KR102106236B1 - Optical film - Google Patents

Abstract

(식 중, Ar 은 방향족 탄화수소 고리 및 방향족 복소 고리로 이루어지는 군에서 선택되는 적어도 하나의 방향 고리를 갖는 2 가의 기를 나타내고, 그 2 가의 기 중에 포함되는 방향 고리의 π 전자의 합계수 (N_π) 는 12 이상이다. D_a 및 D_b 는 각각 독립적으로 단결합,

를 나타내고, G_a 및 G_b 는 각각 독립적으로 2 가의 지환식 탄화수소기를 나타낸다) 로 나타내는 기 및 적어도 하나의 중합성기를 포함하는 화합물을 중합시켜 얻어지는 광학 필름.Equation (A)

(Wherein, Ar represents a divalent group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle, and the total number of π electrons of the aromatic ring contained in the divalent group (N _π ) Is 12 or more D _a and D _b are each independently a single bond,

And G _a and G _b each independently represent a divalent alicyclic hydrocarbon group. An optical film obtained by polymerizing a compound comprising a group and at least one polymerizable group.

Description

Optical film {OPTICAL FILM}

The present invention relates to an optical film.

The flat panel display device (FPD) includes a member using an optical film such as a polarizing plate or a retardation plate. As an optical film, the optical film obtained by superposing | polymerizing, after apply | coating the solution obtained by dissolving a polymerizable 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 the wavelength λnm 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 λnm by the phase difference value (Re (550)) at 550nm. )), Where (Re (λ) / Re (550)) is a wavelength region close to 1, but [Re (450) / Re (550)] <1 and [Re (650) / Re (550)]> It is known that a constant polarization conversion is possible in the wavelength range showing the reverse wavelength dispersion of 1.

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

The present invention,

[1] Equation (A)

(Wherein, Ar represents a divalent group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle, and the total number of π electrons of the aromatic ring contained in the divalent group (N _π ) Is 12 or more D _a and D _b are each independently a single bond,

And 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, and the alicyclic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a cyano group. A group represented by at least one selected from the group consisting of a noo 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 An optical film obtained by polymerizing a compound containing one polymerizable group;

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

(In the formula, Ar, D _a , D _b , G _a and G _b have the same meaning 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, and R ⁵ and R ⁶ independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms) and the optical film according to [1], which is a compound containing a group and at least one polymerizable group. ;

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

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

Or a single bond, R ⁵ and R ⁶ have the same meaning as defined in [2]. A ¹ and A ² each independently represent a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group, and the alicyclic hydrocarbon group and the aromatic hydrocarbon group are halogen atoms, alkyl groups having 1 to 4 carbon atoms, and fluoro groups having 1 to 4 carbon atoms. It may be substituted with 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 the optical film according to [2], which is a compound containing a group and at least one polymerizable 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] And 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. It may be substituted, and at least one methylene group constituting the alkylene group 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. The optical film according to [3], which is a compound represented by a genital group);

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

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

(Wherein, Ar, E ¹ , E ² , B ¹ , B ² , F ¹ , F ² , P ¹ , P ² , k and l are from [1], [2], [3], and [4] D ¹ and D ² each independently represent * -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-, and represent R ¹ , R ² , R ³ and R ⁴ have 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, a carbon number 1 Even if it is substituted with at least one selected from the group consisting of fluoroalkyl groups having 4 to 4, alkoxy groups having 1 to 4 carbon atoms, cyano groups and nitro groups And at least one methylene group constituting the alicyclic hydrocarbon group may be substituted with -O-, -S- or -NH-).

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

(Wherein, Z ¹ is a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, a carboxyl group, a fluoro group having 1 to 6 carbon atoms Alkyl group, alkoxy group having 1 to 6 carbon atoms, alkylthio group having 1 to 6 carbon atoms, N-alkylamino group having 1 to 6 carbon atoms, N, N-dialkylamino group having 2 to 12 carbon atoms, N-alkyl having 1 to 6 carbon atoms Represents a sulfamoyl group or an N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms Q ¹ and Q ³ are each independently -CR ⁷ R ^8- , -S-, -NR ^7- , -CO- or -O-, and R ⁷ and R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 4. Carbon atoms Y ¹ , Y ² and Y ³ are each independently an aromatic hydrocarbon group which may be substituted 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 * Optical film according to [1], [2], [3], [4], [5] or [7], which is -NR ¹ -CO- (* represents a binding 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 * The optical film according to [6], wherein -NR ¹ -CO- (* represents a binding site with Ar);

[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 phase difference 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 phase difference value (Re (550)) at a wavelength of 550 nm is 250 to 300 nm;

[14] Equation (A)

(Wherein, Ar represents a divalent group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle, and the total number of π electrons of the aromatic ring contained in the divalent group (N _π ) Is 12 or more D _a and D _b are each independently a single bond,

And 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, and the alicyclic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a cyano group. A group represented by at least one selected from the group consisting of a noo 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 containing one polymerizable group and formula (4)

(Wherein, A ¹¹ represents an aromatic hydrocarbon group, an alicyclic hydrocarbon group or a heterocyclic group, the aromatic hydrocarbon group, an alicyclic hydrocarbon group and a heterocyclic group is a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms 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

Or a single bond, R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms, and R ¹⁴ and R ¹⁵ may combine 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, an alkyl group having 1 to 13 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, a fluoroalkyl group having 1 to 13 carbon atoms, an N-alkylamino group having 1 to 13 carbon atoms, a cyano group, or a nitro group, or It represents a polymerizable group bonded through 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. t represents the integer of 1-5) The composition containing the compound represented by;

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

(Wherein, Ar has the same meaning as defined in [14]. D ¹ and D ² are each independently * -O-CO- (* represents a binding site with Ar),

And R ¹ , R ² , R ³ and R ⁴ have 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 , 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, 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, R ⁵ and R ⁶ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms. B ¹ 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, and the alicyclic hydrocarbon group and the aromatic hydrocarbon group are halogen atoms, alkyl groups having 1 to 4 carbon atoms, and fluoro groups having 1 to 4 carbon atoms. It may be substituted with 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. F ¹ and F ² each independently represent an alkylene group having 1 to 12 carbon atoms, and the alkylene group is 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. In addition, at least one methylene group constituting the alkylene group may be substituted with -O- or -CO-. Any one of P ¹ and P ² represents a polymerizable group, the other represents a hydrogen atom or a polymerizable group) The composition according to [14], which is a compound represented by;

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

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

[18] A color filter comprising a color filter layer, an alignment film, and the optical film according to any one of [1] to [13] laminated in this order;

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

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

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

[22] Equation (1)

(Wherein, Ar represents a divalent group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle, and the total number of π electrons of the aromatic ring contained in the divalent group (N _π ) Is 12 or more, D ¹ and D ² are each independently * -O-CO- (* represents a binding site with Ar),

And R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms. G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group, and the alicyclic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a cyano group. At least one methylene group constituting the alicyclic hydrocarbon group may be substituted with -O-, -S- or -NH-. E ¹ and E ² are each independently

Or a single bond, R ⁵ and R ⁶ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms. B ¹ 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, and the alicyclic hydrocarbon group and the aromatic hydrocarbon group are halogen atoms, alkyl groups having 1 to 4 carbon atoms, and fluoro groups having 1 to 4 carbon atoms. It may be substituted with 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. F ¹ and F ² each independently represent an alkylene group having 1 to 12 carbon atoms, and the alkylene group is 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. In addition, at least one methylene group constituting the alkylene group may be substituted with -O- or -CO-. 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 Formulas (2) and (3);

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

(Wherein, Z ¹ is a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, a carboxyl group, a fluoro group having 1 to 6 carbon atoms Alkyl group, alkoxy group having 1 to 6 carbon atoms, alkylthio group having 1 to 6 carbon atoms, N-alkylamino group having 1 to 6 carbon atoms, N, N-dialkylamino group having 2 to 12 carbon atoms, N-alkyl having 1 to 6 carbon atoms Represents a sulfamoyl group or an N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms Q ¹ and Q ³ are each independently -CR ⁷ R ^8- , -S-, -NR ^7- , -CO- or -O-, and R ⁷ and R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 4. Carbon atoms Y ¹ , Y ² and Y ³ are each independently an aromatic hydrocarbon group which may be substituted 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 described in any one of [22] to [24], wherein * -NR ¹ -CO- (* represents a binding site with Ar);

[26] The compounds 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, characterized in that a solution containing a compound according to any one of [22] to [26] is applied onto a supporting substrate or an alignment film formed on a supporting substrate and dried;

[28] A method for producing an optical film comprising polymerizing an unpolymerized film obtained by the production method described in [27]; Is to provide.

The optical film of the present invention, the following formula (A)

(Wherein, Ar represents a divalent group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle, and the total number of π electrons of the aromatic ring contained in the divalent group (N _π ) Is 12 or more D _a and D _b are each independently a single bond,

And 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, and the alicyclic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a cyano group. A group represented by at least one selected from the group consisting of a noo 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 that can transmit light and has an optical function. The optical function means refraction, birefringence, and the like. The retardation film, which is a kind of optical film, is used to convert linearly polarized light into circularly polarized light or elliptically polarized light, or, conversely, to convert circularly polarized light or elliptical polarized light into linearly polarized light.

By having the group represented by the formula (A), the optical film of the present invention enables 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 a divalent group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle, and the total number of π electrons (N _π ) of the aromatic ring contained in the divalent group is 12 or more. , Preferably it is 12 or more and 22 or less, More preferably, it is 13 or more and 22 or less.

It is preferable that Ar is a divalent group having at least two aromatic rings selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle.

Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, anthracene ring, and a phenanthroline ring. Examples of the aromatic heterocyclic ring include furan ring, pyrrole ring, thiophene ring, pyridine ring, thiazole ring, and benzothia And sol rings. Especially, a benzene ring, a thiazole ring, and a benzothiazole ring are preferable.

It is preferable that Ar is any group of groups represented by the following formulas (Ar-1) to (Ar-13).

(Wherein, Z ¹ is a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, a carboxyl group, a fluoro group having 1 to 6 carbon atoms Alkyl group, alkoxy group having 1 to 6 carbon atoms, alkylthio group having 1 to 6 carbon atoms, N-alkylamino group having 1 to 6 carbon atoms, N, N-dialkylamino group having 2 to 12 carbon atoms, N-alkyl having 1 to 6 carbon atoms Represents a sulfamoyl group or an N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms Q ¹ and Q ³ are each independently -CR ⁷ R ^8- , -S-, -NR ^7- , -CO- or -O-, and R ⁷ and R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 4. Carbon atoms Y ¹ , Y ² and Y ³ are each independently an aromatic hydrocarbon group which may be substituted 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)

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

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

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

As the alkylsulfonyl group having 1 to 6 carbon atoms, methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, butylsulfonyl group, isobutylsulfonyl group, sec-butylsulfonyl group, tert-butylsulfonyl group, 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, and a methyl sulfonyl 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, nonafluorobutyl group, and the like. A fluoroalkyl group is preferable, a C1-C2 fluoroalkyl group is more preferable, and a trifluoromethyl group is particularly preferable.

As the alkoxy group having 1 to 6 carbon atoms, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, etc. Examples thereof include an alkoxy group having 1 to 4 carbon atoms, more preferably an alkoxy group having 1 to 2 carbon atoms, and particularly preferably a methoxy group.

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

As an N-alkylamino group having 1 to 6 carbon atoms, N-methylamino group, N-ethylamino group, N-propylamino group, N-isopropylamino group, N-butylamino group, N-isobutylamino group, N-sec-butylamino group , N-tert-butylamino group, N-pentylamino group, N-hexylamino group and the like. N-alkylamino groups having 1 to 4 carbon atoms are preferable, N-alkylamino groups having 1 to 2 carbon atoms are more preferable, N-methylamino group is particularly preferred.

As the N, N-dialkylamino group having 2 to 12 carbon atoms, 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., and N having 2 to 8 carbon atoms , N-dialkylamino group is preferred, a C 2-4 N, N-dialkylamino group is more preferred, and a N, N-dimethylamino group is particularly preferred.

As the N-alkyl sulfamoyl group having 1 to 6 carbon atoms, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N -Isobutylsulfamoyl group, N-sec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N-hexylsulfamoyl group, and the like, N having 1 to 4 carbon atoms -An alkyl sulfamoyl group is preferable, an N-alkyl sulfamoyl group having 1 to 2 carbon atoms is more preferable, and an N-methylsulfamoyl group is particularly 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 A dihexyl sulfamoyl group, etc., N, N-dialkylsulfamoyl group having 2 to 8 carbon atoms is preferable, N, N-dialkylsulfamoyl group having 2 to 4 carbon atoms is more preferable, N, The 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, it is preferably an 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, and having 1 to 2 carbon atoms. An alkyl group is preferable, and a methyl group is more preferable.

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

Examples of the aromatic hydrocarbon groups for Y ¹ , Y ² and Y ³ include aromatic hydrocarbon groups having 6 to 20 carbon atoms such as phenyl group, naphthyl group, anthryl group, phenanthryl group and biphenyl group, and phenyl group and naphthyl group It is preferable, and a phenyl group is more preferable. The aromatic heterocyclic group contains 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. The aromatic heterocyclic group of 20 is mentioned, and a furyl group, a pyrrolyl group, a thienyl group, a pyridinyl group, and a thiazolyl group are preferable.

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

Halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, a carboxyl group, a fluoroalkyl group having 1 to 6 carbon atoms, and 1 to 6 carbon atoms Alkoxy group, an alkylthio group having 1 to 6 carbon atoms, an N-alkylamino group having 1 to 6 carbon atoms, an N, N-dialkylamino group having 2 to 12 carbon atoms, an N-alkylsulphamoyl group having 1 to 6 carbon atoms, and 2 to 6 carbon atoms. As the N, N-dialkylsulfamoyl group of 12, the same ones as described above can be mentioned.

As Y ¹ , Y ² and Y ³ , it is preferably a group independently represented by the following formulas (Y-1) to (Y-6).

