JP2012077057A - Method for production of dihydroxybenzene compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method capable of obtaining a hydroxybenzene compound as a product having less brownish color at high yield.SOLUTION: The method for production of a hydroxybenzene compound represented by formula (1-1) includes a process (1) of making an oxidant act on a compound represented by formula (2-1), and a process (2) of reducing the product obtained by the above process (1). In the formulas, Qs are each independently -CRR-, -S-, -NR-, -CO- or -O-; Rand Rare each independently hydrogen or a 1-4C alkyl group; Yis an aromatic hydrocarbon or heteroaromatic group; and Zand Zare each independently a methyl group or an ethyl group.

Description

  The present invention relates to a method for producing a dihydroxybenzene compound.

For display devices such as liquid crystal display devices, optical films such as polarizing films and retardation films are used. It is also known to use a polymer of a polymerizable liquid crystal compound produced from 2-aryl-4,7-dihydroxybenzothiazole as the optical film.
As a method for producing 2-aryl-4,7-dihydroxybenzothiazole, 2,5-dimethoxyaniline is reacted with an arylcarboxylic acid chloride to amidate, then the amide is thioamidated with Lawesson's reagent, and cyclized with potassium ferricyanide. To give 2-aryl-4,7-dimethoxybenzothiazole, and deprotecting the methoxy group by mixing 2-aryl-4,7-dimethoxybenzothiazole and pyridine hydrochloride at high temperature to give 2-aryl There is a method of obtaining -4,7-dihydroxybenzothiazole (see Patent Document 1).

JP 2010-31223 A

  In the conventional method for producing a dihydroxybenzene compound, particularly, the step of deprotecting the methoxy group with pyridine hydrochloride is performed at a high temperature. Therefore, a part of the obtained dihydroxybenzene compound is decomposed to produce a brownish product. In some cases, it was obtained.

The present invention provides the following [1] to [6].
[1] A method for producing a dihydroxybenzene compound represented by the formula (1-1) including the step (1) and the step (2).

[In Formula (1-1), Q ¹ each independently represents —CR ¹ R ² —, —S—, —NR ¹ —, —CO—, or —O—. R ¹ and R ² each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
Y ¹ represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent. ]
(1) A step of causing an oxidizing agent to act on the compound represented by the formula (2-1)

[In Formula (2-1), Q ¹ and Y ¹ represent the same meaning as described above. Z ¹ and Z ² each independently represent a methyl group or an ethyl group. ]
(2) A step of reducing the product obtained in step (1)

[2] The production method according to [1], wherein the oxidizing agent is silver nitrate, cerium (IV) ammonium nitrate, or Koser reagent.
[3] The production method according to [1] or [2], wherein the reduction is reduction with sodium dithionite, reduction with a metal hydride, reduction with a metal hydride complex compound, or catalytic hydrogen reduction.
[4] The production method according to any one of [1] to [3], wherein the reduction is a reduction performed in a mixed solvent of water and a cyclic ether.

[5] A formula comprising a step of esterifying the compound represented by the formula (1-1) produced by the production method according to any one of [1] to [4] and the compound (7-1) ( LC-1) The manufacturing method of the liquid crystal compound represented.

[In Formula (7-1), D ¹ and D ² each independently represents a single bond or a divalent linking group.
G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group, and the hydrogen atom contained in the alicyclic hydrocarbon group is a halogen atom, —R ³ , —OR ³ , or a cyano group. Alternatively, it may be substituted with a nitro group, and the —CH ₂ — group contained in the alicyclic hydrocarbon group may be substituted with —O—, —S— or —NH—.
A ¹ and A ² each independently represent a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group, and hydrogen contained in the alicyclic hydrocarbon group and the aromatic hydrocarbon group The atom may be substituted with a halogen atom, —R ³ , —OR ³ , a cyano group, or a nitro group.
R ³ represents an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a fluorine atom.
B ¹ , B ² , E ¹ and E ² each independently represent a single bond or a divalent linking group.
k and l each independently represents an integer of 0 to 3. When k is an integer of 2 or more, the plurality of A ¹ and B ¹ may be the same as or different from each other. If l is an integer of 2 or more, plural A ² and B ² may be the same or different from each other.
F ¹ and F ² each independently represent an alkanediyl group having 1 to 12 carbon atoms, and a hydrogen atom contained in the alkanediyl group may be substituted with a halogen atom, and is contained in the alkanediyl group The —CH ₂ — group may be substituted with —O— or —CO—.
P ¹ and P ² each independently represent a hydrogen atom or a polymerizable group. ]

[In Formula (LC-1), D ¹ , D ² , G ¹ , G ² , B ¹ , B ² , E ¹ , E ² , A ¹ , A ² , k, l, F ¹ , F ² , P ¹ , P ² , Y ¹ and Q ¹ represent the same meaning as described above. ]

[6] An optical film comprising at least one selected from the group consisting of a liquid crystal compound obtained by the production method according to [5] and a polymer thereof.

  According to the method for producing a dihydroxybenzene compound of the present invention, a dihydroxybenzene compound can be obtained as a product with a high yield and a little brown taste.

In the present specification, R ^{1 to} R ¹⁰ used in the chemical formula represent the following meanings.
R ¹ and R ² each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
R ³ represents an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a fluorine atom.
R ⁴ represents an alkyl group having 1 to 6 carbon atoms.
R ⁵ represents an alkyl group having 1 to 4 carbon atoms.
R ⁶ represents an alkyl group having 1 to 6 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a fluorine atom.
R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.

Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, and tert-butyl group.
Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, and hexyl group.

Examples of the group having 1 to 4 carbon atoms in which the hydrogen atom contained in the alkyl group is substituted with a fluorine atom include a fluoromethyl group, a trifluoromethyl group, a fluoroethyl group, a pentafluoroethyl group, a heptafluoropropyl group, and a nonafluoro group. Examples thereof include a fluorinated alkyl group such as a butyl group.
Examples of the group having 1 to 6 carbon atoms in which the hydrogen atom contained in the alkyl group is substituted with a fluorine atom include a fluoromethyl group, a trifluoromethyl group, a fluoroethyl group, a pentafluoroethyl group, a heptafluoropropyl group, and a nonafluoro group. Examples thereof include a fluorinated alkyl group such as a butyl group.

  The method for producing a dihydroxybenzene compound of the present invention comprises (1) a step of causing an oxidizing agent to act on a compound represented by formula (2-1) (hereinafter sometimes referred to as “compound (2-1)”), and ( 2) A step of reducing the product obtained in (1) is included. Thereby, a compound represented by the formula (1-1) as a product (hereinafter sometimes referred to as “compound (1-1)”) is obtained.

[In Formula (2-1), Q ¹ each independently represents —CR ¹ R ² —, —S—, —NR ¹ —, —CO—, or —O—. R ¹ and R ² each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
Y ¹ represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent.
Z ¹ and Z ² each independently represent a methyl group or an ethyl group. ]

[In Formula (1-1), Q ¹ and Y ¹ represent the same meaning as described above. ]

Q ¹ is preferably —O— or —S—, and more preferably —S— because synthesis is easy.
As Z ¹ and Z ² , a methyl group is preferable because raw materials are easily available.

Y ¹ is a monovalent aromatic hydrocarbon group or monovalent aromatic heterocyclic group which may have a substituent. As the substituent that Y ¹ may have, a halogen atom, —R ³ , a cyano group, a nitro group, —SO ₂ R ⁴ , —SOR ⁴ , —SR ⁴ , —OR ⁴ , a carboxy group, or —NR ¹ R ⁵ is mentioned.
Y ¹ is, for example, a group represented by formula (Y ¹ -1) to formula (Y ¹ -7).

