JP2011207765A - Compound, optical film and method for producing optical film - Google Patents

Abstract

【選択図】なしThe present invention provides a new compound that provides an optical film capable of uniform polarization conversion in a wide wavelength range.
A compound containing a divalent group represented by formula (1-1) or formula (1-2). [Z1 and Z2 are hydrogen atoms, Q1 and Q2 are -CR1R2-, -S-, -NR2-, -CO- or -O-, and G1 and G2 are divalent alicyclic hydrocarbons. Represents a group. ]

[Selection figure] None

Description

  The present invention relates to a compound, an optical film, and a method for producing an optical film.

A flat panel display (FPD) includes members using optical films such as a polarizing plate and a retardation plate. For example, an optical film obtained by polymerizing a solution obtained by dissolving a polymerizable compound represented by the following formula (trade name; LC242, manufactured by BASF) in a solvent on a support substrate is used for the optical film. Film is known. The optical film is known to perform polarization conversion, but is not known to perform uniform polarization conversion in a wide wavelength range.

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

  There is a need for a polymerizable compound that provides an optical film that performs uniform polarization conversion in a wide wavelength range.

The present invention is the following inventions.
1. The compound containing the bivalent group represented by Formula (1-1) or Formula (1-2).

[In Formula (1-1) and Formula (1-2), Z ¹ and Z ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, or a carbon number. An alkylsulfinyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, a carboxy group, a fluoroalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylsulfanyl group having 1 to 6 carbon atoms, C1-C6 N-alkylamino group, C2-C12 N, N-dialkylamino group, C1-C6 N-alkylsulfamoyl group or C2-C12 N, N- Represents a dialkylsulfamoyl group.
Q ¹ and Q ² each independently represent —CR ¹ R ² —, —S—, —NR ² —, —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 optionally substituted polycyclic aromatic hydrocarbon group or polycyclic aromatic heterocyclic group.
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. The hydrogen atom contained in 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, a cyano group, or a nitro group. The —CH ₂ — group contained in the alicyclic hydrocarbon group may be substituted with —O—, —S—, or —NH—. ]

［式（２−１）及び式（２−２）中、Ｚ^１、Ｚ^２、Ｑ^１、Ｑ^２、Ｙ^１、Ｄ^１、Ｄ^２、Ｇ^１及びＧ^２は、上記と同じ意味を表す。
Ｅ^１及びＥ^２は、それぞれ独立に、単結合又は２価の連結基を表す。
Ｂ^１及びＢ^２は、それぞれ独立に、単結合又は２価の連結基を表す。
Ａ^１及びＡ^２は、それぞれ独立に、２価の脂環式炭化水素基又は２価の芳香族炭化水素基を表す。該２価の脂環式炭化水素基及び２価の芳香族炭化水素基に含まれる水素原子は、ハロゲン原子、炭素数１〜４のアルキル基、炭素数１〜４アルコキシ基、シアノ基又はニトロ基で置換されていてもよい。該炭素数１〜４のアルキル基及び該炭素数１〜４アルコキシ基に含まれる水素原子は、フッ素原子で置換されていてもよい。
ｋ及びｌは、それぞれ独立に、０〜３の整数を表す。ｋが２以上の整数である場合、複数のＡ^１及びＢ^１は互いに同一であっても異なっていてもよい。ｌが２以上の整数である場合、複数のＡ^２及びＢ^２は互いに同一であっても異なっていてもよい。］ 2. 1. containing a divalent group represented by formula (2-1) or formula (2-2) The described compound.

[In Formula (2-1) and Formula (2-2), Z ¹ , Z ² , Q ¹ , Q ² , Y ¹ , D ¹ , D ² , G ¹ and G ² represent the same meaning as described above. .
E ¹ and E ² each independently represents a single bond or a divalent linking group.
B ¹ and B ² each independently represent a single bond or a divalent linking group.
A ¹ and A ² each independently represent a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group. The hydrogen atom contained in the divalent alicyclic hydrocarbon group and divalent aromatic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group. It may be substituted with a group. The hydrogen atom contained in the alkyl group having 1 to 4 carbon atoms and the alkoxy group having 1 to 4 carbon atoms may be substituted with a fluorine atom.
k and l each independently 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 being the same or different. ]

［式（３−１）及び式（３−２）中、Ｚ^１、Ｚ^２、Ｑ^１、Ｑ^２、Ｙ^１、Ｄ^１、Ｄ^２、Ｇ^１、Ｇ^２、Ｅ^１、Ｅ^２、Ｂ^１、Ｂ^２、Ａ^１、Ａ^２、ｋ及びｌは、上記と同じ意味を表す。
Ｆ^１及びＦ^２は、それぞれ独立に、炭素数１〜１２のアルカンジイル基を表す。該アルカンジイル基に含まれる水素原子は、炭素数１〜５のアルキル基、炭素数１〜５のアルコキシ基又はハロゲン原子で置換されていてもよく、該アルカンジイル基に含まれる−ＣＨ_２−は、−Ｏ−又は−ＣＯ−で置換されていてもよい。
Ｐ^１及びＰ^２は、それぞれ独立に、水素原子又は重合性基を表す。］ 3. 1. represented by formula (3-1) or formula (3-2) Or 2. The described compound.

[In Formula (3-1) and Formula (3-2), Z ¹ , Z ² , Q ¹ , Q ² , Y ¹ , D ¹ , D ² , G ¹ , G ² , E ¹ , E ² , B ¹ , B ² , A ¹ , A ² , k and l represent the same meaning as described above.
F ¹ and F ² each independently represents an alkanediyl group having 1 to 12 carbon atoms. The hydrogen atom contained in the alkanediyl group may be substituted with an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a halogen atom, and —CH ₂ — contained in the alkanediyl group. May be substituted with -O- or -CO-.
P ¹ and P ² each independently represent a hydrogen atom or a polymerizable group. ]

［式（Ｙ^１−１）及び式（Ｙ^１−４）中、＊印は結合手を表し、Ｚ^３は、それぞれ独立に、ハロゲン原子、炭素数１〜６のアルキル基、シアノ基、ニトロ基、ニトロソ基、炭素数１〜６のアルキルスルホニル基、炭素数１〜６のアルキルスルフィニル基、カルボキシ基、炭素数１〜６のフルオロアルキル基、炭素数１〜６のアルコキシ基、炭素数１〜６のアルキルスルファニル基、炭素数２〜８のＮ，Ｎ−ジアルキルアミノ基、炭素数１〜４のＮ−アルキルアミノ基、スルファモイル基、炭素数１〜６のＮ−アルキルスルファモイル基又は炭素数２〜１２のＮ，Ｎ−ジアルキルスルファモイル基を表す。
Ｖ^１は、−ＣＯ−、−Ｓ−、−ＮＲ^３−、−Ｏ−、−Ｓｅ−又は−ＳＯ_２−を表す。
Ｗ^１〜Ｗ^５は、それぞれ独立に、−ＣＲ^３＝又は−Ｎ＝を表す。
ただし、Ｖ^１及びＷ^１〜Ｗ^５のうち少なくとも１つは、Ｓ、Ｎ、Ｏ又はＳｅを含む基を表す。
Ｒ^３は、水素原子又は炭素数１〜４のアルキル基を表す。
ａは、それぞれ独立に、０〜３の整数を表す。］ 4). 1. Y ¹ is a group represented by formula (Y ¹ -1) or formula (Y ¹ -4) ~ 3. The compound in any one of these.

[In formula (Y ¹ -1) and formula (Y ¹ -4), * represents a bond, and Z ³ each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, or a nitro group. Group, nitroso group, alkylsulfonyl group having 1 to 6 carbon atoms, alkylsulfinyl group having 1 to 6 carbon atoms, carboxy group, fluoroalkyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, carbon number 1 -6 alkylsulfanyl group, N, N-dialkylamino group having 2 to 8 carbon atoms, N-alkylamino group having 1 to 4 carbon atoms, sulfamoyl group, N-alkylsulfamoyl group having 1 to 6 carbon atoms, or An N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms is represented.
V ¹ represents —CO—, —S—, —NR ³ —, —O—, —Se— or —SO ₂ —.
W ¹ to ^W-5 each independently represent a -CR ³ = or -N =.
However, at least one of V ¹ and W ^{1 to} W ⁵ represents a group containing S, N, O, or Se.
R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
a represents the integer of 0-3 each independently. ]

［式（Ｙ^３−１）及び式（Ｙ^３−３）中、Ｚ^３、ａ、Ｖ^１及びＷ^１は、上記と同じ意味を表す。］ 5. 1. Y ¹ is a group represented by the formula (Y ³ -1) or the formula (Y ³ -3). ~ 4. The compound in any one of these.

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

6). ^3. V ₁ is -S-, -NR ³ -or -O-. Or 5. The described compound.

7). 1. G ₁ and G ₂ are trans-1,4-cyclohexanediyl groups ~ 6. The compound in any one of these.

8). A ¹ and A ² are each independently a 1,4-phenylene group or a 1,4-cyclohexanediyl group, and the hydrogen atoms contained in the 1,4-phenylene group and 1,4-cyclohexanediyl group are 1. It may be substituted with a halogen atom, an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, a cyano group or a nitro group. ~ 7. The compound in any one of these.

9. Of B ¹ and ^{B 2, B 1} and ^{B 2} are attached only ^{A 1} or ^{A 2} are each _{independently, -CH 2 -CH 2 -, -} CO-O -, - O-CO-, -CO-NH -, - NH- CO -, - O-CH 2 -, - is CH 2 -O- or a single bond,
Of B ¹ and ^{B 2, B 1} and ^{B 2} are attached with the ^{F 1} or ^{F 2} are each independently, -O -, - CO-O -, - O-CO -, - O-CO- 1. O—, —CO—NH—, —NH—CO— or a single bond. ~ 8. The compound in any one of these.

10. 2. P ¹ and P ² are each independently a hydrogen atom, an acryloyloxy group or a methacryloyloxy group (provided that at least one of P ¹ and P ² represents an acryloyloxy group or a methacryloyloxy group). ~ 9. The compound in any one of these.

11. 1. -10. The composition containing any one of these, and the compound represented by Formula (20).
^{P 11 -E 11 - (B 11} -A 11) t -B 12 -G (20)
[In the formula (20), A ¹¹ represents a divalent aromatic hydrocarbon group, alicyclic hydrocarbon group or heterocyclic group, and the aromatic hydrocarbon group, alicyclic hydrocarbon group and heterocyclic group The hydrogen atom contained in is a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an N-alkylamino group having 1 to 6 carbon atoms, or N, N- having 2 to 12 carbon atoms. It may be substituted with a dialkylamino group, a nitro group, a cyano group or a sulfanyl group.
B ¹¹ and ^{B 12} are each ^{independently, -CR 14 R 15 -, -} C≡C -, - CH = CH -, - CH 2 -CH 2 -, - O -, - S -, - C (= O)-, -C (= O) -O-, -O-C (= O)-, -O-C (= O) -O-, -C (= S)-, -C (= S). -O-, -OC (= S)-, -CH = N-, -N = CH-, -N = N-, -C (= O) -NR < ¹⁶ >-, -NR < ¹⁶ > -C (= O) —, —OCH ₂ —, —OCF ₂ —, —NR ¹⁶ —, —CH ₂ O—, —CF ₂ O—, —CH═CH—C (═O) —O—, —O—C ( = O) -CH = CH- or a single bond. R ¹⁴ and R ¹⁵ each independently represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms, and R ¹⁴ and R ¹⁵ are connected to form an alkanediyl group having 4 to 7 carbon atoms. Also good. R ¹⁶ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
E ¹¹ represents an alkanediyl group having 1 to 12 carbon atoms. The hydrogen atom contained in the alkanediyl group may be substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogen atom.
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, carbon A hydrogen atom contained in the alkanediyl group, which is a N, N-dialkylamino group having 2 to 26, a cyano group, or a nitro group, or a polymerizable group bonded via an alkanediyl group having 1 to 12 carbon atoms. The atom may be substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogen atom.
t represents an integer of 1 to 5. If t is an integer of 2 or more, a plurality of A ¹¹ and B ¹¹ may be the being the same or different. ]

  12 Furthermore, it contains a polymerization initiator. The composition as described.

  13. 11. The polymerization initiator is a polymerization initiator containing an acetophenone compound. Composition.

  14 1. -10. An optical film obtained by polymerizing the compound according to any one of the above.

  15. 11. ~ 13. An optical film obtained by polymerizing the composition according to any one of the above.

  16. 13. For a λ / 4 plate having a retardation value (Re (550)) of 113 to 163 nm at a wavelength of 550 nm Or 15. The optical film as described.

  17. 13. For a λ / 2 plate having a retardation value (Re (550)) of 250 to 300 nm at a wavelength of 550 nm Or 15. The optical film as described.

  18. 14 -17. A polarizing plate comprising any one of the optical film and polarizing film.

  19. 14 -17. A color filter formed by forming the optical film according to any one of the above on an alignment film coated on a color filter substrate.

  20. 19. A liquid crystal display device comprising the described color filter.

  21. 18. A flat panel display comprising a liquid crystal panel comprising the polarizing plate described.

  22. 18. An organic electroluminescence display provided with the organic electroluminescent panel containing the polarizing plate of description.

  23. 1. -10. The manufacturing method of the unpolymerized film which apply | coats the solution containing the compound in any one of these to a support base material, and is dried.

  24. 1. -10. A method for producing an unpolymerized film, wherein a solution containing the compound according to any one of the above is applied onto an alignment film formed on a supporting substrate and dried.

  25. 23. Or 24. The manufacturing method of the optical film which hardens the unpolymerized film obtained by the manufacturing method of the unpolymerized film of description by superposition | polymerization.

  According to the compound of this invention, the optical film which performs uniform polarization conversion in a wide wavelength range can be manufactured.

It is the schematic which shows the color filter 1 which concerns on this invention. It is the schematic which shows the liquid crystal display device 5 which concerns on this invention. It is the schematic which shows the polarizing plate 30 which concerns on this invention. It is the schematic which shows the bonding product 21 of the liquid crystal panel 20 and the polarizing plate 30 of the liquid crystal display device which concerns on this invention. It is the schematic which shows the organic electroluminescent panel 23 of the organic electroluminescent display apparatus which concerns on this invention.

The compound of this invention contains the bivalent group represented by Formula (1-1) or Formula (1-2).

[In Formula (1-1) and Formula (1-2), Z ¹ and Z ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, or a carbon number. An alkylsulfinyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, a carboxy group, a fluoroalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylsulfanyl group having 1 to 6 carbon atoms, C1-C6 N-alkylamino group, C2-C12 N, N-dialkylamino group, C1-C6 N-alkylsulfamoyl group or C2-C12 N, N- Represents a dialkylsulfamoyl group.
Q ¹ and Q ² each independently represent —CR ¹ R ² —, —S—, —NR ² —, —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 optionally substituted polycyclic aromatic hydrocarbon group or polycyclic aromatic heterocyclic group.
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. The hydrogen atom contained in 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, a cyano group, or a nitro group. The methylene group contained in the alicyclic hydrocarbon group may be substituted with —O—, —S—, or —NH—. ]

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

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

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

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

  Examples of the fluoroalkyl group having 1 to 6 carbon atoms include a fluoromethyl group, a trifluoromethyl group, a fluoroethyl group, a pentafluoroethyl group, a heptafluoropropyl group, and a nonafluorobutyl group. A fluoroalkyl group is preferred, a C1-C2 fluoroalkyl group is more preferred, and a trifluoromethyl group is particularly preferred.

  Examples of the alkoxy group having 1 to 6 carbon atoms include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, and hexyloxy group. An alkoxy group having 1 to 4 carbon atoms is preferable, an alkoxy group having 1 to 2 carbon atoms is more preferable, and a methoxy group is particularly preferable.

  Examples of the alkylsulfanyl group having 1 to 6 carbon atoms include methylsulfanyl group, ethylsulfanyl group, propylsulfanyl group, isopropylsulfanyl group, butylsulfanyl group, isobutylsulfanyl group, sec-butylsulfanyl group, tert-butylsulfanyl group, pentylsulfanyl group Group, hexylsulfanyl group, and the like, an alkylsulfanyl group having 1 to 4 carbon atoms is preferable, an alkylsulfanyl group having 1 to 2 carbon atoms is more preferable, and a methylsulfanyl group is particularly preferable.