(Wherein, Z ² is a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, a carboxyl group, a fluoro group having 1 to 6 carbon atoms Alkyl group, alkoxy group having 1 to 6 carbon atoms, thioalkyl group having 1 to 6 carbon atoms, N-alkylamino group having 1 to 6 carbon atoms, N, N-dialkylamino group having 2 to 12 carbon atoms, N-alkyl alcohol having 1 to 6 carbon atoms 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 from 0 to 5, a ₂ represents an integer from 0 to 4 , b ₁ represents an integer from 0 to 3, and b ₂ represents an integer from 0 to 2)

It is more preferable that Y ¹ , Y ² and Y ³ are independently groups represented by formula (Y-1) or formula (Y-3) from the viewpoint of easy production of compound (A).

W ¹ and W ² are preferably independently a hydrogen atom, a cyano group, or a methyl group, and more preferably a hydrogen atom.

It is preferable that m is 0 or 1. It is preferable that n is 0.

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

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

As a specific example of the group represented by Formula (Ar-1)-Formula (Ar-4), the group represented by Formula (ar-1)-Formula (ar-29) is mentioned.

As a specific example of group represented by Formula (Ar-5), group represented by Formula (ar-30)-Formula (ar-39) is mentioned.

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

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

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

As a specific example of group represented by Formula (Ar-11), group represented by Formula (ar-150)-Formula (ar-159) is mentioned.

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

As a specific example of the group represented by Formula (Ar-13), the group represented by Formula (ar-180)-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 are each independently a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, iso Butyl group, tert-butyl group, etc.).

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 binding 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). R ¹ , R ² , R ³ and R ⁴ are preferably each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom, a methyl group or an ethyl group.

G _a and G _b 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, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a cyano group. It may be substituted with at least one selected from the group consisting of a furnace group and a nitro group.

Examples of the divalent alicyclic hydrocarbon group include an alicyclic hydrocarbon group which may contain a hetero atom represented by the following formulas (g-1) to (g-10), and a bivalent 5- or 6-membered alicyclic hydrocarbon. It is preferable to be a group, a 1,4-cyclohexylene group is more preferable, and a trans-1,4-cyclohexylene group is particularly preferable.

The groups represented by the formulas (g-1) to (g-10) include alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, isopropyl group and tert-butyl group; Alkoxy groups having 1 to 4 carbon atoms such as methoxy groups and ethoxy groups; A fluoroalkyl group having 1 to 4 carbon atoms such as trifluoromethyl group; Fluoroalkoxy groups having 1 to 4 carbon atoms such as trifluoromethoxy groups; Cyano group; Nitro group; It may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom.

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

The polymerizable group may be any group that can be involved in the polymerization reaction of the compound (A), and specifically, a vinyl group, p-stilbene group, acryloyl group, metacroyl group, acryloyloxy group, and metacroyloxy 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, etc. have. Among them, a radically polymerizable group or a cationic polymerizable group is preferable in view of being suitable for photopolymerization, and an acryloyl group or a metacroyl group is more preferable in view of easy handling and easy production of compound (A). The royl group is particularly preferred.

The polymerizable group may be directly bonded to the terminal of the group represented by formula (A), but is preferably bonded through at least one divalent linking group.

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

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

Or it is preferable that it is a compound containing a group represented by 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 the following formula (C)

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

Or a single bond, R ⁵ and R ⁶ represent 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, and the alicyclic hydrocarbon group and the aromatic hydrocarbon group are halogen atoms, alkyl groups having 1 to 4 carbon atoms, and fluoro groups having 1 to 4 carbon atoms. It may be substituted with 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. It is more preferable that k and l each independently represent a compound represented by a group represented by 0 to 3), and 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. Represents an alkylene group, 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, and at least one methylene constituting the alkylene group. The group may be substituted with -O- or -CO- It is particularly preferable that any one 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 each independently -O-, -S-, -CO-O- or -O-CO-. It is more preferable that E ¹ is -CO-O- and E ² is -O-CO-.

Examples of the divalent alicyclic hydrocarbon group or divalent aromatic hydrocarbon group represented by A ¹ and A ² include groups represented by the formulas (g-1) to (g-10), and the following formulas (a-1) to (a). The group represented by -8) is mentioned, and the group represented by formula (a-1) or formula (g-1) is preferable, and a 1,4-phenylene group or 1,4-cyclohexylene group is more preferable.

The groups represented by the formulas (a-1) to (a-8) include alkyl groups having 1 to 4 carbon atoms, such as methyl group, ethyl group, isopropyl group, and tert-butyl group; Alkoxy groups having 1 to 4 carbon atoms such as methoxy groups and ethoxy groups; A fluoroalkyl group having 1 to 4 carbon atoms such as trifluoromethyl group; Fluoroalkoxy groups having 1 to 4 carbon atoms such as trifluoromethoxy groups; Cyano group; Nitro group; It may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom.

It is preferable that A ¹ and A ² are the same group in view of easy production of a compound containing a group represented by formula (C) or a compound represented by formula (D), and 1,4-phenylene group or 1,4-cyclo It is more preferably a hexylene group, and particularly preferably a 1,4-phenylene group.

It is preferable that B ¹ and B ² are the same group from the viewpoint of easy production of a compound containing a group represented by formula (C) or a compound represented by formula (D). B ¹ and B ^{2 which} are only bonded to A ¹ or A ² are each independently -CH ₂ -CH _2- , -CO-O-, -O-CO-, -CO-NH-, -NH-CO-, It is preferable that it is -O-CH _2- , -CH ₂ -O- or a single bond, and -CO-O- from the viewpoint of liquid crystallinity of the compound containing the group represented by formula (D) and the compound represented by formula (D) Or -O-CO- is preferred. B ¹ and B ² in combination with 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 of k and l is an integer of 5 or less, it is more preferable that it is an integer of 4 or less, and it is especially preferable to satisfy the following formulas (2) and (3).

As a compound represented by Formula (D), the 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),

And R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms. G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group, and the alicyclic hydrocarbon group and its aromatic heterocyclic group are a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, and a carbon number of 1 to 4 carbon atoms. 4 may be substituted with at least one selected from the group consisting of an alkoxy group, a cyano group, and a nitro group, and at least one methylene group constituting the alicyclic hydrocarbon group may be substituted with -O-, -S- or -NH-. ) Is preferred.

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 it is -CO- (* represents a binding 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). R ¹ , R ² , R ³ and R ⁴ are preferably each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom, a methyl group or an ethyl group.

As specific examples of G ¹ and G ² , groups represented by the formulas (g-1) to (g-10) are mentioned, and groups represented by the formula (g-1) are preferable, and 1,4-cyclohexylene The group is more preferable, and the trans-1,4-cyclohexylene group is particularly preferable.

The following formula (1-A) and formula (1-B)

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

Specific examples of the compound (1) include the compounds shown in Tables 1 to 2 below.

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

In Table 1, the compound (x ′) is a group represented by Ar, a group represented by formula (ar-78), a group represented by Ar, a group represented by formula (ar-79), or a group represented by Ar represented by formula (ar-78) It means any one of the mixture of the group compound represented by) and the group compound represented by Formula (ar-79).

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

Representative examples of the compounds listed in Table 1 are shown below.

The method for producing compound (A) will be described below using compound (1) as an example.

Compound (1) is a known organic synthesis reaction (e.g., condensation reaction, esterification reaction, Williamson reaction, Ullman reaction) described in Methoden der Organischen Chemie, Organic Reactions, Organic Syntheses, Comprehensive Organic Synthesis, New Experimental Chemistry Course, etc. Reaction, Vitech reaction, shift base production reaction, benzylation reaction, sonogashira reaction, Suzuki-Miyaura reaction, Negishi reaction, Kumada reaction, Hiyama reaction, Buchwald-Heartwig reaction, Plidel Kraft reaction, Heck reaction, Aldol reaction etc.) can be manufactured by appropriately combining according to the structure.

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

In the formula, Ar represents the same meaning as described above and the compound represented by 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 described above) By reacting the compound represented by formula (1-3)

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

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

As specific examples of the esterifying agent, 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-yloxytripyrrolidinophosphoniumhexafluorophosphate, 1H-benzo Triazole-1-yloxytris (dimethylamino) phosphoniumhexafluorophosphate, N, N, N ', N'-tetramethyl-O- (N-succinimidyl) uroniumtetrafluoro Late, N- (1,2,2,2-tetrachloroethoxycarbonyloxy) succinimide, N-carbobenzoxysuccinimide, 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, pentachloro trichloroacetate And phenyl esters.

The compound represented by the formula (1-2) and the compound represented by the formula (1-4) may be reacted after being converted to the corresponding acid chloride.

The optical film of the present invention is obtained by polymerizing compound (A). One type of compound (A) may be polymerized, or two or more types of compound (A) may be polymerized. Moreover, you may polymerize the liquid crystal compound (hereinafter abbreviated as a liquid crystal compound) which has a polymerizable group other than compound (A) and compound (A).

As a liquid crystal compound, three pieces of "molecular structure and liquid crystal properties" of the liquid crystal handbook (edited by the liquid crystal edition editing committee, published by Maruzen Corporation on October 30, 2000), 3.2 "non-chiral rod-like liquid crystal molecules" and 3.3 "chiral Among the compounds described in "Bar-like Liquid Crystal Molecules", compounds having a polymerizable group can be mentioned.

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

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

(Wherein, A ¹¹ represents an aromatic hydrocarbon group, an alicyclic hydrocarbon group or a heterocyclic group, the aromatic hydrocarbon group, an alicyclic hydrocarbon group and a heterocyclic group is a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms 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

Or a single bond, R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms, and R ¹⁴ and R ¹⁵ may combine 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, an alkyl group having 1 to 13 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, a fluoroalkyl group having 1 to 13 carbon atoms, an N-alkylamino group having 1 to 13 carbon atoms, a cyano group, or a nitro group, or It represents a polymerizable group bonded through 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. and t (representing an integer of 1 to 5) (hereinafter abbreviated as compound (4)).

The polymerizable group in the formula (4) may be any group that can be polymerized with the compound (A), and may be a vinyl group, vinyloxy group, p-stilbene group, acryloyl group, acryloyloxy group, or metacroyl group, Metacroyloxy 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, etc. Can be lifted. Among them, a radical polymerizable group or a cationic polymerizable group is preferable in view of being suitable for photopolymerization, and an acryloyloxy group, a metacroyloxy group, or a vinyloxy group is preferable in that it is easy to handle and easy to manufacture a liquid crystal compound. .

The aromatic hydrocarbon group, alicyclic hydrocarbon group and heterocyclic group of A ¹¹ preferably have 3 to 18 carbon atoms, more preferably 5 to 12 carbon atoms, and particularly preferably 5 or 6 carbon atoms.

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

(In the formula, P ¹¹ , E ¹¹ , B ¹¹ , A ¹¹ , B ¹² and t have the same meaning as above, E ¹² represents an alkylene group having 1 to 12 carbon atoms, and the alkylene group has 1 to 6 carbon atoms. It may be substituted with 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, 1 carbon atom; It represents an alkoxy group of 13 to 13, a fluoroalkyl group of 1 to 13 carbon atoms, an N-alkylamino group of 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.

(Wherein, A ¹² to A ¹⁵ each independently represents an aromatic hydrocarbon group, an alicyclic hydrocarbon group or a heterocyclic group, the aromatic hydrocarbon group, an alicyclic hydrocarbon group and a heterocyclic group is a halogen atom, an alkyl group having 1 to 6 carbon atoms, It may be substituted with at least one selected from the group consisting of an alkoxy group having 1 to 6 carbon atoms, an N-alkylamino group having 1 to 6 carbon atoms, a nitro group, a cyano group, and a mercapto group, wherein B ¹³ to B ¹⁶ are each independently

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

The compounds represented by the formulas (4-1), (4-2), (1), (II), (III), (IV) and (V) are P ¹¹ and E ¹¹ It is preferable to select P ¹¹ , E ¹¹ , P ¹² and E ¹² such that the bond between and the bond between P ¹² and E ¹² is an ether bond or an ester bond.

Specific examples of the compound (4) include the following formulas (I-1) to (I-5), formulas (II-1) to (II-6), and formulas (III-1) to (III-) And compounds represented by formulas (IV-1) to (IV-14) and (V-1) to (V-5). In the following formula, k represents the integer of 1-11. The following liquid crystal compound is preferable from the viewpoint of availability, such as commercially available, which is easy to synthesize.

When polymerizing the compound (A) and the liquid crystal compound, the amount of the liquid crystal compound used is usually 90 parts by weight or less when the total amount of the compound (A) and the liquid crystal compound is 100 parts by weight.

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

As the polymerization initiator, a photopolymerization initiator is preferable. Examples of the photopolymerization initiator include benzoin compounds, benzophenone compounds, benzyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, iodonium salts, and sulfonium salts. As specific examples of such a photopolymerization initiator, Irgacure 907 (IRGACURE 907; manufactured by Chiba Japan Co., Ltd.), Irgacure 184 (IRGACURE 184; manufactured by Chiba Japan Co., Ltd.), Irgacure 651 (IRGACURE 651; Chiba Japan) IRGACURE 819 (manufactured by IRGACURE 819; manufactured by Chiba Japan), Irgacure 250 (IRGACURE 250; manufactured by Chiba Japan), Irgacure 369 (IRGACURE 369; manufactured by Chiba Japan), Sei SEIKUOL BZ (manufactured by Seiko Chemicals Co., Ltd.), SEIKUOL Z (manufactured by Seiko Chemicals Co., Ltd.), Seikool BEE (SEIKUOL BEE; manufactured by Seiko Chemicals Co., Ltd.), Kayakure BP100 (KAYACURE BP100; manufactured by Nippon Gunpowder Co., Ltd.) , Kayakuure UVI-6992 (KAYACURE UVI-6992; manufactured by Dow), Adeka Optomer SP-152 (ADEKA OPTOMER SP-152; manufactured by ADEKA Co., Ltd.), Adeka Optomer SP-170 (ADEKA OPTOMER SP-170; ADEKA Co., Ltd.) There.

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

The wavelength dispersion property of the optical film of the present invention can be arbitrarily determined by adjusting the content of the structural unit derived from the compound (A) in the optical film. When the content of the structural unit derived from the compound (A) in the optical film increases, the resulting optical film exhibits flatter wavelength dispersion properties, and furthermore, reverse wavelength dispersion properties.

