonate solution and then 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 obtained solution was reacted by stirring at 60 ° C for 3 hours. After the reaction was completed, 1400 g of pure water was added to the obtained reaction mixture. The precipitated solid was taken out, washed with a water / methanol mixed solution (volume ratio = 2/1), further washed with heptane, and dried in vacuo to give 72 g of a compound represented by the formula (d '' ''). Yield: 79% (based on the compound represented by the formula (b '' '').

(3) 25.1 g of the compound represented by the obtained formula (d '' ''), 1.06 g of dimethylaminopyridine, 20 g of trans-1,4-cyclohexanedicarboxylic acid monoethoxymethyl ester and 70 ml of chloroform were mixed. The resulting mixture was ice-cooled and stirred under a nitrogen atmosphere. A 50 ml chloroform solution of 19.5 g of dicyclohexylcarbodiimide was added dropwise to the mixture. After completion of the dropwise addition, the reaction was stirred at room temperature. 200 ml of chloroform and 200 ml of heptane were added to the obtained reaction mixture. Precipitated precipitate was filtered off. After the obtained solution was washed with 2N hydrochloric acid, the insoluble component was removed by filtration. The obtained filtrate was dried over anhydrous sodium sulfate, filtered and concentrated.

The obtained concentrate, 1.46 g of pure water, 1.40 g of 3,5-di-tert-butyl-4-hydroxytoluene, 2.46 g of p-toluenesulfonic acid monohydrate and 200 ml of tetrahydrofuran were mixed. The obtained mixture was stirred at 70 ° C. for 2 hours under a nitrogen atmosphere to react. After the reaction mixture was allowed to cool to room temperature, the precipitate precipitate was removed by filtration. The obtained filtrate was concentrated under reduced pressure at room temperature. 800 ml of pure water was added to the residue. The precipitate which precipitated 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 further washed with heptane. The obtained powder was dried in vacuo to obtain 30.1 g of the compound represented by the formula (e '' ''). Yield: 84% (based on the compound represented by the formula (d`` '')).

Example 28-2

In Example 5-2, except for using the compound represented by formula (e '' '') obtained in Example 28-1, instead of the compound represented by formula (VII-a), Example 5-2 was used. It carried out similarly and obtained the compound represented by following formula (VII-4). Yield: 69% (based on the compound represented by the formula (e '' '')).

As a result of performing the phase transition temperature of the compound represented by obtained formula (X-4) by texture observation with a polarization microscope, the compound represented by Formula (X-4) shows a smectic phase from 163 degreeC to 167 degreeC at the time of temperature rising. It showed that the nematic phase was shown from 167 degreeC to 220 degreeC, and the nematic phase was shown from 220 degreeC to 156 degreeC at the time of temperature drop, and it turned out that it crystallizes.

Example 29

(1) 12.5 g of the compound represented by the formula (VII-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. The solution obtained by dissolving 19.7 g of dicyclohexylcarbodiimide in 30 g of chloroform was dripped at the obtained mixture at room temperature. The obtained mixture was stirred and reacted. The obtained reaction mixture was filtrated and 12 g of 2N hydrochloric acid was added to the filtrate and stirred. The obtained mixture was separated to obtain 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. It was crystallized by adding heptane to the concentrated residue. The crystals were taken out by filtration and dried in vacuo to obtain the compound represented by the formula (g) as a pale yellow powder.

(2) The compound represented by obtained formula (g) and tetrahydrofuran were mixed. The obtained solution, pure water 1.18g, 3, 5- di-tert- butyl- 4-hydroxytoluene 1.40g, 1.55g of p-toluenesulfonic acid monohydrate, and 115 ml of tetrahydrofuran were mixed. The obtained mixture was stirred at 70 ° C. for 2 hours under a nitrogen atmosphere to react. After the reaction mixture was allowed to cool to room temperature, the resulting precipitate was taken out by filtration. The obtained powder was washed with tetrahydrofuran and further washed with heptane. The obtained powder was dried in vacuo to obtain 18 g of the compound represented by the formula (h). Yield: 70% (based on the compound represented by formula (VII-a)).

(3) 25.36 g of triphosgen and 125 g of tetrahydrofuran were mixed under ice cooling. 37g of 4-hydroxybutyl acrylate and 28.0g of dimethylaniline were dripped at the obtained mixed solution. The obtained mixture was reacted by stirring at room temperature for 2 hours. To the obtained reaction mixture, a solution obtained by dissolving 49.9 g of the compound represented by the formula (a) and 49.9 g of pyridine in 50 ml of tetrahydrofuran was added dropwise. The resulting mixture was allowed to react by stirring overnight at room temperature. The white precipitate was removed by filtration, and the obtained filtrate was concentrated under reduced pressure. After adding 120 ml of ethanol to the residue, 44 g of p-toluenesulfonic acid monohydrate was added to adjust the pH of the solution to 4. The obtained solution was stirred at room temperature for 1 hour and poured into 1000 g of ice. The supernatant was removed by decantation, the obtained lower layer and water / ethanol (volume ratio = 1/3) were mixed, and the supernatant was removed by decantation. The obtained lower layer was washed with heptane and decanted to obtain 50.0 g of the compound represented by the formula (i). Yield: 70% (based on 4-hydroxybutyl acrylate).