Wherein ^(Y 1 -1) ~ formula ^(Y 1 -7), ^{Z 3} are each independently a halogen atom, -R ^1, a cyano group, a nitro _{^{group, -SO 2 R 4, -SOR 4}} , - It represents SR ⁴ , —OR ⁴ , a carboxy group or —NR ¹ R ⁵ .
V ¹ and V ² each independently represent —CO—, —NR ³ —, —SO ₂ —, or a group 16 element.
W ^{1 to} W ⁶ each independently represent —CH═ or —N═.
However, at least one of V ¹ , V ² and W ^{1 to} W ⁶ represents a group containing C, S, N, O or Se.
a represents an integer of 0 to 5.
b represents an integer of 0 to 3.
c represents an integer of 0 to 2.
When a or b is an integer of 2 or more, the plurality of Z ³ may be the same as or different from each other.
* Represents a bond. ]

Y ¹ is more preferably any one of the groups represented by the formula (Y ² -1) to the formula (Y ² -7) in that the compound is excellent in stability and easy to synthesize.

Wherein ^(Y 2 -1) ~ formula ^{(Y 2 -7), Z 3} , a, b, c , and * are the same as defined above.
J ¹ and J ² each independently represent —CO—, —NR ¹ —, or a group 16 element.
L ¹ represents —CH═ or —N═. ]

Further, Y ¹ is more preferably a group represented by the formula (Y ³ -1) to the formula (Y ³ -4) in that the production of the compound (1-1) is easy.
L ¹ is more preferably —CH═.

[In Formula (Y ³ -1) to Formula (Y ³ -4), Z ³ , a, b, c, J ¹ , and * represent the same meaning as described above. ]

As —SO ₂ R ⁴ in Z ³ , methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, butylsulfonyl group, isobutylsulfonyl group, sec-butylsulfonyl group, tert-butylsulfonyl group, pentylsulfonyl group Hexylsulfonyl group and the like.

-SOR ⁴ in Z ³ includes methylsulfinyl group, ethylsulfinyl group, propylsulfinyl group, isopropylsulfinyl group, butylsulfinyl group, isobutylsulfinyl group, sec-butylsulfinyl group, tert-butylsulfinyl group, pentylsulfinyl group, hexyl And the group sulfinyl.

The -SR ⁴ in Z ^3, methylsulfanyl group, ethylsulfanyl group, propylsulfanyl group, isopropyl sulfanyl group, butylsulfanyl group, isobutyl sulfanyl group, sec- butylsulfanyl group, tert- butylsulfanyl group, pentylsulfamoyl sulfanyl group, a hexyl And a sulfanyl group.

Examples of —OR ⁴ in Z ³ include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, and a hexyloxy group.

As —NR ¹ R ⁵ in Z ³ , N-methylamino group, N-ethylamino group, N-propylamino group, N-isopropylamino group, N-butylamino group, N-isobutylamino group, N-sec N-monoalkylamino groups such as -butylamino group, N-tert-butylamino group, N-pentylamino group, N-hexylamino group; 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, N-dialkylamino group such as, N-dihexylamino group.

Z ³ includes hydrogen atom, halogen atom, methyl group, ethyl group, isopropyl group, sec-butyl group, pentyl group, hexyl group, cyano group, nitro group, methylsulfonyl group, carboxy group, trifluoromethyl group, methoxy Group, methylsulfanyl group, N, N-dimethylamino group or N-methylamino group is preferred, hydrogen atom, halogen atom, methyl group, ethyl group, isopropyl group, sec-butyl group, pentyl group, hexyl group, cyano group Nitro group and trifluoromethyl group are more preferable, and hydrogen atom, methyl group, ethyl group, isopropyl group, sec-butyl group, pentyl group and hexyl group are particularly preferable.

V ¹ and V ² are preferably each independently —S—, —NR ¹ — or —O—.

  Preferable examples of compound (1-1) include the following compounds (A-001) to (A-076).

  Preferable examples of compound (2-1) include the following compound (B-001) to compound (B-076).

  Step (1) is a step of causing an oxidizing agent to act on compound (2-1). By mixing the compound (2-1) and the oxidizing agent in a solvent, a product containing a compound represented by the formula (3-1) (hereinafter sometimes referred to as “compound (3-1)”) is obtained. can get.

[In Formula (2-1), Q ¹ , Y ¹ , Z ¹ and Z ² represent the same meaning as described above. ]

［式（３−１）中、Ｑ^１及びＹ^１は上記と同じ意味を表す。］

[In Formula (3-1), Q ¹ and Y ¹ represent the same meaning as described above. ]

Examples of the oxidizing agent include silver nitrate, silver oxide, Jones reagent, Kiliani reagent, Thiele reagent, potassium permanganate, osmium tetroxide, cerium (IV) ammonium nitrate and other metal oxides, peracetic acid, t-butyl hydroperoxide, etc. Examples include organic peroxides, halogen derivatives such as Koser reagent (compound represented by the following formula), and ozone. Among these, as the oxidizing agent, silver nitrate, cerium (IV) ammonium nitrate, and Koser reagent are preferable, and cerium (IV) ammonium nitrate is more preferable. These oxidizing agents are preferable in that there are few side reactions.

The solvent in the oxidation reaction is not particularly limited as long as it is stable against the oxidizing agent.
When cerium (IV) ammonium nitrate is used as the oxidizing agent, ether solvents such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, methyl cellosolve, ethyl cellosolve, alcohol solvents such as methanol, ethanol, isopropanol, water, acetic acid, Acetonitrile, acetone, dimethyl sulfoxide, dimethylacetamide, dimethylformamide or mixtures thereof are preferred.

  Especially, the mixed solvent containing water and water is preferable, and the mixed solvent of water and a water-soluble organic solvent is more preferable. Examples of the water-soluble organic solvent include alcohol solvents such as tetrahydrofuran, methanol, ethanol, isopropanol, acetone, acetonitrile, dimethyl sulfoxide, dimethylacetamide, and dimethylformamide. Acetonitrile is preferred because of its excellent stability. With these solvents, the reaction proceeds quickly and the solubility of the produced compound (3-1) tends to be low, so that the product can be easily obtained. When the reaction solution is a two-layer system composed of an aqueous layer and an organic layer, a surfactant such as tetrabutylammonium bromide and a phase transfer catalyst such as crown ether may be used.

  The amount of the oxidizing agent used is preferably 1 equivalent to 10 equivalents, more preferably 1 equivalent to 8 equivalents, and more preferably 1 equivalent to 4 equivalents with respect to the compound (2-1).

  The temperature at which the reaction liquid obtained by mixing the compound (2-1) and the oxidizing agent is not particularly limited, but is preferably −20 ° C. to 100 ° C., more preferably 0 ° C. to 80 ° C., and 0 ° C. to 60 ° C. Further preferred.

  When the product precipitates in the reaction solution, the product (3-1) can be obtained as a purified product by filtering the precipitated product. When the product does not precipitate, the reaction solution may be replaced with water and the deposited precipitate may be collected by filtration. When the reaction solvent is a mixed solvent of water and an organic solvent, a precipitate obtained by removing the organic solvent by distillation under reduced pressure or the like may be collected by filtration. You may wash | clean with alcohol, such as methanol, in order to raise the purity of the compound (3-1) in a product.

  Step (2) is a step of reducing the product obtained in step (1). By this step, a product containing compound (1-1) as a main component is obtained.