In order to obtain the optical film exhibiting the required wavelength dispersion characteristics, for example, it may be as follows. First, about 2 to 5 types of compositions containing a liquid crystal compound and a compound (A) having different structural units derived from the compound (A) are prepared, and optical films of the same film thickness are prepared using the respective compositions. . The phase difference value of the obtained optical film is measured, and the correlation between the content of the structural unit derived from the compound (A) and the phase difference value of the optical film is obtained. Based on the obtained correlation, the content of the structural unit derived from the compound (A) necessary for the optical film at the film thickness to exhibit the desired retardation value is determined, and the liquid crystal compound and the compound (A) are brought to the content. A composition containing is prepared and polymerized.

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

First, a composition containing compound (A) is prepared by mixing compound (A) with the liquid crystal compound and the polymerization initiator. When forming the obtained composition, it is preferable to prepare a solution containing the compound (A) using an organic solvent when preparing the composition, since it can be easily formed. Moreover, additives, such as a polymerization inhibitor, a photosensitizer, and a leveling agent, may be used as needed.

As a polymerization inhibitor, a hydroquinone compound having a substituent such as hydroquinone or an alkyl ether, a catechol compound having a substituent such as an alkyl ether such as butyl catechol, a pyrogallol compound, 2,2,6,6-tetramethyl- And radical supplements such as 1-piperidinyloxy radicals, thiophenol compounds, β-naphthylamine compounds, and β-naphthol compounds.

By using a polymerization inhibitor, control of the polymerization reaction is facilitated, and stability of the obtained optical film can be improved. The amount of the polymerization inhibitor used is usually 0.1 parts by weight to 30 parts by weight, and preferably 0.5 parts by weight to 10 parts by weight based on 100 parts by weight of the liquid crystal compound and the compound (A) in total. Within the above range, the compound (A) can be polymerized without disturbing the alignment of the 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, and rubrene.

By using a photosensitizer, a polymerization reaction can be performed with high sensitivity. The amount of the photosensitizer used is usually 0.1 parts by weight to 30 parts by weight, and preferably 0.5 parts by weight to 10 parts by weight based on 100 parts by weight of the liquid crystal compound and the compound (A) in total. Within the above range, the compound (A) can be polymerized without disturbing the alignment of the liquid crystal compound.

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

By using a leveling agent, the optical film can be smoothed. In addition, in the manufacturing process of the optical film, the fluidity of the composition containing the compound (A) may be controlled, or the crosslinking density of the obtained optical film may be adjusted. The amount of the leveling agent used is usually 0.1 parts by weight to 30 parts by weight, and preferably 0.5 parts by weight to 10 parts by weight based on 100 parts by weight of the liquid crystal compound and the compound (A) in total. Within the above range, the compound (A) can be polymerized without disturbing the alignment of the liquid crystal compound.

As the organic solvent, an organic solvent capable of dissolving the compound (A), a liquid crystal compound, or the like 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 alone or in combination of two or more. In particular, the composition containing the compound (A) and the liquid crystal compound is excellent in compatibility, and can be dissolved in an alcohol solvent, an ester solvent, a ketone solvent, a non-chlorine-based aliphatic hydrocarbon solvent, and a non-chlorine-based aromatic hydrocarbon solvent, and thus a halogenated hydrocarbon. It 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 about 0.1 to 7 Pa · s, in consideration of the coating properties of the composition.

In addition, the concentration of the solid content in the solution containing the compound (A) is usually 5 to 50% by weight. When the concentration of the solid content is 5% or more, the optical film does not become too thin, and tends to provide a birefringence required for optical compensation of the liquid crystal panel. Moreover, when the concentration of the solid content is 50% or less, the viscosity of the composition is not excessively small, and unevenness in the film thickness of the optical film tends to be less likely, which is preferable.

An optical film can be obtained by applying a solution containing such a compound (A) on a supporting substrate, drying and polymerizing it.

When a solution containing compound (A) is applied on a supporting substrate and dried, an unpolymerized film is obtained. When the unpolymerized film exhibits a liquid crystal phase such as a nematic phase, the resulting optical film exhibits birefringence due to mono-domain orientation. The unpolymerized film is usually oriented at about 0 to 120 ° C, preferably at 25 to 80 ° C, so a supporting substrate that does not necessarily have sufficient heat resistance can be used. In addition, since the unpolymerized film is not crystallized even after being cooled to about 10 to 30 ° C after orientation, handling is easy.

The film thickness can be prepared by appropriately adjusting the concentration of the compound (A) in the solution containing the compound (A) or the amount of the solution applied to the supporting substrate. In the case of a solution in which the amount of the compound (A) is constant, the phase difference value (retardation value, Re (λ)) of the obtained optical film is expressed by the formula (7)

Re (λ) = d × Δn (λ) (7)

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

Extrusion coating method, direct gravure coating method, reverse gravure coating method, CAP coating method, die coating method etc. are mentioned as a coating method to a support base material. The coating method using a coater, such as a dip coater, a bar coater, and a spin coater, is also mentioned.

Examples of the supporting substrate include glass, plastic sheets, plastic films, and translucent films. Examples of the translucent film include polyolefin films such as polyethylene, polypropylene, and norbornene polymers; 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.

Even in a process in which the strength of the optical film is required, such as an adhesion process of an optical film, a transport process, and a storage process, by using a supporting base material, there is no damage to the optical film and can be handled easily.

After forming the alignment film on the supporting substrate, it is preferable to apply a solution containing the compound (A) on the alignment film. It is preferable that the alignment film has solvent resistance that does not dissolve in the solution upon application of the solution containing the compound (A). Moreover, it is preferable that an alignment film has heat resistance in the heat processing for removal of a solvent and alignment of liquid crystal molecules. Moreover, it is preferable that it is an alignment film in which peeling due to friction or the like does not occur during rubbing. As such an alignment film, it is preferable that it consists of a polymer or a composition containing a polymer.

Examples of the polymer include polyamide or gelatin compound having an amide bond in the molecule, polyimide having an imide bond in the molecule, and polyamic acid, a hydrolyzate thereof, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, polyoxa And polymers such as sol, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid, or polyacrylic acid ester. These polymers may be used alone or in combination of two or more. 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, anionic 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. The solvent is 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; Aromatic hydrocarbon solvents such as toluene, xylene, and chlorobenzene, and nitrile solvents such as 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 alone or in combination of two or more.

You may form an alignment film using a commercially available alignment film material as it is. Commercially available alignment film materials include Sunever (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, since it is not necessary to perform refractive index control by stretching, the in-plane non-uniformity of birefringence is reduced, and a large optical film capable of supporting a large-sized flat panel display (FPD) on a supporting substrate can be provided. You can.

As a method of forming an alignment film on a support substrate, a commercially available alignment film material or a compound serving as a material for the alignment film is applied as a solution, and thereafter, a method of annealing is exemplified.

The thickness of the alignment film is usually 10 nm to 10000 nm, and preferably 10 nm to 1000 nm. With the above range, the compound (A) or the like can be oriented at a desired angle on the alignment film. If necessary, the alignment film may be subjected to a rubbing treatment, or the alignment film may be subjected to polarized UV irradiation.

As a method of rubbing an alignment film, a method of bringing a rubbing roll wound with a rotating rubbing cloth into contact with an alignment film carried on a stage and conveyed is exemplified.

The method of laminating an unpolymerized film on an alignment film laminated on such a supporting substrate can reduce production costs compared to a method of manufacturing a liquid crystal cell and injecting a liquid crystal compound into the liquid crystal cell, and also by a 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-forming property to remove most solvents before performing a polymerization reaction.

Examples of the method for removing the solvent include methods such as natural drying, ventilation drying, and vacuum drying. The temperature at the time of removing the solvent by heating is preferably 10 to 120 ° C, and more preferably 25 to 80 ° C. The heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes. If the heating temperature and the heating time are within the above ranges, a supporting substrate that does not necessarily have sufficient heat resistance can be used as the supporting substrate.

By polymerizing and curing the obtained unpolymerized film, a film having a fixed orientation of compound (A), that is, a polymerized film is obtained. An optical film having a small refractive index change in the plane direction of the film and a large refractive index change in the normal direction of the film is obtained.

The method of polymerizing the unpolymerized film may be appropriately determined depending on the type of the liquid crystal compound and the compound (A). If the polymerizable group in the compound (A) and the liquid crystal compound is a photopolymerizable group, a photopolymerization method is used, and if the polymerizable group is a thermal polymerizable group, a thermal polymerization method is used. According to the photopolymerization method, the compound (A) and the liquid crystal having a photopolymerizable polymerizable group can be polymerized at a low temperature, and the heat resistance of the supporting substrate is widened, and industrial production is easy. It is preferred to use compounds. Further, from the viewpoint of film-forming properties, a photopolymerization method is preferred. The photopolymerization reaction is performed by irradiating an unpolymerized film with visible light, ultraviolet light, or laser light. From the viewpoint of handling, ultraviolet light is particularly preferred. Light irradiation may be performed at a temperature at which the compound (A) takes a liquid crystal phase. At this time, the polymerized film may be patterned by masking or the like.

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

The optical film of the present invention is a thin film in comparison with a stretched film that gives a retardation by stretching a polymer.

By peeling the supporting substrate, a film in which an alignment film and an optical film are laminated is obtained. Moreover, an optical film can be obtained by peeling an alignment film.

The optical film thus obtained has excellent transparency and is used as a film for various displays. The thickness of the optical film is different depending on the retardation value of the optical film, as described above. The thickness is preferably 0.1 to 10 μm, and more preferably 0.5 to 3 μm in view of reducing optical elasticity.

The retardation value of the optical film exhibiting birefringence is usually about 50 to 500 nm, and preferably 100 to 300 nm.

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

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

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

The optical film of the present invention can also be used for an antireflection film such as an antireflection (AR) film, a polarizing film, a retardation film, an elliptical polarizing film, a viewing angle enlargement film, or an optical compensation film for compensating the viewing angle of a transmissive liquid crystal display.

Although the optical film of this invention shows excellent optical characteristics even if it is 1 sheet, you may use it by laminating multiple sheets. Moreover, you may use it in combination with another film. Specific examples in combination with other films include an elliptical polarizing plate in which the optical film of the present invention is bonded to a polarizing film, and a broadband circular polarizing plate in which the optical film of the present invention is further bonded to the elliptical polarizing plate as a broadband λ / 4 plate. You can.

Since the optical film of the present invention can be formed by applying and polymerizing on a supporting substrate or an alignment film, as shown in Fig. 1, a broadband, for example, λ / 4, An optical film can be formed.

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

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

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

Subsequently, on the obtained alignment film 3, a solution containing the compound (A) whose content of the compound (A) was adjusted so that the obtained optical film had desired wavelength dispersion characteristics was prepared, and the thickness to be a desired retardation value was obtained. The solution is applied as much as possible to form the optical film 2.

By using the color filter 1, a thinner liquid crystal display device can be manufactured. As an example, a schematic diagram showing a liquid crystal display device 5 according to the present invention is shown in FIG. 2.

In the liquid crystal display device 5 shown in FIG. 2, on the polarizing plate 6, the substrate 7 facing the backlight, such as a glass substrate, is fixed via adhesive. The optical film 2 'is formed on the color filter layer 4' manufactured on the substrate 7 via 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. On the backlight side, a substrate 11 such as a glass substrate is fixed to the polarizing plate 10 through an adhesive. In addition, a thin film transistor (TFT) and an insulating layer 12 for actively driving the liquid crystal layer are formed on the substrate 11, and further, a transparent electrode 13 made of Ag, Al or ITO (Indium Tin Oxide) 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 in which the number of sheets of the optical film is less than that of a conventional liquid crystal display device, so that a thinner liquid crystal display device can be manufactured.

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 formed by crystallizing by depositing and patterning a gate electrode made of Mo or MoW, a gate insulating film and amorphous silicon on borosilicate glass, and annealing amorphous silicon with an excimer laser is then formed. , TFTs of n-channel and p-channel can be formed by doping P, B, etc. in the regions on both sides of the gate electrode. Further, by forming the insulating layer 12 made of SiO ₂ , a substrate on the backlight side is obtained. Further, by sputtering ITO on the backlight-side substrate 11, the transparent electrode 13 for a full transmission type display device can be laminated on the backlight-side substrate. Further, by using Ag, Al or the like instead of ITO, a reflective electrode 13 'for a total reflection type display device is obtained. Further, by appropriately combining a reflective electrode and a transparent electrode, an electrode on the backlight side for a semi-transmissive liquid crystal display device is also obtained.

On the other hand, a color filter layer 4 'is formed on the opposing substrate 7. By using R, G, and B color filters together, a full color liquid crystal display device is also obtained. Next, an alignment film 3 'is formed by applying and rubbing an oriented polymer on the color filter layer 4'. A composition containing the compound (A) according to the present invention is applied onto the alignment film 3 ', and heated to a temperature range in which the liquid crystal phase is taken, and polymerized by ultraviolet irradiation to form the optical film 2'. After forming the optical film, the counter electrode 8 can be formed by sputtering ITO. Further, a liquid crystal display device 5 can be manufactured by forming an alignment film on the counter electrode to form a liquid crystal phase 9 and finally assembling the substrate on the backlight side.

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

Next, the polarizing plate of this invention and FPD provided with the polarizing plate are demonstrated.

The polarizing plate of this invention contains the optical film and polarizing film of this invention, and is normally obtained by laminating | stacking the optical film and polarizing film of this invention. Specifically, it is obtained by directly attaching a film having a polarizing function, that is, one side or both sides of the polarizing film, or using the adhesive to the optical film of the present invention. In this specification, "adhesive" means both an adhesive and an adhesive. Hereinafter, the polarizing plate of this invention is demonstrated using FIGS. 3-5.

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

In the polarizing plate 30a shown in Fig. 3 (a), the laminate 14 and the polarizing film 15 are directly adhered to each other, and the laminate 14 includes a supporting substrate 16, an alignment film 17, and an optical film ( 18). The polarizing plate 30a is laminated in the order of the supporting substrate 16, the alignment film 17, the optical film 18, and the polarizing film 15.

In the polarizing plate 30b shown in Fig. 3 (b), the laminate 14 and the polarizing film 15 are bonded through the adhesive layer 19.

In the polarizing plate 30c shown in Fig. 3 (c), the laminate 14 and the laminate 14 'are directly adhered, and the laminate 14' and the polarizing film 15 are directly adhered.

In the polarizing plate 30d shown in Fig. 3 (d), the laminated body 14 and the laminated body 14 'are adhered through the adhesive layer 19, and further, the polarizing film 15 on the laminated body 14' This is directly adhered.