(4) 6.1 g of the compound represented by formula (h), 6.0 g of the compound represented by formula (i), 0.26 g of dimethylaminopyridine, and 20 ml of chloroform were mixed. 10 ml of chloroform solutions of 5.30 g of dicyclohexylcarbodiimide were added dropwise to the obtained mixture under ice cooling. The obtained mixture was stirred and reacted. After the reaction was completed, the reaction mixture was filtered to remove insoluble content. 2N hydrochloric acid was added to the obtained filtrate and liquid-separated. After drying the obtained organic layer, it filtered by Celite and concentrated under reduced pressure. The residue was crystallized by adding methanol. The obtained precipitate was taken out and dissolved in chloroform. 500 mg of activated carbon was added to the obtained solution, and the mixture was left to stand overnight, followed by Celite filtration. The obtained filtrate and ethanol were mixed, the produced precipitate was taken out by filtration, washed with heptane, and dried in vacuo to obtain 2.8 g of the compound represented by the formula (X-5). Yield: 25% (based on the compound represented by formula (h)).

As a result of performing the phase transition temperature of the compound represented by obtained formula (VII-5) by texture observation with a polarization microscope, the compound represented by Formula (VII-5) shows a smectic phase from 142 degreeC to 163 degreeC at the time of temperature rising. It showed that the nematic phase was shown from 163 degreeC to 224 degreeC, and it crystallized by showing a nematic phase to 108 degreeC at the time of temperature drop.

Example 30

(1) 30.73 g of p-hydroxybenzoic acid benzyl, 31 g of trans-1,4-cyclohexanedicarboxylic acid monoethoxymethyl ester, 31.95 g of dicyclohexylcarbodiimide, 1.64 g of dimethylaminopyridine and 200 ml of dehydrated chloroform Was mixed. The obtained mixture was stirred at room temperature under a nitrogen atmosphere to react. 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 then dried over anhydrous sodium sulfate. After sodium sulfate was filtered, methanol / water (volume ratio = 50/50) was added to the filtrate. The obtained crystal was taken out by filtration. The crystals were washed with heptane and pure water, and then dried in vacuo to give 58.0 g of the compound represented by the formula (j). Yield: 98% (based on benzyl p-hydroxybenzoic acid).

(2) 50.0 g of the compound represented by the obtained Formula (j) and 150 ml of tetrahydrofuran were mixed. 2 g of acetic acid and 7.5 g of palladium carbon were added to the obtained mixture, and the mixture was stirred under a nitrogen atmosphere. The mixture was depressurized and stirred under a hydrogen atmosphere. When the consumption of hydrogen was stopped, the mixture was placed in a nitrogen atmosphere, and the reaction mixture was filtered through Celite. The obtained filtrate was concentrated with an evaporator. The concentrated residue was washed with methanol / water (volume ratio = 50/50) and dried in vacuo to give 32.0 g of the compound represented by the formula (k). Yield: 80% (based on the compound represented by formula (j)).

(3) 16 g of the compound represented by obtained formula (k), 6.91 g of acrylic acid (4-hydroxybutyl), 10.88 g of dicyclohexylcarbodiimide, 0.56 g of dimethylaminopyridine, 2,6-di-tert-butyl-4 10 mg of methylphenol and 80 ml of dehydrated chloroform were mixed. The obtained mixture was stirred at room temperature under a nitrogen atmosphere to react. 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 then dried over anhydrous sodium sulfate. After removing sodium sulfate, it concentrated and obtained 18.5g of compounds represented by said formula (l). Yield: 85% (based on the compound represented by formula (j)).

(4) 18.5 g of the compound represented by obtained formula (l), 0.87 g of pure water, 0.87 g of p-toluenesulfonic acid monohydrate, and 80 ml of tetrahydrofuran were mixed. The obtained mixture was stirred and reacted at 60 ° C. under a nitrogen atmosphere. The reaction mixture was left to cool to room temperature and then concentrated. 200 ml of heptane was added to the concentrated residue, and the precipitated precipitate was taken out by filtration. The precipitate was washed with pure water and dried in vacuo to obtain 7.5 g of the compound represented by the formula (m). Yield: 40% (based on the compound represented by formula (l)).

(5) 4.95 g of the compound represented by obtained formula (m), 1.70 g of a compound represented by formula (VII-a), 2.95 g of dicyclohexylcarbodiimide, 0.29 g of dimethylaminopyridine, and 40 ml of dehydrated chloroform were mixed. The obtained mixture was stirred at room temperature under a nitrogen atmosphere to react. 20 ml of heptane was added to the reaction mixture, and the resulting precipitate was filtered off. The obtained filtrate was washed with 1N hydrochloric acid and then dried over anhydrous sodium sulfate. After sodium sulfate was removed by filtration, it was concentrated under reduced pressure with an evaporator. Ethyl acetate was added to the concentrated residue, and then concentrated under reduced pressure. 300 ml of methanol cooled in an ice bath was added to the concentrated residue. The precipitate which precipitated was taken out, it wash | cleaned with heptane, and it dried in vacuo, and obtained 2.9 g of compounds represented by said formula (VII-6). Yield: 45% (based on the compound represented by formula (m)).