  Examples of the N-alkylamino group having 1 to 6 carbon atoms include N-methylamino group, N-ethylamino group, N-propylamino group, N-isopropylamino group, N-butylamino group, N-isobutylamino group, N-sec-butylamino group, N-tert-butylamino group, N-pentylamino group, N-hexylamino group and the like can be mentioned, and an N-alkylamino group having 1 to 4 carbon atoms is preferable, and 1 to N-alkylamino group of 2 is more preferable, and N-methylamino group is particularly preferable.

  Examples of the N, N-dialkylamino group having 2 to 12 carbon atoms include N, N-dimethylamino group, N-methyl-N-ethylamino group, N, N-diethylamino group, N, N-dipropylamino group, N, N-diisopropylamino group, N, N-dibutylamino group, N, N-diisobutylamino group, N, N-dipentylamino group, N, N-dihexylamino group and the like can be mentioned. An N, N-dialkylamino group is preferable, an N, N-dialkylamino group having 2 to 4 carbon atoms is more preferable, and an N, N-dimethylamino group is particularly preferable.

  Examples of the N-alkylsulfamoyl group having 1 to 6 carbon atoms include N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N- Butylsulfamoyl group, N-isobutylsulfamoyl group, N-sec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N-hexylsulfamoyl group, etc. N-alkylsulfamoyl group having 1 to 4 carbon atoms is preferable, N-alkylsulfamoyl group having 1 to 2 carbon atoms is more preferable, and N-methylsulfamoyl group is particularly preferable.

  Examples of the N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms include N, N-dimethylsulfamoyl group, N-methyl-N-ethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-dipropylsulfamoyl group, N, N-diisopropylsulfamoyl group, N, N-dibutylsulfamoyl group, N, N-diisobutylsulfamoyl group, N, N-dipentylsulfamoyl group, N, N-dihexylsulfamoyl group etc. are mentioned, N2-N-dialkylsulfamoyl group having 2 to 8 carbon atoms is preferable, and N, N-dialkylsulfamoyl group having 2 to 4 carbon atoms is more preferable. N, N-dimethylsulfamoyl group is particularly preferred.

Z ¹ and Z ² are hydrogen atom, halogen atom, methyl group, cyano group, nitro group, carboxy group, methylsulfonyl group, trifluoromethyl group, methoxy group, methylsulfanyl group, N-methylamino group, N, N -A dimethylamino group, an N-methylsulfamoyl group or an N, N-dimethylsulfamoyl group is preferred.

Examples of the alkyl group having 1 to 4 carbon atoms in R ¹ and R ² include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a tert-butyl group. An alkyl group is preferable, and a methyl group is more preferable.
Q ¹ and Q ² are each independently preferably —S—, —NH—, —N (CH ₃ ) — or —CO—, and more preferably —S— or —CO—.

As the group represented by the formula (1-1-A) contained in the divalent group represented by the formula (1-1), the formula (1-1-1) to the formula (1-1-18) The group represented by these is mentioned.

As the group represented by the formula (1-2-A) contained in the divalent group represented by the formula (1-2), the formula (1-2-1) to the formula (1-2-5) The group represented by these is mentioned.

Y ¹ represents a substituted or unsubstituted polycyclic aromatic hydrocarbon group or a substituted or unsubstituted polycyclic aromatic heterocyclic group. The polycyclic aromatic hydrocarbon group refers to a condensed polycyclic aromatic hydrocarbon group or a group derived from an aromatic ring assembly. “Polycyclic aromatic hydrocarbon group” means an aromatic hydrocarbon group having at least two aromatic rings, and a condensed aromatic hydrocarbon group formed by condensation of two or more aromatic rings and 2 An aromatic hydrocarbon group formed by combining at least one aromatic ring is exemplified. “Polycyclic aromatic heterocyclic group” means an aromatic heterocyclic group having at least one heteroaromatic ring and having at least one ring selected from the group consisting of an aromatic ring and a heteroaromatic ring. An aromatic heterocyclic group formed by condensing one or more aromatic heterocycles with one or more rings selected from the group consisting of aromatic rings and heteroaromatic rings, and at least one heteroaromatic ring and aromatic An aromatic heterocyclic group formed by combining with at least one ring selected from the group consisting of a ring and a heteroaromatic ring.
The polycyclic aromatic hydrocarbon group and the polycyclic aromatic heterocyclic group may be unsubstituted or may have a substituent. Examples of the substituent include a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, a nitroso group, an alkylsulfinyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, a carboxy group, and carbon. C1-C6 fluoroalkyl group, C1-C6 alkoxy group, C1-C6 alkylsulfanyl group, C1-C4 N-alkylamino group, C2-C8 N, N- Examples thereof include a dialkylamino group, a sulfamoyl group, an N-alkylsulfamoyl group having 1 to 6 carbon atoms, and an N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms.
Y ¹ is preferably, for example, a group represented by formula (Y ¹ -1) to formula (Y ¹ -7), and is represented by formula (Y ¹ -1) or formula (Y ¹ -4). More preferably, it is a group.

[In formulas (Y ¹ -1) to (Y ¹ -7), * represents a bond, and Z ³ each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, or nitro. Group, nitroso group, alkylsulfonyl group having 1 to 6 carbon atoms, alkylsulfinyl group having 1 to 6 carbon atoms, carboxy group, fluoroalkyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, carbon number 1 -6 alkylsulfanyl group, C1-C4 N-alkylamino group, C2-C8 N, N-dialkylamino group, sulfamoyl group, C1-C6 N-alkylsulfamoyl group or An N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms is represented.
V ¹ and V ² each independently represent —CO—, —S—, —NR ³ —, —O—, —Se— or —SO ₂ —.
W ¹ to ^W-5 each independently represent a -CR ³ = or -N =.
However, at least one of V ¹ , V ^2, and W ^{1 to} W ⁵ includes S, N, O, or Se.
R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
a represents the integer of 0-3 each independently. when a is an integer of 2 or more, a plurality of Z ³ may be the being the same or different.
b represents the integer of 0-2 each independently. If b is an integer of 2 or more, a plurality of Z ³ may be the being the same or different. ]

Group represented by the formula ^(Y 1 -1) is preferably any one of groups represented by the formula ^(Y 2 -1) ~ formula ^(Y 2 -6).
Group represented by the formula ^(Y 1 -2) is preferably a group represented by the formula ^(Y 2 -7) or formula ^(Y 2 -9), a group represented by the formula ^(Y 1 -3) is it is preferably a group represented by the formula ^(Y 2 -8) or formula ^(Y 2 -10).
The group represented by the formula (Y ¹ -4) is preferably any one of groups represented by the formula (Y ² -11) to the formula (Y ² -13).
The group represented by the formula (Y ¹ -5) is preferably any one of groups represented by the formula (Y ² -14) to the formula (Y ² -16).
Among these, a group represented by the formula (Y ³ -1) or the formula (Y ³ -3) is more preferable.

Wherein ^(Y 2 -1) ~ formula ^{(Y 2 -16), Z 3} , a, b, V 1, V 2 and ^W 1 to ^W-5 are the same as defined above. ]

[In formula (Y ³ -1) to formula (Y ³ -6), Z ³ , a, b, V ¹ , V ² and W ¹ represent the same meaning as described above. ]

A halogen atom in Z ³ , an alkyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, an alkylsulfinyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, and 1 to 6 carbon atoms Alkoxy group having 1 to 6 carbon atoms, N, N-dialkylamino group having 2 to 8 carbon atoms, N-alkylamino group having 1 to 4 carbon atoms, N-alkylsulfone having 1 to 6 carbon atoms Examples of the famoyl group and the N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms are the same as those described above.
Among these, Z ³ is a halogen atom, methyl group, ethyl group, isopropyl group, sec-butyl group, pentyl group, hexyl group, cyano group, nitro group, methylsulfonyl group, nitroso group, carboxy group, trifluoromethyl group. , A methoxy group, a methylsulfanyl group, an N, N-dimethylamino group or an N-methylamino group, preferably a halogen atom, a methyl group, an ethyl group, an isopropyl group, a sec-butyl group, a pentyl group, a hexyl group, a cyano group, A nitro group and a trifluoromethyl group are more preferable, and a methyl group, an ethyl group, an isopropyl group, a sec-butyl group, a pentyl group, and a hexyl group are particularly preferable.

V ₁ and V ₂ are preferably each independently —S—, —NR ³ — or —O—.

W ^{1 to} W ⁵ are preferably each independently —CR ³ ═ or —N═.

At least one of V ¹ , V ² and W ^{1 to} W ⁵ preferably contains S, N or O.

a is preferably 0 or 1. b is preferably 0.
Specific examples of Y ¹ include groups represented by formula (ar-1) to formula (ar-840). In the following groups, Me represents a methyl group, Et represents an ethyl group, and * represents a bond.

In Formula (1-1) and Formula (1-2), D ¹ and D ² each independently represent a single bond or a divalent linking group. Examples of the divalent linking group include —CO—O—, —O—CO—, —C (═S) —O—, —O—C (═S) —, —CR ⁴ R ⁵ —, — ^{CR 4 R 5 -CR 6 R 7} -, - O-CR 4 R 5 -, - CR 4 R 5 -O -, - CR 4 R 5 -O-CR 6 R 7 -, - CR 4 R 5 -O ^{-CO -, - O-CO-} CR 4 R 5 -, - CR 4 R 5 -O-CO-CR 6 R 7 -, - CR 4 R 5 -CO-O-CR 6 R 7 -, - NR 8 ^{-CR 4 R 5 -, - CR} 4 R 5 -NR 8 -, - CO-NR 8 -, - NR 8 -CO -, - O -, - S -, - NR 8 - , and ^-CR 4 = CR ⁵ -Etc. are mentioned. R ⁴ , R ⁵ , R ⁶ and R ⁷ 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, etc. ). R ⁸ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc.).

D ¹ and D ² are * —O—CO—, * —O—C (═S) —, * —O—CR ⁴ R ⁵ —, * —NR ⁸ —CR ⁴ R ⁵ — or * —NR ^8. It is preferably —CO—, more preferably * —O—CO—, * —O—C (═S) —, or * —NR ⁸ —CO—. Here, * represents a bond with the group represented by the formula (1-1-A) or the group represented by the formula (1-2-A). R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom, a methyl group or an ethyl group. R ⁸ is preferably a hydrogen atom, a methyl group or an ethyl group.

In Formula (1-1) and Formula (1-2), G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group, and the hydrogen atom of 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, a cyano group, or a nitro group, the alicyclic hydrocarbon The group —CH ₂ — may be replaced by —O—, —S— or NH—.
Examples of the divalent alicyclic hydrocarbon group include divalent alicyclic hydrocarbon groups in which the number of carbon atoms and heteroatoms constituting the ring is 3 to 10 and 0 to 2, respectively. g-1) to groups represented by formula (g-10) may be mentioned, and a 5-membered or 6-membered alicyclic hydrocarbon group is more preferable.

  The hydrogen atom contained in the groups represented by the above formulas (g-1) to (g-10) is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an isopropyl group, or a tert-butyl group; An alkoxy group having 1 to 4 carbon atoms such as an ethoxy group; a fluoroalkyl group having 1 to 4 carbon atoms such as a trifluoromethyl group; a fluoroalkoxy group having 1 to 4 carbon atoms such as a trifluoromethoxy group; a cyano group; A nitro group; optionally substituted by a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom.

G ¹ and G ² are preferably a group represented by the formula (g-1), more preferably a 1,4-cyclohexanediyl group, and a trans-1,4-cyclohexanediyl group. It is particularly preferred.

  The compound of the present invention is preferably a compound containing a divalent group represented by the formula (2-1) or the formula (2-2).

[In Formula (2-1) and Formula (2-2), Z ¹ , Z ² , Q ¹ , Q ² , Y ¹ , D ¹ , D ² , G ¹ and G ² represent the same meaning as described above. .
E ¹ and E ² each independently represents a single bond or a divalent linking group.
B ¹ and B ² each independently represent a single bond or a divalent linking group.
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 Atom is substituted with halogen atom, alkyl group having 1 to 4 carbon atoms, fluoroalkyl group having 1 to 4 carbon atoms, alkoxy group having 1 to 4 carbon atoms, fluoroalkoxy group having 1 to 4 carbon atoms, cyano group or nitro group May be.
k and l each independently represents an integer of 0 to 3. ]

Examples of the divalent linking group of E ¹ and ^{E 2,} for _{^{example, -CR 9 R 10 -, -}} CH 2 -CH 2 -, - O -, - S -, - CO-O -, - O-CO- , —O—CO—O—, —C (═S) —O—, —O—C (═S) —, —O—C (═S) —O—, —CO—NR ¹¹ —, —NR _{^{11 -CO -, - O-CH}} 2 -, - CH 2 -O -, - S-CH 2 -, - CH 2 -S -, - NR 11 -, - CR 9 = CR 10 - , and the like. R ⁹ and R ¹⁰ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms. R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

E ¹ and E ² are —CO—O—, —O—CO—, —O—CO—O—, —CO—NR ¹¹ —, —NR ¹¹ —CO—, —CH ₂ —O—, —CH. ₂ -S- or a single bond is preferable, and -CO-O- is more preferable.

Examples of the divalent linking group for B ¹ and ^{B 2,} for _{^{example, -CR 9 R 10 -, -}} CH 2 -CH 2 -, - O -, - S -, - CO-O -, - O-CO- , —O—CO—O—, —C (═S) —O—, —O—C (═S) —, —O—C (═S) —O—, —CO—NR ¹¹ —, —NR _{^{11 -CO -, - O-CH}} 2 -, - CH 2 -O -, - S-CH 2 -, - CH 2 -S -, - NR 11 -, - CR 9 = CR 10 - , and the like.

In that the preparation of the compounds of the present invention is easy, ^{B 2} that is bonded only to ^{B 1} and ^{A 2} are bonded only to ^{A 1} are each _{independently, -CH} 2 -CH 2 _-, - It is preferably CO—O—, —O—CO—, —CO—NH—, —NH—CO—, —O—CH ₂ —, —CH ₂ —O— or a single bond. In particular, -CO-O- or -O-CO- is preferable in that it exhibits high liquid crystallinity.
B ¹ and B ² are preferably the same in that the production of the compound of the present invention is easier.

Examples of the divalent alicyclic hydrocarbon group or aromatic hydrocarbon group in A ¹ and A ² include groups represented by the above formula (g-1) to formula (g-10), and a formula (a-1 ) To C6-20 divalent aromatic hydrocarbon groups represented by formula (a-8).

  The hydrogen atoms of the groups represented by the above formulas (a-1) to (a-8) are an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an isopropyl group or a tert-butyl group; a methoxy group Or an alkoxy group having 1 to 4 carbon atoms such as an ethoxy group; a fluoroalkyl group having 1 to 4 carbon atoms such as a trifluoromethyl group; a fluoroalkoxy group having 1 to 4 carbon atoms such as a trifluoromethoxy group; a cyano group; Group; may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom.

Among them, as A ¹ and A ² , a 1,4-phenylene group or a 1,4-cyclohexanediyl group is preferable, and a 1,4-phenylene group is more preferable in terms of easy production of the compound of the present invention. preferable. A ¹ and A ² are preferably the same in that the production of the compound of the present invention is easier.

  From the viewpoint of liquid crystallinity of the compound of the present invention, k and l are preferably 0-2. The sum of k and l is preferably 5 or less, and more preferably 4 or less.

  The compound of the present invention is more preferably a compound represented by Formula (3-1) or Formula (3-2).

[In Formula (3-1) and Formula (3-2), Z ¹ , Z ² , Q ¹ , Q ² , Y ¹ , D ¹ , D ² , G ¹ , G ² , E ¹ , E ² , B ¹ , B ² , A ¹ , A ² , k and l represent the same meaning as described above.
F ¹ and F ² each independently represents an alkanediyl group having 1 to 12 carbon atoms. The hydrogen atom contained in the alkanediyl group may be substituted with an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a halogen atom, and —CH ₂ — contained in the alkanediyl group. May be replaced by -O- or -CO-.
P ¹ and P ² each independently represent a hydrogen atom or a polymerizable group. ]

The alkanediyl group having 1 to 12 carbon atoms in F ¹ and F ² is — (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 -,-(CF _{2) 8} - _{preferably, - (CH 2) 4 -} , - (CH 2) 6 - is more preferable.
B ¹ bonded to F ¹ and B ² bonded to F ² are each independently —O—, —CO—O—, —O—CO—, —O—CO—O—, — CO-NH-, -NH-CO- or a single bond is preferable.