In the polarizing plate 30e shown in Fig. 3 (e), the laminate 14 and the laminate 14 'are adhered through the adhesive layer 19, and the laminate 14' and the polarizing film 15 are attached. It has a structure adhered through the adhesive layer 19 '.

Instead of the laminate 14, an optical film 18 from which the support substrate 16 and the alignment film 17 are peeled from the laminate 14 may be used, and the support substrate 16 is peeled from the laminate 14 You may use the film which consists of one alignment film 17 and the optical film 18. Instead of the layered product 14 ', an optical film 18' obtained by peeling the support substrate 16 'and the alignment film 17' from the layered product 14 'may be used, and it is supported from the layered product 14'. You may use the film which consists of the alignment film 17 'which peeled the base material 16' and the optical film 18 '.

The polarizing plate of this invention may laminate | stack multiple laminated bodies, and these multiple laminated bodies may be all the same or different.

The polarizing film 15 may be a film having a polarizing function, specifically, a film stretched by adsorbing iodine or a dichroic dye to a polyvinyl alcohol-based film, a stretched film of a polyvinyl alcohol-based film, and iodine or a dichroic dye. And adsorbed films.

It is preferable that the adhesive used for the adhesive layer 19 and the adhesive layer 19 'is an adhesive with high transparency and excellent heat resistance. Examples of such adhesives include acrylic adhesives, epoxy adhesives, and urethane adhesives.

The flat panel display device of the present invention is provided with the optical film of the present invention. Specifically, the liquid crystal display device provided with the adhesive product of the polarizing plate of the present invention and the liquid crystal panel, or the polarizing plate of the present invention and the light emitting layer And an organic EL display device having a bonded organic EL panel.

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 an 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 product 21 is formed by bonding the polarizing plate 30 of the present invention and the liquid crystal panel 20 through the adhesive layer 22. By applying a voltage to the liquid crystal panel 20 using an electrode (not shown), the liquid crystal molecules are driven, and black and white display can be performed.

5 is a schematic diagram showing an organic EL panel 23 of the organic EL display device of the present invention. The organic EL panel 23 is formed by bonding the polarizing film 30 of the present invention and the light emitting layer 24 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 the present invention is capable of constant polarization conversion in a wide wavelength range.

1 is a schematic diagram showing a color filter 1 of the present invention.
2 is a schematic diagram showing a liquid crystal display device 5 of the present invention.
3 is a schematic view showing a polarizing plate 30 of the present invention.
4 is a schematic view showing an 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 diagram showing an organic EL panel 23 of the organic EL display device of the present invention.
Explanation of reference numerals for main parts of the drawing
1, 1 ': Color filter
2, 2 ': Optical film
3, 3 ': alignment film
4, 4 ': Color filter layer
5: liquid crystal display device
6, 10: polarizing plate
7, 11: substrate
8: counter electrode
9: liquid crystal layer
12: TFT, insulating layer
13: transparent electrode
13 ': reflective electrode
30, 30a, 30b, 30c, 30d, 30e: polarizing plate
14, 14 ': laminate
15: polarizing film
16, 16 ': Support
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: emitting layer

Hereinafter, the present invention will be described in more detail by examples, but the present invention is not limited to these examples.

Example 1-1

(1) According to the method described in JP 2004-262884 A, hydroxyquinone and dihydropyran were reacted to obtain a compound represented by the formula (a).

(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 resulting mixture was reacted at 90 ° C under a nitrogen atmosphere, and then further reacted at 100 ° C. The resulting reaction mixture was allowed to cool to room temperature. After stirring by adding methyl isobutyl ketone to the reaction mixture, the organic layer and the aqueous layer were separated. The obtained organic layer was washed with pure water, an aqueous sodium hydroxide solution, and again with pure water. Anhydrous sodium sulfate was added to the organic layer after washing, followed by dehydration treatment. After the sodium sulfate was removed by filtration, the obtained filtrate was concentrated under reduced pressure. Methanol was added to the obtained residue, and the precipitated precipitate was taken out by filtration. The extracted precipitate was dried in vacuo to obtain 126 g of the compound represented by the formula (b). Yield: 91% (based on 6-bromohexanol).

(3) 126 g of the compound represented by the 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 resulting solution was ice-cooled, and 58.1 g of acryloyl chloride was added dropwise under a nitrogen atmosphere, and reacted at room temperature. Pure water was added and stirred to the obtained reaction mixture. The organic layer and the water layer were separated, and the obtained organic layer was washed with hydrochloric acid water, saturated aqueous sodium carbonate solution, and further pure water. Anhydrous sodium sulfate was added to the organic layer after washing and 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 obtained compound represented by the formula (c), 200 ml of tetrahydrofuran was further added. After adding hydrochloric acid to the obtained solution, it was reacted under nitrogen atmosphere at 60 ° C. Saturated brine was added to the reaction mixture, stirred, and separated into an organic layer and an aqueous layer. Anhydrous sodium sulfate was added to the obtained organic layer, followed by dehydration treatment. After the sodium sulfate was removed by filtration, the obtained filtrate was concentrated under reduced pressure. Hexane was added to the obtained concentrate, and the mixture was stirred under ice cooling. The precipitated solid was taken out by filtration. The extracted solid was dried in vacuo to obtain 90 g of a compound represented by the formula (d). Yield: 79% (based on compound represented by formula (c)).

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

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

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

(6) 56.8 g of the compound represented by formula (d) obtained in (4) above, 2.65 g of dimethylaminopyridine, 50 g of trans-1,4-cyclohexanedicarboxylic acid monoethoxymethyl ester and 300 ml of chloroform were mixed. . The resulting mixture was ice-cooled under a nitrogen atmosphere, and a solution consisting of 48.79 g of dicyclohexylcarbodiimide and 50 ml of chloroform was added dropwise. After completion of dropping, the resulting mixture was stirred at room temperature to react. After completion of the reaction, 200 ml of chloroform and 200 ml of heptane were added to the reaction mixture. The resulting mixture was filtered to remove insolubles. The obtained filtrate was washed with 2N hydrochloric acid. The obtained mixture was filtered to remove insoluble matters, and then dried over anhydrous sodium sulfate. After removing sodium sulfate by filtration, the obtained filtrate was concentrated. The obtained solid was dried in vacuo to obtain 100 g of a 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 reacted by stirring at 50 ° C under a nitrogen atmosphere. After completion of the reaction, 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 precipitated precipitate was taken out by filtration. The extracted precipitate was washed with pure water and dried in vacuo. The obtained powder was dissolved in chloroform, and the obtained solution was passed through silica gel, and then filtered. The filtrate was mixed with 400 ml of chloroform, and the obtained 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 extracted solid was dried under vacuum to obtain 64.1 g of a compound represented by the formula (e). Yield: 76% (based on compound represented by formula (d)).

Example 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. to react. After completion of the reaction, the reaction mixture was cooled and water was added. The precipitated precipitate was taken out by filtration. The extracted precipitate was washed with water and hexane to obtain 8.7 g of a compound represented by the formula (ii-a). Yield: 89% (based on 4,7-dimethoxy-2-phenylbenzothiazole).

Example 1-3

(1) 2.55 g of the compound represented by the formula (ii-a), 9.67 g of the compound represented by the formula (e), 0.28 g of dimethylaminopyridine and 50 ml of chloroform were mixed. To the obtained mixture, 40 ml of a chloroform solution containing 5.31 g of dicyclohexylcarbodiimide was added dropwise under ice cooling. The resulting mixture was stirred to react. After completion of the reaction, 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 concentrated residue and ice-cooled. The precipitated precipitate was taken out by filtration, washed with heptane, and then dried in vacuo to obtain 6.1 g of the compound represented by the formula (ii-1). Yield: 56% (based on compound represented by formula (ii-a)).

As a result of conducting the phase transition temperature of the obtained compound represented by formula (ii-1) by texture observation with a polarization microscope, the compound represented by formula (ii-1) has a smectic phase from 96 ° C to 115 ° C at elevated temperature. It showed that it showed a nematic phase from 115 degreeC to 226 degreeC, and it showed the nematic phase from 226 degreeC to 50 degreeC at the time of temperature fall.

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 stirred at 80 ° C. Further, 94.4 g of benzyl bromide was added and stirred to react. The resulting reaction mixture was allowed to cool and poured into ice. The precipitated precipitate was taken out by filtration. The extracted precipitate was washed with a water / methanol mixture 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 put on a silica gel column, and eluted with 500 ml of a chloroform / heptane mixed solution (volume ratio = 1/4). Subsequently, the compound represented by the formula (f) was eluted with a chloroform / heptane mixed solution (volume ratio = 1/2). The obtained solution containing the compound represented by formula (f) was concentrated to obtain 63 g of compound represented by formula (f). 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 resulting mixture was stirred to react. The reaction mixture was filtered. The obtained filtrate was dried, and then concentrated under reduced pressure. Ethyl acetate was added to the obtained residue, and the obtained solution was concentrated under reduced pressure. After adding methanol to the obtained residue, it was ice-cooled. The precipitated precipitate was taken out by filtration and dried under vacuum to obtain 11.4 g of a compound represented by formula (ii-b). Yield: 78% (based on compound represented by formula (ii-a)).

(3) 11.4 g of the compound represented by the obtained formula (ii-b), 1.14 g of 10% palladium-carbon (55% hydrous), 0.1 ml of acetic acid and 200 ml of tetrahydrofuran were mixed. After removing oxygen from the mixture obtained using nitrogen gas, the mixture was reacted by reducing the pressure and stirring under a hydrogen atmosphere. 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 under vacuum to obtain 4.7 g of a compound represented by formula (ii-c). Yield: 55% (based on compound represented by formula (ii-b)).

(4) 4.41 g of the compound represented by the obtained formula (ii-c), 4.65 g of the compound represented by the formula (d), 0.22 g of dimethylaminopyridine and 30 ml of chloroform were mixed. To the obtained mixture, 20 ml of a chloroform solution containing 4.36 g of dicyclohexylcarbodiimide was added dropwise under ice cooling. The resulting mixture was stirred to react. After completion of the reaction, the reaction mixture was filtered. The obtained filtrate was dried, and then concentrated under reduced pressure. Ethyl acetate was added to the concentrated residue to dissolve. The obtained solution was concentrated under reduced pressure. Methanol was added to the concentrated residue, followed by ice cooling. The precipitated precipitate was taken out by filtration and dried under vacuum to obtain 4.80 g of a compound represented by formula (ii-1). Yield: 58% (based on 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 resulting mixture was reacted by stirring at 60 ° C. 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 washed with hexane to obtain 139.6 g of a compound represented by formula (VII-d).

(2) 90.0 g of the compound represented by the obtained formula (VII-d), 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetan-2,4-disulfide 65.0 g and 3132 g of toluene were mixed. The obtained mixture was stirred and reacted at 80 ° C. After completion of the reaction, the obtained reaction mixture was cooled and 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 a compound represented by formula (VII-e). Yield: 99.5% (based on compound represented by formula (VII-d)).

(3) 93.8 g of a compound represented by the obtained formula (VII-e), 315 g of sodium hydroxide and 5250 g of water were mixed. The resulting mixture was stirred under ice cooling, and an aqueous solution containing 174.3 g of potassium ferricyanide was added under ice cooling. The resulting mixture was stirred to react. After completion of the reaction, the precipitated solid was taken out by filtration. The taken-out solid was washed with cold water and hexane to obtain 88.2 g of a compound represented by formula (VII-f). Yield: 95% (based on compound represented by 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 the obtained reaction mixture was cooled, water was added. The precipitated precipitate was washed with water, hexane and chloroform to obtain 7.7 g of a compound represented by formula (VII-a). Yield: 74% (based on compound represented by formula (VII-f)).

Example 3-2

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

Example 4-1

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

Example 4-2

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

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

Example 5-1

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

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

(3) In Example 3-1 (3), Example 3-, 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 Formula (VII-d). Yield: 52% (based on compound represented by 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 resulting mixture was ice-cooled, and 100 g of boron tribromide was added. The obtained mixture was stirred and reacted at 70 ° C. After completion of the reaction, the reaction mixture was cooled to room temperature. The reaction mixture was further ice-cooled and 1588 g of water was added. The precipitated precipitate was taken out by filtration, washed with water and chloroform to obtain 16.5 g of a compound represented by the formula (VII-a). Yield: 86% (based on compound represented by formula (VII-d)).

Example 5-2

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

As a result of performing the phase transition temperature of the obtained compound represented by formula (VII-1) by texture observation with a polarization microscope, the compound represented by formula (VII-1) has a smectic phase from 160 ° C to 169 ° C at elevated temperature. It showed that it showed a nematic phase from 169 degreeC to 224 degreeC, and it showed that it showed a nematic phase from 224 degreeC to 154 degreeC at the time of temperature fall.

Example 6-1

(1) 43.0 g of 2,5-dimethoxyaniline, 59.7 g of triethylamine and 499.7 g of dehydrated chloroform were mixed. To the obtained mixture, 50.0 g of isonicotinoyl chloride hydrochloride was added. The resulting mixture was reacted by stirring at 60 ° C. After completion of the reaction, the reaction mixture was cooled 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 a compound represented by the formula (VII-b). Yield: 99% (based on 2,5-dimethoxyaniline).

(2) 70.0 g of the compound represented by the obtained formula (VII-b), 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetan-2,4-disulfide 65.8 g and 2436 g of toluene were mixed. The obtained mixture was stirred and reacted at 80 ° C. After completion of the reaction, the reaction mixture was cooled, then concentrated to obtain a compound represented by the formula (VII-c).

(3) The obtained compound represented by formula (VII-c), 333 g of sodium hydroxide and 5550 g of water were mixed, and the resulting mixture was stirred under ice cooling. An aqueous solution containing 184.3 g of potassium ferricyanide was added to the mixture under ice cooling, and the mixture was stirred and reacted. After completion of the reaction, 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 compound represented by 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 for reaction. After completion of the reaction, the reaction mixture was cooled. Water was added to the reaction mixture, and the precipitated precipitate was collected by filtration. The extracted precipitate was washed with water and chloroform to obtain 3.4 g of a compound represented by the formula (VII-a). Yield: 68% (based on compound represented by formula (VII-d)).