As a result of performing the phase transition temperature of the compound represented by obtained formula (VII-6) by texture observation with a polarization microscope, the compound represented by Formula (VII-6) shows a smectic phase from 124 degreeC to 135 degreeC at the time of temperature rising. It showed that the nematic phase was shown from 135 degreeC to 220 degreeC, and the nematic phase was shown from 220 degreeC to 103 degreeC at the time of temperature drop, and it turned out that it crystallizes.

Example 31

(1) 30 g of compounds represented by formula (b), 1.40 g of 3,5-di-tert-butyl-4-hydroxytoluene, 15.5 g of triethylamine, and 1.00 g of 1,3-dimethyl-2-imidazolidinone And 300 ml of tetrahydrofuran were mixed. 16.0 g of methacryloyl chloride was added dropwise to the obtained solution while ice-cooling in a nitrogen atmosphere. The obtained mixture was stirred at room temperature for 3 hours to react. After the completion of the reaction, p-toluenesulfonic acid monohydrate was added to the reaction mixture to adjust the pH to 2. Pure water 1.47g was added to the mixture, and stirred for 3 hours at room temperature. 100 ml of heptane was added to the obtained mixture, and 2N hydrochloric acid was added. The obtained mixture was separated to obtain an organic layer. The organic layer was concentrated under reduced pressure, and 1000 g of ice was added to the concentrated residue and crystallized by vigorous stirring. The crystals were taken out, washed with water / methanol (volume ratio = 2/1), further washed with heptane and pure water, and dried in vacuo to give 12.4 g of the compound represented by the formula (n). Yield: 44% (based on the compound represented by formula (b)).

(2) 12.0 g of the compound represented by the obtained Formula (n), 0.53 g of dimethylaminopyridine, 10.0 g of trans-1,4-cyclohexanedicarboxylic acid monoethoxymethyl ester, and 50 ml of chloroform were mixed. The obtained solution was ice-cooled and stirred in nitrogen atmosphere, and the 20 mL chloroform solution of 9.8g of dicyclohexylcarbodiimide was dripped. The resulting mixture was reacted by stirring at room temperature. 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 resulting filtrate was washed with 2N hydrochloric acid. After insoluble components were removed by filtration, the filtrate was dried over anhydrous sodium sulfate. Sodium sulfate was removed by filtration and then concentrated. The resulting concentrated residue, 0.73 g of pure water, 1.40 g of 3,5-di-tert-butyl-4-hydroxytoluene, 1.15 g of p-toluenesulfonic acid monohydrate and 100 ml of tetrahydrofuran were mixed. The obtained mixture was stirred for 3 hours at 70 ° C under a nitrogen atmosphere to react. After the reaction mixture was allowed to cool to room temperature, the resulting precipitate was removed by filtration. The obtained filtrate was concentrated under reduced pressure at room temperature. 200 ml of heptane was added to the residue. The precipitated precipitate was taken out by filtration, washed with pure water and dried in vacuo. The obtained powder was dissolved in chloroform, and the obtained solution was filtered through silica gel. The filtrate was mixed with 400 ml of chloroform and crystallized by addition of heptane. The crystals were taken out by filtration and dried in vacuo to obtain 12.2 g of the compound represented by the formula (o). Yield: 68% (based on the compound represented by formula (n)).

(3) In the same manner as in Example 5-2 in Example 5-2, except that the compound represented by formula (o) obtained in the above (2) was used instead of the compound represented by the formula (e), 6.7 g of compounds represented by the above formula (VII-7) were obtained. Yield: 55% (based on the compound represented by the formula (VII-a)).

Example 32

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

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

(3) 40 g of the compound represented by obtained formula (q), 1.40 g of 3,5-di-tert-butyl-4-hydroxytoluene, 31.8 g of dimethylaniline and chloroform were mixed. 15.5 g of acryloyl chloride was added dropwise to the obtained mixture while cooling with ice under a nitrogen atmosphere. The obtained mixture was stirred at room temperature for 3 hours to react. After the reaction was completed, pH was adjusted to 2 by adding p-toluenesulfonic acid monohydrate to the reaction mixture. Pure water 1.64g was added to the obtained mixture, and it stirred at room temperature for 1 hour. 100 ml of heptane was added to the obtained mixture, 2N hydrochloric acid was further added, and the mixture was separated. The obtained organic layer was treated with activated carbon, filtered through celite, and the resulting filtrate was concentrated under reduced pressure. The concentrate was poured into heptane and the supernatant heptane layer was removed by decantation. The lower layer pale red viscous liquid was vacuum dried for 2 days to obtain 26.0 g of the compound represented by the formula (r). Yield: 71% (based on the compound represented by formula (q)).