[In Formula (1-1), Q ¹ and Y ¹ represent the same meaning as described above. ]

  Examples of the reduction method include boron compounds such as borane and diborane; metal hydrides such as hydrazine, diisobutylaluminum hydride, lithium aluminum hydride, sodium borohydride, and lithium borohydride; metal hydrides and Lewis acids. A method using a reducing agent such as sodium dithionite and a method of catalytic hydrogen reduction using palladium carbon as a catalyst. Among these, the method of reducing using sodium dithionite is preferable from the viewpoint of safety and the ability to perform the reaction in an aqueous system.

  In the method using a boron compound or a metal hydride as a reducing agent, the reaction is preferably performed in an ether solvent such as tetrahydrofuran, dioxane, or ethylene glycol dimethyl ether.

  In the method of catalytic hydrogen reduction using palladium carbon as a catalyst, the reaction is preferably carried out in an ether solvent such as tetrahydrofuran, dioxane or ethylene glycol dimethyl ether, or an alcohol solvent such as methanol, ethanol or isopropanol. A catalytic amount of acid may be added to accelerate the reaction.

Examples of the reduction method using sodium dithionite include the following methods, and [2] is particularly preferable.
[1] A method in which the product obtained in step (1) is dispersed and reacted in a sodium nitrite solution. [2] After the product obtained in step (1) is dissolved in a nonpolar solvent in advance, Method of mixing with aqueous solution of sodium dithionite and reacting in a two-layer system [3] Dissolving the product obtained in step (1) in an organic solvent and dispersing sodium dithionite in the solution for reaction How to make

  The solvent used for dissolving sodium nitrite in [1] includes water, a mixed solvent of water and an ether solvent (for example, tetrahydrofuran, dioxane and the like), and water and an alcohol solvent (for example, methanol, ethanol, isopropanol and the like). And a mixed solvent. In particular, when a mixed solvent of water and an ether solvent or a mixed solvent of water and an alcohol solvent is used, the reaction tends to proceed rapidly.

Examples of the nonpolar solvent used in [2] include chloroform, dichloromethane, carbon tetrachloride, tetrachloroethane, trichloroethane, toluene, ether and the like. In the reaction, a surfactant such as tetrabutylammonium bromide or a phase transfer catalyst such as crown ether may be used.
Examples of the organic solvent used in [3] include tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, methyl cellosolve, and ethyl cellosolve.

The reaction temperature of the reduction reaction is not particularly limited, but in any of the above methods, −20 ° C. to 100 ° C. is preferable, 0 ° C. to 80 ° C. is more preferable, and 15 ° C. to 60 ° C. is particularly preferable.
The amount of the reducing agent used is preferably 1 equivalent to 100 equivalents, more preferably 1 equivalent to 50 equivalents, relative to the amount of the compound (3-1) contained in the product obtained in the step (1). 1 equivalent-30 equivalent is more preferable.

  Preferable examples of compound (3-1) include the following compound (C-001) to compound (C-076).

  The compound (1-1) thus obtained and the compound represented by the formula (7-1) (hereinafter sometimes referred to as “compound (7-1)”) are subjected to an esterification reaction, whereby the formula (LC− 1) (hereinafter may be referred to as “compound (LC-1)”).

[In Formula (7-1), D ¹ and D ² each independently represents a single bond or a divalent linking group.
G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group, and the hydrogen atom contained in the alicyclic hydrocarbon group is a halogen atom, —R ³ , —OR ³ , or a cyano group. Alternatively, it may be substituted with a nitro group, and the —CH ₂ — group contained in the alicyclic hydrocarbon group may be substituted with —O—, —S— or —NH—.
A ¹ and A ² each independently represent a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group, and hydrogen contained in the alicyclic hydrocarbon group and the aromatic hydrocarbon group The atom may be substituted with a halogen atom, —R ³ , —OR ³ , a cyano group, or a nitro group.
R ³ represents an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a fluorine atom.
B ¹ , B ² , E ¹ and E ² each independently represent a single bond or a divalent linking group.
k and l each independently represents an integer of 0 to 3. When k is an integer of 2 or more, the plurality of A ¹ and B ¹ may be the same as or different from each other. If l is an integer of 2 or more, plural A ² and B ² may be the same or different from each other.
F ¹ and F ² each independently represent an alkanediyl group having 1 to 12 carbon atoms, and a hydrogen atom contained in the alkanediyl group may be substituted with a halogen atom, and is contained in the alkanediyl group The —CH ₂ — group may be substituted with —O— or —CO—.
P ¹ and P ² each independently represent a hydrogen atom or a polymerizable group. ]

［式（ＬＣ−１）中、Ｄ^１、Ｄ^２、Ｇ^１、Ｇ^２、Ｂ^１、Ｂ^２、Ｅ^１、Ｅ^２、Ａ^１、Ａ^２、ｋ、ｌ、Ｆ^１、Ｆ^２、Ｐ^１、Ｐ^２、Ｙ^１及びＱ^１は、上記と同じ意味を表す。］

[In Formula (LC-1), D ¹ , D ² , G ¹ , G ² , B ¹ , B ² , E ¹ , E ² , A ¹ , A ² , k, l, F ¹ , F ² , P ¹ , P ² , Y ¹ and Q ¹ represent the same meaning as described above. ]

Examples of the divalent linking group for D ¹ and D ² include —CO—O—, —CS—O—, —CR ⁷ R ⁸ —, —CR ⁷ R ⁸ —CR ⁹ R ¹⁰ —, —O—. ^{CR 7 R 8 -, - CR} 7 R 8 -O-CR 9 R 10 -, - CR 7 R 8 -O-CO -, - O-CO-CR 7 R 8 -, - CR 7 R 8 -O- ^{CO-CR 9 R 10 -,} - CR 7 R 8 -CO-O-CR 9 R 10 -, - NR 1 -CR 7 R 8 -, - CO-NR 1 -, - O -, - S -, - NR < ¹ >-, -CR < ⁷ > = CR < ⁸ >-etc. are mentioned.

D ¹ and ^D 2 are, * - O-CO -, * - O-CS -, * - O-CR 7 R 8 -, * - NR 1 -CR 7 R 8 - or ^* -NR 1 -CO- ( * Represents a bond with a benzene ring.) Is preferred, * -O-CO-, * -O-CS- and * -O-CH ₂ -are more preferred, and * -O-CO- is more preferred. When D ¹ and D ² are these groups, the synthesis of the compound (1-1) is easy. In the group represented by D ¹ and D ² , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, a hydrogen atom, a methyl group or It is more preferably an ethyl group, and R ¹ is preferably a hydrogen atom, a methyl group or an ethyl group.

Examples of G ¹ and G ² include alicyclic hydrocarbon groups that may include a hetero atom represented by the formula (g-1) to the formula (g-10), and a 5-membered or 6-membered ring group. Is preferred.

The hydrogen atom contained in the groups represented by the above formulas (g-1) to (g-10) may be substituted with a halogen atom, —R ³ , —OR ³ , a cyano group or a nitro group.

G ¹ and G ² are preferably a cyclohexane-1,4-diyl group, and more preferably a trans-cyclohexane-1,4-diyl group.

Examples of the divalent linking group for ^{B 1,} B 2, ^{E 1} and ^{E 2,} for _{^{example, -CR 7 R 8 -, -}} CH 2 -CH 2 -, - O -, - S -, - CO-O- , —O—CO—O—, —CS—O—, —O—CS—O—, —CO—NR ¹ —, —CH ₂ —O—, —CH ₂ —S—, —NR ¹ —, — CR ⁷ = CR ⁸ -and a single bond are exemplified.

E ¹ and E ² are preferably —CO—O—, —O—CO—O—, —CO—NR ¹ —, —CH ₂ —O—, —CH ₂ —S— and a single bond, -O- is more preferable.