Example 6-2

2.24 g of the compound represented by the formula (VII-a) obtained in Example 6-1, 8.37 g of the compound represented by the formula (e), 0.24 g of dimethylaminopyridine and 50 ml of chloroform were mixed. To the obtained mixture, 30 ml of a chloroform solution containing 4.95 g of dicyclohexylcarbodiimide was added dropwise under ice cooling. The resulting mixture was stirred to react. After completion of the reaction, the reaction mixture was filtered. The obtained filtrate was dried, and then concentrated under reduced pressure. Ethyl acetate was added to the concentrated residue to dissolve. After the obtained solution was concentrated under reduced pressure, 200 ml of methanol was added to the concentrated residue and ice-cooled. The precipitated precipitate was taken out by filtration, washed with heptane and dried in vacuo to obtain 4.4 g of a compound represented by the formula (VII-1). Yield: 43% (based on 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 stirred at room temperature to react. After completion of the reaction, 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, 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) In Example 5-1, except for using the compound represented by Formula (VII'-b) obtained in (1) above, instead of the compound represented by Formula (VII-b), Example 5-1. It carried out similarly and obtained the compound represented by said formula (VIII'-a).

Example 7-2

In Example 5-2, in the same manner as in Example 5-2, except that the compound represented by Formula (VII'-a) obtained in (2) above was used instead of the compound represented by Formula (VII-a). The compound represented by the following formula (VII'-1) was obtained. Yield: 73% (based on compound represented by formula (VII'-a)).

As a result of conducting the phase transition temperature of the obtained compound represented by formula (VII'-1) by texture observation with a polarization microscope, the compound represented by formula (VII'-1) is smeared from 127 ° C to 154 ° C at elevated temperature. It was found that a tick phase was exhibited, a nematic phase was exhibited from 154 ° C to 217 ° C, and a nematic phase was exhibited from 217 ° C to 113 ° C at a temperature drop.

Example 8

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

Example 9

(1) In Example 5-1, it was carried out in the same manner as in Example 5-1, except that 2-thiophenecarbonyl chloride was used instead of 4-nitrobenzoyl chloride, and the following formula (VII-a) The compound represented by was obtained.

(2) In Example 5-2, in the same manner as 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). Then, a compound represented by the following formula (VII-1) was obtained. Yield: 84% (based on compound represented by formula (VII-a)).

As a result of performing the phase transition temperature of the obtained compound represented by formula (VII-1) by texture observation with a polarization microscope, the compound represented by formula (VII-1) has a smectic phase from 101 ° C to 106 ° C at elevated temperature. It showed that it showed a nematic phase from 106 degreeC to 180 degreeC or more, and showed a nematic phase up to 81 degreeC at the time of temperature fall, and crystallized.

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 chloride was added dropwise to the obtained mixture under ice cooling. The resulting 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 washed with hexane to obtain 82.1 g of a compound represented by the formula (xi-b). Yield: 91% (based on 2,5-dimethoxyaniline).

(2) 81 g of the compound represented by the obtained formula (xi-b), 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetan-2,4-disulfide 64.7 g and 500 g of toluene were mixed. The obtained mixture was stirred and reacted at 80 ° C. 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) A red viscous liquid containing the compound represented by the obtained formula (xi-c), 73.8 g of sodium hydroxide and 750 g of water were mixed, and the resulting mixture was stirred under ice cooling. To the mixture, an aqueous solution containing 257.8 g of potassium ferricyanide was added under ice cooling. The resulting mixture was stirred to react. After completion of the reaction, 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 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 the obtained reaction mixture was cooled, water was added. The precipitated precipitate was taken out by filtration and washed with water and hexane to obtain 36.4 g of the compound represented by the formula (xi-a).

Example 10-2

In Example 5-2, in the same manner as in Example 5-2, except that the compound represented by Formula (xi-a) obtained in Example 10-1 was used instead of the compound represented by Formula (VII-a). This was carried out to obtain a compound represented by the following formula (xi-1). Yield: 55% (based on compound represented by formula (xi-a)).

As a result of conducting the phase transition temperature of the obtained compound represented by formula (xi-1) by texture observation with a polarization microscope, the compound represented by formula (xi-1) has a smectic phase from 111 ° C to 125 ° C at elevated temperature. It showed that it showed a nematic phase from 125 degreeC to 242 degreeC, and showed the nematic phase from 242 degreeC to 82 degreeC at the time of temperature fall.

Example 11

(1) In Example 5-1, except that 4-nitrobenzoyl chloride was used instead of 3,5-dimethylbenzoyl chloride, it was carried out in the same manner as in Example 5-1, and the following formula (xvi-a) The compound represented by was obtained.

(2) In Example 5-2, in the same manner as 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). Then, a compound represented by the following formula (xvi-1) was obtained. Yield: 78% (based on compound represented by formula (xvi-a)).

As a result of performing the phase transition temperature of the obtained compound represented by the formula (xvi-1) by texture observation with a polarization microscope, the compound represented by the formula (xvi-1) exhibits a smectic phase from 91 ° C to 100 ° C at elevated temperature. It showed that it showed a nematic phase from 100 degreeC to 210 degreeC, and was thermally polymerized.

Example 12-1

(1) 11.0 g of 4,7-dimethoxy-2-phenylbenzothiazole and 288 g of glacial acetic acid were mixed. A solution obtained by mixing 4.0 g of concentrated nitric acid and 14.4 g of glacial acetic acid was added dropwise to the obtained mixture. The resulting mixture was stirred at room temperature to react. After completion of the reaction, 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 a compound represented by the formula (xvii-d). The compound represented by the formula (xvii-d) was a mixture of two isomers having different nitro group substitution positions. Yield: 92% (based on 4,7-dimethoxy-2-phenylbenzothiazole).

(2) In Example 5-1, except for using the compound represented by Formula (xvii-d) obtained in (1) above, instead of the compound represented by Formula (VII-d), Example 5-1 and It carried out similarly and obtained the compound represented by said Formula (xvii-a). The compound represented by the formula (xvii-a) was a mixture of two isomers having different nitro group substitution positions.

Example 12-2

In Example 5-2, in the same manner as in Example 5-2, except that the compound represented by Formula (xvii-a) obtained in Example 12-1 was used instead of the compound represented by Formula (VII-a). This was carried out to obtain a compound represented by the following formula (xvii-1). Yield: 53% (based on compound represented by formula (xvii-a)).

As a result of conducting the phase transition temperature of the obtained compound represented by formula (xvii-1) by texture observation with a polarization microscope, the compound represented by formula (xvii-1) has a smectic phase from 129 ° C to 148 ° C at elevated temperature. It showed that it showed a nematic phase from 148 degreeC to 186 degreeC, and showed the nematic phase from 186 degreeC to 105 degreeC at the time of temperature fall.

Example 13

(1) In Example 5-1, it was carried out in the same manner as in Example 5-1, except that pentafluorobenzoyl chloride was used instead of 4-nitrobenzoyl chloride, and represented by the following formula (xviii-a). The compound was obtained.

(2) In Example 5-2, in the same manner as 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). Then, a compound represented by the following formula (xviii-1) was obtained. Yield: 82% (based on compound represented by formula (xviii-a)).

As a result of performing the phase transition temperature of the obtained compound represented by the formula (xviii-1) by texture observation with a polarization microscope, the compound represented by the formula (xviii-1) has a smectic phase from 124 ° C to 166 ° C at elevated temperature. It showed that it showed a nematic phase from 166 degreeC to 199 degreeC, and showed a nematic phase from 199 degreeC to 79 degreeC at the time of temperature fall.

Example 14-1

(1) 58.7 g of 2,5-dimethoxyaniline, 77.5 g of triethylamine and 400 g of dehydrated chloroform were mixed. To the obtained mixture, 50.0 g of 2-furancarboxylic acid chloride was added under ice cooling. The resulting mixture was stirred at room temperature for 1 hour to react. The obtained reaction mixture was poured into water, and the obtained mixture was separated to separate an organic layer. 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 the compound represented by the obtained formula (xix-b), 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetan-2,4-disulfide 34.0 g and 120 g of toluene were mixed. The resulting mixture was stirred at 80 ° C for 8 hours to react. After the obtained reaction mixture was cooled, it was concentrated to obtain a red viscous liquid containing the compound represented by the formula (xix-c).

(3) The red viscous liquid containing the compound represented by the 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. To the mixture, an aqueous solution containing 145.3 g of potassium ferricyanide was added under ice cooling. The resulting mixture was stirred to react. 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 a compound represented by the formula (xix-d). Yield: 46% (based on 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 completion of the reaction, the reaction mixture was cooled and water was added. The precipitated precipitate was taken out by filtration, washed with water, hexane, and toluene, and 7.68 g of a compound represented by the formula (xix-a) was obtained. Yield: 96% (based on compound represented by formula (xix-d)).

Example 14-2

In Example 5-2, instead of the compound represented by Formula (VII-a), the same as Example 5-2 except that the compound represented by Formula (xix-a) obtained in Example 14-1 was used. This was carried out to obtain a compound represented by the following formula (xix-1). Yield: 78% (based on compound represented by formula (xix-a)).

As a result of performing the phase transition temperature of the obtained compound represented by the formula (xix-1) by texture observation with a polarization microscope, the compound represented by the formula (xix-1) has a smectic phase from 91 ° C to 130 ° C at elevated temperature. It showed that it showed a nematic phase from 130 degreeC to 180 degreeC or more, and showed a nematic phase up to 62 degreeC at the time of temperature fall, and crystallized.

Example 15

(1) In Example 5-1, except for 4-nitrobenzoyl chloride, 5-chloro-2-thiophenecarbonyl chloride was used in the same manner as in Example 5-1, and the following formula ( The compound represented by xx-a) was obtained.

(2) In Example 5-2, in the same manner as 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). Then, a compound represented by the following formula (xx-1) was obtained. Yield: 40% (based on compound represented by formula (xx-a)).

As a result of performing the phase transition temperature of the obtained compound represented by the formula (xx-1) by texture observation with a polarization microscope, the compound represented by the formula (xx-1) has a smectic phase from 110 ° C to 114 ° C at elevated temperature. It showed that it showed a nematic phase from 114 degreeC to 160 degreeC or more, and it showed that it showed a nematic phase up to 69 degreeC at the time of temperature fall, and crystallized.

Example 16-1

(1) 59.3 g of 2,5-dimethoxyaniline, 78.4 g of triethylamine and 500 g of dehydrated chloroform were mixed. 57.1 g of 3-thiazolecarboxylic acid chloride was added dropwise to the obtained mixture under ice cooling. The resulting mixture was stirred at room temperature to react. After completion of the reaction, 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 with 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 a compound represented by the formula (xxi-b). Yield: 75% (based on 2,5-dimethoxyaniline).

(2) 77 g of the compound represented by the obtained formula (xxi-b), 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetan-2,4-disulfide 61.3 g and 500 g of toluene were mixed. The obtained mixture was stirred and reacted at 80 ° C. 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 the obtained formula (xxi-c), 70.0 g of sodium hydroxide and 750 g of water were mixed, and the resulting mixture was stirred under ice cooling. An aqueous solution containing 245.0 g of potassium ferricyanide was added to the mixture under ice cooling. The resulting mixture was stirred to react. 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 a compound represented by the formula (xxi-d). Yield: 57% (based on compound represented by 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 precipitated precipitate was taken out by filtration, washed with water, hexane, and toluene to obtain 39.9 g of a compound represented by the formula (xxi-a). Yield: 100% (based on compound represented by formula (xxi-d)).

Example 16-2

In Example 5-2, instead of the compound represented by Formula (VII-a), the same as Example 5-2 except that the compound represented by Formula (xxi-a) obtained in Example 16-1 was used. This was carried out to obtain a compound represented by the following formula (xxi-1). Yield: 71% (based on compound represented by formula (xxi-a)).

As a result of performing the phase transition temperature of the obtained compound represented by the formula (xxi-1) by texture observation with a polarization microscope, the compound represented by the formula (xxi-1) has a nematic phase from 162 ° C to 246 ° C at elevated temperature. It was found that a nematic phase was exhibited from 246 ° C to 120 ° C 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. To the obtained mixture, 54.6 g of 4-methylsulfonylbenzoic acid chloride was added under ice cooling. The resulting mixture was stirred at room temperature to react. After completion of the reaction, 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). Further, it was washed with a heptane / ethyl acetate mixed solution (volume ratio = 3/1) to obtain 52.2 g of the compound represented by the formula (xxiii-b) as white crystals. Yield: 62% (based on 2,5-dimethoxyaniline).

(2) 54.5 g of a compound represented by the obtained formula (xxiii-b), 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetan-2,4-disulfide 64.7 g and 500 g of toluene were mixed, and the obtained mixture was stirred at 80 ° C for reaction. After 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) A red viscous liquid containing the compound represented by the obtained formula (xxiii-c), 37.2 g of sodium hydroxide and 380 g of water were mixed, and the resulting mixture was stirred under ice cooling. An aqueous solution containing 163.5 g of potassium ferricyanide was added to the mixture under ice cooling. The resulting mixture was stirred to react. After 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, and further recrystallized with toluene, represented by the formula (xxiii-d) 25.2 g of compound was obtained. Yield: 47% (based on 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 precipitated precipitate was washed with water, hexane, and toluene to obtain 7.8 g of the compound represented by the formula (xxiii-a). Yield: 85% (based on compound represented by formula (xxiii-d)).

Example 17-2

In Example 5-2, instead of the compound represented by Formula (VII-a), the same as Example 5-2 except that the compound represented by Formula (xxiii-a) obtained in Example 17-1 was used. This was carried out to obtain a compound represented by the following formula (xxiii-1). Yield: 46% (based on compound represented by formula (xxiii-a)).

As a result of performing the phase transition temperature of the obtained compound represented by the formula (xxiii-1) by texture observation with a polarization microscope, the compound represented by the formula (xxiii-1) is smectic from 137 ° C to 146 ° C at elevated temperature. It showed that it showed a nematic phase from 146 degreeC to 170 degreeC or more, and showed a nematic phase up to 78 degreeC at the time of temperature fall, and crystallized.

Example 18

(1) In Example 3-1, except for using 4-fluorobenzoyl chloride in place of 4-bromobenzoyl chloride, the same procedure as in Example 3-1 was carried out, and the following formula (xxiv-a) The compound represented by was obtained.

(2) In Example 5-2, except for using the compound represented by Formula (xxiv-a) obtained in (1) above, instead of the compound represented by Formula (VII-a), Example 5-2 and It carried out similarly and obtained the compound represented by following formula (xxiv-1). Yield: 54% (based on compound represented by formula (xxiv-a)).