(4) 15.0 g of the compound represented by obtained formula (r), 0.58 g of dimethylaminopyridine, 10.9 g of trans-1,4-cyclohexanedicarboxylic acid monoethoxymethyl ester, and 40 ml of chloroform were mixed. The obtained mixture was ice-cooled and stirred in a nitrogen atmosphere, and a 10 ml chloroform solution of 10.6 g of dicyclohexylcarbodiimide was added dropwise. The resulting mixture was reacted by stirring at room temperature. After completion of the reaction, 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 then insoluble components were removed by filtration. The filtrate was dried over anhydrous sodium sulfate, filtered with silica gel, and concentrated. The obtained concentrate, 0.79 g of pure water, 1.40 g of 3,5-di-tert-butyl-4-hydroxytoluene, 1.25 g of p-toluenesulfonic acid monohydrate, and 150 ml of tetrahydrofuran were mixed. The obtained mixture was stirred for 3 hours at 70 ° C under a nitrogen atmosphere to react. After the reaction mixture was allowed to cool to room temperature, the resulting precipitate was removed by filtration. The obtained filtrate was concentrated under reduced pressure at room temperature. 300 g of ice was added and stirred to the obtained residue, and the precipitated precipitate was taken out by filtration. The precipitate was washed with heptane and dried in vacuo. The obtained powder was dissolved in chloroform, and the obtained solution was filtered through silica gel. The filtrate was mixed with 400 ml of chloroform and crystallized by adding heptane to the obtained solution. The crystals were taken out, washed with ethanol / water (volume ratio = 2/3), and dried in vacuo to give 17.9 g of the compound represented by the formula (s). Yield: 86% (based on the compound represented by formula (r)).

(5) In the same manner as in Example 5-2 in Example 5-2, except that the compound represented by formula (s) obtained in the above (4) was used instead of the compound represented by the formula (e), 0.7 g of compounds represented by the above formula (VII-8) were obtained. Yield: 4.5% (based on the compound represented by formula (VII-a)).

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 obtained mixture was reacted by stirring at 80 ° C under a nitrogen atmosphere. The reaction mixture was allowed to cool to room temperature and then poured into a mixture of 1000 g of water and 500 g of methyl isobutyl ketone / heptane (weight ratio = 3/2). The obtained mixture was stirred and then separated. The organic layer obtained was washed with pure water, then dried over anhydrous sodium sulfate and filtered. After the filtrate was concentrated, heptane was added to the obtained residue, and the precipitated solid was taken out by filtration. The solid was vacuum dried to obtain 150 g of the compound represented by the formula (u). Yield: 75% (based on trans-4-hydroxycyclohexanecarboxylic acid).

(2) 30.5 g of the compound represented by obtained 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 obtained mixture was ice-cooled and stirred in a nitrogen atmosphere, and 29.57 g of dicyclohexylcarbodiimide was added dropwise. After completion of the dropwise addition, the mixture was stirred. 200 ml of chloroform and 200 ml of heptane were added to the obtained reaction mixture, and the resulting precipitate was removed by filtration. The obtained filtrate was washed three times with pure water, then dried over anhydrous sodium sulfate and filtered. The obtained filtrate was concentrated, methanol was added to the residue, and the mixture was stirred. The precipitated solid was taken out by filtration, mixed with methanol and filtered. The obtained powder was dried in vacuo to give 42 g of the compound represented by the formula (v). Yield: 90% (based on the compound represented by formula (u)).

(3) 23 g of the compound represented by the obtained Formula (v) was dissolved in 150 ml of tetrahydrofuran. 1.2 g of 10% palladium / carbon (50% hydrous) was added to the obtained solution under nitrogen atmosphere. The resulting mixture was reduced in pressure and then stirred under room temperature, atmospheric pressure and 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 component was removed by filtration. The obtained filtrate was concentrated. The concentrated residue was washed with water / methanol (volume ratio = 1/1) followed by water. The obtained crystal was taken out and dried in vacuo to obtain 17.8 g of the compound represented by the formula (w). Yield: 97% (based on the compound represented by formula (v)).

(4) 16 g of the compound represented by the obtained formula (w), 0.55 g of dimethylaminopyridine, 6.47 g of 4-hydroxybutyl acrylate, and 100 ml of chloroform were mixed. The obtained mixture was ice-cooled and stirred in a nitrogen atmosphere, and a 50 ml chloroform solution of 10.19 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride was added dropwise. The obtained mixture was stirred and reacted. 200 ml of toluene was added to the obtained reaction mixture, and it filtered. The obtained filtrate was concentrated under reduced pressure. Toluene was added to the concentrated residue, and the obtained solution was washed with 1N hydrochloric acid. The solution was dried over anhydrous sodium sulfate, filtered and concentrated. The obtained residue was dried in vacuo to give 18.5 g of the compound represented by the formula (x).

(5) 18.5g of compounds represented by obtained formula (x), 0.97g of pure water, 0.85g of p-toluenesulfonic acid monohydrate, and 100 ml of tetrahydrofuran were mixed. The obtained mixture was stirred and reacted at 50 ° C. under a nitrogen atmosphere. 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. Precipitated precipitate was taken out by filtration, washed with pure water and then dried in vacuo to give 15.4 g of the compound represented by the formula (t). Yield: 81% (based on the compound represented by formula (w)).