B ¹ and B ² are preferably the same type of group from the viewpoint of easy production of the compound (LC-1). Further since the manufacture is easier compound (LC-1), is ^{B 2} are attached to only ^{B 1} and ^{A 2} are bonded only to ^{A 1,} each _{independently,} -CH ₂ -CH 2 - , —CO—O—, —CO—NH—, —O—CH ₂ — or a single bond is preferred, and —CO—O— is more preferred in that the compound of the present invention exhibits particularly high liquid crystallinity. preferable.
B ¹ bonded to F ¹ and B ² bonded to F ² are each independently —O—, —CO—O—, —O—CO—O—, —CO—NH— or A bond is preferred.

Examples of the divalent alicyclic hydrocarbon group for A ¹ and A ² include groups represented by the above formulas (g-1) to (g-10). The divalent aromatic hydrocarbon group having 6 to 20 carbon atoms in ^{A 1} and ^{A 2,} including but represented by the formula (a-1) ~ formula (a-8).

  A part of hydrogen atoms of the groups represented by the above formulas (a-1) to (a-8) is an alkyl having about 1 to 4 carbon atoms such as a methyl group, an ethyl group, an isopropyl group or a tert-butyl group. Group: alkoxy group having about 1 to 4 carbon atoms such as methoxy group or ethoxy group; trifluoromethyl group; trifluoromethyloxy group; cyano group; nitro group; substituted with halogen atom such as fluorine atom, chlorine atom or bromine atom May be.

A ¹ and A ² are preferably the same type of groups. A ¹ and A ² are preferably a p-phenylene group and a cyclohexane-1,4-diyl group, and more preferably a p-phenylene group. When A ¹ and A ² are the above groups, the production of the compound (LC-1) is easy.

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

As F ¹ and F ² , — (CH ₂ ) ₃ —, — (CH ₂ ) ₄ —, — (CH ₂ ) ₅ —, — (CH ₂ ) ₆ —, — (CH ₂ ) ₇ —, — ( CH ₂ ) ₈ —, — (CH ₂ ) ₉ —, — (CH ₂ ) ₁₀ —, — (CF ₂ ) ₄ —, — (CF ₂ ) ₆ — and — (CF ₂ ) ₈ — are preferred, and — ( CH ₂ ) ₄ — and — (CH ₂ ) ₆ — are more preferred.

P ¹ and P ² each independently represent a hydrogen atom or a polymerizable group. At least one of P ¹ and P ² is preferably a polymerizable group, and more preferably both P ¹ and P ² are polymerizable groups. If P ¹ and P ² are these groups, the resulting optical film tends to be excellent in film hardness.
The polymerizable group may be any group that can participate in the polymerization reaction of the compound (LC-1), and specifically includes a vinyl group, a vinyloxy group, a styryl group, and a p- (2-phenylethenyl) phenyl group. , Acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, carboxy group, acetyl group, hydroxy group, carbamoyl group, C1-C4 N-alkylamino group, amino group, oxiranyl group, oxetanyl group, formyl group , Isocyanato group or isothiocyanato group. Among them, a group bonded to F ¹ or F ² via an ether bond or an ester bond is preferable, and a radical polymerizable group or a cationic polymerizable group is preferable in that it is suitable for photopolymerization, and handling is easy. An acryloyloxy group or a methacryloyloxy group is more preferable, and an acryloyloxy group is particularly preferable in terms of easy production of the compound of the invention.

^{-D 1 -G 1 -E 1 - (} A 1 -B 1) k -F 1 -P 1 and ^{-D 2 -G 2 -E 2 - (} A 2 -B 2) of l ^-F 2 -P ² Specific examples include groups represented by formula (R-1) to formula (R-104). * (Asterisk) represents a bond. Moreover, n in a formula (R-1)-a formula (R-104) represents the integer of 2-12. The cyclohexane ring is preferably a trans isomer.

The ^{-D 1 -G 1 -E 1 - (} A 1 -B 1) k -F 1 -P 1 and ^{-D 2 -G 2 -E 2 - (} A 2 -B 2) l -F 2 -P 2 Among the specific examples, the compounds (R-1) to (R-40) are more preferable because the number of synthesis steps is small and the optical properties are excellent, and the liquid crystallinity of the compound (1-1) is excellent. Compounds (R-1) to (R-36) are particularly preferable.

In order to obtain the compound (LC-1) from the compound (1-1), the compound (7-1) is reacted with oxalyl dichloride and thionyl chloride to form an acid chloride, and then reacted with the compound (1-1). And a method of subjecting compound (7-1) and compound (1-1) to dehydration condensation using a condensing agent.
In order to produce an acid chloride, N, N-dimethylformamide or N-methylimidazolidine may be appropriately added as a catalyst.
From the viewpoint of stability of the compound (7-1), the esterification reaction is more preferably dehydration condensation using a condensing agent.

  Examples of the condensing agent include 1-cyclohexyl-3- (2-morpholinoethyl) carbodiimide met-para-toluenesulfonate, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide, 1-ethyl-3- ( 3-dimethylaminopropyl) carbodiimide hydrochloride (partially water-soluble carbodiimide: commercially available as WSC), bis (2,6-diisopropylphenyl) carbodiimide, bis (trimethylsilyl) carbodiimide, N, N′-diisopropylcarbodiimide, etc. Carbodiimide, 2-methyl-6-nitrobenzoic anhydride, 2,2′-carbonylbis-1H-imidazole, 1,1′-oxalyldiimidazole, diphenylphosphoryl azide, 1 (4-nitrobenzenesulfo ) -1H-1,2,4-triazole, 1H-benzotriazol-1-yloxytripyrrolidinophosphonium hexafluorophosphate, 1H-benzotriazol-1-yloxytris (dimethylamino) phosphonium hexafluorophosphate, N , N, N ′, N′-tetramethyl-O— (N-succinimidyl) uronium tetrafluoroborate, N- (1,2,2,2-tetrachloroethoxycarbonyloxy) succinimide, N-carbobenzoxysuccinimide , O- (6-chlorobenzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium tetrafluoroborate, O- (6-chlorobenzotriazol-1-yl) -N, N , N ′, N′-Tetramethyluronium hexafluorophor Fate, 2-bromo-1-ethylpyridinium tetrafluoroborate, 2-chloro-1,3-dimethylimidazolinium chloride, 2-chloro-1,3-dimethylimidazolinium hexafluorophosphate, 2-chloro-1- Examples include methylpyridinium iodide, 2-chloro-1-methylpyridinium paratoluenesulfonate, 2-fluoro-1-methylpyridinium paratoluenesulfonate, and trichloroacetic acid pentachlorophenyl ester. From the standpoint of reactivity, cost, and usable solvent, as the condensing agent, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride Bis (2,6-diisopropylphenyl) carbodiimide, bis (trimethylsilyl) carbodiimide, N, N′-diisopropylcarbodiimide, and 2,2′-carbonylbis-1H-imidazole are more preferable.

  Examples of the compound (LC-1) include compounds represented by the formula (A1-1) to the formula (A200-8). * Represents a linking part. For example, the compound represented by the formula (A1-1) is a compound represented as follows.