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

Example 19

(1) In Example 3-1, except for using 4-trifluoromethylbenzoyl chloride in place of 4-bromobenzoyl chloride, the same procedure as in Example 3-1 was carried out to give the following formula (xxv- The compound represented by a) was obtained.

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

As a result of performing the phase transition temperature of the obtained compound represented by the formula (xxv-1) by texture observation with a polarization microscope, the compound represented by the formula (xxv-1) has a nematic phase from 135 ° C to 193 ° C at elevated temperature. It was found that the nematic phase was exhibited from 193 ° C to 114 ° C at the time of temperature drop.

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 a 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 the obtained reaction mixture was filtered, the obtained filtrate was concentrated under reduced pressure. Methanol was added to the concentrated residue and stirred. The precipitate was taken out by filtration and dried under vacuum to obtain 0.4 g of the compound represented by the formula (xxvi-a). Yield: 12% (based on 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. To the obtained mixture, 0.9 g of dicyclohexylcarbodiimide was dissolved in 4.7 g of chloroform, and the resulting solution was added dropwise at room temperature. The resulting mixture was stirred. After filtering the mixture, 12 g of 2N hydrochloric acid was added and 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 a compound represented by the formula (xxvi-1). Yield: 54% (based on 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 the obtained mixture was cooled to room temperature, 3.1 g of dicyclohexylcarbodiimide was dissolved in 9.4 g of tetrahydrofuran, and the resulting solution was added dropwise at room temperature. The resulting mixture was stirred. After the obtained reaction mixture was filtered, the obtained filtrate was concentrated under reduced pressure. Methanol was added to the concentrated residue and stirred. The precipitate was taken out by filtration, and then dried in vacuo to obtain 0.4 g of a compound represented by the formula (xxvii-a). Yield: 13% (based on 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. To the obtained mixture, 0.9 g of dicyclohexylcarbodiimide was dissolved in 4.6 g of chloroform, and the resulting solution was added dropwise 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 a compound represented by the formula (xxvii-1). Yield: 25% (based on compound represented by formula (xxvii-a)).

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

Example 22

In Example 5-2, except for using 1,4-dihydroxyanthraquinone in place of the compound represented by formula (VII-a), the same procedure as in Example 5-2 was carried out and the following formula (VII 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 obtained compound represented by formula (VII-1) by texture observation with a polarization microscope, the compound represented by formula (VII-1) has a smectic phase from 125 ° C to 128 ° C at elevated temperature. It showed that it showed a nematic phase from 128 degreeC to 200 degreeC or more, and showed a nematic phase up to 106 degreeC at the time of temperature fall, and crystallized.

Example 23

12.5 g of the compound represented by formula (e), 0.4 g of 4-dimethylaminopyridine, 2.9 g of 1,5-dihydroxyanthraquinone and 100 g of chloroform were mixed. To the obtained mixture, 9.3 g of dicyclohexylcarbodiimide was dissolved in 25 g of chloroform, and the resulting solution was added dropwise at room temperature. The resulting mixture was stirred to react. To the obtained reaction mixture, 124 g of 1N hydrochloric acid was added and stirred. The obtained mixture was filtered, and the obtained filtrate was separated to obtain an organic layer. The organic layer was concentrated and methanol was added to the residue. The obtained mixture was filtered, and solid matter was taken out. The obtained solid 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 formula (e), 0.4 g of 4-dimethylaminopyridine, 2.9 g of 1,2-dihydroxyanthraquinone and 100 g of chloroform were mixed. To the obtained mixture, 9.3 g of dicyclohexylcarbodiimide was dissolved in 25 g of chloroform, and the resulting solution was added dropwise at room temperature. The resulting mixture was stirred to react. To the obtained reaction mixture, 124 g of 1N hydrochloric acid was added and stirred. The obtained mixture was filtered, and the obtained filtrate was separated to obtain an organic layer. After the organic layer was concentrated, methanol was added to the residue. The obtained mixture was filtered, and solid matter was taken out. The obtained solid was dried to obtain 10.3 g of a compound represented by the following formula (xxix-1). Yield: 82% (based on 1,2-dihydroxyanthraquinone). As a result of heating the obtained mixture and checking the phase transition temperature, the liquid crystal phase was not observed and was dissolved at 105 ° C.

Example 25

(1) 23 g of trans-cinnamic acid, 75.5 g of 1H-benzotriazol-1-yloxytripyrrolidinophosphoniumhexafluorophosphate, 15.7 g of triethylamine, 1.9 g of dimethylaminopyridine and dehydrated N, N-dimethylacetamide 200 g were mixed. The obtained mixture was shaded while being ice-cooled and stirred. 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. After the organic layer was concentrated under reduced pressure, methanol was added to the obtained residue to crystallize. Crystals were taken out by filtration and dried in vacuo. The filtrate was allowed to stand overnight at room temperature. The precipitated crystal was taken out by filtration and dried under vacuum. 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 the compound represented by the obtained formula (xxxii-b), 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetan-2,4-disulfide 22.27 g and 500 g of toluene were mixed, and the obtained mixture was stirred and reacted at 80 ° C. After the obtained reaction mixture was cooled, it was concentrated to obtain a red viscous solid containing the compound represented by the formula (xxxii-c).

(3) Red viscous solid containing the compound represented by the obtained formula (xxxii-c), 25.4 g of sodium hydroxide and 750 g of water were mixed, and the obtained mixture was stirred under ice cooling. To the mixture, an aqueous solution containing 95.1 g of potassium ferricyanide was added 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 compound represented by 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 the obtained reaction mixture was cooled, water was added. The precipitated precipitate was taken out and washed with water and hexane to obtain 10.8 g of a compound represented by the 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. To the obtained mixture, 0.92 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride was added and stirred. The obtained mixture was filtered through celite, and the obtained filtrate was concentrated under reduced pressure. The residue was developed by column chromatography using chloroform as the eluent, and then developed using chloroform / acetone (volume ratio = 95/5) as the eluent. The adsorption layer of orange color was recovered, and the obtained solution was concentrated under reduced pressure. The residue was crystallized with ethanol. 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 compound represented by formula (xxxii-a)).

As a result of conducting the phase transition temperature of the obtained compound represented by the formula (xxxii-1) by texture observation with a polarization microscope, the compound represented by the formula (xxxii-1) is at a temperature rise from 125 ° C to 180 ° C or higher and is nematic. It showed that it showed a nematic phase to 55 degreeC at the time of temperature fall, and crystallized.

Example 26

(1) In Example 1-1, it was carried out in the same manner as in Example 1-1 except that 4-bromobutanol was used instead of 6-bromohexanol, and represented by the following formula (e '') The compound was obtained.

(2) In Example 5-2, the same formula as in Example 5-2 was carried out in the same manner as in Example 5-2, except that the compound represented by Formula (e '') was used instead of the compound represented by Formula (VII-a). The compound represented by (VII-2) was obtained. Yield: 72% (based on 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-bromoundecanol and 280 g of N, N-dimethylacetamide were mixed. The resulting mixture was stirred under a nitrogen atmosphere at 90 ° C, and then stirred at 110 ° C for reaction. After the obtained reaction mixture was cooled at room temperature, it was poured into 1680 g of pure water. The precipitated precipitate was taken out by filtration. The precipitate was washed with 400 ml of a 6N aqueous sodium hydroxide solution, washed with heptane and dried in vacuo to obtain 83 g of the compound represented by the formula (b '' '). Yield 82% (based on 11-bromoundecanol).

(2) 80 g of the compound represented by the obtained formula (b '' '), 3,5-di-tert-butyl-4-hydroxytoluene 1.40 g, dimethylaniline 61.2 g, 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 resulting mixture under ice cooling under a nitrogen atmosphere. The resulting mixture was stirred at room temperature to react. After completion of the reaction, the reaction mixture was washed with 2N hydrochloric acid and saturated aqueous sodium carbonate solution, and then concentrated. To the obtained concentrate, 700 ml of methanol was added, 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 completion of the reaction, 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 vacuum dried to obtain 62 g of the compound represented by the formula (d '' '). Yield: 84% (based on compound represented by 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 under nitrogen atmosphere and stirred. To the mixture, 27.3 g of dicyclohexylcarbodiimide was added dropwise to a 50 ml chloroform solution. After completion of dropping, the mixture was stirred and reacted at room temperature. 200 ml of chloroform and 200 ml of heptane were added to the obtained reaction mixture. The precipitated precipitate was filtered. After the obtained filtrate was washed with 2N hydrochloric acid, insoluble components were removed by filtration. The obtained filtrate was dried over anhydrous sodium sulfate, filtered and concentrated.

The resulting 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 and reacted at 70 ° C for 3 hours under a nitrogen atmosphere. After the reaction mixture was allowed to cool to room temperature, the precipitated 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, filtered through a 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 a compound represented by the formula (e '' '). Yield: 82% (based on compound represented by formula (d '' ')).

Example 27-2

In Example 5-2, in the same manner as in Example 5-2, except that the compound represented by Formula (e '' ') obtained in Example 27-1 was used instead of the compound represented by Formula (VII-a). This was carried out to obtain a compound represented by the following formula (VII-3). Yield: 82% (based on compound represented by formula (e '' ')).

As a result of performing the phase transition temperature of the obtained compound represented by formula (VII-3) by texture observation with a polarizing microscope, the compound represented by formula (VII-3) has a smectic phase from 164 ° C to 174 ° C at elevated temperature. It was found that a nematic phase was exhibited from 174 ° C to 195 ° C, and at a temperature of 195 ° C to 167 ° C, a nematic phase, and a smectic phase from 167 ° C to 151 ° C, and crystallization.

Example 28-1

(1) 88.5 g of the compound represented by the formula (a), 35.5 g of sodium hydroxide, 75 g of 8-chlorooctanol and 300 g of N, N-dimethylacetamide were mixed. The resulting mixture was stirred under a nitrogen atmosphere at 90 ° C, and then stirred at 100 ° C for 2 hours to react. After the obtained reaction mixture was cooled to room temperature, it was poured into 600 g of pure water. The precipitated precipitate was taken out by filtration. The precipitate was washed with 400 ml of a 6N aqueous sodium hydroxide solution, washed with heptane and dried in vacuo to obtain 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 '' ''), 3,5-di-tert-butyl-4-hydroxytoluene 1.40 g, dimethylaniline 86.4 g, 1,3-dimethyl-2-imida 1.00 g of zolidinone and chloroform were mixed. 42.11 g of acryloyl chloride was added dropwise to the resulting mixture under ice cooling under a nitrogen atmosphere. The resulting mixture was stirred at room temperature for 2 hours to react. After completion of the reaction, the reaction mixture was washed with 2N hydrochloric acid and saturated aqueous sodium carbonate solution, and then concentrated. To the obtained concentrate, 300 ml of methanol was added, 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 completion of the reaction, 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 obtain 72 g of a compound represented by the formula (d '' ''). Yield: 79% (based on compound represented by 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 under nitrogen atmosphere and stirred. A 50 ml chloroform solution of 19.5 g dicyclohexylcarbodiimide was added dropwise to the mixture. After completion of dropping, the mixture was stirred and reacted at room temperature. 200 ml of chloroform and 200 ml of heptane were added to the obtained reaction mixture. The precipitated precipitate was filtered. After the obtained solution was washed with 2N hydrochloric acid, insoluble components were 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 and reacted at 70 ° C for 2 hours under a nitrogen atmosphere. After the reaction mixture was allowed to cool to room temperature, the precipitated 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 precipitated precipitate was taken out by filtration, washed with pure water and dried in vacuo. The obtained powder was washed with ethanol / water (volume ratio = 2/3), and then further washed with heptane. The obtained powder was dried in vacuo to obtain 30.1 g of a compound represented by the formula (e '' ''). Yield: 84% (based on compound represented by formula (d '' '')).

Example 28-2

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

As a result of performing the phase transition temperature of the obtained compound represented by formula (VII-4) by texture observation with a polarizing microscope, the compound represented by formula (VII-4) has a smectic phase from 163 ° C to 167 ° C at elevated temperature. It showed that it showed a nematic phase from 167 degreeC to 220 degreeC, and it showed the nematic phase from 220 degreeC to 156 degreeC at the time of temperature fall, and it turned out to crystallize.

Example 29

(1) 12.5 g of the compound represented by formula (VII-a), 1.06 g of 4-dimethylaminopyridine, 20.0 g of compound represented by formula (f) and 50 g of chloroform were mixed. To the obtained mixture, 19.7 g of dicyclohexylcarbodiimide was dissolved in 30 g of chloroform, and the resulting solution was added dropwise at room temperature. The resulting mixture was stirred to react. The obtained reaction mixture was filtered, and 12 g of 2N hydrochloric acid was added to the obtained 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 precipitated precipitate was removed by filtration, and the filtrate was concentrated under reduced pressure. The concentrated residue was crystallized by adding heptane. 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 obtained compound represented by formula (g) and tetrahydrofuran were mixed. The obtained solution, 1.18 g of pure water, 1.40 g of 3,5-di-tert-butyl-4-hydroxytoluene, 1.55 g of p-toluenesulfonic acid monohydrate and 115 ml of tetrahydrofuran were mixed. The obtained mixture was stirred and reacted at 70 ° C for 2 hours under a nitrogen atmosphere. 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 a compound represented by the formula (h). Yield: 70% (based on compound represented by formula (VII-a)).

(3) Triphosgene 25.36g and tetrahydrofuran 125g were mixed under ice cooling. To the obtained mixed solution, 37 g of 4-hydroxybutyl acrylate and 28.0 g of dimethylaniline were added dropwise. The resulting mixture was stirred at room temperature for 2 hours to react. A solution obtained by dissolving 49.9 g of a compound represented by formula (a) and 49.9 g of pyridine in 50 ml of tetrahydrofuran was added dropwise to the obtained reaction mixture. The resulting mixture was stirred and reacted overnight at room temperature. The white precipitate was removed by filtration, and the obtained filtrate was concentrated under reduced pressure. After 120 ml of ethanol was added to the residue, the pH of the solution was adjusted to 4 by adding 44 g of p-toluenesulfonic acid monohydrate. The resulting solution was stirred at room temperature for 1 hour and poured onto 1000 g of ice. The supernatant was removed by decantation, the resulting lower layer was mixed with water / ethanol (volume ratio = 1/3), 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 the formula (h), 6.0 g of the compound represented by the formula (i), 0.26 g of dimethylaminopyridine and 20 ml of chloroform were mixed. 10 mL of a chloroform solution of 5.30 g of dicyclohexylcarbodiimide was added dropwise to the obtained mixture under ice cooling. The resulting mixture was stirred to react. After the reaction was completed, the reaction mixture was filtered to remove insoluble matters. 2N hydrochloric acid was added to the obtained filtrate, and it was separated. After drying the obtained organic layer, it was filtered through celite and concentrated under reduced pressure. The residue was crystallized by adding methanol. The obtained precipitate was taken out and dissolved in chloroform. To the obtained solution, 500 mg of activated carbon was added, left overnight, and filtered through celite. The obtained filtrate and ethanol were mixed, and 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 (VII-5). Yield: 25% (based on compound represented by formula (h)).