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 both P ¹ and P ² are polymerized in that the film hardness of the optical film obtained from the compound of the present invention tends to be excellent. It is more preferable that it is a sex group.
The polymerizable group may be any group that can participate in the polymerization reaction of the compound of the present invention, and specifically includes a vinyl group, a vinyloxy group, a styryl group, a p- (2-phenylethenyl) phenyl group, and acryloyl. Group, methacryloyl group, acryloyloxy group, methacryloyloxy group, carboxy group, acetyl group, hydroxy group, carbamoyl group, C1-C4 N-alkylamino group, amino group, epoxy group, oxetanyl group, formyl group, isocyanato Group or isothiocyanato group. Among them, a radical polymerizable group or a cationic polymerizable group is preferable in that it is suitable for photopolymerization, an acryloyloxy group or a methacryloyloxy group is more preferable in terms of easy handling and easy production of the compound of the present invention, An acryloyloxy group is particularly preferred.
The polymerizable group may be directly bonded to F ¹ and F ² , but is bonded through one or more divalent linking groups (for example, the divalent linking group in B ¹ and B ² above). It is preferable to do.

^{-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-134). * (Asterisk) represents a bond with the group represented by the formula (1-1-A) or the group represented by the formula (1-2-A), and n represents an integer of 2 to 12.

  Examples of the compound of the present invention include compounds represented by formula (A1-1) to formula (A73-8). In addition, * represents a bond, for example, the compound represented by the formula (A1-1) is the following compound.

The manufacturing method of the compound of this invention is demonstrated.
The compounds of the present invention are known organic synthesis reactions described in Methoden der Organischen Chemie, Organic Reactions, Organic Syntheses, Comprehensive Organic Synthesis, New Experimental Chemistry Course, etc. Ullmann reaction, Wittig reaction, Schiff base formation reaction, benzylation reaction, Sonogashira reaction, Suzuki-Miyaura reaction, Negishi reaction, Kumada reaction, Kashiyama reaction, Buchwald-Heartwig reaction, Friedel-Craft reaction, Heck reaction, Aldol reaction, etc. ) Can be manufactured by appropriately combining depending on the structure.

For example, in the case of a compound represented by formula (3-1) or formula (3-2) in which D ¹ and D ² are * —O—CO—, formula (11-1)

（式中、Ａｒは、式（１−１）又は式（１−２）で表される２価の基を表す。）
で示される化合物と式（１１−２）

(In the formula, Ar represents a divalent group represented by Formula (1-1) or Formula (1-2).)
And a compound represented by formula (11-2)

（式中、Ｇ^１、Ｅ^１、Ａ^１、Ｂ^１、Ｆ^１、Ｐ^１及びｋは上記と同一の意味を表す。）
で示される化合物とを反応させることにより、式（１１−３）

(In the formula, G ¹ , E ¹ , A ¹ , B ¹ , F ¹ , P ¹ and k represent the same meaning as described above.)
Is reacted with a compound represented by the formula (11-3)

（式中、Ａｒ、Ｇ^１、Ｅ^１、Ａ^１、Ｂ^１、Ｆ^１、Ｐ^１及びｋは上記と同一の意味を表す。）
で示される化合物を得、得られた式（１１−３）で示される化合物と式（１１−４）

(In the formula, Ar, G ¹ , E ¹ , A ¹ , B ¹ , F ¹ , P ¹ and k represent the same meaning as described above.)
And a compound represented by the formula (11-3) obtained and a compound represented by the formula (11-4)

（式中、Ｇ^２、Ｅ^２、Ａ^２、Ｂ^２、Ｆ^２、Ｐ^２及びｌは上記と同一の意味を表す。）
で示される化合物とを反応させることにより製造することができる。
なお、Ｇ^１とＧ^２、Ｅ^１とＥ^２、Ａ^１とＡ^２、Ｂ^１とＢ^２、Ｆ^１とＦ、Ｐ^１とＰ^２及びｋとｌが、それぞれ全て同じである場合には、式（１１−１）で示される化合物と２当量以上の式（１１−２）化合物とを反応させることにより、一段階で目的の化合物を製造することができる。

(In the formula, G ² , E ² , A ² , B ² , F ² , P ² and l have the same meaning as described above.)
It can manufacture by making the compound shown by react.
When G ¹ and G ² , E ¹ and E ² , A ¹ and A ² , B ¹ and B ² , F ¹ and F, P ¹ and P ^2, and k and l are all the same, By reacting the compound represented by the formula (11-1) with 2 equivalents or more of the compound of the formula (11-2), the target compound can be produced in one step.

  The reaction between the compound represented by the formula (11-1) and the compound represented by the formula (11-2) and the reaction represented by the compound represented by the formula (11-3) and the compound represented by the formula (11-4) It is preferable to carry out in the presence of 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-nitrobenzenesulfonyl) ) -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 hexafluorophos 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 paratoluene sulfonate, 2-fluoro-1-methylpyridinium paratoluene sulfonate, and trichloroacetic acid pentachlorophenyl ester. Since there are many choices 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 preferred.

  The composition of the present invention contains the compound of the present invention and a liquid crystal compound different from the compound of the present invention (hereinafter sometimes referred to as “liquid crystal compound”).

Specific examples of liquid crystal compounds include: Chapter 3 of the Liquid Crystal Handbook (Edited by the Liquid Crystal Handbook Editorial Committee, published by Maruzen Co., Ltd., October 30, 2000). .3 Among compounds described in chiral rod-like liquid crystal molecules, compounds having a polymerizable group may be mentioned.
The liquid crystal compounds may be used alone or in combination with a plurality of different liquid crystal compounds.

  By using a composition containing the compound of the present invention and a liquid crystal compound, the optical film obtained by polymerizing the composition, optical properties such as wavelength dispersion value and retardation value, and thermophysical properties are adjusted to desired values. You can also

  Examples of the liquid crystal compound include a compound represented by the formula (20) (hereinafter sometimes referred to as “compound (20)”).

^{P 11 -E 11 - (B 11} -A 11) t -B 12 -G (20)
[In the formula (20), A ¹¹ represents an aromatic hydrocarbon group, an alicyclic hydrocarbon group or a heterocyclic group, and is contained in the aromatic hydrocarbon group, alicyclic hydrocarbon group and heterocyclic group. The hydrogen atom is a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an N-alkylamino group having 1 to 6 carbon atoms, or an N, N-dialkylamino group having 2 to 12 carbon atoms. , A nitro group, a cyano group or a sulfanyl group may be substituted.
B ¹¹ and ^{B 12} are each ^{independently, -CR 14 R 15 -, -} C≡C -, - CH = CH -, - CH 2 -CH 2 -, - O -, - S -, - C (= O)-, -C (= O) -O-, -O-C (= O)-, -O-C (= O) -O-, -C (= S)-, -C (= S). -O-, -OC (= S)-, -CH = N-, -N = CH-, -N = N-, -C (= O) -NR < ¹⁶ >-, -NR < ¹⁶ > -C (= O) —, —OCH ₂ —, —OCF ₂ —, —NR ¹⁶ —, —CH ₂ O—, —CF ₂ O—, —CH═CH—C (═O) —O—, —O—C ( = O) -CH = CH- or a single bond. R ¹⁴ and R ¹⁵ each independently represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms, and R ¹⁴ and R ¹⁵ are connected to form an alkanediyl group having 4 to 7 carbon atoms. Also good. R ¹⁶ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
E ¹¹ represents an alkanediyl group having 1 to 12 carbon atoms. The hydrogen atom contained in the alkanediyl group may be substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogen atom.
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, carbon A hydrogen atom contained in the alkanediyl group, which is a N, N-dialkylamino group having 2 to 26, a cyano group, or a nitro group, or a polymerizable group bonded via an alkanediyl group having 1 to 12 carbon atoms. The atom may be substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogen atom.
t represents an integer of 1 to 5. If t is an integer of 2 or more, a plurality of A ¹¹ and B ¹¹ may be the being the same or different. ]

In particular, the polymerizable group in P ¹¹ and G may be any group that can be polymerized with the compound of the present invention, such as a vinyl group, a vinyloxy group, a styryl group, a p- (2-phenylethenyl) phenyl group, Acryloyl group, acryloyloxy group, methacryloyl group, methacryloyloxy group, carboxy group, acetyl group, hydroxy group, carbamoyl group, amino group, C1-C4 N-alkylamino group, epoxy group, oxetanyl group, formyl group, -N = C = O or N = C = S. Among them, a radically polymerizable group or a cationically polymerizable group is preferable in terms of high photopolymerization reactivity, an acryloyloxy group or a methacryloyloxy group in terms of easy handling and easy production of a liquid crystal compound. Or a vinyloxy group is more preferable.

It aromatic hydrocarbon group A ^11, the number of carbon atoms in the alicyclic hydrocarbon group and the heterocyclic group, respectively, for example, 3 to 18, preferably from 5 to 12, 5 or 6 Is particularly preferred.

  As a compound (20), the compound represented by Formula (20-1) and Formula (20-2) is mentioned, for example.

^{P 11 -E 11 - (B 11} -A 11) t1 -B 12 -E 12 -P 12 (20-1)
^{P 11 -E 11 - (B 11} -A 11) t2 -B 12 -F 11 (20-2)
[In Formula (20-1) and Formula (20-2), P ¹¹ , E ¹¹ , B ¹¹ , A ¹¹ , B ¹² represent the same meaning as described above.
F ¹¹ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 13 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, a fluoroalkyl group having 1 to 13 carbon atoms, an N-alkylamino group having 1 to 13 carbon atoms, An N, N-dialkylamino group, a cyano group or a nitro group having 2 to 26 carbon atoms is represented.
E ¹² represents an alkanediyl group having 1 to 12 carbon atoms, and the alkanediyl group may have an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogen atom.
P ¹² represents a polymerizable group.
t ¹ and ^{t 2} is an integer of 1-5. ]

  Further, the compounds represented by the formulas (20-1) and (20-2) are represented by the formula (I), the formula (II), the formula (III), the formula (IV), or the formula (V). Compounds.

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

In the compounds represented by formula (20-1), formula (20-2), formula (I), formula (II), formula (III), formula (IV), and formula (V), P ¹¹ and E ¹¹ is preferably bonded via an ether bond or an ester bond, and P ¹² and E ¹² are preferably bonded via an ether bond or an ester bond.

  Specific examples of the liquid crystal compound include formulas (I-1) to (I-5), formulas (B1-1) to (B20-8), and formulas (C1-1) to (C4-8). Compounds represented by formula (I) such as compounds shown: Compounds represented by formula (II) such as compounds represented by formula (II-1) to formula (II-6); Formula (III-1) to formula A compound represented by formula (III) such as a compound represented by (III-19); a compound represented by formula (IV) such as a compound represented by formula (IV-1) to formula (IV-14); Examples thereof include compounds represented by formula (V) such as compounds represented by V-1) to formula (V-5). In the formula, k represents an integer of 1 to 11, and * represents a bond. These liquid crystal compounds are preferable liquid crystal compounds because they are easy to synthesize or are commercially available and easily available.

  In the case of using a composition containing a liquid crystal compound for the purpose of controlling the thermophysical properties of the obtained optical film, the formula (I-1) to the formula (I-5), in that the obtained optical film has excellent reliability. Formula (B1-1) to Formula (B20-8), Formula (C1-1) to Formula (C4-8), Formula (II-1) to Formula (II-6), Formula (III-1) to Formula The liquid crystal compound represented by (III-19) is preferred, and is excellent in compatibility with the compound of the present invention, from the formula (I-1) to the formula (I-5), the formula (B1-1) to the formula (B20). -8), a liquid crystal compound represented by formula (C1-1) to formula (C4-8), formula (III-1) to formula (III-19) is more preferably contained. The liquid crystal compounds represented by formula (B1-1) to formula (B20-8) and formula (C1-1) to formula (C4-8) are preferable in that an optical film exhibiting reverse wavelength dispersion is obtained.

  The usage-amount of a liquid crystal compound is 90 mass parts or less with respect to a total of 100 mass parts of a liquid crystal compound and the compound of this invention.

  The composition of the present invention is preferably a composition further containing 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, acetophenone 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 acetophenone compound include α, α-diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) 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] propane- Examples include 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 acetophenone compound is preferable in that the resulting optical film tends to have high heat resistance and moist heat resistance. Of these, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone is more preferable.

  The content of the polymerization initiator in the composition of the present invention is 0.1 to 30 parts by mass, preferably 0.5 mass with respect to 100 parts by mass in total of the liquid crystal compound and the compound of the present invention. Part to 10 parts by mass. Within the above range, the compound of the present invention can be polymerized without disturbing the alignment of the 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 the photosensitizer, the polymerization reaction of the compound of the present invention 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 mass part-30 mass parts with respect to a total of 100 mass parts of a liquid crystal compound and the compound of this invention, Preferably it is 0.5 mass part-10 mass. Part. If it is in the said range, the compound of this invention can be polymerized, without disturbing the orientation of a 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 or the compound of the present invention 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 and the compound of this invention, Preferably it is 0.5 mass part-10 mass parts. is there. Within the above range, the compound of the present invention can be polymerized without disturbing the alignment of the 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 amount of the leveling agent used is, for example, 0.01 to 30 parts by mass, preferably 0.05 to 30 parts by mass with respect to 100 parts by mass in total of the liquid crystal compound and the compound of the present invention. 10 parts by mass. Within the above range, the compound of the present invention can be polymerized without disturbing the alignment of the liquid crystal compound.

  The composition of the present invention preferably contains an organic solvent in terms of fluidity. The organic solvent is an organic solvent that can dissolve the compound of the present invention, a liquid crystal compound, etc., and may be any solvent that is inert to the polymerization reaction. Specifically, methanol, ethanol, ethylene glycol, isopropyl alcohol, Alcohol solvents such as propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, ethyl lactate; acetone, methyl ethyl ketone, cyclo Ketone solvents such as pentanone, cyclohexanone, 2-heptanone, and methyl isobutyl ketone; non-chlorinated aliphatic hydrocarbon solvents such as pentane, hexane, and heptane; toluene, xylene, phenol Non-chlorinated aromatic hydrocarbon solvents such as nitriles; Nitrile solvents such as acetonitrile; Ether solvents such as propylene glycol monomethyl ether, tetrahydrofuran and dimethoxyethane; Chlorinated hydrocarbon solvents such as chloroform and chlorobenzene; Phenol; . 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.

Content of an organic solvent is 10-10,000 mass parts with respect to 100 mass parts of compounds of this invention, Preferably it is 100-5,000 mass parts.
When the composition of the present invention contains an organic solvent, the viscosity is from 0.1 to 10 mPa · s, preferably from 0.1 to 7 mPa · s, in that it tends to cause unevenness in the film thickness of the optical film. s.
Moreover, the density | concentration of solid content in the composition of this invention is 2-50 mass%, and 5-50 mass% is preferable. 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 organic solvent from the composition of this invention.

  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.

  Although the wavelength dispersion characteristic of the optical film of the present invention has a structural unit derived from the compound of the present invention in the optical film, the wavelength dispersion characteristic of the optical film can be adjusted by adjusting the content of the structural unit. it can. If the content of the structural unit derived from the compound of the present invention in the structural units in the optical film is increased, flatter wavelength dispersion characteristics and further reverse wavelength dispersion characteristics are exhibited.

Specifically, the composition of the present invention is prepared such that an optical film containing the content of the structural unit derived from the compound of the present invention determined by the operations shown in the following (a) to (e) is obtained. The composition may be polymerized.
(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 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 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 polymerizing the compound of the present invention. One type of the compound of the present invention may be polymerized, or two or more types of the compound of the present invention may be polymerized. Moreover, the optical film of the present invention can also be produced by polymerizing the composition of the present invention.

From the viewpoint of ease of film formation, it is preferable to use a solution in which the compound of the present invention is dissolved in an organic solvent, and an optical film can be obtained by applying the solution on a supporting substrate, drying and polymerizing. . The solid content concentration in the solution is, for example, 2 to 50% by mass, and preferably 5 to 50% by mass.
An unpolymerized film is obtained by applying a solution of the compound of the present invention on a supporting substrate and drying. When the unpolymerized film exhibits a liquid crystal phase such as a nematic phase, the obtained optical film exhibits birefringence due to monodomain alignment.