  Since the compound (1-1) obtained by the production method of the present invention is obtained as a product with little coloring, the compound (LC-1) produced using this as a raw material also tends to be obtained as a product with little coloring. . The optical film of this invention is an optical film containing at least 1 sort (s) chosen from the group which consists of a compound (LC-1) and its polymer. By including the above, an optical film having excellent transmittance in the visible light region is obtained. The optical film of the present invention is prepared, for example, by adjusting a liquid crystal composition containing the compound (LC-1) obtained by the production method of the present invention, a polymerization initiator, a leveling agent and a solvent, and placing the liquid crystal composition on the alignment film. It can be obtained by coating and polymerizing the compound (LC-1) in the coating film. If necessary, the liquid crystal composition contains a liquid crystal compound different from the compound (LC-1) (hereinafter sometimes referred to as “liquid crystal compound (A)”), a photosensitizer, and a polymerization inhibitor. Also good. Each component contained in the liquid crystal composition may be used alone or in combination of two or more.

  Specific examples of the liquid crystal compound (A) include the liquid crystal handbook (edited by the Liquid Crystal Handbook Editorial Committee, published by Maruzen Co., Ltd., October 30, 2000), Chapter 3, Molecular Structure and Liquid Crystallinity, 3.2 Non-Chiral Examples thereof include rod-shaped liquid crystal molecules and compounds described in 3.3 chiral rod-shaped liquid crystal molecules. Of these, compounds having a polymerizable group and exhibiting liquid crystallinity are preferred.

  The composition of the present invention preferably contains a polymerization initiator. The polymerization initiator preferably contains a photopolymerization initiator, and the photopolymerization initiator is preferably a photopolymerization initiator that generates radicals by light irradiation.

  Examples of the photopolymerization initiator include benzoin compounds, benzophenone compounds, alkylphenone compounds, acylphosphine oxide compounds, triazine compounds, iodonium salts, and sulfonium salts.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like.
Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl). ) Benzophenone, 2,4,6-trimethylbenzophenone and the like.

  Examples of the alkylphenone compound include α, α-diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1,2-diphenyl-2,2-dimethoxy-1-ethanone, 2-hydroxy-2 -Methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] Examples include propan-1-one oligomers.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, and the like.
Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxy Naphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6 [2- (5-Methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1 , 3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloro Methyl) -6 [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the photopolymerization initiator include Irgacure 907, Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369 (all manufactured by Ciba Japan Co., Ltd.), Sake All BZ, Sake All Z, Sake All BEE (and above, All manufactured by Seiko Chemical Co., Ltd.), kayacure BP100 (manufactured by Nippon Kayaku Co., Ltd.), Kayacure UVI-6992 (manufactured by Dow), Adekaoptomer SP-152 or Adekaoptomer SP-170 (all stocks) Commercially available photopolymerization initiators such as TADE-A, TAZ-PP (manufactured by Nippon Siebel Hegner) and TAZ-104 (manufactured by Sanwa Chemical Co., Ltd.) can also be used.

  As the photopolymerization initiator, an alkylphenone compound and an acylphosphine oxide compound are preferable in that the obtained optical film tends to have high heat resistance and heat and humidity resistance.

  The content of the polymerization initiator in the composition of the present invention is 0.1 part by mass to 30 parts by mass, preferably 0.5 part by mass to 10 parts by mass with respect to a total of 100 parts by mass of the liquid crystal compound. is there. Here, the total of liquid crystal compounds refers to the total amount of the compound (LC-1) and the liquid crystal compound (A). If it is in the said range, a compound (LC-1) can be polymerized, after suppressing disorder of the alignment of the said liquid crystal compound.

  The composition of the present invention may contain a photosensitizer. Examples of the photosensitizer include xanthone compounds such as xanthone or thioxanthone (for example, 2,4-diethylthioxanthone, 2-isopropylthioxanthone), anthracene compounds having a substituent such as anthracene or alkoxy group (for example, dibutoxy). Anthracene, etc.), phenothiazine or rubrene.

  By using a photosensitizer, the polymerization reaction of the compound (LC-1) can be performed with high sensitivity, or the temporal stability of the optical film obtained by polymerization can be improved. Moreover, as content of a photosensitizer, it is 0.1-30 mass parts with respect to a total of 100 mass parts with a liquid crystal compound, Preferably it is 0.5-10 mass parts. If it is in the said range, a compound (LC-1) can be polymerized, after suppressing disorder of the alignment of the said liquid crystal compound.

  The composition of the present invention may contain a polymerization inhibitor. As a polymerization inhibitor, hydroquinone compounds having a substituent such as hydroquinone or alkoxy group, catechol compounds having a substituent such as an alkyl group such as butylcatechol, pyrogallol compounds, 2,2,6,6-tetramethyl-1- Examples include radical scavengers such as piperidinyloxy radicals, thiophenol compounds, β-naphthylamine compounds, and β-naphthol compounds.

  By using a polymerization inhibitor, the polymerization of the liquid crystal compound (A) and the compound (LC-1) can be easily controlled, and the stability of the obtained optical film can be improved. Moreover, content of a polymerization inhibitor is 0.1 mass part-30 mass parts with respect to a total of 100 mass parts of a liquid crystal compound, Preferably it is 0.5 mass part-10 mass parts. If it is in the said range, a compound (LC-1) can be polymerized, after suppressing disorder of the alignment of the said liquid crystal compound.

  Furthermore, the composition of the present invention may contain a leveling agent. As a leveling agent, for example, an additive for radiation-curing coatings (by Big Chemie Japan: BYK-352, BYK-353, BYK-361N), a coating additive (Toray Dow Corning: SH28PA, DC11PA, ST80PA), Paint additives (Shin-Etsu Chemical Co., Ltd .: KP321, KP323, X22-161A, KF6001) or fluorine-based additives (DIC Corporation: F-445, F-470, F-479) can be used. .

  By using a leveling agent, a smoother optical film can be obtained. Furthermore, in the production process of the optical film, the fluidity of the composition of the present invention can be controlled, and the crosslinking density in the obtained optical film can be adjusted. The specific numerical value of the usage-amount of a leveling agent is 0.01 mass part-30 mass parts with respect to a total of 100 mass parts of a liquid crystal compound, for example, Preferably it is 0.05 mass part-10 mass parts. If it is in the said range, disorder of the alignment of a liquid crystal compound can be suppressed.

  The composition of the present invention preferably contains a solvent in terms of fluidity. The solvent may be any solvent that can dissolve the compound of the present invention, liquid crystal compound, etc., and may be any solvent that is inert to the polymerization reaction. Specifically, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol Alcohol solvents such as ethylene glycol methyl ether and ethylene glycol butyl ether; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate and ethyl lactate; acetone, methyl ethyl ketone, cyclopentanone Ketone solvents such as cyclohexanone, 2-heptanone and methyl isobutyl ketone; non-chlorinated aliphatic hydrocarbon solvents such as pentane, hexane and heptane; toluene, xylene, phenol and the like Nitrile solvents such as acetonitrile; non-chlorinated aromatic hydrocarbon solvent of propylene glycol monomethyl ether, tetrahydrofuran, ether solvents such as dimethoxyethane; chloroform, chlorinated hydrocarbon solvents such as chlorobenzene; phenol; and the like. These organic solvents may be used alone or in combination. In particular, the compound of the present invention and the composition of the present invention are excellent in compatibility and can be dissolved in alcohol solvents, ester solvents, ketone solvents, non-chlorinated aliphatic hydrocarbon solvents and non-chlorinated aromatic hydrocarbon solvents. The film can be formed without using a chlorinated hydrocarbon solvent such as chloroform.

The content of the solvent is preferably 50% by mass to 98% by mass and more preferably 50-95% by mass with respect to the composition of the present invention.
Conversely, the concentration of the solid content in the composition of the present invention is 2 to 50% by mass, preferably 5 to 50% by mass. When the solid content concentration is 2% by mass or more, the optical film does not become too thin, and an optical film having a birefringence necessary for optical compensation of the liquid crystal panel tends to be obtained. Moreover, when the concentration of the solid content is 50% by mass or less, the viscosity of the composition does not become too small, and unevenness of the film thickness of the optical film tends to hardly occur. Here, solid content means the component remove | excluding the solvent from the composition of this invention.
In the case where the composition of the present invention contains a solvent, the viscosity is 0.1 to 10 mPa · s, preferably 0.1 to 7 mPa · s, in that it tends to be difficult to cause unevenness in the film thickness of the optical film. It is.