As a result of performing the phase transition temperature of the obtained compound represented by formula (VII-5) by texture observation with a polarization microscope, the compound represented by formula (VII-5) has a smectic phase from 142 ° C to 163 ° C at elevated temperature. It showed that it showed a nematic phase from 163 degreeC to 224 degreeC, and it showed that it showed a nematic phase up to 108 degreeC at the time of temperature fall, and crystallized.

Example 30

(1) 30.73 g of p-hydroxybenzoate, 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 Were mixed. The resulting mixture was reacted by stirring at room temperature under a nitrogen atmosphere. 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 filtering sodium sulfate, methanol / water (volume ratio = 50/50) was added to the filtrate. The obtained crystals were taken out by filtration. After washing the crystal with heptane and pure water, it was dried in vacuo to obtain 58.0 g of a compound represented by the formula (j). Yield: 98% (based on benzyl p-hydroxybenzoate).

(2) 50.0 g of the compound represented by the obtained formula (j) and 150 ml of tetrahydrofuran were mixed. To the obtained mixture, 2 g of acetic acid and 7.5 g of palladium carbon were added and stirred under a nitrogen atmosphere. The mixture was depressurized and then stirred under a hydrogen atmosphere. When the consumption of hydrogen was stopped, the atmosphere was nitrogen, 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 obtain 32.0 g of the compound represented by the formula (k). Yield: 80% (based on compound represented by formula (j)).

(3) 16 g of the compound represented by the 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 resulting mixture was reacted by stirring at room temperature under a nitrogen atmosphere. To the reaction mixture, 40 ml of heptane was added, 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 was concentrated to obtain 18.5 g of the compound represented by the formula (l). Yield: 85% (based on compound represented by formula (j)).

(4) 18.5 g of the compound represented by the 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 resulting mixture was reacted by stirring at 60 ° C under a nitrogen atmosphere. The reaction mixture was allowed 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 compound represented by formula (l)).

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

As a result of performing the phase transition temperature of the obtained compound represented by formula (VII-6) by texture observation with a polarization microscope, the compound represented by formula (VII-6) has a smectic phase from 124 ° C to 135 ° C at elevated temperature. It showed that it showed a nematic phase from 135 degreeC to 220 degreeC, and it showed the nematic phase from 220 degreeC to 103 degreeC at the time of temperature fall, and it turned out to crystallize.

Example 31

(1) 30 g of compound represented by formula (b), 3,5-di-tert-butyl-4-hydroxytoluene 1.40 g, triethylamine 15.5 g, 1,3-dimethyl-2-imidazolidinone 1.00 g And 300 ml of tetrahydrofuran were mixed. 16.0 g of methacryloyl chloride was added dropwise to the obtained solution while being ice-cooled under a nitrogen atmosphere. The resulting mixture was stirred at room temperature for 3 hours to react. After the reaction was completed, p-toluenesulfonic acid monohydrate was added to the reaction mixture to adjust the pH to 2. To the mixture, 1.47 g of pure water was added and stirred at room temperature for 3 hours. To the obtained mixture, 100 ml of heptane was added, 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 crystallized by adding 1000 g of ice to the concentrated residue and stirring vigorously. The crystals were taken out, washed with water / methanol (volume ratio = 2/1), further washed with heptane and pure water, and vacuum dried to obtain 12.4 g of a compound represented by the formula (n). Yield: 44% (based on 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 resulting solution was ice-cooled and stirred under a nitrogen atmosphere, and a 20 ml chloroform solution of 9.8 g of dicyclohexylcarbodiimide was added dropwise. The resulting mixture was stirred at room temperature to react. After completion of the reaction, 200 ml of chloroform and 200 ml of heptane were added to the reaction mixture. The resulting precipitate was removed by filtration, and the obtained filtrate was washed with 2N hydrochloric acid. After the insoluble component was 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 and reacted at 70 ° C for 3 hours under a nitrogen atmosphere. 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 adding heptane. The crystals were taken out by filtration and dried under vacuum to obtain 12.2 g of a compound represented by the formula (o). Yield: 68% (based on compound represented by formula (n)).

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

Example 32

(1) 119 g of 2-tert-butyl hydroquinone, 0.23 g of p-toluenesulfonic acid monohydrate and 480 ml of tetrahydrofuran were mixed. 50 g of dihydropyran was added dropwise to the obtained mixture under ice cooling. After the resulting 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 left standing. The precipitated crystal was taken out by filtration, washed with pure water, and then vacuum dried to obtain 39 g of a pale purple powder of the compound represented by the formula (p). Yield: 26% (based on dihydropyran).

(2) 39 g of the compound represented by the 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 reacted by stirring at 100 ° C for 6 hours under a nitrogen atmosphere. 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 phase was dissolved in methyl isobutyl ketone, and the separated aqueous layer was removed. The organic layer was concentrated and dried in vacuo to obtain 42 g of a pale red viscous liquid containing the compound represented by the formula (q). Yield: 77% (based on compound represented by formula (p)).

(3) 40 g of the compound represented by the 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 being ice-cooled under a nitrogen atmosphere. The resulting mixture was stirred at room temperature for 3 hours to react. After the reaction was completed, p-toluenesulfonic acid monohydrate was added to the reaction mixture to adjust the pH to 2. To the obtained mixture, 1.64 g of pure water was added and stirred at room temperature for 1 hour. To the obtained mixture, 100 ml of heptane was added, 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 obtained filtrate was concentrated under reduced pressure. The concentrate was poured into heptane, and the supernatant heptane layer was removed by decantation. The lower red viscous liquid was dried under vacuum for 2 days to obtain 26.0 g of the compound represented by the formula (r). Yield: 71% (based on compound represented by formula (q)).

(4) 15.0 g of the compound represented by the 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 resulting mixture was ice-cooled under a nitrogen atmosphere, stirred, and 10.6 g of dicyclohexylcarbodiimide was added dropwise to a 10 ml chloroform solution. The resulting mixture was stirred at room temperature to react. After completion of the reaction, 100 ml of heptane was added to the reaction mixture, and the resulting precipitate was removed by filtration. After the obtained filtrate was washed with 2N hydrochloric acid, insoluble components were removed by filtration. The filtrate was dried over anhydrous sodium sulfate, filtered through 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 and reacted at 70 ° C for 3 hours under a nitrogen atmosphere. 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 to the obtained residue, stirred, 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 obtain 17.9 g of the compound represented by the formula (s). Yield: 86% (based on compound represented by formula (r)).

(5) In Example 5-2, in the same manner as in Example 5-2, except that the compound represented by Formula (s) obtained in (4) was used instead of the compound represented by Formula (e), 0.7 g of the compound represented by the formula (VII-8) was obtained. Yield: 4.5% (based on 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. After the reaction mixture was allowed to cool to room temperature, it was poured into a mixture of 1000 g of water and 500 g of methylisobutylketone / heptane (weight ratio = 3/2). After the obtained mixture was stirred, it was separated. The obtained organic layer was washed with pure water, dried over anhydrous sodium sulfate, and filtered. After the filtrate was concentrated, heptane was added to the obtained residue, and the precipitated solid was taken out by filtration. The solid was dried in vacuo 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 the 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 resulting mixture was ice-cooled under a nitrogen atmosphere, stirred, and 29.57 g of dicyclohexylcarbodiimide was added dropwise. It stirred after completion | finish of dripping. 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 3 times with pure water, dried over anhydrous sodium sulfate, and filtered. The obtained filtrate was concentrated, and methanol was added to the obtained residue and stirred. The precipitated solid was taken out by filtration, mixed with methanol, and then filtered. The obtained powder was dried in vacuo to obtain 42 g of a compound represented by the formula (v). Yield: 90% (based on compound represented by formula (u)).

(3) 23 g of the compound represented by the obtained formula (v) was dissolved in 150 ml of tetrahydrofuran. To the obtained solution, 1.2 g of 10% palladium / carbon (50% water) was added under a nitrogen atmosphere. The resulting mixture was reduced in pressure, and then stirred under room temperature, normal pressure, and a hydrogen atmosphere. After completion of the reaction, the reaction mixture was filtered under a nitrogen atmosphere. Toluene was added to the obtained filtrate, and insoluble components were removed by filtration. The obtained filtrate was concentrated. The concentrated residue was washed with water / methanol (volume ratio = 1/1), then water. The obtained crystal was taken out and dried under vacuum to obtain 17.8 g of a compound represented by the formula (w). Yield: 97% (based on 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-hydroxybutylacrylate and 100 ml of chloroform were mixed. The resulting mixture was ice-cooled under a nitrogen atmosphere and stirred, and a 50 ml chloroform solution of 10.19 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride was added dropwise. The resulting mixture was stirred to react. 200 ml of toluene was added to the obtained reaction mixture, and 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 obtain 18.5 g of a compound represented by the formula (x).

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

Example 33-2

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

As a result of performing the phase transition temperature of the obtained compound represented by formula (VII-9) by texture observation with a polarization microscope, the compound represented by formula (VII-9) has a smectic phase from 146 ° C to 159 ° C at elevated temperature. It exhibited a melting point and exhibited a nematic phase from 159 ° C to 121 ° C at a temperature drop, and it was found that crystallization occurred.

Example 34

In Example 33-2, the same procedure as in Example 33-2 was carried out for the following Formula (VII-9), except that the compound represented by Formula (VIIa) was used instead of the compound represented by Formula (VII-a). The compound represented by was obtained.

Example 35

A 2% aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified type, manufactured by Wako Pure Chemical Industries, Ltd.) was applied onto the glass substrate, followed by drying by heating to obtain a film having a thickness of 89 nm. After performing the rubbing treatment on the surface of the obtained film, the solution of the composition shown in Table 3 below was applied to the surface on which the rubbing treatment was performed by a spin coat method. After drying on a 100 ° C hot plate for 1 minute, ultraviolet light at 1200 mJ / cm 2 was irradiated while heating at 100 ° C. to obtain an optical film having a film thickness of 1.04 μm.

In addition, in Table 3, "%" represents content in a solution. "L1" means LC242 commercially available from BASF, "Irg907" refers to Irgacure 907 manufactured by Chiba Japan Co., Ltd., and "Irg819" refers to Irgacure 819 manufactured by Chiba Japan Co., Ltd. (IRGACURE 819) respectively. In addition, "L2" means BYK361N by Big Chemical Japan Corporation.

Example 36

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

Example 37

A 2% aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified type, manufactured by Wako Pure Chemical Industries, Ltd.) was applied onto the glass substrate, followed by drying by heating to obtain a film having a thickness of 89 nm. After performing the rubbing treatment on the surface of the obtained film, the solution of the composition shown in Table 3 above was applied on the surface on which the rubbing treatment was performed by spin coating. After drying on an 80 ° C hot plate for 1 minute, it was further dried at 210 ° C for 1 minute. The resulting unpolymerized film was heated at 190 ° C while irradiating with 1200 mJ / cm 2 of ultraviolet light to obtain an optical film with a film thickness of 2.43 µm.

Example 38

A 2% aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified type, manufactured by Wako Pure Chemical Industries, Ltd.) was applied onto the glass substrate, followed by drying by heating to obtain a film having a thickness of 89 nm. After performing the rubbing treatment on the surface of the obtained film, the solution of the composition shown in Table 3 above was applied on the surface on which the rubbing treatment was performed by spin coating. After drying on an 80 ° C hot plate for 1 minute, it was further dried at 210 ° C for 1 minute. The resulting unpolymerized film was heated at 190 ° C. and irradiated with 1200 mJ / cm 2 of ultraviolet light to obtain an optical film having a film thickness of 1.52 μm.

Example 39

A 2% aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified type, manufactured by Wako Pure Chemical Industries, Ltd.) was applied onto the glass substrate, followed by drying by heating to obtain a film having a thickness of 89 nm. After performing the rubbing treatment on the surface of the obtained film, the solution of the composition shown in Table 3 above was applied on the surface on which the rubbing treatment was performed by spin coating. After drying for 1 minute on an 80 ° C hot plate, it was further dried at 160 ° C. The resulting unpolymerized film was heated at 160 ° C. and irradiated with 1200 mJ / cm 2 of ultraviolet light to obtain an optical film having a film thickness of 2.27 μm.

Example 40

A 2% aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified type, manufactured by Wako Pure Chemical Industries, Ltd.) was applied onto the glass substrate, followed by drying by heating to obtain a film having a thickness of 89 nm. After performing the rubbing treatment on the surface of the obtained film, the solution of the composition shown in Table 3 above was applied on the surface on which the rubbing treatment was performed by spin coating. After drying on an 80 ° C hot plate for 1 minute, it was further dried at 140 ° C. The resulting unpolymerized film was heated at 140 ° C. and irradiated with 1200 mJ / cm 2 of ultraviolet light to obtain an optical film with a film thickness of 1.59 μm.

Example 41

A 2% aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified type, manufactured by Wako Pure Chemical Industries, Ltd.) was applied onto the glass substrate, followed by drying by heating to obtain a film having a thickness of 89 nm. After performing the rubbing treatment on the surface of the obtained film, the solution of the composition shown in Table 3 above was applied on the surface on which the rubbing treatment was performed by spin coating. After drying for 1 minute on an 80 ° C hot plate, it was further dried at 150 ° C. The resulting unpolymerized film was heated at 190 ° C. and irradiated with 1200 mJ / cm 2 of ultraviolet light to obtain an optical film with a film thickness of 2.11 μm.