The film thickness of the optical film can be adjusted by appropriately adjusting the content of the compound of the present invention in the solution of the compound of the present invention and the coating amount of the solution on the supporting substrate. 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 solution of the compound 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 a solution of the compound of the present invention on the alignment film. The alignment film preferably has a solvent resistance that does not dissolve in the solution of the compound of the present invention. 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, since it is not necessary to perform refractive index control by stretching, in-plane variation of 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 temperature at which the solvent is removed by heating is preferably 0 to 250 ° C, more preferably 50 to 220 ° C, and still more preferably 80 to 170 ° C. In addition, the heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes. As long as 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 in which the orientation of the compound of the present invention is fixed, that is, a polymerized film is obtained. Therefore, a film that is not easily affected by birefringence due to heat can be obtained.

The method for polymerizing the unpolymerized film may be appropriately determined according to the type of the liquid crystal compound and the compound of the present invention. If the polymerizable group in the compound of the present invention and the liquid crystal compound is photopolymerizable, the photopolymerization method is used, and if the polymerizable group is thermopolymerizable, 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. It is preferable to use the compound of the present invention having a group and a liquid crystal compound. Photopolymerization is also preferred from the viewpoint of film formability. The photopolymerization reaction is performed by irradiating an unpolymerized film with visible light, ultraviolet light, or laser light. In view of easy handling, ultraviolet light is particularly preferable. The light irradiation may be performed at a temperature at which the compound of the present invention takes a liquid crystal phase. At this time, the polymerized film can be patterned by masking or the like.
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 supporting substrate, a film in which the alignment film and the optical film are laminated is obtained. Further, the alignment film can be peeled to obtain an optical film.

  The optical film thus obtained is excellent in transparency and used as various display films. 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 about 50 to 500 nm, preferably 100 to 300 nm.

  Such a thin film capable of uniform polarization conversion in a wider wavelength range 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 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, the film thickness may be adjusted to Re (550) of the obtained optical film of 113 to 163 nm, preferably 135 to 140 nm, particularly preferably about 137.5 nm. In this 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.

  Only by using a small amount of the compound of the present invention, the wavelength dispersion characteristic of the optical film can be shifted to a value close to 1, and the desired wavelength dispersion characteristic can be prepared by a simple method.

The optical film of the present invention is 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.

FIG. 1 is a schematic view showing a color filter 1 according to the present invention.
The color filter 1 is a color filter in which the optical film 2 of the present invention is formed on the color filter layer 4 via an alignment film 3.

An example of a method for manufacturing such a color filter 1 will be described below. First, an alignment polymer is laminated on the color filter layer 4 and a rubbing process is performed to form the alignment film 3. The orientation polymer may be laminated using an ink jet method.
Subsequently, a solution of the compound of the present invention in which the content of the compound of the present invention is adjusted so that the obtained optical film has a desired wavelength dispersion characteristic is prepared on the obtained alignment film 3, and a desired solution is obtained. The solution is applied so that the thickness becomes a phase difference value, and the optical film 2 is formed.

  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.

FIG. 2 is a schematic view showing a liquid crystal display device 5 according to the present invention.
In the liquid crystal display device 5 shown in FIG. 2, a substrate 7 facing a backlight such as a glass substrate is fixed on a polarizing plate 6 with an adhesive. An optical film 2 ′ is formed on the color filter layer 4 ′ formed on the substrate 7 via an alignment film 3 ′. Further, a counter electrode 8 is formed on the optical film 2 ′, and a 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 with an adhesive, and a thin film transistor (TFT) and an insulating layer 12 for actively driving a liquid crystal layer are formed on the substrate 11. Further, a transparent electrode 13 and / or a reflective electrode 13 ′ made of Ag, Al or ITO (Indium Tin Oxide) is formed on the TFT. The configuration of the liquid crystal display device 5 shown in FIG. 2 is a configuration in which the number of optical films is smaller than that of a conventional liquid crystal display device, and a thinner liquid crystal display device can be manufactured.

An example of a manufacturing method of the liquid crystal display device 5 in which the color filter 1 ′ is formed on the liquid crystal layer side of one substrate will be described below. On the substrate on the backlight side, a gate electrode made of Mo, MoW or the like, a gate insulating film, and amorphous silicon are deposited and patterned on a borosilicate glass, and the amorphous silicon is crystallized by annealing with an excimer laser. A semiconductor thin film can be formed, and then n-channel and p-channel TFTs can be formed by doping the regions on both sides of the gate electrode with P, B, or the like. Further, the substrate on the backlight side is obtained by forming the insulating layer 12 made of SiO ₂ . Further, by sputtering ITO on the backlight side substrate 11, the transparent electrode 13 for the total transmission display device can be laminated on the backlight side substrate. Similarly, a reflective electrode 13 'for a total reflection display device can be obtained by using Ag, Al or the like instead of ITO. Further, a backlight electrode for a transflective liquid crystal display device can be obtained by appropriately combining a reflective electrode and a transparent electrode.

  On the other hand, the color filter layer 4 ′ is formed on the opposing substrate 7. By using R, G, and B color filters in combination, a full-color liquid crystal display device can be obtained. Next, an alignment polymer is applied on the color filter layer 4 'and rubbed to form an alignment film 3'. A solution of the compound of the present invention is applied onto the alignment film 3 'and polymerized to form an optical film 2' by irradiation with ultraviolet rays while heating to a temperature range that takes a liquid crystal phase. After forming the optical film, the counter electrode 8 can be formed by sputtering ITO. Further, an alignment film is formed on the counter electrode, the liquid crystal phase 9 is formed, and finally the liquid crystal display device 5 is manufactured by assembling together with the substrate on the backlight side.

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

Subsequently, the polarizing plate of the present invention and the FPD provided with the polarizing plate will be described below. The polarizing plate of the present invention includes the optical film of the present invention and a film having a polarizing function (polarizing film). It is obtained by laminating the optical film and polarizing film. Specifically, it is obtained by laminating the optical film of the present invention directly on one side or both sides of the polarizing film or using an adhesive. In this specification, an adhesive means both an adhesive and a pressure-sensitive adhesive. Hereinafter, the polarizing plate of the present invention will be described with reference to FIGS.

Fig.3 (a)-FIG.3 (e) are schematic which shows the polarizing plate 1 which concerns on this invention.
In the polarizing plate 30 a shown in FIG. 3A, the laminate 14 and the polarizing film 15 are directly bonded, and the laminate 14 includes a support substrate 16, an alignment film 17, and an optical film 18. The polarizing plate 30 a is laminated in the order of the support substrate 16, the alignment film 17, the optical film 18, and the polarizing film 15.

  In the polarizing plate 30 b shown in FIG. 3B, the laminate 14 and the polarizing film 15 are bonded together with an adhesive layer 19 interposed therebetween.

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

  In the polarizing plate 30d shown in FIG. 3D, the laminate 14 and the laminate 14 'are bonded together via the adhesive layer 19, and the polarizing film 15 is directly bonded onto the laminate 14'.

  In the polarizing plate 30e shown in FIG. 3 (e), the laminated body 14 and the laminated body 14 ′ are bonded through the adhesive layer 19, and the laminated body 14 ′ and the polarizing film 15 are further bonded through the adhesive layer 19 ′. To show the configuration.

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

  The polarizing plate of the present invention may be formed by laminating a plurality of laminates, and the plurality of laminates may be all the same or different.

  The polarizing film 15 may be a film having a polarizing function. For example, a film obtained by stretching a polyvinyl alcohol film by adsorbing iodine or a dichroic dye, or a film obtained by stretching a polyvinyl alcohol film to obtain iodine or a dichroic dye. Examples include adsorbed films.

  The adhesive used for the adhesive layer 19 and the adhesive layer 19 ′ is preferably an adhesive having high transparency and excellent heat resistance. Examples of such adhesives include acrylic adhesives, epoxy adhesives, urethane adhesives, and the like.

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

  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.

  FIG. 4 is a schematic view showing a bonded product 21 between the liquid crystal panel 20 and the polarizing plate 30 of the liquid crystal display device of the present invention. The bonded product 21 is obtained by bonding the polarizing plate 30 of the present invention and the liquid crystal panel 20 through an 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.

  FIG. 5 is a schematic view showing an organic EL panel 23 of the organic EL display device of the present invention. The organic EL panel 23 is formed by bonding the polarizing film 30 of the present invention and the light emitting layer 24 through an adhesive layer 25.

  In the organic EL panel, the polarizing film 30 functions as a broadband circularly polarizing plate. The light emitting layer 24 is at least one layer made of a conductive organic compound.

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

Example 1
<Synthesis Example of Compound (A1-1)>
Compound (A1-1) was synthesized according to the following scheme.

[Synthesis Example of Compound (1-a)]
2,5-dimethoxyaniline 21.5 g (140 mmol), benzothiophene-2-carboxylic acid 25.0 g (140 mmol) and dehydrated chloroform 125.3 g were mixed and reacted. To the resulting mixture, 1.71 g (14 mmol) of N, N-dimethylaminopyridine was added. The obtained mixture was cooled in an ice bath, 31.8 g (154 mmol) of N, N′-dicyclohexylcarbodiimide was added, and the mixture was reacted for 1 hour. Thereafter, the mixture was returned to room temperature, and the resulting mixture was filtered by passing through silica gel to remove precipitates, and then concentrated under reduced pressure. The residue was crystallized by adding a 1/2 (v / v) solution of ethyl acetate-heptane. The precipitated crystals were filtered and dried under vacuum to obtain 33.4 g of compound (1-a) as a pale yellow powder. The yield was 76% based on 2,5-dimethoxyaniline.

[Synthesis Example of Compound (1-b)]
Compound (1-a) 33.35 g (106 mmol), 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetan-2,4-disulfide (Lawson reagent) 22.4 g ( 55.0 mmol) and 200 g of toluene were mixed, and the resulting mixture was heated to 80 ° C. for reaction. After cooling, the mixture was concentrated to obtain a red viscous solid containing the compound (1-b) and a decomposition product of Lawson reagent as main components.

[Synthesis Example of Compound (1-c)]
The mixture containing the compound (1-b) obtained in the previous section, 25.5 g (639 mmol) of sodium hydroxide and 580 g of water were mixed, and the resulting mixture was reacted under ice cooling. Subsequently, an aqueous solution containing 95.6 g (290 mmol) of potassium ferricyanide was added to the mixture under ice-cooling, and reacted at room temperature for 12 hours. The precipitated yellow precipitate was collected by filtration. The precipitate collected by filtration was washed with water and then with hexane, washed with ethanol, and vacuum-dried to obtain 19.5 g of a pale yellow solid containing compound (1-c) as a main component. The yield was 56% based on the compound (1-a).

[Synthesis Example of Compound (1-d)]
Compound (1-c) 19.5 g (59.6 mmol) and pyridinium chloride 97.5 g (5 times mass) were mixed, heated to 180 ° C. and reacted for 2 hours. After cooling the obtained liquid mixture, water was added, and the resulting precipitate was collected by filtration and washed with water and then with hexane to obtain 18 g of a solid containing compound (1-d) as a main component. The yield was 95% based on the compound (1-c).

[Synthesis Example of Compound (A1-1)]
Compound (1-d) 5.00 g (16.7 mmol), compound (A) 14.68 g (35.1 mmol), dimethylaminopyridine 0.20 g (1.67 mmol) and chloroform 60 mL were mixed. To the resulting mixture, 7.68 g (40.1 mmol) of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride was added under ice cooling. The resulting reaction solution was stirred, filtered through silica gel, and concentrated under reduced pressure. Methanol was added to the residue for crystallization. The crystals were collected by filtration and redissolved in chloroform. Methanol was added to the resulting solution while stirring, and the resulting white precipitate was collected by filtration and dried under vacuum to obtain 10.9 g of compound (A1-1) as a white powder. The yield was 59% based on the compound (1-d).

¹ H-NMR (CDCl ₃ ) of the compound (A1-1): δ (ppm) 1.45 to 1.85 (m, 24H), 2.35 to 2.83 (m, 12H), 3.92 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. 37-6.44 (m, 2H), 6.87-7.02 (m, 8H), 7.22 (s, 2H), 7.40-7.46 (m, 2H), 7.83 7.89 (m, 3H)

  The phase transition temperature of the obtained compound (A1-1) was confirmed by texture observation with a polarizing microscope. Compound (A1-1) exhibits a smectic phase from 147 ° C. to 155 ° C. at the time of temperature increase, exhibits a nematic phase from 155 ° C. to 180 ° C. or more, and exhibits a nematic phase to 93 ° C. at the time of temperature decrease. .

(Example 2)
<Synthesis Example of Compound (A5-1)>
Compound (A5-1) was synthesized according to the following scheme.

[Synthesis Example of Compound (5-a)]
2,5-dimethoxyaniline 18.9 g (123 mmol), benzofuran-2-carboxylic acid 20.0 g (123 mmol) and dehydrated chloroform 125.0 g were mixed and reacted. To the obtained mixed solution, 1.51 g (12 mmol) of N, N-dimethylaminopyridine was added. The resulting mixture was cooled in an ice bath, 28.0 g (136 mmol) of N, N′-dicyclohexylcarbodiimide was added and allowed to react for 1 hour. Thereafter, the temperature was returned to room temperature, and the reaction was carried out overnight. The resulting mixture was filtered through silica gel to remove white precipitates and brown components, and then concentrated under reduced pressure. The residue was crystallized by adding a 1/2 (v / v) solution of ethyl acetate-heptane. The precipitated crystals were filtered and vacuum-dried to obtain 14.4 g of compound (5-a) as a pale yellow powder. The yield was 39% based on 2,5-dimethoxyaniline.

[Synthesis Example of Compound (5-b)]
Compound (5-a) 13.0 g (44 mmol), 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetan-2,4-disulfide (Lawson reagent) 9.2 g ( 23.0 mmol) and 100 g of toluene were mixed, and the resulting mixture was heated to 80 ° C. and reacted for 5 hours. After cooling, the mixture was concentrated to obtain a red viscous solid containing the compound (5-b) and a decomposition product of Lawson reagent as main components.

[Synthesis Example of Compound (5-c)]
The mixture containing the compound (5-b) obtained in the previous section, 10.5 g (262 mmol) of sodium hydroxide and 250 g of water were mixed, and the resulting mixture was reacted under ice cooling. Subsequently, an aqueous solution containing 39.3 g (119 mmol) of potassium ferricyanide was added and reacted under ice cooling. The reaction was allowed to proceed for 12 hours at room temperature, and the yellow precipitate that had precipitated was collected by filtration. The precipitate collected by filtration was washed with water and then with hexane, washed with ethanol, and vacuum-dried to obtain 9.3 g of a pale yellow solid containing compound (5-c) as a main component. The yield was 69% based on the compound (5-a).

[Synthesis Example of Compound (5-d)]
Compound (5-c) 7.0 g (22.5 mmol) and pyridinium chloride 35.0 g (5 times mass) were mixed, heated to 180 ° C. and reacted for 2 hours. After cooling the obtained mixture, water was added, and the resulting precipitate was collected by filtration and washed with water and hexane to obtain 6.5 g of a solid containing compound (5-d) as a main component. The yield was 100% based on the compound (5-c).

[Synthesis Example of Compound (A5-1)]
Compound (5-d) 1.60 g (5.65 mmol), compound (A) 4.96 g (11.9 mmol), dimethylaminopyridine 0.07 g (0.56 mmol) and chloroform 30 mL were mixed. To the resulting mixture, 1.71 g (13.6 mmol) of N, N′-diisopropylcarbodiimide was added under ice cooling. The resulting reaction solution was reacted at room temperature overnight, filtered through silica gel, and then concentrated under reduced pressure. Methanol was added to the residue for crystallization. The crystals were collected by filtration and redissolved in chloroform. Methanol was added to the resulting solution while stirring, and the resulting white precipitate was collected by filtration, washed with ethanol, and dried under vacuum to obtain 4.73 g of compound (A5-1) as a white powder. The yield was 77% based on the compound (5-d).