  The optical film of the present invention refers to a film that can transmit light and has an optical function. The optical function means refraction, birefringence and the like. A retardation film, which is a kind of optical film, is used for converting linearly polarized light into circularly polarized light or elliptically polarized light, or conversely converting circularly polarized light or elliptically polarized light into linearly polarized light.

  The optical film of the present invention has a structural unit derived from the compound obtained by the production method of the present invention, and the wavelength dispersion characteristic of the optical film can be adjusted by changing the content of the structural unit. If the content of the structural unit derived from the compound obtained by the production method of the present invention in all the structural units contained in the optical film is increased, the birefringence increases as the wavelength increases (so-called reverse wavelength dispersion characteristic). It tends to be easy to show.

Specifically, according to the present invention, an optical film including the content of a structural unit derived from a compound obtained by the production method of the present invention determined by the operations shown in the following (a) to (e) can be obtained. What is necessary is just to prepare a composition.
(A) About 2 to 5 types of compositions of the present invention having different contents of the compound of the present invention are prepared.
(B) About each prepared composition, it is the same film thickness, and manufactures the optical film from which content of the structural unit derived from the compound obtained by the manufacturing method of this invention differs.
(C) Obtain the retardation value of the optical film obtained in (b).
(D) Based on the retardation value obtained in (c), the correlation between the content of the structural unit derived from the compound obtained by the production method of the present invention and the retardation value of the optical film is obtained.
(E) From the correlation obtained in (d), the content of the structural unit derived from the compound of the present invention necessary to give a desired retardation value to the optical film having the above film thickness is determined.
A value obtained by dividing the phase difference value Re (λ) at a certain wavelength λ by the phase difference value Re (550) at 550 nm (Re (λ) / Re (550)) is close to 1, or [Re (450) / Uniform polarization conversion is possible in the wavelength range showing the reverse wavelength dispersion of Re (550)] <1 and [Re (650) / Re (550)]> 1.

The optical film of the present invention can be obtained by applying the composition of the present invention, drying, light irradiation and / or heating to polymerize the polymerizable component contained in the composition.
When the film of the present invention applied and dried exhibits a liquid crystal phase such as a nematic phase, the resulting optical film exhibits birefringence due to monodomain alignment.

The film thickness of the optical film is adjusted by appropriately adjusting the content of the compound obtained by the production method of the present invention contained in the composition of the present invention and the coating amount of the composition of the present invention on the supporting substrate. be able to. When the amount of the compound of the present invention is constant, the retardation value (retardation value, Re (λ)) of the obtained optical film is expressed by the formula (7).
Re (λ) = d × Δn (λ) (7)
(In the formula, Re (λ) represents a retardation value at a wavelength λnm, d represents a film thickness, and Δn (λ) represents a birefringence at a wavelength λnm.)
Therefore, in order to obtain a desired Re (λ), the film thickness d and Δn (λ) may be adjusted.

  Examples of the method for applying the composition of the present invention to the supporting substrate include an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a CAP coating method, and a die coating method. Moreover, the method of apply | coating using coaters, such as a dip coater, a bar coater, or a spin coater, etc. are mentioned.

  As said support base material, glass, a plastic sheet, a plastic film, or a translucent film can be mentioned, for example. Examples of the translucent film include polyolefin films such as polyethylene, polypropylene and norbornene polymers, polyvinyl alcohol films, polyethylene terephthalate films, polymethacrylate films, polyacrylate films, cellulose ester films, and polyethylene naphthalate films. , Polycarbonate film, polysulfone film, polyethersulfone film, polyetherketone film, polyphenylene sulfide film or polyphenylene oxide film.

  Even in processes where the strength of the optical film is required, such as an optical film bonding process, a transport process, and a storage process, the support substrate can be used and can be easily handled without tearing.

  After forming the alignment film on the supporting substrate, it is preferable to apply the composition of the present invention on the alignment film. The alignment film preferably has solvent resistance that does not dissolve in the composition when the composition of the present invention is applied. In addition, the alignment film preferably has heat resistance in the heat treatment for solvent removal and liquid crystal alignment. Furthermore, it is preferable that peeling due to friction or the like does not occur during rubbing. Such an alignment film is preferably composed of an alignment polymer or a composition containing an alignment polymer.

  Examples of the orientation polymer include polyamides and gelatins having an amide bond in the molecule, polyimides having an imide bond in the molecule, and polyamic acid, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, polyacrylamide which are hydrolysates thereof. Mention may be made of polymers such as oxazole, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid or polyacrylic acid esters. These polymers may be used alone, or two or more kinds thereof may be mixed or copolymerized. These polymers can be easily obtained by polycondensation such as dehydration and deamination, chain polymerization such as radical polymerization, anion polymerization, and cation polymerization, coordination polymerization, and ring-opening polymerization.

  These orientation polymers are dissolved in a solvent and used as a solution. The solvent is not particularly limited, but specifically water; alcohol solvent such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether; ethyl acetate, butyl acetate, ethylene glycol Ester solvents such as methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, methyl isobutyl ketone; pentane, hexane, heptane, etc. Non-chlorinated aliphatic hydrocarbon solvents; Non-chlorinated aromatic hydrocarbon solvents such as toluene and xylene; Nitrile solvents such as acetonitrile; Propylene glycol mono Chirueteru, tetrahydrofuran, ether solvents such as dimethoxyethane; chloroform, chlorinated hydrocarbon solvents such as chlorobenzene; and the like. These organic solvents may be used alone or in combination.

  The alignment film may be formed using a commercially available alignment film material as it is. Examples of commercially available alignment film materials include Sunever (registered trademark, manufactured by Nissan Chemical Industries, Ltd.) or Optmer (registered trademark, manufactured by JSR Corporation).

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

  Examples of a method for forming an alignment film on a supporting substrate include a method in which a commercially available alignment film material or a compound serving as an alignment film material is applied as a solution on a supporting substrate and then annealed. .

  The thickness of the alignment film is 10 nm to 10000 nm, preferably 10 nm to 1000 nm. If it is the said range, the compound of this invention etc. can be oriented at a desired angle on this alignment film.

  If necessary, the alignment film may be rubbed, or the alignment film may be subjected to polarized UV irradiation, and the compound of the present invention can be aligned in a desired direction by such treatment. That is, the shape and inclination of the refractive index ellipsoid showing the birefringence state of the manufactured optical film can be adjusted.

  As a method for rubbing the alignment film, for example, a method in which a rubbing cloth is wound and a rotating rubbing roll is brought into contact with the alignment film being carried on the stage can be mentioned.

  The method of laminating an unpolymerized film on an alignment film laminated on such a support substrate can reduce the production cost as compared with a method of producing a liquid crystal cell and injecting a liquid crystal compound into the liquid crystal cell. Furthermore, it is possible to produce a roll film.

  Examples of the method for removing the solvent include natural drying, ventilation drying, and reduced pressure drying. The drying temperature is preferably 0 to 250 ° C, more preferably 0 to 200 ° C, and still more preferably 30 to 190 ° C. Further, the drying time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes. If the drying temperature and the drying time are within the above ranges, a supporting substrate that is not necessarily sufficient in heat resistance can be used as the supporting substrate.