Example 42

A 2% aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified type, manufactured by Wako Pure Chemical Industries, Ltd.) was applied onto the glass substrate, followed by drying by heating to obtain a film having a thickness of 89 nm. After performing the rubbing treatment on the surface of the obtained film, the solution of the composition shown in Table 3 above was applied on the surface on which the rubbing treatment was performed by spin coating. After drying for 1 minute on an 80 ° C hot plate, it was further dried at 160 ° C. The resulting unpolymerized film was heated at 160 ° C. and irradiated with 1200 mJ / cm 2 of ultraviolet light to obtain an optical film having a film thickness of 1.56 μm.

Example 43

A 2% aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified type, manufactured by Wako Pure Chemical Industries, Ltd.) was applied onto the glass substrate, followed by drying by heating to obtain a film having a thickness of 89 nm. After performing the rubbing treatment on the surface of the obtained film, the solution of the composition shown in Table 3 above was applied on the surface on which the rubbing treatment was performed by spin coating. After drying on an 80 ° C hot plate for 1 minute, it was further dried at 170 ° C. The resulting unpolymerized film was heated at 170 ° C. and irradiated with 1200 mJ / cm 2 of ultraviolet light to obtain an optical film having a film thickness of 1.40 μm.

Example 44

A 2% aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified type, manufactured by Wako Pure Chemical Industries, Ltd.) was applied onto the glass substrate, followed by drying by heating to obtain a film having a thickness of 89 nm. After performing the rubbing treatment on the surface of the obtained film, the solution of the composition shown in Table 3 above was applied on the surface on which the rubbing treatment was performed by spin coating. After drying on an 80 ° C hot plate for 1 minute, it was further dried at 140 ° C for 1 minute. The resulting unpolymerized film was heated at 140 ° C. and irradiated with 1200 mJ / cm 2 of ultraviolet light to obtain an optical film having a film thickness of 1.50 μm.

Comparative Example 1

A 2% aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified type, manufactured by Wako Pure Chemical Industries, Ltd.) was applied onto the glass substrate, followed by drying by heating to obtain a film having a thickness of 89 nm. After performing the rubbing treatment on the surface of the obtained film, the solution of the composition shown in Table 3 above was applied on the surface on which the rubbing treatment was performed by spin coating. After drying on an 80 ° C hot plate for 1 minute, it was further dried at 150 ° C for 1 minute. The resulting unpolymerized film was heated at 100 ° C. and irradiated with 1200 mJ / cm 2 of ultraviolet light to obtain an optical film having a film thickness of 0.88 μm.

<Measurement of optical properties>

In the wavelength range of 450 nm to 700 nm, the phase difference value of the manufactured optical film was measured using a measuring device (KOBRA-WR, manufactured by Oji Measurement Equipment Co., Ltd.), and the phase difference value Re (450) of a wavelength of 450 nm was attached to the program attached to the device ), The phase difference value Re (550) of wavelength 550 nm and the phase difference value Re (650) of wavelength 650 nm were calculated. Table 4 shows the results.

Example 45

(1) 4.9 g of a compound represented by 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. To the obtained mixture, a solution obtained by dissolving 46.2 g of dicyclohexylcarbodiimide in 98 g of dehydrated pyridine was added dropwise. The resulting mixture was reacted by stirring at 60 ° C. The reaction mixture was filtered, and the obtained filtrate was concentrated. 196 g of chloroform was added to the concentrate, and washed with 2N hydrochloric acid 196 g. The obtained solution was purified by 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 the obtained formula (TC-1), 2.3 g of the compound represented by the formula (e), 0.07 g of 4-dimethylaminopyridine and 75 g of chloroform were mixed. To the obtained mixture, a solution obtained by dissolving 1.4 g of dicyclohexylcarbodiimide in 19 g of chloroform was added dropwise. The resulting mixture was stirred at room temperature to react. The reaction mixture was filtered, chloroform was added to the obtained filtrate, and washed with 94 g of 2N hydrochloric acid. Methanol was added to the obtained solution under reduced pressure. The solid material was taken out and washed with methanol to obtain 1.2 g of a compound represented by the formula (TM-1). Yield: 24% (based on compound represented by formula (TC-1)).

The phase transition temperature of the compound represented by the obtained formula (TM-1) was carried out by texture observation with a polarization microscope. The compound represented by formula (TM-1) exhibits a smectic phase from 148 ° C to 153 ° C at elevated temperature, and a nematic phase from 153 ° C to 173 ° C, and at low temperature, from 170 ° C to 102 ° C It turned out that it showed a tick shape.

Example 46

A 2% aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified type, manufactured by Wako Pure Chemical Industries, Ltd.) was applied onto the glass substrate, followed by drying by heating to obtain a film having a thickness of 89 nm. After performing the rubbing treatment on the surface of the obtained film, the solution of the composition shown in Table 5 below was applied on the surface on which the rubbing treatment was performed by a spin coat method. After drying on a hot plate at 170 ° C for 1 minute, 9600 mJ / cm 2 of ultraviolet light was irradiated while heating at 130 ° C. to obtain an optical film having a film thickness of 1.353 μm.

In addition, in Table 5, "%" represents content in a solution. "L1" means LC242 commercially available from BASF, and "Irg819" means Irgacure 819 manufactured by Chiba Japan Co., Ltd. (IRGACURE 819). In addition, "L2" means BYK361N by Big Chemical Japan Corporation.

Comparative Example 2

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

About the produced optical film, the phase difference value in wavelength 547nm was measured using the measuring device (KOBRA-WR, Oji measurement equipment company make). In addition, the film thickness (d) derived from the polymerizable compound of the optical film was measured using a laser microscope (LEXT, manufactured by Olympus Co., Ltd.). The birefringence (Δn) was calculated from the phase difference value at a wavelength of 547 nm and the film thickness (d). Moreover, the phase difference values at wavelengths 447 nm and 628 nm were measured, and wavelength dispersion characteristics Re (447) / Re (547) and Re (628) / Re (547) were calculated. Table 6 shows the results.

Examples 47-63 and Comparative Example 3

A 2% aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified type, Wako Pure Chemical Industries, Ltd.) was applied onto a glass substrate, followed by drying by heating to obtain a film having a thickness of 89 nm. After performing the rubbing treatment on the surface of the obtained film, the solution of the composition shown in Table 7 below was applied to 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, "%" represents content in a solution. "L1" means LC242 commercially available from BASF, "Irg907" refers to Irgacure 907 manufactured by Chiba Japan Co., Ltd., and "Irg819" refers to Irgacure 819 manufactured by Chiba Japan Co., Ltd. (IRGACURE 819) respectively. In addition, "L2" means BYK361N by Big Chemical Japan Corporation.

<Measurement of optical properties>

The front phase difference value of the prepared optical film was measured using a measuring device (KOBRA-WR, manufactured by Oji Scientific Instruments). In addition, since the glass substrate used for the substrate has no birefringence, the front phase difference value of the optical film produced on the glass substrate can be obtained by measuring the film with the glass substrate with a measuring instrument. Front phase difference values were measured at wavelengths of 447.3 nm, 546.9 nm, and 627.8 nm, respectively, and Re (447.3) / Re (546.9) (hereinafter abbreviated as α) and Re (627.8) / Re (546.9) (hereinafter, β ). Moreover, the film thickness (d) (micrometer) of the part derived from an optical film was measured using the laser microscope (LEXT, Olympus company make). Table 8 shows the results. 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 methyl isobutyl ketone / heptane (weight ratio = 3/2). The obtained mixture was separated. The obtained organic layer was washed with pure water, dried and filtered. The filtrate was concentrated, and heptane was added to the obtained concentrated residue. The precipitated solid was taken out by filtration and dried under vacuum to obtain 150 g of a compound represented by the formula (g '). Yield: 75% (based on trans-4-hydroxycyclohexanecarboxylic acid).

(2) 30 g of the compound represented by the 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 under nitrogen atmosphere at 40 ° C, and then stirred at room temperature for reaction. Heptane was added to the obtained reaction mixture, and the resulting precipitate was removed by filtration. The obtained filtrate was washed with hydrochloric acid, dried and filtered. The obtained filtrate was concentrated, methanol was added to the obtained residue and heated. The obtained solution was allowed to cool, and the precipitated crystal was taken out to obtain 32.0 g of a compound represented by the formula (h '). Yield: 62% (based on compound represented by formula (g ')).

(3) 32.0 g of the compound represented by the obtained formula (h ') and 150 ml of 2-propanol were mixed. To the obtained solution, 0.7 g of acetic acid and 6.40 g of palladium / carbon were added and stirred under a nitrogen atmosphere. The resulting mixture was reduced in pressure, and then stirred and reacted under a hydrogen atmosphere. After completion of the reaction, after nitrogen substitution, 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 obtain 24.0 g of the compound represented by the formula (j '). Yield: 97% (based on compound represented by formula (h ')).

(4) 0.97 g of the compound represented by formula (ii-a), 2.73 g of the compound represented by formula (j ') obtained in (3) above, 0.11 g of 4-dimethylaminopyridine and 87 g of chloroform were mixed. To the obtained mixture, a solution obtained by dissolving 2.0 g of dicyclohexylcarbodiimide in 22 g of chloroform was added dropwise. The resulting mixture was stirred to react. 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 solid matter was taken out. The taken-out solid was washed with methanol to obtain 2.7 g of a compound represented by the formula (ii-2). Yield: 81% (based on compound represented by formula (ii-a)).

Example 65

1.87 g of the compound represented by the formula (VII-a), 3.96 g of the compound represented by the formula (j '), 0.16 g of 4-dimethylaminopyridine and 127 g of chloroform were mixed. To the obtained mixture, a solution obtained by dissolving 2.9 g of dicyclohexylcarbodiimide in 32 g of chloroform was added dropwise. The resulting mixture was stirred to react. 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 solid matter was taken out. The taken-out solid was washed with methanol to obtain 4.1 g of a compound represented by the following formula (VII-2). Yield: 78% (based on compound represented by formula (VII-a)).

Example 66

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

Examples 67-68 and Comparative Example 4

A 2% aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified type, manufactured by Wako Pure Chemical Industries, Ltd.) was applied onto the glass substrate, followed by drying by heating to obtain a film having a thickness of 89 nm. After performing the rubbing treatment on the surface of the obtained film, the solution of the composition shown in Table 9 below was applied to 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, "%" represents content in a solution. "L1" means LC242 commercially available from BASF, and "Irg819" means Irgacure 819 manufactured by Chiba Japan Co., Ltd. (IRGACURE 819). In addition, "L2" means BYK361N by Big Chemical Japan Corporation.

<Measurement of optical properties>

The front phase difference value of the prepared optical film was measured using a measuring device (KOBRA-WR, manufactured by Oji Scientific Instruments). In addition, since the glass substrate used for the substrate has no birefringence, the front phase difference value of the optical film produced on the glass substrate can be obtained by measuring the film with the glass substrate with a measuring instrument. Front phase difference values were measured at wavelengths of 447.3 nm, 546.9 nm, and 627.8 nm, respectively, and Re (447.3) / Re (546.9) (hereinafter abbreviated as α) and Re (627.8) / Re (546.9) (hereinafter, β ). Moreover, the film thickness (d) (micrometer) of the part derived from an optical film was measured using the laser microscope (LEXT, Olympus company make). Table 10 shows the results. The birefringence (Δn) was calculated by dividing the value of Re (546.9) by the film thickness (d).

The optical film of the present invention is capable of constant polarization conversion in a wide wavelength range.

Claims (14)

As an optical film obtained by polymerizing the compound represented by the formula (1), the phase difference value Re (450) having a wavelength of 450 nm and the phase difference value Re (550) having a wavelength of 550 nm are
Re (450) / Re (550) ≤ 1.009
Satisfying, optical film.
P ¹ -F ^1- (B ¹ -A ¹ ) _k -E ¹ -G ¹ -D ¹ -Ar-D ² -G ² -E ^2- (A ² -B ² ) _l -F ² -P ² ( One)
[In formula (1),
Ar represents a divalent group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle, and the number N _π of π electrons contained in the aromatic ring in the Ar group is 12 or more.
D ¹ and D ² are each independently * -O-CO- (* represents a position to be bonded to Ar), -CR ¹ R ^2- , * -O-CR ¹ R ² -(* is, Ar represents a position bonded to), or * -CR ¹ R ² -O- (* represents a position bonded to Ar), and R ¹ and R ² are each independently a hydrogen atom or a carbon number The alkyl group of 1-4 is shown.
G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group.
E ¹ and E ² represent * -CO-O- (* represents a binding site with G ¹ or G ² ).
B ¹ and B ² represent -O-.
A ¹ and A ² each independently represent a divalent aromatic hydrocarbon group.
k and l each independently represent an integer of 1 to 3.
F ¹ and F ² each independently represent an alkylene group having 1 to 12 carbon atoms. The hydrogen atom contained in the alkylene group may be substituted with an alkyl group having 1 to 5 carbon atoms, or the methylene group contained in the alkylene group may be substituted with -O- or -CO-.
P ¹ and P ² each independently represent a hydrogen atom or a polymerizable group (however, at least one of P ¹ and P ² represents a polymerizable group).] According to claim 1,
The optical film in which D ¹ and D ² are each independently * -O-CO- (* represents a binding site with Ar). delete The method of claim 1 or 2,
The optical film in which P ¹ and P ² are acryloyl groups or methacryloyl groups. The method of claim 1 or 2,
The optical film whose compound represented by Formula (1) is a compound which shows a nematic phase. The method of claim 1 or 2,
An optical film in which k and l are both 1. The method of claim 1 or 2,
An optical film in which Ar is a divalent group having a benzothiazole ring. The method of claim 1 or 2,
An optical film for a λ / 4 plate having a phase difference value (Re (550)) of 113 to 163 nm at a wavelength of 550 nm. The method of claim 1 or 2,
An optical film for a λ / 2 plate having a phase difference value (Re (550)) of 250 to 300 nm at a wavelength of 550 nm. A polarizing plate comprising the optical film and the polarizing film according to claim 1 or 2. A color filter formed by forming the optical film according to claim 1 or 2 on an oriented polymer applied directly onto a color filter substrate. A flat panel display device comprising a liquid crystal panel comprising the polarizing plate according to claim 10. An organic EL display device comprising the organic electroluminescence panel comprising the polarizing plate according to claim 10. A liquid crystal display device comprising the color filter according to claim 11.

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