¹ H-NMR (CDCl ₃ ) of compound (A5-1): δ (ppm) 1.45 to 1.91 (m, 24H), 2.35 to 2.83 (m, 12H), 3.92 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 to 6.44 (m, 2H), 6.87 to 7.01 (m, 8H), 7.25 (s, 2H), 7.31 to 7.34 (t, 1H), 7.40 to 7.42 (t, 1H), 7.55 to 7.60 (m, 2H), 7.68 to 7.71 (d, 1H)

  The phase transition temperature of the obtained compound (A5-1) was confirmed by texture observation with a polarizing microscope. Compound (A5-1) exhibited a nematic phase from 139 ° C. to 180 ° C. or higher when the temperature was increased, and crystallized by exhibiting a nematic phase from 93 ° C. when the temperature was decreased.

(Example 3)
<Synthesis Example of Compound (A6-1)>
Compound (A6-1) was synthesized according to the following scheme.

[Synthesis example of 5-methylbenzofuran-2carboxylic acid]
50 g (367 mmol) of 5-methylsalicylaldehyde, 101.51 g (734 mmol) of potassium carbonate, 11.84 g (37 mmol) of tetrabutylammonium bromide, 30.48 g (37 mmol) of potassium iodide and toluene were mixed and heated to 80 ° C. did. To the obtained dispersion, 114.1 g (477 mmol) of diethyl bromomalonate was added dropwise and reacted at 110 ° C. (toluene boiling point reflux) for 24 hours. To the obtained brown solution, 3 mL of 3 g of potassium hydroxide dissolved was added and reacted for another 24 hours. The resulting reaction solution was cooled to room temperature and then concentrated under reduced pressure using an evaporator. To the residue, 40 g of potassium hydroxide and 400 mL of ethanol were added and stirred at 80 ° C. for 1 hour. After cooling to room temperature, ethanol was distilled off with an evaporator. The residue was dissolved in 500 mL of pure water and 500 g of ice, and the pH was adjusted to 3 with 2N sulfuric acid. The deposited yellow precipitate was collected by filtration, further washed with 1000 mL of pure water and vacuum dried to obtain 43.7 g of 5-methylbenzofuran-2carboxylic acid as a pale yellow powder. The yield was 68% based on 4-methylsalicylaldehyde.

[Synthesis Example of Compound (6-a)]
2,4-dimethoxyaniline 30.4 g (199 mmol), 5-methyl-benzofuran-2-carboxylic acid 35.0 g (123 mmol), triethylamine 20.1 g (199 mmol), N, N′-dimethylaminopyridine 4.85 g ( 3.97 mmol) and 175.0 g of dehydrated N, N′-dimethylacetamide were mixed. After cooling the obtained solution in an ice bath, 92.28 g (219 mmol) of 1H-benzotriazol-1-yloxytris (dimethylamino) phosphonium hexafluorophosphate (hereinafter referred to as BOP reagent) was added, and 24 hours at room temperature. Reacted for hours. A mixed solution of water and methanol (2 parts by volume of water and 1 part by volume of methanol) was added to the obtained mixture to cause crystallization. The obtained precipitate was collected by filtration, washed with a mixed solution of water-methanol (water 1 volume part, methanol 1 volume part), and vacuum-dried to obtain 23.8 g of compound (6-a) as a pale yellow powder. The yield was 39% based on 2,5-dimethoxyaniline.

[Synthesis Example of Compound (6-b)]
Compound (6-a) 23.8 g (77 mmol), 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetan-2,4-disulfide (Lawson reagent) 16.1 g ( 40.0 mmol) and 80 g of toluene were mixed, and the resulting mixture was heated to 80 ° C. and reacted for 8 hours. After cooling, the mixture was concentrated to obtain a red viscous solid containing the compound (6-b) and a decomposition product of Lawson reagent as main components.

[Synthesis Example of Compound (6-c)]
A mixture containing the compound (6-b) obtained in the previous item, 18.4 g (459 mmol) of sodium hydroxide and 400 g of water were mixed, and the resulting mixture was stirred under ice cooling. Subsequently, an aqueous solution containing 68.7 g (209 mmol) of potassium ferricyanide was added and reacted under ice cooling. The reaction was allowed to proceed for 24 hours at room temperature, and the precipitated yellow precipitate was collected by filtration. The precipitate collected by filtration was washed with water and then with hexane, washed with ethanol, and vacuum-dried to obtain 14.8 g of a pale yellow solid containing compound (6-c) as a main component. The yield was 59% based on the compound (6-a).

[Synthesis Example of Compound (6-d)]
Compound (6-c) 14.8 g (45.5 mmol) and pyridinium chloride 74.0 g (5 times mass) were mixed, heated to 180 ° C. and reacted for 2 hours. After cooling the obtained mixture, water was added, and the resulting precipitate was collected by filtration and washed with water and toluene to obtain 10.4 g of a solid containing compound (6-d) as a main component. The yield was 77% based on the compound (6-c).

[Synthesis Example of Compound (A6-1)]
1.70 g (5.72 mmol) of the compound (6-d), 5.02 g (12.0 mmol) of the compound (A), 0.07 g (0.56 mmol) of dimethylaminopyridine and 30 mL of chloroform were mixed. To the obtained mixture, 1.73 g (13.7 mmol) of N, N′-diisopropylcarbodiimide was added under ice cooling. The resulting reaction solution was reacted at room temperature overnight, filtered through silica gel, and then concentrated under reduced pressure. Methanol was added to the residue for crystallization. The crystals were collected by filtration and redissolved in chloroform. Methanol was added to the resulting solution while stirring, and the resulting white precipitate was collected by filtration, washed with heptane, and dried under vacuum to obtain 4.72 g of compound (A6-1) as a white powder. The yield was 75% based on the compound (6-d).

¹ H-NMR (CDCl ₃ ) of the compound (A6-1): δ (ppm) 1.45 to 1.85 (m, 24H), 2.34 to 2.83 (m, 12H), 2.84 ( s, 3H), 3.92 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 to 6.44 (m, 2H), 6.87 to 7.01 (m, 8H), 7.22 (m, 3H), 7.44 to 7.47 ( m, 3H)

  The phase transition temperature of the obtained compound (A6-1) was confirmed by texture observation with a polarizing microscope. Compound (A6-1) exhibited a nematic phase from 146 ° C. to 190 ° C. or higher when the temperature was raised, and crystallized by exhibiting a nematic phase up to 100 ° C. when the temperature was lowered.

Example 4
<Synthesis Example of Compound (A10-1)>
Compound (A10-1) was synthesized according to the following scheme.

[Synthesis example of 5-isobutylbenzofuran]
4-Isopropylphenol (40 g, 266 mmol) was dissolved in N, N′-dimethylacetamide (240.0 g). After the solution was cooled in an ice bath, 10.9 g (453 mmol) of sodium hydride was added in 10 portions. The mixture was stirred at room temperature for 1 hour, and when hydrogen generation was completed, 33.17 g (266 mmol) of chloroacetaldehyde dimethyl acetal was added dropwise. After stirring for 5 hours at 80 ° C. and confirming the completion of the reaction, the reaction solution was added to 1000 mL of water and 400 mL of methyl isobutyl ketone to separate the layers. The organic layer was collected, and the organic layer was washed twice with 800 mL of pure water. After collecting the organic layer, it was dehydrated with anhydrous sodium sulfate and concentrated under reduced pressure with an evaporator to obtain a red viscous liquid. Meanwhile, 400 g of toluene and 2.61 g of orthophosphoric acid were mixed and heated to 110 ° C. A solution prepared by dissolving a red viscous liquid in 100 mL of toluene was added dropwise to the solution. After stirring at 110 ° C. for 3 hours, the mixture was cooled to room temperature. The reaction solution was washed twice with 1N aqueous sodium hydrogen carbonate solution and finally washed with 500 mL of pure water. The organic layer was collected, dehydrated with anhydrous sodium sulfate, concentrated under reduced pressure with an evaporator, and dried under vacuum to obtain 41.9 g of 5-isobutylbenzofuran as a pale red viscous liquid. The yield was 90% based on 4-isopropylphenol.

[Synthesis example of 2-formyl-5-isobutylbenzofuran]
25.77 g (148 mmol) of 5-isobutylbenzofuran was dissolved in 28.4 g (389 mmol) of N, N′-dimethylformamide. After cooling the solution with a water bath, 25 g (163 mmol) of phosphorus oxychloride was added dropwise. The pink solution was stirred at room temperature for 1 hour and then stirred at 100 ° C. for 10 hours. The reaction solution was allowed to cool to room temperature, 100 mL of pure water was added and stirred for 1 hour, and then neutralized with 1N sodium bicarbonate. After adjusting the pH to 8, it was separated from toluene. The organic layer was collected, and 2.6 g of activated carbon was added and filtered. After concentration under reduced pressure using an evaporator, the residue was dissolved in chloroform and subjected to silica gel column chromatography (eluent: chloroform-heptane 1: 1 vol / vol → chloroform 100 vol%). The leading component was taken and concentrated with an evaporator and dried in vacuo to obtain 8.5 g of 2-formyl-5-isobutylbenzofuran as a pale red viscous liquid. The yield was 28% based on 5-isobutylbenzofuran.

[Synthesis example of 5-isobutylbenzofuran-2-carboxylic acid]
16.40 g (81 mmol) of 2-formyl-5-isobutylbenzofuran and 9.43 g (97 mmol) of amidosulfuric acid were mixed with 60 mL of pure water. The mixture was cooled in an ice bath, and a solution of sodium chlorite 8.78 g (97 mmol) in 50 mL of water was added dropwise. The reaction was carried out in a water bath for 36 hours. To the reaction solution, 100 mL of toluene and 5 g of potassium hydroxide were added to adjust the pH to 12. Liquid separation was performed, the aqueous layer was recovered, and the aqueous layer was further washed with 300 mL of toluene. The aqueous layer was collected, and the pH was adjusted to 2 with 2N hydrochloric acid, and then 300 mL of toluene was added for liquid separation. The organic layer was collected, dehydrated with anhydrous sodium sulfate, concentrated under reduced pressure with an evaporator, and dried under vacuum to obtain 6.7 g of 5-isobutylbenzofuran-2-carboxylic acid as a pale red viscous liquid. The yield was 38% based on 2-formyl-5-isobutylbenzofuran.

[Synthesis Example of Compound (10-a)]
2,5-dimethoxyaniline 4.71 g (30.7 mmol), 5-isobutylbenzofuran-2-carboxylic acid 8.71 g (30.7 mmol), triethylamine 3.11 g (30.7 mmol), N, N′-dimethylamino 0.75 g (6.1 mmol) of pyridine and 35.0 g of dehydrated N, N′-dimethylacetamide were mixed. After cooling the obtained solution in an ice bath, 14.28 g (33.8 mmol) of BOP reagent was added and reacted at room temperature for 24 hours. A mixed solution of water and methanol (2 parts by volume of water and 1 part by volume of methanol) was added to the obtained mixture to cause crystallization. The obtained precipitate was collected by filtration, washed with a mixed solution of water-methanol (water 1 volume part, methanol 1 volume part), and vacuum-dried to obtain 5.7 g of compound (10-a) as a pale yellow powder. The yield was 53% based on 2,5-dimethoxyaniline.

[Synthesis Example of Compound (10-b)]
Compound (10-a) 4.7 g, 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetan-2,4-disulfide (Lawson reagent) 9.2 g (23.0 mmol) ) And 100 g of toluene, and the resulting mixture was heated to 80 ° C. and reacted for 5 hours. After cooling, the mixture was concentrated to obtain a red viscous solid containing the compound (10-b) and a decomposition product of Lawson reagent as main components.

[Synthesis Example of Compound (10-c)]
The mixture containing the compound (10-b) obtained in the previous item, 3.1 g (80 mmol) of sodium hydroxide and 50 g of water were mixed, and the resulting mixture was stirred under ice cooling. Subsequently, an aqueous solution containing 11.94 g (36 mmol) of potassium ferricyanide was added and reacted under ice cooling. The reaction was allowed to proceed for 24 hours at room temperature, and the precipitated yellow precipitate was collected by filtration. The precipitate collected by filtration was washed with water, then with hexane, and washed with methanol. To the yellow powder, a solvent of heptane-ethyl acetate 1: 1 (volume ratio) was added, and the mixture was stirred at room temperature for 1 hour, and then allowed to stand overnight in an ice bath. The resulting pale yellow powder was collected by filtration and dried in vacuo to obtain 2.5 g of a pale yellow solid containing the compound (10-c) as a main component. The yield was 51% based on the compound (10-a).

[Synthesis Example of Compound (10-d)]
Compound (10-c) 2.5 g (6.8 mmol) and pyridinium chloride 12.5 g (5 times mass) were mixed, heated to 180 ° C. and reacted for 2 hours. After cooling the obtained mixed liquid, water was added, and the resulting precipitate was collected by filtration and washed with water, toluene, and hexane to obtain 1.8 g of a solid mainly composed of the compound (10-d). . The yield was 77% based on the compound (10-c).

[Synthesis Example of Compound (A10-1)]
Compound (10-d) 1.80 g (5.60 mmol), compound (A) 4.92 g (11.8 mmol), dimethylaminopyridine 0.07 g (0.56 mmol), and chloroform 30 mL were mixed. To the resulting mixture, 1.70 g (13.4 mmol) of N, N′-diisopropylcarbodiimide was added under ice cooling. The resulting reaction solution was reacted at room temperature overnight, filtered through silica gel, and then concentrated under reduced pressure. Methanol was added to the residue for crystallization. The crystals were collected by filtration and redissolved in chloroform. Methanol was added to the resulting solution while stirring, and the resulting white precipitate was collected by filtration, washed with ethanol, and the first component eluted with 80 vol% chloroform-20 vol% acetone was collected by silica gel column chromatography. After concentration under reduced pressure, crystallization was performed with cold methanol. The produced pale yellow powder was collected by filtration and dried in vacuo to obtain 4.60 g of compound (A10-1) as a white powder. The yield was 72% based on the compound (10-d).

¹ H-NMR (CDCl ₃ ) of the compound (A10-1): δ (ppm) 0.81 to 0.87 (t, 3H), 1.29 to 1.31 (d, 3H), 1.48 to 1.79 (m, 26H), 2.35 to 2.47 (m, 8H), 2.63 to 2.83 (m, 5H), 3.93 to 3.97 (m, 4H), 4. 15-4.20 (t, 4H), 5.79-5.84 (dd, 2H), 6.07-6.17 (m, 2H), 6.37-6.44 (m, 2H), 6.87-7.02 (m, 8H), 7.23 (m, 3H), 7.48-7.50 (m, 3H)

  The phase transition temperature of the obtained compound (A10-1) was confirmed by texture observation with a polarizing microscope. Compound (A10-1) exhibited a highly viscous phase from 144 ° C. when the temperature was raised, and showed a clearing point at 169 ° C. When the temperature was lowered, it had a clear nematic phase from 167 ° C. and crystallized with a nematic phase up to 105 ° C.

(Example 5)
<Synthesis Example of Compound (A11-1)>
Compound (A11-1) was synthesized according to the following scheme.

[Synthesis example of 4,6-dimethylbenzofuran]
25 g (205 mmol) of 3,5-dimethylphenol was dissolved in 150.0 g of N, N′-dimethylacetamide. After the solution was cooled with an ice bath, sodium hydroxide 9.82 (246 mmol) was added. The mixture was stirred at room temperature for 1 hour, and 25.49 g (266 mmol) of chloroacetaldehyde dimethyl acetal was added dropwise. The mixture was stirred at 100 ° C. for 15 hours, and the reaction mixture was added to 1000 mL of water and 400 mL of methyl isobutyl ketone to separate the layers. The organic layer was recovered, and the organic layer was washed twice with 500 mL of a 1N sodium hydroxide aqueous solution and twice with 800 mL of pure water. After collecting the organic layer, it was dehydrated with anhydrous sodium sulfate and concentrated under reduced pressure with an evaporator to obtain a pale red viscous liquid. On the other hand, 400 g of toluene and 3.01 g of orthophosphoric acid were mixed and heated to 110 ° C. A solution prepared by dissolving a pale red viscous liquid in 100 mL of toluene was added dropwise to the solution. After stirring at 110 ° C. for 3 hours, the mixture was cooled to room temperature. The reaction solution was washed twice with 1N aqueous sodium hydrogen carbonate solution and finally washed with 500 mL of pure water. The organic layer was collected, dehydrated with anhydrous sodium sulfate, concentrated under reduced pressure with an evaporator, and dried under vacuum to obtain 16.5 g of a light red viscous liquid of 4,6-dimethylbenzofuran. The yield was 55% based on 3,5-dimethylphenol.