Example 33-2

1.44 g of a compound represented by formula (VII-a), 4.24 g of a compound represented by formula (t) obtained in Example 33-1, 0.12 g of dimethylaminopyridine, and chloroform were mixed. A chloroform solution of 2.48 g of dicyclohexylcarbodiimide was added dropwise to the obtained mixture under ice cooling. The obtained mixture was stirred and reacted. The reaction mixture was filtered, the filtrate obtained was dried and then concentrated under reduced pressure. Ethyl acetate was added to the concentrated residue, and concentrated under reduced pressure. Methanol was added to the obtained concentrated residue. Precipitated precipitate was taken out by filtration, washed with ethanol and dried in vacuo to obtain 4.65 g of the compound represented by the following formula (VII-9). Yield: 85% (based on the compound represented by the formula (VII-a)).

As a result of performing the phase transition temperature of the compound represented by obtained formula (VII-9) by texture observation with a polarization microscope, the compound represented by Formula (VII-9) shows a smectic phase from 146 degreeC to 159 degreeC at the time of temperature rising. It showed that a melting point was shown and the nematic phase was shown from 159 degreeC to 121 degreeC at the time of temperature drop, and it crystallized.

Example 34

In the said Example 33-2, it carried out similarly to Example 33-2 except having used the compound represented by Formula (VIIa) instead of the compound represented by Formula (VII-a), and is following Formula (VII-9) The compound shown by was obtained.

Example 35

After apply | coating the 2% aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 fully saponification type, the Wako Pure Chemical Industries, Ltd. product) on the glass substrate, it heat-dried and obtained the film of 89 nm in thickness. After the rubbing treatment was performed on the surface of the obtained film, a solution having the composition shown in Table 3 below was applied on the surface subjected to the rubbing treatment by the spin coating method. After drying for 1 minute on a 100 degreeC hotplate, the ultraviolet-ray of 1200mJ / cm <2> was irradiated, heating at 100 degreeC, and the optical film with a film thickness of 1.04 micrometer was obtained.

In addition, in Table 3, "%" shows content in a solution. "L1" means LC242 sold by BASF Corporation, "Irg907" means Irgacure 907 by Chiba Japan Co., Ltd., and "Irg819" means Irgacure 819 by Chiba Japan Co., Ltd. (IRGACURE). 819) respectively. In addition, "L2" means BYK361N by Big Chemie Japan.

Example 36

After apply | coating 2% aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 perfect saponification type, the Wako Pure Chemical Industries, Ltd.) on the glass substrate, it heat-dried and obtained the film of 89 nm in thickness. After the rubbing treatment was performed on the surface of the obtained film, a solution of the composition shown in Table 3 above was applied on the surface subjected to the rubbing treatment by the spin coating method. After drying for 1 minute on a 100 degreeC hotplate, the ultraviolet-ray of 1200mJ / cm <2> was irradiated, heating at 100 degreeC, and the optical film with a film thickness of 1.28 micrometers was obtained.

Example 37

After apply | coating 2% aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 perfect saponification type, the Wako Pure Chemical Industries, Ltd.) on the glass substrate, it heat-dried and obtained the film of 89 nm in thickness. After the rubbing treatment was performed on the surface of the obtained film, a solution of the composition shown in Table 3 above was applied on the surface subjected to the rubbing treatment by the spin coating method. After drying for 1 minute on an 80 ° C. hot plate, it was further dried at 210 ° C. for 1 minute. Ultraviolet rays of 1200 mJ / cm 2 were irradiated while heating the obtained unpolymerized film at 190 degreeC, and the optical film of 2.43 micrometers in film thickness was obtained.

Example 38

After apply | coating the 2% aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 fully saponification type, the Wako Pure Chemical Industries, Ltd. product) on the glass substrate, it heat-dried and obtained the film of 89 nm in thickness. After the rubbing treatment was performed on the surface of the obtained film, a solution of the composition shown in Table 3 above was applied on the surface subjected to the rubbing treatment by the spin coating method. After drying for 1 minute on an 80 ° C. hot plate, it was further dried at 210 ° C. for 1 minute. The obtained unpolymerized film was irradiated with 1200mJ / cm <2> ultraviolet-rays, heating at 190 degreeC, and the optical film with a film thickness of 1.52 micrometers was obtained.

Example 39

After apply | coating 2% aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 perfect saponification type, the Wako Pure Chemical Industries, Ltd.) on the glass substrate, it heat-dried and obtained the film of 89 nm in thickness. After the rubbing treatment was performed on the surface of the obtained film, a solution of the composition shown in Table 3 above was applied on the surface subjected to the rubbing treatment by the spin coating method. After drying for 1 minute on an 80 ° C. hot plate, it was further dried at 160 ° C. An ultraviolet-ray of 1200 mJ / cm 2 was irradiated while heating the obtained unpolymerized film at 160 degreeC, and the optical film of 2.27 micrometers in film thickness was obtained.

Example 40

After apply | coating the 2% aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 fully saponification type, the Wako Pure Chemical Industries, Ltd. product) on the glass substrate, it heat-dried and obtained the film of 89 nm in thickness. After the rubbing treatment was performed on the surface of the obtained film, a solution of the composition shown in Table 3 above was applied on the surface subjected to the rubbing treatment by the spin coating method. After drying for 1 minute on an 80 ° C. hot plate, it was further dried at 140 ° C. Ultraviolet rays of 1200 mJ / cm 2 were irradiated while heating the obtained unpolymerized film at 140 degreeC, and the optical film with a film thickness of 1.59 micrometers was obtained.