  After drying, the polymerizable component contained in the composition of the present invention is polymerized to obtain a film in which the orientation of the compound of the present invention is fixed. Since the orientation of the optical film of the present invention is fixed, it is not easily affected by birefringence due to heat.

What is necessary is just to determine suitably the method of superposing | polymerizing the polymeric component contained in the composition of this invention according to the kind of compound of this invention. If the polymerizable group of the compound of the present invention is photopolymerizable, the photopolymerization method is used, and if the polymerizable group is heat polymerizable, the thermal polymerization method is used. According to the photopolymerization method, an unpolymerized film can be polymerized at a low temperature, the heat resistance selection range of the supporting substrate is widened, and the photopolymerizable polymerizability is easy in terms of industrial production. Preference is given to using the compounds of the invention having a group. Photopolymerization is also preferred from the viewpoint of film formability. This is performed by irradiating a cured unpolymerized film by a photopolymerization method with visible light, ultraviolet light or laser light. In view of easy handling, ultraviolet light is preferable. Light irradiation is performed at a temperature at which the compound of the present invention takes a liquid crystal phase. It is also possible to obtain the optical film of the present invention patterned by masking and light irradiation.
The birefringence Δn (λ) can be adjusted so as to give a desired phase difference by appropriately adjusting the exposure amount, the heating temperature, and the heating time during polymerization.

  The optical film of the present invention is thinner than a stretched film that gives a phase difference by stretching a polymer.

  By peeling the support substrate, a film in which the alignment film and the optical film of the present invention are laminated is obtained. Furthermore, the alignment film can be peeled off to obtain a film consisting only of the optical film of the present invention.

  The optical film thus obtained is excellent in transparency and used as various films for display devices. As described above, the thickness of the optical film varies depending on the retardation value of the optical film, but is preferably 0.1 to 10 μm, and is 0.2 to 5 μm in terms of reducing photoelasticity. Is more preferable, and 0.5 to 3 μm is particularly preferable.

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

  As described above, the optical film of the present invention that is a thin film and capable of uniform polarization conversion in a wider wavelength range can be used as an optical compensation film in a flat panel display device such as a liquid crystal panel or an organic EL panel.

  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 λ / 2 plate, the content of the structural unit derived from the compound of the present invention in the optical film may be appropriately selected. In the case of a λ / 4 plate, Re (550) of the obtained optical film may be adjusted to a film thickness of 113 to 163 nm, preferably 135 to 140 nm, particularly preferably about 137.5 nm. In such a case, the film thickness may be adjusted so that Re (550) of the obtained optical film is 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 a VA (vertical alignment) mode. When used as an optical film for VA mode, the content of the structural unit derived from the compound of the present invention 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 60 to 80 nm.

The optical film of the present invention is an antireflection film such as an anti-reflection (AR) film, a polarizing film, a retardation film, an elliptical polarizing film, a broadband circular polarizing film, a viewing angle widening film, or a viewing angle compensation optical for a transmissive liquid crystal display. It can also be used for compensation films.
The optical film of the present invention exhibits excellent optical properties even when one sheet is used, but a plurality of sheets may be used by laminating. Moreover, you may use in combination with another film. Specific examples in combination with other films include an elliptically polarizing plate in which the optical film of the present invention is bonded to a polarizing film, and a broadband circle in which the optical film of the present invention is bonded to the polarizing film as a broadband λ / 4 plate. A polarizing plate etc. are mentioned.

  Since the optical film of the present invention can be formed by coating and polymerizing on a support substrate or an alignment film, as shown in FIG. , Λ / 2 optical film can be formed.

  Hereinafter, the present invention will be described in more detail with reference to examples. Unless otherwise specified, “%” and “parts” in the examples are% by mass and parts by mass.

Example 1
[Synthesis of Compound (1-1)]
Compound (A-036) was synthesized according to the following scheme.

<Synthesis Example of Compound (36-b)>
Compound (36-a) 16.0 g, 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetan-2,4-disulfide (Lawson reagent) 9.2 g and toluene 100 g. The resulting mixture was heated to 80 ° C. and reacted for 12 hours. After cooling, the mixture was concentrated to obtain a red viscous solid containing the compound (36-b) and a decomposition product of Lawson reagent as main components.

<Synthesis Example of Compound (B-036)>
The mixture containing the compound (36-b) obtained in the previous item, 11.8 g of sodium hydroxide and 250 g of water were mixed, and the resulting mixture was reacted under ice cooling. Subsequently, an aqueous solution containing 44.17 g of potassium ferricyanide was added and reacted under ice cooling. The reaction was carried out at 60 ° C. for 12 hours, and the yellow precipitate thus deposited was collected by filtration. The precipitate collected by filtration was washed with water and then with hexane and crystallized with toluene. The obtained yellow color was vacuum-dried to obtain 4.1 g of an ocherous solid containing the compound (B-036) as a main component. The yield was 25% based on the compound (36-a).

<Synthesis Example of Compound (C-036) and Compound (A-036)>
5.00 g of compound (B-036) was dissolved in 161.67 g of acetonitrile, and the mixture was stirred at 0 ° C. for 10 minutes in a nitrogen atmosphere. To the solution, 84.24 g of 20% aqueous cerium ammonium nitrate solution was added and stirred for 15 minutes. The precipitated red precipitate was collected by filtration and washed twice with 100 mL of pure water. The obtained red powder was mainly composed of compound (C-036). The crude compound (C-036) was dispersed in 50 mL of tetrahydrofuran and 50 mL of pure water, stirred for 15 minutes under a nitrogen atmosphere, then added with 15 g of sodium nitrite, and stirred at room temperature for 5 hours. Tetrahydrofuran was distilled off from the reaction solution with an evaporator, and the precipitated yellow powder was collected by filtration and dried under vacuum to obtain 4.15 g of compound (A-036). The yield was 90.8% based on the compound (B-036).

¹ H-NMR (DMSO) of compound (A-036): δ (ppm) 2.43 (s, 3H), 2.52 (s, 3H), 6.71 to 6.80 (m, 2H), 7.00 (s, 1H), 7.36 (s, 1H), 7.76 (s, 1H), 9.58 (s, 1H), 9.90 (s, 1H).

(Example 2)
[Synthesis of Compound (LC-1)]
Compound (A36-1) was synthesized according to the following scheme.

<Synthesis of Compound (A36-1)>
Compound (A-036) 3.00g, compound (A) 8.47g, dimethylaminopyridine 0.12g, and chloroform 40mL were mixed. To the resulting mixture, 2.92 g of N, N′-diisopropylcarbodiimide was added under ice cooling. The resulting reaction solution was reacted at room temperature overnight, filtered through celite, and concentrated under reduced pressure. Methanol was added to the residue for crystallization. The crystals were collected by filtration, washed with heptane, and dried under vacuum to obtain 8.73 g of compound (A36-1) as a white powder. The yield was 82% based on the compound (A-036).

¹ H-NMR (CDCl ₃ ) of the compound (A36-1): δ (ppm) 1.45 to 1.85 (m, 24H), 2.36 to 2.87 (m, 18H), 3.93 to 3.97 (t, 4H), 4.15 to 4.20 (t, 4H), 5.79 to 5.84 (dd, 2H), 6.07 to 6.17 (m, 2H), 6. 37-6.45 (m, 2H), 6.87-7.01 (m, 9H), 7.20 (s, 1H), 7.23 (s, 2H), 7.53 (s, 1H)

(Comparative Example 1)
[Synthesis of Compound (1-1)]
Compound A36-1 and Compound A-036 were synthesized according to the following scheme. * (Asterisk) indicates that it was synthesized by a production method not according to the present invention as a comparative example.