[Synthesis example of 2-formyl-4,6-dimethylbenzofuran]
21.62 g (148 mmol) of 4,6-dimethylbenzofuran was dissolved in 28.4 g (389 mmol) of N, N′-dimethylformamide. After cooling the solution with a water bath, 25 g (163 mmol) of phosphorus oxychloride was added dropwise. The pink solution was stirred at room temperature for 1 hour and then stirred at 100 ° C. for 10 hours. The reaction solution was allowed to cool to room temperature, 100 mL of pure water was added and stirred for 1 hour, and then neutralized with 1N sodium bicarbonate. After adjusting the pH to 8, it was separated from toluene. The organic layer was collected, and 2.6 g of activated carbon was added and filtered. After concentration under reduced pressure using an evaporator, the residue was dissolved in chloroform and crystallized with heptane. The crystals were collected by filtration and dried in vacuo to give 19.5 g of 2-formyl-4,6-dimethylbenzofuran as a pale yellow powder. The yield was 76% based on 4,6-dimethylbenzofuran.

[Synthesis Example 1 of 4,6-dimethylbenzofuran-2-carboxylic acid-1]
19.50 g (112 mmol) of 2-formyl-4,6-dimethylbenzofuran and 13.04 g (134 mmol) of amidosulfuric acid were mixed with 100 mL of pure water. The mixture was cooled in an ice bath, and a solution of sodium chlorite 12.15 g (134 mmol) in 100 mL of water was added dropwise. The reaction was carried out in a water bath for 36 hours. To the reaction solution, 100 mL of toluene and 25 g of potassium hydroxide were added to adjust the pH to 12. Liquid separation was performed, the aqueous layer was recovered, and the aqueous layer was further washed with 200 mL of toluene. The aqueous layer was collected, and the pH was adjusted to 2 with 2N hydrochloric acid, and then 400 mL of toluene was added for liquid separation. The organic layer was collected, dehydrated with anhydrous sodium sulfate, concentrated under reduced pressure with an evaporator, and dried under vacuum to obtain 14.27 g of 4,6-dimethylbenzofuran-2-carboxylic acid as a yellow powder. The yield was 67% based on 2-formyl-4,6-dimethylbenzofuran.

  4,6-dimethylbenzofuran-2-carboxylic acid could also be synthesized by the following scheme.

<Synthesis Example 2 of 4,6-dimethylbenzofuran-2-carboxylic acid>

[Synthesis Example of 4,6-dimethylsalicylaldehyde]
150 g (1227 mmol) of 3,5-dimethylphenol, 230.1 g (7674 mmol) of paraformaldehyde, and 175.4 g (1842 mmol) of anhydrous magnesium chloride were dispersed in 900 mL of acetonitrile. After stirring in an ice bath for 30 minutes, 474 g (4681 mmol) of triethylamine was added dropwise over 2 hours. The mixture was reacted in a water bath for 8 hours and at room temperature for 14 hours. The reaction solution was acidified by adding 1500 mL of cold 5N hydrochloric acid, and then separated with 400 mL of ethyl acetate, and the organic layer was recovered. Further, the aqueous layer was separated with 400 mL of ethyl acetate. The organic layer was collected, collected with the previous organic layer, dehydrated with anhydrous sodium sulfate, and concentrated under reduced pressure using an evaporator. The residue was dissolved in 400 mL toluene, 3 g of activated carbon and 20 g of silica gel were added, and the mixture was stirred for 30 minutes at room temperature and filtered. The filtrate was collected, concentrated under reduced pressure with an evaporator, and vacuum-dried to obtain 170 g of an orange viscous liquid of 4,6-dimethylsalicylaldehyde. The yield was 92% based on 3,5-dimethylphenol.

[Synthesis Example 2 of 4,6-dimethylbenzofuran-2-carboxylic acid]
4,6-dimethylsalicylaldehyde 45.0 g (300 mmol), potassium carbonate 101. g (300 mmol) was dispersed in 360 mL of N, N′-dimethylacetamide. After heating to 80 ° C., 50.0 g (300 mmol) of ethyl bromoacetate was added dropwise over 1 hour. The mixture was reacted at 80 ° C. for 4 hours. After cooling the reaction solution to room temperature, 400 mL of methyl isobutyl ketone was added, acidified with 1000 mL of cold 1N hydrochloric acid, and then separated. The organic layer was washed 3 times with 1000 mL of pure water, and the organic layer was recovered. After dehydration with anhydrous sodium sulfate, the solvent was distilled off with an evaporator. To the residue, 40 g of potassium hydroxide and 400 mL of ethanol were added and stirred at 80 ° C. for 1 hour. After cooling to room temperature, the solvent was distilled off with an evaporator and 1000 mL of pure water was added. After confirming that the pH was 12 or more, the aqueous layer was washed twice with toluene and once with heptane. The aqueous layer was recovered, neutralized with 4N-sulfuric acid, and the pH was adjusted to 3. The precipitated yellow precipitate was collected by filtration, washed with pure water, and vacuum-dried to obtain 48.1 g of 4,6-dimethylbenzofuran-2-carboxylic acid as a yellow powder. The yield was 83% based on 4,6-dimethylsalicylaldehyde.

[Synthesis Example of Compound (11-a)]
2,5-dimethoxyaniline 11.49 g (75.0 mmol), 4,6-dimethylbenzofuran-2-carboxylic acid 14.27 g (75.7 mmol), triethylamine 7.59 g (75.0 mmol), N, N'- 1.83 g (15.0 mmol) of dimethylaminopyridine and 100.0 g of dehydrated N, N′-dimethylacetamide were mixed. After cooling the obtained solution in an ice bath, 34.85 g (82.5 mmol) of a BOP reagent was added and reacted at room temperature for 24 hours. A mixed solution of water and methanol (2 parts by volume of water and 1 part by volume of methanol) was added to the obtained mixture to cause crystallization. The resulting precipitate was collected by filtration, washed with a mixed solution of water-methanol (3 parts by volume of water, 2 parts by volume of methanol), and dried under vacuum to obtain 16.2 g of compound (11-a) as a pale yellow powder. The yield was 66% based on 2,5-dimethoxyaniline.

[Synthesis Example of Compound (11-b)]
Compound (11-a) 16.0 g (49 mmol), 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetan-2,4-disulfide (Lawson reagent) 9.2 g ( 30.0 mmol) and 100 g of toluene were mixed, and 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 (11-b) and a decomposition product of Lawson reagent as main components.

[Synthesis Example of Compound (11-c)]
A mixture containing the compound (11-b) obtained in the previous item, 11.8 g (262 mmol) 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 (134 mmol) 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 (11-c) as a main component. The yield was 25% based on the compound (11-a).

[Synthesis Example of Compound (11-d)]
Compound (11-c) 4.0 g (12.0 mmol) and pyridinium chloride 40.0 g (10 times mass) were mixed, heated to 180 ° C., and reacted for 3 hours. The resulting mixture was added to ice and the resulting precipitate was collected by filtration. After hang-washing with water, it was washed with toluene and vacuum-dried to obtain 3.4 g of an ocher solid mainly composed of the compound (11-d). The yield was 93% based on the compound (11-c).

[Synthesis Example of Compound (A11-1)]
Compound (11-d) 3.00 g (9.64 mmol), compound (A) 8.47 g (20.23 mmol), dimethylaminopyridine 0.12 g (0.96 mmol) and chloroform 40 mL were mixed. To the resulting mixture, 2.92 g (23.12 mmol) of N, N′-diisopropylcarbodiimide was added under ice cooling. The resulting reaction solution was reacted at room temperature overnight, filtered through silica gel, and then concentrated under reduced pressure. Methanol was added to the residue for crystallization. The crystals were collected by filtration, redissolved in chloroform, added with 0.3 g of activated carbon, and stirred at room temperature for 1 hour. The solution was filtered, and the filtrate was concentrated under reduced pressure to 1/3 with an evaporator. Methanol was added with stirring, and the resulting white precipitate was collected by filtration, washed with heptane, and dried under vacuum to obtain compound (A11-1). 7.60 g was obtained as a white powder. The yield was 71% based on the compound (11-d).

¹ H-NMR (CDCl ₃ ) of the compound (A11-1): 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)

  The phase transition temperature of the obtained compound (A11-1) was confirmed by texture observation with a polarizing microscope. Compound (A11-1) exhibited a highly viscous intermediate phase from 105 ° C. to 137 ° C. during the temperature increase. Although it was difficult to discriminate the liquid crystal phase, a clear nematic liquid crystal phase was exhibited at 137 ° C. or higher. The nematic liquid crystal phase is up to 180 ° C. or higher. When the temperature is lowered, the nematic liquid crystal phase exhibits a nematic phase up to 61 ° C. and crystallizes.

(Example 6)
<Synthesis Example of Compound (A15-1)>
Compound (A15-1) was synthesized according to the following scheme.

[Synthesis Example of 5-Fluorobenzofuran-2carboxylic acid]
25 g (178 mmol) of 5-fluorosalicylaldehyde, 49.32 g (357 mmol) of potassium carbonate, and 200 g of 2-butanone were mixed and heated to 80 ° C. To the resulting dispersion, 55.5 g (232 mmol) of diethyl bromomalonate was added dropwise and reacted at 100 ° C. for 24 hours. The resulting reddish brown solution was allowed to cool to room temperature and then washed with pure water and a 1 mol / L potassium carbonate aqueous solution. The organic layer was collected, dehydrated with anhydrous sodium sulfate, and concentrated under reduced pressure using an evaporator. To the residue, 25 g of potassium hydroxide and 250 mL of ethanol were added and stirred at 80 ° C. for 2 hours. After cooling to room temperature, ethanol was distilled off with an evaporator. The residue was dissolved in 500 mL of pure water and 500 g of ice, and the pH was adjusted to 3 with 2N sulfuric acid. The deposited pale purple precipitate was collected by filtration, further washed with 1000 mL of pure water and vacuum dried to obtain 23.4 g of 5-fluorobenzofuran-2carboxylic acid as a pale yellow powder. The yield was 73% based on 4-fluorosalicylaldehyde.

[Synthesis Example of Compound (15-a)]
17.01 g (111 mmol) of 2,5-dimethoxyaniline, 20.0 g (111 mmol) of 5-fluorobenzofuran-2carboxylic acid, 11.24 g (111 mmol) of triethylamine, 2.71 g of N, N′-dimethylaminopyridine (22.22 g) 2 mmol) and dehydrated N, N′-dimethylacetamide 100.0 g. After cooling the obtained solution in an ice bath, 51.57 g (33.8 mmol) of BOP reagent was added and reacted at room temperature for 24 hours. A mixed solution of water and methanol (2 parts by volume of water and 1 part by volume of methanol) was added to the obtained mixture to cause crystallization. The resulting precipitate was collected by filtration, washed with a mixed solution of water-methanol (water 1 volume part, methanol 1 volume part), and vacuum-dried to obtain 32.1 g of compound (15-a) as a pale yellow powder. The yield was 92% based on 2,5-dimethoxyaniline.

[Synthesis Example of Compound (15-b)]
Compound (15-a) 32.0 g (101 mmol), 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetan-2,4-disulfide (Lawson reagent) 24.6 g ( 61.0 mmol) and 320 g of toluene were mixed, and the resulting mixture was heated to 80 ° C. and reacted for 24 hours. After cooling, the mixture was concentrated to obtain a yellow solid containing the compound (15-b) and a decomposition product of Lawson reagent as main components.

[Synthesis Example of Compound (15-c)]
The mixture containing the compound (15-b) obtained in the previous item, 21.7 g (543 mmol) of sodium hydroxide and 500 g of water were mixed, and the resulting mixture was stirred under ice cooling. Subsequently, 81.3 g (247 mmol) of potassium ferricyanide was added and reacted. The reaction was allowed to proceed at room temperature for 2 hours, and the yellow precipitate that had precipitated was collected by filtration. The precipitate collected by filtration was washed with water and then with hexane, washed with toluene, and vacuum-dried to obtain 27.1 g of an ocherous solid mainly composed of compound (15-c). The yield was 91% based on the compound (15-a).

[Synthesis Example of Compound (15-d)]
Compound (15-c) 10.0 g (30 mmol) and pyridinium chloride 50.0 g (5 times mass) were mixed, heated to 180 ° C. and reacted for 2 hours. After cooling the obtained mixture, water was added, and the resulting precipitate was collected by filtration and washed with water, hexane, and toluene to obtain 6.0 g of a solid mainly composed of the compound (15-d). . The yield was 66% based on the compound (15-c).

[Synthesis Example of Compound (A15-1)]
Compound (15-d) 3.00 g (9.96 mmol), compound (A) 8.75 g (20.9 mmol), dimethylaminopyridine 0.12 g (1.00 mmol) and chloroform 50 mL were mixed. To the resulting mixture, 3.02 g (23.9 mmol) of N, N′-diisopropylcarbodiimide was added under ice cooling. The resulting reaction solution was reacted at room temperature overnight, filtered through silica gel, and then concentrated under reduced pressure. Methanol was added to the residue for crystallization. The crystals were collected by filtration and redissolved in chloroform. After adding 0.3 g of activated carbon and stirring for 1 hour, the mixture was filtered. The filtrate was concentrated with an evaporator, methanol was added with stirring, and the resulting white precipitate was collected by filtration. The precipitate was washed with heptane and dried under vacuum to obtain 8.20 g of compound (A15-1) as a white powder. The yield was 75% based on the compound (15-d).

¹ H-NMR (CDCl ₃ ) of the compound (A15-1): δ (ppm) 1.46 to 1.90 (m, 24H), 2.36 to 2.84 (m, 12H), 3.93 to 3.98 (t, 4H), 4.15 to 4.20 (t, 4H), 5.80 to 5.84 (dd, 2H), 6.07 to 6.17 (m, 2H), 6. 37-6.44 (m, 2H), 6.87-7.02 (m, 8H), 7.14-7.19 (dt, 1H), 7.28 (s, 2H), 7.33- 7.37 (dd, 1H), 7.50-7.55 (m, 2H)

  The phase transition temperature of the obtained compound (A15-1) was confirmed by texture observation with a polarizing microscope. Compound (A15-1) exhibited a highly viscous phase from 143 ° C. to 178 ° C. at the time of temperature rise, and it was difficult to distinguish the liquid crystal phase. However, it showed a clear nematic phase at 178 ° C. or higher and exhibited a nematic phase up to 200 ° C. or higher. When the temperature was lowered, the nematic phase was exhibited up to 110 ° C. and crystallized.

(Example 7)
<Synthesis Example of Compound (A57-1)>
Compound (A57-1) was synthesized according to the following scheme.

[Synthesis example of 5-propylbenzofuran-2carboxylic acid]
4-Propylsalicylaldehyde 27.8 g (169 mmol), potassium carbonate 46.81 g (339 mmol), tetrabutylammonium bromide 11.84 g (37 mmol), potassium iodide 30.48 g (37 mmol) and toluene were mixed, and the mixture was heated to 80 ° C. Warmed up. To the obtained dispersion, 52.6 g (477 mmol) of diethyl bromomalonate and 2.8 g of 18-crown-6 were added dropwise and reacted at 110 ° C. (toluene boiling point reflux) for 24 hours. The obtained reddish brown reaction liquid was cooled to room temperature and then concentrated under reduced pressure using an evaporator. To the residue, 27.8 g of potassium hydroxide and 278 mL of ethanol were added and stirred at 80 ° C. for 1 hour. After cooling to room temperature, ethanol was distilled off with an evaporator. The residue was dissolved in 500 mL of pure water and 500 g of ice, and the pH was adjusted to 3 with 2N sulfuric acid. The precipitated yellow precipitate was collected by filtration, further washed with 1000 mL of pure water and vacuum dried to obtain 5.8 g of 5-propylbenzofuran-2carboxylic acid as a pale yellow powder. The yield was 17% based on 4-propylsalicylaldehyde.

[Synthesis Example of Compound (57-a)]
2,5-dimethoxyaniline 4.3 g (27.9 mmol), 5-propyl-benzofuran-2-carboxylic acid 5.7 g (27.9 mmol), triethylamine 2.82 g (27.9 mmol), N, N′-dimethyl 0.68 g (5.6 mmol) of aminopyridine and 30.0 g of dehydrated N, N′-dimethylacetamide were mixed. After cooling the obtained solution in an ice bath, 12.96 g (30.7 mmol) of a BOP reagent was added and reacted at room temperature for 24 hours. A mixed solution of water and methanol (2 parts by volume of water and 1 part by volume of methanol) was added to the obtained mixture to cause crystallization. The resulting precipitate was collected by filtration, washed with a mixed solution of water-methanol (water 1 volume part, methanol 1 volume part), and vacuum-dried to obtain 6.33 g of compound (57-a) as a pale yellow powder. The yield was 67% based on 2,5-dimethoxyaniline.