Example 41

After apply | coating the 2% aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 fully saponification type, the Wako Pure Chemical Industries, Ltd. product) on the glass substrate, it heat-dried and obtained the film of 89 nm in thickness. After the rubbing treatment was performed on the surface of the obtained film, a solution of the composition shown in Table 3 above was applied on the surface subjected to the rubbing treatment by the spin coating method. After drying for 1 minute on an 80 ° C. hot plate, it was further dried at 150 ° C. The obtained unpolymerized film was irradiated with 1200 mJ / cm <2> ultraviolet-rays, heating at 190 degreeC, and the optical film of 2.11 micrometers of film thicknesses was obtained.

Example 42

After apply | coating the 2% aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 fully saponification type, the Wako Pure Chemical Industries, Ltd. product) on the glass substrate, it heat-dried and obtained the film of 89 nm in thickness. After the rubbing treatment was performed on the surface of the obtained film, a solution of the composition shown in Table 3 above was applied on the surface subjected to the rubbing treatment by the spin coating method. After drying for 1 minute on an 80 ° C. hot plate, it was further dried at 160 ° C. The obtained unpolymerized film was irradiated with 1200 mJ / cm <2> ultraviolet-rays, heating at 160 degreeC, and the optical film of 1.56 micrometers of film thicknesses was obtained.

Example 43

After apply | coating 2% aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 perfect saponification type, the Wako Pure Chemical Industries, Ltd.) on the glass substrate, it heat-dried and obtained the film of 89 nm in thickness. After the rubbing treatment was performed on the surface of the obtained film, a solution of the composition shown in Table 3 above was applied on the surface subjected to the rubbing treatment by the spin coating method. After drying for 1 minute on an 80 ° C. hot plate, it was further dried at 170 ° C. The obtained unpolymerized film was irradiated with 1200 mJ / cm <2> ultraviolet-rays, heating at 170 degreeC, and the optical film of 1.40 micrometers of film thicknesses was obtained.

Example 44

After apply | coating the 2% aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 fully saponification type, the Wako Pure Chemical Industries, Ltd. product) on the glass substrate, it heat-dried and obtained the film of 89 nm in thickness. After the rubbing treatment was performed on the surface of the obtained film, a solution of the composition shown in Table 3 above was applied on the surface subjected to the rubbing treatment by the spin coating method. After drying for 1 minute on an 80 ° C. hot plate, it was further dried at 140 ° C. for 1 minute. The obtained unpolymerized film was irradiated with 1200 mJ / cm <2> ultraviolet-rays, heating at 140 degreeC, and the optical film of 1.50 micrometers of film thicknesses was obtained.

Comparative Example 1

After apply | coating the 2% aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 fully saponification type, the Wako Pure Chemical Industries, Ltd. product) on the glass substrate, it heat-dried and obtained the film of 89 nm in thickness. After the rubbing treatment was performed on the surface of the obtained film, a solution of the composition shown in Table 3 above was applied on the surface subjected to the rubbing treatment by the spin coating method. After drying for 1 minute on an 80 ° C. hot plate, it was further dried at 150 ° C. for 1 minute. Ultraviolet rays of 1200 mJ / cm 2 were irradiated while heating the obtained unpolymerized film at 100 degreeC, and the optical film of 0.88 micrometer of film thicknesses was obtained.

Measurement of Optical Properties

In the wavelength range of 450 nm to 700 nm, the retardation value of the manufactured optical film is measured using a measuring instrument (KOBRA-WR, Oji Measurement Instruments Co., Ltd.), and the retardation value Re (450) having a wavelength of 450 nm in the apparatus accessory program. ), A retardation value Re (550) having a wavelength of 550 nm, and a retardation value Re (650) having 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 (VII-a), 1.7 g of trans-4-n-pentylcyclohexanecarboxylic acid, 0.21 g of 4-dimethylaminopyridine and 392 g of dehydrated pyridine were mixed. The solution obtained by dissolving dicyclohexylcarbodiimide 46.2g in 98 g of dehydrated pyridine was dripped at the obtained mixture. The obtained mixture was stirred at 60 ° C for reaction. The reaction mixture was filtered and the filtrate obtained was concentrated. 196 g of chloroform was added to the concentrate, and the mixture was washed with 196 g of 2N hydrochloric acid. The obtained solution was purified by a silica gel column under reduced pressure to obtain 2.8 g of a compound represented by the formula (TC-1). Yield: 70% (based on trans-4-n-pentylcyclohexanecarboxylic acid)

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

The phase transition temperature of the compound represented by obtained formula (TM-1) was implemented by texture observation by a polarizing microscope. The compound represented by a formula (TM-1) shows a smectic phase from 148 degreeC to 153 degreeC at the time of temperature rising, shows a nematic phase from 153 degreeC to 173 degreeC, and it is nema from 170 degreeC to 102 degreeC at the time of temperature reduction. It turned out that it shows a tick phase.