<Synthesis Example of Compound (A-036) ^* >
Compound (B-036) 4.0 g and pyridinium chloride 40.0 g (10-fold mass) were mixed, heated to 200 ° C., and reacted for 3 hours. The resulting mixture was added to ice and the resulting precipitate was collected by filtration. After rinsing with water, it was washed with toluene and vacuum dried to obtain 3.4 g of a brown solid mainly composed of compound (A-036) ^* . The yield was 93% based on the compound (36-c).

[Synthesis of Compound (LC-1)]
Compound (A-036) ^* 3.00 g, 8.47 g of compound (A), 0.12 g of dimethylaminopyridine and 40 mL of chloroform were mixed. To the resulting mixture, 2.92 g of N, N′-diisopropylcarbodiimide was added under ice cooling. The resulting reaction solution was reacted at room temperature overnight, filtered through celite, and concentrated under reduced pressure. Methanol was added to the residue for crystallization. The crystals were collected by filtration, washed with heptane, and dried under vacuum to obtain 8.65 g of compound (A36-1) ^* as a brown powder. The yield was 81% based on the compound (A-036) ^* .

¹ H-NMR (CDCl ₃ ) of Compound (A36-1) ^* : δ (ppm) 1.45 to 1.85 (m, 24H), 2.36 to 2.87 (m, 18H), 3.93 To 3.97 (t, 4H), 4.15 to 4.20 (t, 4H), 5.79 to 5.84 (dd, 2H), 6.07 to 6.17 (m, 2H), 6 .37-6.45 (m, 2H), 6.87-7.01 (m, 9H), 7.20 (s, 1H), 7.23 (s, 2H), 7.53 (s, 1H) )

<Measurement of absorbance of compound>
For the compound (A36-1) obtained in Example 2 and the compound (A36-1) ^* obtained in Comparative Example 1, the UV-visible light spectrum of each 1 mM chloroform solution is UV2450 (manufactured by JASCO). And measured. Table 1 shows the absorbance and molar extinction coefficient ε of each compound at 400 nm.

(Example 3)
<Adjustment of liquid crystal composition>
The following components were mixed to prepare a liquid crystal composition.
Compound (LC-1); Compound (A36-1) obtained in Example 2 19.4 parts Polymerization initiator; Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (Irgacure 819; manufactured by BASF Japan Ltd.) 0.58 parts Leveling agent; polyacrylate compound (BYK-361N; manufactured by Big Chemie Japan) 0.02 parts Solvent; cyclopentanone 80 parts

<Example of optical film production>
A 2% by weight aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified type, manufactured by Wako Pure Chemical Industries, Ltd.) was applied to a glass substrate, and after drying, a film having a thickness of 89 nm was formed. Subsequently, the surface of the obtained film was rubbed, and the liquid crystal composition obtained above was applied to the rubbed surface by a spin coat method and dried at 150 ° C. for 1 minute. Subsequently, an ultraviolet ray having an integrated light amount of 2400 mJ / cm ² (365 nm reference) was irradiated at 95 ° C. to obtain an optical film.

<Evaluation of optical film>
The front retardation value of the optical film was measured using a measuring machine (KOBRA-WR, manufactured by Oji Scientific Instruments). In addition, since the glass substrate used for the base material has no birefringence, the front retardation value of the optical film produced on the glass substrate can be obtained by measuring the film with the glass substrate with a measuring machine. . The obtained optically measured 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)] (referred to as α). And [Re (627.8) / Re (546.9)] (referred to as β). Moreover, the film thickness (micrometer) of the optical film was measured using the laser microscope (LEXT, Olympus company make). Δn was calculated by dividing the value of Re (546.9) by the film thickness (Δn = Re (546.9) / d). The transmittance at each wavelength was measured by UV2450 (manufactured by JASCO). The results are shown in Table 2.

(Comparative Example 2)
A liquid crystal composition was prepared in the same manner as in Example 3, except that the compound (A36-1) obtained in Example 2 was replaced with the compound (A36-1) ^* obtained in Comparative Example 1. Further, an optical film was produced in the same manner as in Example 3, and evaluated. The results are shown in Table 2.

  From the above results, it was confirmed that according to the production method of the present invention, a dihydroxybenzene compound was obtained as a product with a brown color suppressed in a high yield without requiring a high temperature reaction. Moreover, according to the liquid crystal compound manufactured from the dihydroxybenzene compound as a product obtained by the manufacturing method of the present invention, it was confirmed that an optical film having a high transmittance in the visible light region, that is, a little colored film, can be obtained.

  According to the method for producing a dihydroxybenzene compound of the present invention, a dihydroxybenzene compound can be obtained as a product with a high yield and a little brown taste.

Claims (6)

The manufacturing method of the dihydroxybenzene compound represented by Formula (1-1) including a process (1) and a process (2).

[In Formula (1-1), Q ¹ each independently represents —CR ¹ R ² —, —S—, —NR ¹ —, —CO—, or —O—. R ¹ and R ² each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
Y ¹ represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent. ]
(1) A step of causing an oxidizing agent to act on the compound represented by the formula (2-1)

[In Formula (2-1), Q ¹ and Y ¹ represent the same meaning as described above. Z ¹ and Z ² each independently represent a methyl group or an ethyl group. ]
(2) A step of reducing the product obtained in step (1)   The production method according to claim 1, wherein the oxidizing agent is silver nitrate, cerium (IV) ammonium nitrate, or a Koser reagent.   The production method according to claim 1 or 2, wherein the reduction is reduction with sodium nitrite, reduction with metal hydride, reduction with metal hydride complex or catalytic hydrogen reduction.   The production method according to claim 1, wherein the reduction is reduction performed in a mixed solvent of water and a cyclic ether. In formula (LC-1) including the step of esterifying the compound represented by formula (1-1) produced by the production method according to claim 1 and compound (7-1) A method for producing a liquid crystal compound represented.

[In Formula (7-1), D ¹ and D ² each independently represents a single bond or a divalent linking group.
G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group, and the hydrogen atom contained in the alicyclic hydrocarbon group is a halogen atom, —R ³ , —OR ³ , or a cyano group. Alternatively, it may be substituted with a nitro group, and the —CH ₂ — group contained in the alicyclic hydrocarbon group may be substituted with —O—, —S— or —NH—.
A ¹ and A ² each independently represent a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group, and hydrogen contained in the alicyclic hydrocarbon group and the aromatic hydrocarbon group The atom may be substituted with a halogen atom, —R ³ , —OR ³ , a cyano group, or a nitro group.
R ³ represents an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a fluorine atom.
B ¹ , B ² , E ¹ and E ² each independently represent a single bond or a divalent linking group.
k and l each independently represents an integer of 0 to 3. When k is an integer of 2 or more, the plurality of A ¹ and B ¹ may be the same as or different from each other. If l is an integer of 2 or more, plural A ² and B ² may be the same or different from each other.
F ¹ and F ² each independently represent an alkanediyl group having 1 to 12 carbon atoms, and a hydrogen atom contained in the alkanediyl group may be substituted with a halogen atom, and is contained in the alkanediyl group The —CH ₂ — group may be substituted with —O— or —CO—.
P ¹ and P ² each independently represent a hydrogen atom or a polymerizable group. ]

[In Formula (LC-1), D ¹ , D ² , G ¹ , G ² , B ¹ , B ² , E ¹ , E ² , A ¹ , A ² , k, l, F ¹ , F ² , P ¹ , P ² , Y ¹ and Q ¹ represent the same meaning as described above. ]   An optical film comprising at least one selected from the group consisting of a liquid crystal compound obtained by the production method according to claim 5 and a polymer thereof.