[Synthesis Example of Compound (57-b)]
Compound (57-a) 6.0 g (17 mmol), 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetan-2,4-disulfide (Lawson reagent) 9.2 g ( 23.0 mmol) and 100 g of toluene were mixed, and the resulting mixture was heated to 80 ° C. and reacted for 5 hours. After cooling, the mixture was concentrated to obtain a red viscous solid containing the compound (57-b) and a decomposition product of Lawson reagent as main components.

[Synthesis Example of Compound (57-c)]
The mixture containing the compound (57-b) obtained in the previous section, 4.5 g (112 mmol) of sodium hydroxide and 50 g of water were mixed, and the resulting mixture was stirred under ice cooling. Subsequently, 16.8 g (51 mmol) of potassium ferricyanide was added and reacted under ice cooling. The reaction was allowed to proceed at room temperature for 48 hours, and the yellow precipitate that had precipitated was collected by filtration. The precipitate collected by filtration was washed with water and then with hexane, washed with ethanol, and vacuum-dried to obtain 2.8 g of a pale yellow solid mainly composed of compound (57-c). The yield was 42% based on the compound (57-a).

[Synthesis Example of Compound (57-d)]
2.70 g (7.64 mmol) of compound (57-c) and 13.5 g (5 times mass) of pyridinium chloride were mixed, heated to 180 ° C. and reacted for 2 hours. After cooling the obtained mixed liquid, water was added, and the resulting precipitate was collected by filtration and washed with water and hexane to obtain 2.4 g of a solid containing the compound (57-d) as a main component. The yield was 97% based on the compound (57-c).

[Synthesis Example of Compound (A57-1)]
1.85 g (5.69 mmol) of the compound (57-d), 5.00 g (11.9 mmol) of the compound (A), 0.07 g (0.56 mmol) of dimethylaminopyridine and 20 mL of chloroform were mixed. To the obtained mixture, 1.72 g (13.7 mmol) of N, N′-diisopropylcarbodiimide was added under ice cooling. The resulting reaction solution was reacted at room temperature overnight, filtered through silica gel, and then concentrated under reduced pressure. Methanol was added to the residue for crystallization. The crystals were collected by filtration and redissolved in chloroform. Methanol was added to the resulting solution while stirring, and the resulting white precipitate was collected by filtration, washed with ethanol, and dried under vacuum to obtain 3.85 g of compound (A57-1) as a white powder. The yield was 77% based on the compound (57-d).

¹ H-NMR (CDCl ₃ ) of the compound (A57-1): δ (ppm) 0.94 to 0.99 (t, 3H), 1.45 to 1.86 (m, 26H), 2.35 to 2.47 (m, 8H), 2.67 to 2.83 (m, 6H), 3.92 to 3.97 (m, 4H), 4.15 to 4.20 (t, 4H), 5. 79-5.84 (dd, 2H), 6.07-6.17 (m, 2H), 6.37-6.44 (m, 2H), 6.87-7.01 (m, 8H), 7.25 (s, 2H), 7.46-7.49 (m, 4H)

  The phase transition temperature of the obtained compound (A57-1) was confirmed by texture observation with a polarizing microscope. The compound (A57-1) exhibits a highly viscous phase from 131 ° C. to 143 ° C. when the temperature is raised, and gives a clear nematic phase from 143 ° C. Furthermore, the compound (A57-1) exhibited a nematic phase up to 180 ° C. or higher, and crystallized by exhibiting a nematic phase up to 100 ° C. when the temperature was lowered.

(Example 8)
<Synthesis Example of Compound (A25-1)>
Compound (A25-1) was synthesized according to the following scheme.

[Synthesis Example of Compound (25-a)]
2,5-dimethoxyaniline 15.8 g (103 mmol), thieno [3,2-b] thiophene-2-carboxylic acid 19.0 g (113 mmol) triethylamine 10.4 g (199 mmol), N, N′-dimethylaminopyridine 4 .85 g (3.97 mmol) and dehydrated N, N′-dimethylacetamide 95.0 g were mixed. After the obtained solution was cooled in an ice bath, 47.9 g (113 mmol) of BOP reagent was added and reacted at room temperature for 24 hours. A mixed solution of water and methanol (2 parts by volume of water and 1 part by volume of methanol) was added to the obtained mixture to cause crystallization. The resulting precipitate was collected by filtration, washed with a mixed solution of water-methanol (water 1 volume part, methanol 1 volume part), and vacuum-dried to obtain 21.0 g of compound (25-a) as a yellow powder. The yield was 64% based on 2,5-dimethoxyaniline.

[Synthesis Example of Compound (25-b)]
Compound (25-a) 27.0 g (85 mmol), 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetan-2,4-disulfide (Lawson reagent) 17.8 g ( 44.0 mmol) and 122 g of toluene were mixed, and the resulting mixture was heated to 80 ° C. and reacted for 5 hours. The precipitate deposited after cooling was collected by filtration to obtain a brown solid mainly composed of the compound (25-b) and a decomposition product of Lawson reagent.

[Synthesis Example of Compound (25-c)]
26.4 g of the mixture containing the compound (25-b) obtained in the previous item, 18.9 g (472 mmol) of sodium hydroxide and 450 g of water were mixed, and the resulting mixture was reacted under ice cooling. Subsequently, an aqueous solution containing 70.7 g (215 mmol) of potassium ferricyanide was added and reacted under ice cooling. The reaction was allowed to proceed for 12 hours at room temperature, and the yellow precipitate that had precipitated was collected by filtration. The precipitate collected by filtration was washed with water and then with hexane, washed with ethanol, and vacuum-dried to obtain 15 g of a yellow solid containing compound (25-c) as a main component. The yield was 58% based on the compound (25-a).

[Synthesis Example of Compound (25-d)]
Compound (25-c) 15.0 g (48.2 mmol) and pyridinium chloride 75.0 g (5 times mass) were mixed, heated to 180 ° C. and reacted for 3 hours. After cooling the resulting mixture, water is added, and the resulting precipitate is collected by filtration and washed with water, hot toluene, and hexane to obtain 6.6 g of a solid mainly composed of compound (25-d). It was. The yield was 45% based on the compound (25-c).

[Synthesis Example of Compound (A25-1)]
Compound (25-d) 2.0 g (6.6 mmol), compound (A) 5.76 g (13.8 mmol), dimethylaminopyridine 0.08 g (0.65 mmol) and chloroform 30 mL were mixed. To the resulting mixture, 1.98 g (15.7 mmol) of N, N′-diisopropylcarbodiimide was added under ice cooling. The resulting reaction solution was reacted at room temperature overnight, 0.8 g of activated carbon was added, and the mixture was allowed to stand overnight, filtered through silica gel, and concentrated under reduced pressure. Methanol was added to the residue for crystallization. The crystals were collected by filtration and redissolved in chloroform. Methanol was added to the resulting solution while stirring, and the resulting brown precipitate was collected by filtration, washed with ethanol, and dried under vacuum to obtain 4.30 g of compound (A25-1) as a light brown powder. The yield was 60% based on the compound (25-d).

¹ H-NMR (CDCl ₃ ) of the compound (A25-1): δ (ppm) 1.26 to 1.87 (m, 24H), 2.33 to 2.81 (m, 12H), 3.92 to 3.96 (t, 4H), 4.15 to 4.20 (t, 4H), 5.79 to 5.84 (dd, 2H), 6.07 to 6.17 (m, 2H), 6. 37-6.44 (m, 2H), 6.87-7.01 (m, 8H), 7.18 (s, 2H), 7.23-7.31 (d, 1H), 7.52- 7.54 (d, 1H), 7.82 (s, 1H)

  The phase transition temperature of the obtained compound (A25-1) was confirmed by texture observation with a polarizing microscope. Compound (A25-1) exhibits a smectic phase from 175 ° C. to 180 ° C. during heating, a nematic phase from 180 ° C. to 238 ° C. or higher, and exhibits a clearing point at 238 ° C. When the temperature was lowered, a nematic phase was exhibited up to 168 ° C. and crystallized.

Example 9
<Synthesis Example of Compound (A41-1)>
Compound (41-d) was synthesized according to the following scheme.

[Synthesis Example of Compound (41-a)]
While the vessel was mixed and reacted with 35.4 g (231 mmol) of 2,5-dimethoxyaniline, 46.7 g (462 mmol) of triethylamine and 400 g of dehydrated chloroform, 50.0 g (231 mmol) of 4-phenylbenzoyl chloride was added. The mixed solution was heated to 60 ° C., aged for 3 hours, cooled to room temperature, and poured into water. The separated organic layer was taken out and washed with water and then with hydrochloric acid. The obtained organic layer was concentrated to obtain 76.6 g of a solid of compound (41-a). The yield was 98% based on 2,5-dimethoxyaniline.

[Synthesis Example of Compound (41-b)]
In the same manner as in the synthesis example of compound (1-b), a solid containing the compound (41-b) and a decomposition product of Lawson reagent as main components was obtained.

[Synthesis Example of Compound (41-c)]
In the same manner as in the synthesis example of compound (1-c), a solid containing compound (41-c) as the main component was obtained.

[Synthesis Example of Compound (41-d)]
In the same manner as in the synthesis example of compound (1-d), a solid containing compound (41-d) as the main component was obtained.

[Synthesis Example of Compound (A41-1)]
In the same manner as in the synthesis example of compound (A1-1), compound (A41-1) was obtained. The yield was 68% based on the compound (41-d).

¹ H-NMR (CDCl ₃ ) of the compound (A41-1): δ (ppm) 1.44 to 1.82 (m, 24H), 2.32 to 2.64 (m, 12H), 3.91 to 3.97 (t, 4H), 4.14 to 4.20 (t, 4H), 5.79 to 5.84 (m, 2H), 6.07 to 6.18 (m, 2H), 6. 36 to 6.44 (m, 2H), 6.85 to 7.01 (m, 8H), 7.37 to 7.90 (m, 9H), 8.13 to 8.17 (m, 2H)

  The phase transition temperature of the crystal of the compound (A41-1) was confirmed by texture observation with a polarizing microscope. As the temperature was raised, it changed to a smectic phase around 214 ° C. When the temperature was further increased, the nematic phase changed to around 234 ° C. When the temperature was further increased, it changed to an isotropic phase around 275 ° C. When the temperature was lowered from here, it became a nematic phase around 269 ° C., became a smectic phase around 227 ° C., and returned to a crystal around 204 ° C. That is, it was found that the compound (A41-1) exhibited a smectic phase from 214 ° C. to 234 ° C. and a nematic phase from 234 ° C. to 275 ° C. when the temperature was raised. Further, it was found that a nematic phase was exhibited from 269 ° C. to 227 ° C. and a smectic phase was exhibited from 227 ° C. to 204 ° C. when the temperature was lowered.

(Example 10)
<Synthesis Example of Compound (A43-1)>
[Synthesis Example of Compound (43-d)]
In the synthesis example of compound (41-d), the following method was used except that 4- (4-normalpropylphenyl) benzoyl chloride was used instead of 4-phenylbenzoyl chloride as a starting material and amidation was performed. Compound (43-d) was synthesized according to the reaction scheme.

[Synthesis Example of Compound (A43-1)]
Compound (A43-1) was obtained in the same manner as in the synthesis example of compound (1-1) except that the starting compound (1-d) was changed to compound (43-d). The yield was 65% based on the compound (43-d).

¹ H-NMR (CDCl ₃ ) of the compound (A43-1): δ (ppm) 0.95 to 1.01 (t, 3H) 1.44 to 1.87 (m, 26H), 2.34 to 2 .83 (m, 14H), 3.92 to 3.98 (t, 4H), 4.14 to 4.21 (t, 4H), 5.79 to 5.84 (m, 2H), 6.07 -6.18 (m, 2H), 6.36-6.44 (m, 2H), 6.86-7.02 (m, 8H), 7.20-7.31 (m, 4H), 7 .56 to 7.60 (d, 2H), 7.69 to 7.73 (d, 2H), 8.07 to 8.11 (d, 2H)

  The phase transition temperature of the crystal of the compound (A43-1) was confirmed by texture observation with a polarizing microscope. As the temperature was raised, it changed to an isotropic phase around 143 ° C. When the temperature was lowered from here, the crystal returned to around 118 ° C. That is, it was found that the compound (A43-1) does not show a liquid crystal phase.

(Example 11)
<Synthesis Example of Compound (A66-1)>
Compound (A66-1) was synthesized according to the following scheme.

[Synthesis Example of Compound (66-a)]
2,3-dicyanohydroquinone 10.0 g (62 mmol), potassium hydroxide 35.0 g (624 mmol) and water 70.0 g were mixed, and the mixture was heated at 100 ° C. with stirring. The obtained mixture was cooled to room temperature, 40.0 g of sulfuric acid was added, and the mixture was further stirred. Ethyl acetate was added to the resulting mixture and stirred, and the organic layer was taken out. The obtained organic layer was concentrated under reduced pressure, the solvent was removed, and the residue was dried in vacuo to obtain 8.5 g (42.6 mmol) of compound (66-a). The yield was 68% based on 2,3-dicyanohydroquinone.

[Synthesis Example of Compound (66-b)]
Compound (66-a) 10.0 g (50.5 mmol), 2-amino-6-methoxybenzothiazole 19.1 g (106.0 mmol) and tetrahydrofuran 200.0 g were mixed, and the mixture was stirred at 70 ° C. Heated. The obtained mixed solution was cooled to room temperature, 12.5 g (60.6 mmol) of N, N′-dicyclohexylcarbodiimide was dissolved in 37.5 g of tetrahydrofuran, added dropwise at room temperature, and then heated at 80 ° C. with stirring for 36 hours. Stir. The obtained mixture was allowed to cool to room temperature, and the white precipitate was removed by filtration. The obtained filtrate was concentrated under reduced pressure, the solvent was removed, and the residue was crystallized from chloroform. The resulting pale green powder was filtered and washed with chloroform. The obtained light green powder was dissolved again in tetrahydrofuran and crystallized by adding methanol. The produced green precipitate was filtered and then vacuum-dried to obtain 2.8 g of compound (66-b). The yield was 16% based on the compound (66-a).

[Synthesis Example of Compound (A66-1)]
2.1 g (6.13 mmol) of compound (66-b), 0.18 (1.47 mmol) of 4-dimethylaminopyridine, 6.16 g (14.72 mmol) of compound (A), and 123 g of chloroform were mixed. Subsequently, a solution obtained by dissolving 4.56 g (22.1 mmol) of N, N′-dicyclohexylcarbodiimide in 10.7 g of chloroform was added dropwise to the obtained mixed solution at room temperature and stirred. After filtering the obtained mixture, 62 g of 2N hydrochloric acid was added and stirred, the liquid was separated, and the organic layer was taken out. After the above liquid separation operation was repeated twice, the liquid separation organic layer was recovered, dried over anhydrous sodium sulfate, the solvent was distilled off with an evaporator, methanol was added and the mixture was stirred. The produced precipitate was filtered and then vacuum-dried to obtain 4.1 g of Compound (A66-1). The yield was 59% based on the compound (66-b).

¹ H-NMR (CDCl ₃ ) of the compound (A66-1): δ (ppm) 1.45 to 1.85 (m, 12H), 2.29 to 2.56 (m, 8H), 2.56 to 2.75 (2tt, 4H), 3.89 (s, 3H), 3.92 to 3.97 (t, 4H), 4.16 to 4.19 (t, 4H), 5.79 to 5. 84 (dd, 2H), 6.07 to 6.17 (m, 2H), 6.37 to 6.44 (m, 2H), 6.86 to 7.01 (m, 8H), 7.08 to 7.13 (dd, 1H), 7.32 (d, 1H), 7.50 to 7.52 (m, 2H), 8.00 (d, 1H)

  The phase transition temperature of the obtained compound (A66-1) was confirmed by texture observation with a polarizing microscope. Compound (A66-1) showed a highly viscous phase from 125 ° C. to 140 ° C. at the time of temperature rise, and it was difficult to distinguish the liquid crystal phase. However, a clear liquid crystal phase was exhibited at 140 ° C. or higher.