Example 46

After apply | coating the 2% aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 fully saponification type, the Wako Pure Chemical Industries, Ltd. product) on the glass substrate, it heat-dried and obtained the film of 89 nm in thickness. After the rubbing treatment was performed on the surface of the obtained film, the solution of the composition shown in Table 5 below was applied by the spin coating method on the surface on which the rubbing treatment was performed. After drying for 1 minute on a 170 degreeC hotplate, the ultraviolet-ray of 9600 mJ / cm <2> was irradiated, heating at 130 degreeC, and the optical film with a film thickness of 1.353 micrometers was obtained.

In addition, in Table 5, "%" shows content in a solution. "L1" means LC242 sold by BASF Corporation, and "Irg819" means Irgacure 819 (IRGACURE 819) by the Chiba Japan Corporation. In addition, "L2" means BYK361N by Big Chemie Japan.

Comparative Example 2

The optical film was manufactured like Example 46 except having apply | coated by the spin coat method using the solution of the said Table 5, drying for 1 minute on 45 degreeC hotplate, and irradiating an ultraviolet-ray at room temperature. .

About the manufactured optical film, the retardation value in wavelength 547nm was measured using the measuring device (KOBRA-WR, the Oji measuring instrument company make). In addition, the film thickness (d) derived from the polymeric compound of an optical film was measured using the laser microscope (LEXT, Olympus Corporation). The birefringence (Δn) was calculated from the phase difference value and the film thickness (d) at a wavelength of 547 nm. In addition, retardation values at wavelengths 447 nm and 628 nm were measured, and the wavelength dispersion characteristics Re (447) / Re (547) and Re (628) / Re (547) were calculated. The results are shown in Table 6.

Examples 47-63 and Comparative Example 3

After apply | coating 2% aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 perfect saponification type, Wako Pure Chemical Industries, Ltd.) on the glass substrate, it heat-dried and obtained the film of 89 nm in thickness. After the rubbing treatment was performed on the surface of the obtained film, a solution of the composition shown in Table 7 was applied on the surface subjected to the rubbing treatment by spin coating, dried, and then irradiated with ultraviolet rays to obtain an optical film.

In addition, in Table 7, "%" shows content in a solution. "L1" means LC242 sold by BASF Corporation, "Irg907" means Irgacure 907 by Chiba Japan Co., Ltd., and "Irg819" means Irgacure 819 by Chiba Japan Co., Ltd. (IRGACURE). 819) respectively. In addition, "L2" means BYK361N by Big Chemie Japan.

Measurement of Optical Properties

The front phase difference value of the manufactured optical film was measured using the measuring device (KOBRA-WR, the Oji measuring instrument company make). Moreover, since the glass substrate used for a base material does not have birefringence, the front phase difference value of the optical film manufactured on the glass substrate can be obtained by measuring the film with a glass substrate with a measuring device. The front retardation values were measured at wavelengths 447.3 nm, 546.9 nm and 627.8 nm, respectively, and Re (447.3) / Re (546.9) (hereinafter abbreviated as α) and Re (627.8) / Re (546.9) (hereinafter β) Is abbreviated). In addition, the film thickness (d) (micrometer) of the part derived from an optical film was measured using the laser microscope (LEXT, Olympus company). The results are shown in Table 8. The birefringence (Δn) was 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 obtained mixture was reacted by stirring at 80 ° C under a nitrogen atmosphere. After the reaction mixture was allowed to cool, it was poured into a solution consisting of water and methylisobutylketone / heptane (weight ratio = 3/2). The obtained mixture was separated. The organic layer obtained was washed with pure water, dried and filtered. The filtrate was concentrated and heptane was added to the resulting concentrated residue. The precipitated solid was taken out by filtration and dried in vacuo to obtain 150 g of the compound represented by the formula (g '). Yield: 75% (based on trans-4-hydroxycyclohexanecarboxylic acid).

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

(3) 32.0 g of the compound represented by the obtained formula (h ') and 150 ml of 2-propanol were mixed. 0.7 g of acetic acid and 6.40 g of palladium / carbon were added to the obtained solution, and the mixture was stirred under a nitrogen atmosphere. The resulting mixture was reduced in pressure and then stirred under a hydrogen atmosphere to react. After completion | finish of reaction, after nitrogen-substituting, the reaction mixture was filtered through Celite and the obtained filtrate was concentrated. The concentrated residue was washed with pure water and then dried in vacuo to give 24.0 g of the compound represented by the formula (j '). Yield: 97% (based on the compound represented by 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 were mixed. The solution obtained by dissolving dicyclohexylcarbodiimide 2.0g in 22 g of chloroform was dripped at the obtained mixture. The obtained mixture was stirred and reacted. The precipitated solid was removed by filtration, and the obtained filtrate was washed with hydrochloric acid. Methanol was added to the obtained solution under reduced pressure, and the solid was taken out. Solids extracted were washed with methanol to obtain 2.7 g of the compound represented by the formula (ii-2). Yield: 81% (based on the compound represented by formula (ii-a)).

Example 65

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

Example 66

In the same manner as in Example 65, the compound represented by the following Formula (VII-10) was synthesized in a yield of 73%.

Examples 67-68 and Comparative Example 4

After apply | coating the 2% aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 fully saponification type, the Wako Pure Chemical Industries, Ltd. product) on the glass substrate, it heat-dried and obtained the film of 89 nm in thickness. After the rubbing treatment was performed on the surface of the obtained film, a solution having the composition shown in Table 9 was applied on the surface subjected to the rubbing treatment by spin coating, dried, and then irradiated with ultraviolet rays to obtain an optical film.

In addition, in Table 9, "%" shows content in a solution. "L1" means LC242 sold by BASF Corporation, and "Irg819" means Irgacure 819 (IRGACURE 819) by the Chiba Japan Corporation. In addition, "L2" means BYK361N by Big Chemie Japan.

Measurement of Optical Properties

The front phase difference value of the manufactured optical film was measured using the measuring device (KOBRA-WR, the Oji measuring instrument company make). Moreover, since the glass substrate used for a base material does not have birefringence, the front phase difference value of the optical film manufactured on the glass substrate can be obtained by measuring the film with a glass substrate with a measuring device. The front retardation values were measured at wavelengths 447.3 nm, 546.9 nm and 627.8 nm, respectively, and Re (447.3) / Re (546.9) (hereinafter abbreviated as α) and Re (627.8) / Re (546.9) (hereinafter β) Is abbreviated). In addition, the film thickness (d) (micrometer) of the part derived from an optical film was measured using the laser microscope (LEXT, Olympus company). The results are shown in Table 10. The birefringence (Δn) was calculated by dividing the value of Re (546.9) by the film thickness (d).

The optical film of this invention is possible for constant polarization conversion in a wide wavelength range.

Claims (5)

The composition for optical films containing 10 weight part or more of compounds containing group represented by Formula (A), and polymeric group, and 90 weight part or less of compound represented by Formula (4) (However, compound (A) and formula (4) The total of the compound represented by 100 parts by weight).
-G ^a -D ^a -Ar ^a -D ^b -G ^b- (A)
[In Formula (A), Ar ^a represents the bivalent group which has at least 1 aromatic ring selected from the group which consists of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and the number of (pi) electrons in the aromatic ring in Ar ^a group N (pi) is , 12 or more.
D ^a and D ^b are each independently 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 ¹ R ² -NR ^3- , -CO-NR ^1- , or -NR ¹ -CO-. R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.
G ^a and G ^b each independently represent a divalent alicyclic hydrocarbon group. The hydrogen atom contained in this alicyclic hydrocarbon group may be substituted by the halogen atom, a C1-C4 alkyl group, a C1-C4 fluoroalkyl group, a C1-C4 alkoxy group, a cyano group, or a nitro group, and the alicyclic The methylene group contained in a formula hydrocarbon group may be substituted by -O-, -S-, or -NH-.]
P ¹¹ -E ^11- (B ¹¹ -A ¹¹ ) _t -B ¹² -G (4)
[In Formula (4), A <^11> represents an aromatic hydrocarbon group, an alicyclic hydrocarbon group, or a heterocyclic group, and the hydrogen atom contained in this aromatic hydrocarbon group, an alicyclic hydrocarbon group, and a heterocyclic group is a halogen atom, C1-C1 It may be substituted by the alkyl group of 6, a C1-C6 alkoxy group, a C1-C6 alkylamino group, a nitro group, a nitrile group, or a mercapto group.
B ¹¹ and B ¹² are each independently —CR ¹⁴ R ¹⁵ —, —CH═CH—, —CH ₂ —CH ₂ —, —O—, —C (═O) —, —C (═O) -O-, -OC (= O) - , -OC (= O) -O-, -CH = N-, -N = CH-, -N = N-, -OCH 2 -, -OCF 2 -, -NR ^14- , -CH ₂ O-, -CF ₂ O-, or a single bond. R <^14> and R <^15> may respectively independently represent a hydrogen atom, a fluorine atom, or a C1-C4 alkyl group, and R <^14> and R <^15> may connect and comprise a C4-C7 alkylene group.
E ¹¹ is, represents an alkylene group having 1 to 12 carbon atoms. The hydrogen atom contained in this alkylene group may be substituted by the C1-C6 alkyl group, the C1-C6 alkoxy group, or a halogen atom.
P ¹¹ represents a polymerizable group.
G is a C1-C13 alkyl group, a C1-C13 alkoxy group, a C1-C13 fluoroalkyl group, or a nitrile group, or represents a polymeric group couple | bonded through a C1-C12 alkylene group, and the alkylene The hydrogen atom contained in a group may be substituted by the C1-C6 alkyl group, the C1-C6 alkoxy group, or a halogen atom. t represents the integer of 1-5.] The method of claim 1,
Furthermore, the composition for optical films containing a polymerization initiator. The manufacturing method of the unpolymerized film which apply | coats the composition for optical films of Claim 1 or 2 on the orientation film formed on the support base material, and is dried. The manufacturing method of the optical film which hardens the unpolymerized film obtained by the manufacturing method of the unpolymerized film of Claim 3 by superposition | polymerization. The optical film obtained by hardening | curing the unpolymerized film obtained by the manufacturing method of the unpolymerized film of Claim 3 by superposition | polymerization.

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