(Examples 12 to 24, Comparative Example 1)
<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 subjected to a rubbing treatment, and the composition having the composition shown in Table 1 was applied to the surface subjected to the rubbing treatment by a spin coating method, and the drying temperature shown in Table 2 was applied for 1 minute. Dried. Next, while heating up to the temperature at the time of light irradiation described in Table 2, ultraviolet rays having an integrated light amount described in Table 2 were irradiated to form an optical film having a film thickness described in Table 3.
Table 1 shows the content rate (mass%) of each structural component with respect to the whole composition.

LC242: Liquid crystal compound polymerization initiator of the following formula commercially available from BASF: Irgacure 819 (manufactured by Ciba Japan Co., Ltd.)
Leveling agent: BYK361N (manufactured by Big Chemie Japan)
Solvent: cyclopentanone

<Measurement of optical properties>
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 d (micrometer) of the optical film was measured using the laser microscope (LEXT, Olympus company make). The results are shown in Table 3. Δn was calculated by dividing the value of Re (546.9) by the film thickness (Δn = Re (546.9) / d).

(Example 25)
<Synthesis Example 2 of Compound (A11-1)>
Compound (A11-1) was synthesized according to the following scheme.

[Synthesis Example of 4,6-dimethylbenzofuran-2-carboxylic acid]
146.6 g (976 mmol) of 4,6-dimethylsalicylaldehyde and 330.7 g (2392 mmol) of potassium carbonate were dispersed in 700 mL of N, N′-dimethylacetamide. After warming to 80 ° C., 190.5 g (976 mmol) of tert-butyl bromoacetate was added dropwise over 30 minutes. The mixture was reacted at 130 ° C. for 2 hours. After cooling the reaction solution to room temperature, 600 mL of methyl isobutyl ketone was added, and the mixture was separated with 1200 mL of pure water. Further, the organic layer was washed twice with 1000 mL of pure water to recover the organic layer. After dehydration with anhydrous sodium sulfate, the solvent was distilled off with an evaporator. The residue was dissolved in 240 g of acetic acid, 72 g of an aqueous hydrobromic acid solution was added, and the mixture was stirred at 40 ° C. for 1 hour. After allowing to cool to room temperature, 150 g of 1N hydrochloric acid was added and the precipitated white powder was collected by filtration. The obtained white powder was further washed with 1N-hydrochloric acid and then vacuum-dried to obtain 81.7 g of 4,6-dimethylbenzofuran-2-carboxylic acid as a yellow powder. The yield was 44% based on 4,6-dimethylsalicylaldehyde.

[Synthesis Example of Compound (11-a)]
96.6 g (631.0 mmol) of 2,5-dimethoxyaniline, 80.0 g (421 mmol) of 4,6-dimethylbenzofuran-2-carboxylic acid and 400.0 g of chloroform were mixed. The obtained suspension was placed in an ice bath. After cooling, a mixed solution of 88.7 g (463 mmol) of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and 300 g of chloroform was added over 4 hours and reacted at room temperature for 48 hours. The obtained mixed solution was concentrated and crystallized by adding a mixed solution of 1N hydrochloric acid and methanol (2 parts by volume of water, 1 part by volume of methanol) The resulting precipitate was collected by filtration and mixed with water and methanol. (2 parts by volume of water, 1 part by volume of methanol) was added.The precipitated pale yellow precipitate was collected by filtration, and mixed with water-methanol (2 parts by volume of water, 1 part by volume of methanol). Kiyoshi, and dried under vacuum, a pale yellow powder as the compound (11-a) was obtained 124.2 g. The yield was 91% in the 4,6-dimethyl-benzofuran-2-carboxylic acid standards.

[Synthesis Example of Compound (11-b)]
Compound (11-a) 123.0 g (378 mmol), 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetan-2,4-disulfide (Lawson reagent) 9.2 g ( 227.0 mmol) and 1200 g of toluene were mixed, and the resulting mixture was heated to 110 ° C. and reacted for 8 hours. After cooling to room temperature, the solution was separated with a 1N sodium hydroxide aqueous solution. The organic layer was collected and 800 mL of n-heptane was added. The precipitated yellow precipitate was collected by filtration, washed with n-heptane, and vacuum-dried to obtain 109.2 g of a bright yellow powder mainly containing the compound (11-b). The yield was 85% based on the compound (11-a).

[Synthesis Example of Compound (11-c)]
60.0 g (176 mmol) of the compound (11-b), 53.8 g (959 mmol) of potassium hydroxide and 1000 g of water were mixed, and the resulting mixture was stirred under ice cooling. Subsequently, 133.0 g (404 mmol) of potassium ferricyanide and 51 g of methanol were added and reacted. The reaction was allowed to proceed for 36 hours at room temperature, and the precipitated yellow precipitate was collected by filtration. The precipitate collected by filtration was washed with a mixed solvent of n-heptane and toluene (3 parts by volume of heptane, 1 part by volume of toluene), and the resulting yellow powder was vacuum-dried to contain compound (11-c) as a main component. 51.3 g of a yellow solid was obtained. The yield was 86% based on the compound (11-b).

[Synthesis Example of Compound (11-d)]
Compound (11-c) 40.0 g (118 mmol) and pyridinium chloride 400.0 g (10 times mass) were mixed, heated to 180 ° 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 36.6 g of a yellow solid containing compound (11-d) as a main component. The yield was 99% based on the compound (11-c).

[Synthesis Example of Compound (A11-1)]
35.0 g (112.4 mmol) of the compound (11-d), 98.8 g (236.1 mmol) of the compound (A), 1.37 g (11.2 mmol) of dimethylaminopyridine, and 700 mL of toluene were mixed. 55.6 g (269.8 mmol) of N, N′-dicyclohexylcarbodiimide was added to the resulting mixture under ice cooling. The resulting reaction solution was reacted at room temperature overnight, filtered through silica gel, and then concentrated under reduced pressure. Methanol was added to the residue for crystallization. The crystals were collected by filtration, redissolved in chloroform, added with 2.3 g of activated carbon, and stirred at room temperature for 1 hour. The solution was filtered, and the filtrate was concentrated under reduced pressure to 1/3 with an evaporator. Methanol was added with stirring, and the resulting white precipitate was collected by filtration, washed with heptane, and dried under vacuum to obtain compound (A11-1). 74.5 g was obtained as a white powder. The yield was 60% based on the compound (11-d).

(Example 26)
<Synthesis Example 3 of Compound (A11-1)>
Compound (A-11) was synthesized in the same manner as in Synthesis Example 2 of Compound (A11-1) except that ethyl chloroacetate was used instead of tert-butyl bromoacetate.

(Example 27)
<Synthesis Example of Compound (A61-1)>
Compound (A61-1) was synthesized according to the following scheme.

[Synthesis Example of 3,6-dimethylsalicylaldehyde]
50 g (409 mmol) of 2,5-dimethylphenol, 30.7 g (1023 mmol) of paraformaldehyde, and 58.4 g (613.9 mmol) of anhydrous magnesium chloride were dispersed in 500 mL of tetrahydrofuran. After stirring in an ice bath for 30 minutes, 82.83 g (818.6 mmol) of triethylamine was added dropwise over 2 hours. The mixture was reacted in a water bath for 8 hours and at room temperature for 120 hours. The reaction solution was acidified by adding 1500 mL of cold 5N hydrochloric acid, and extracted twice with 400 mL of ethyl acetate, and the organic layer was collected. The organic layer was dehydrated with anhydrous sodium sulfate and filtered through Celite, and the filtrate was concentrated under reduced pressure at 40 ° C. or lower with an evaporator. The residue was dissolved in 100 mL toluene and 600 mL n-heptane was added to the solution. 30 g of silica gel was added to the solution and stirred for 1 hour, followed by filtration. The filtrate was concentrated under reduced pressure, and n-heptane was added to the residue for extraction, and heptane was distilled off to obtain 10.5 g of 3,6-dimethylsalicylaldehyde as a yellow liquid. The yield was 17% based on 2,5-dimethylphenol.

[Synthesis Example of 4,7-dimethylbenzofuran-2-carboxylic acid]
10.48 g (70 mmol) of 3,6-dimethylsalicylaldehyde and 23.63 g (171 mmol) of potassium carbonate were dispersed in 70 mL of N, N′-dimethylacetamide. After heating to 80 ° C., 13.61 g (70 mmol) of tert-butyl bromoacetate was added dropwise over 10 minutes. The mixture was reacted at 130 ° C. for 3 hours. After cooling the reaction solution to room temperature, 200 mL of methyl isobutyl ketone was added, followed by separation with 1000 mL of pure water. Further, the organic layer was washed twice with 300 mL of pure water to recover the organic layer. After dehydration with anhydrous sodium sulfate, the solvent was distilled off with an evaporator. The residue was dissolved in 40 g of acetic acid, 8 g of an aqueous hydrobromic acid solution was added, and the mixture was stirred at 40 ° C. for 1 hour. After cooling to room temperature, 10 g of 1N aqueous hydrochloric acid was added and the precipitated white powder was collected by filtration. The obtained white powder was further washed with 1N aqueous hydrochloric acid and then with n-heptane, and then vacuum-dried to obtain 7.31 g of 4,7-dimethylbenzofuran-2-carboxylic acid as a white powder. The yield was 55% based on 3,6-dimethylsalicylaldehyde.

[Synthesis Example of Compound (61-a)]
2.82 g (57.6 mmol) of 2,5-dimethoxyaniline and 7.30 g (38.4 mmol) of 4,7-dimethylbenzofuran-2-carboxylic acid were dispersed in 38 g of chloroform. The resulting suspension was cooled in an ice bath, and then a mixture of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride 8.09 g (42.2 mmol) and chloroform 50 g was added over 4 hours. In addition, the reaction was allowed to proceed at room temperature for 24 hours. To the reaction solution, 1.18 g (7.7 mmol) of 2,5-dimethoxyaniline was further added and reacted for 48 hours. The obtained mixed solution was concentrated, and 400 g of a mixed solution of 1N hydrochloric acid and methanol (2 parts by volume of hydrochloric acid, 1 part by volume of methanol) and 150 g of heptane were added to the residue for crystallization. The resulting precipitate was collected by filtration, and a hydrochloric acid water-methanol mixed solution (hydrochloric acid water 2 parts by volume, methanol 1 part by volume) was added. The precipitated pale yellowish green precipitate was collected by filtration and further washed with a mixed solution of water and methanol (water 2 parts by volume, methanol 1 part by volume). The obtained pale yellowish green precipitate was washed with a mixed solution of 1N-KOH aqueous solution-methanol (1 part by volume of potassium hydroxide, 2 parts by volume of methanol) and then with 150 g of water and collected by filtration. Vacuum drying gave 8.82 g of compound (61-a) as a pale yellow powder. The yield was 71% based on 4,7-dimethylbenzofuran-2-carboxylic acid.

[Synthesis Example of Compound (61-b)]
Compound (61-a) 8.82 g (27 mmol), 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetan-2,4-disulfide (Lawson reagent) 6.58 g ( 16 mmol) and 88 g of toluene were mixed, and the resulting mixture was heated to 110 ° C. and reacted for 12 hours. After cooling, the precipitated orange solid was removed by filtration, and heptane was added to the filtrate for crystallization. The deposited yellow precipitate was collected by filtration and vacuum dried to obtain 4.7 g of compound (61-b) as a bright yellow powder. The yield was 51% with compound (61-a).

[Synthesis Example of Compound (61-c)]
Compound (61-b) 4.27 g (13 mmol), potassium hydroxide 3.83 g (68 mmol) and water 73 g were mixed, and the resulting mixture was reacted under ice-cooling. Subsequently, 11.23 g (34 mmol) of potassium ferricyanide was added under ice cooling, and then 15 g of methanol was added for reaction. The reaction was allowed to proceed for 12 hours at room temperature, and the yellow precipitate that had precipitated was collected by filtration. The collected precipitate was washed with water, methanol and ethanol, and a pale yellow precipitate was collected by filtration. The obtained yellow powder was vacuum-dried to obtain 3.08 g of a pale yellow solid mainly composed of the compound (61-c). The yield was 73% based on the compound (61-a).

[Synthesis Example of Compound (61-d)]
Compound (61-c) 3.08 g (9.1 mmol) and pyridinium chloride 15.4 g (5 times mass) were mixed, heated to 190 ° C. and reacted for 7 hours. The resulting mixture was added to ice and the resulting precipitate was collected by filtration. It was washed with water, washed with toluene, and vacuum-dried to obtain 2.41 g of an ocherous solid containing the compound (61-d) as a main component. The yield was 85% based on the compound (61-c).

[Synthesis Example of Compound (A61-1)]
The compound (61-d) 2.41 g (7.74 mmol), the compound (A) 6.80 g (16.25 mmol), dimethylaminopyridine 0.09 g (0.77 mmol), and chloroform 38 mL were mixed. To the resulting mixture, 2.34 g (18.58 mmol) of N, N′-diisopropylcarbodiimide was added under ice cooling. The resulting reaction solution was reacted at room temperature overnight, filtered through silica gel, and then concentrated under reduced pressure. Methanol was added to the residue for crystallization. The crystals were collected by filtration, redissolved in chloroform, added with 0.3 g of activated carbon, and stirred at room temperature for 1 hour. The solution was filtered, and the filtrate was concentrated under reduced pressure to 1/3 with an evaporator. Methanol was added with vigorous stirring, and the resulting white precipitate was collected by filtration, washed with heptane, and dried in vacuo to give compound (A61-1). Was obtained as an off-white powder. The yield was 53% based on the compound (61-d).

¹ H-NMR (CDCl ₃ ) of the compound (A61-1): δ (ppm) 1.45 to 1.82 (m, 24H), 2.34 to 2.85 (m, 18H), 3.92 to 3.97 (t, 4H), 4.15 to 4.20 (t, 4H), 5.80 to 5.84 (dd, 2H), 6.07 to 6.18 (m, 2H), 6. 37-6.44 (m, 2H), 6.87-7.02 (m, 8H), 7.02-7.13 (m, 2H), 7.24 (s, 2H), 7.57 ( s, 1H)

  The phase transition temperature of the obtained compound (A61-1) was confirmed by texture observation with a polarizing microscope. Compound (A61-1) exhibits a highly viscous phase from 136 ° C. to 138 ° C. when the temperature is raised, and gives a clear nematic phase from 138 ° C. Furthermore, the compound (A61-1) exhibited a nematic phase up to 150 ° C. or higher, and crystallized by exhibiting a nematic phase up to 90 ° C. when the temperature was lowered.

(Example 28)
<Synthesis Example of Compound (A69-1)>
Compound (A69-1) was synthesized according to the following scheme.

[Synthesis example of 3-cyclohexyl 6-methyl salicylaldehyde]
100 g (526 mmol) of 2-cyclohexyl lu 5-methylphenol, 39.5 g (1314 mmol) of paraformaldehyde, and 75.0 g (788.3 mmol) of anhydrous magnesium chloride were dispersed in 900 mL of tetrahydrofuran. After stirring in an ice bath for 30 minutes, 106.4 g (1051 mmol) of triethylamine was added dropwise over 2 hours. The mixture was reacted in a water bath for 8 hours and at room temperature for 96 hours. The reaction solution was acidified by adding 1500 mL of cold 5N hydrochloric acid, and extracted twice with 400 mL of ethyl acetate, and the organic layer was collected. The organic layer was dehydrated with anhydrous sodium sulfate and then concentrated under reduced pressure at 40 ° C. or lower with an evaporator. The residue was dissolved in 100 mL toluene and 600 mL n-heptane was added to the solution. 38 g of silica gel was added to the solution, and the solvent was removed with an evaporator. The residue was extracted by adding n-heptane, and heptane was distilled off to obtain 35.2 g of 4,6-dimethylsalicylaldehyde as yellow crystals that slowly crystallized. The yield was 31% based on 2-cyclohexyl lu 5-methylphenol.

[Synthesis example of 4-methyl-7-cyclohexylbenzofuran-2-carboxylic acid]
35.0 g (213 mmol) of 3-cyclohexyl lu 6-methyl salicylaldehyde and 72.2 g (552 mmol) of potassium carbonate were dispersed in 300 mL of N, N′-dimethylacetamide. After heating to 80 ° C., 41.6 g (213 mmol) of tert-butyl bromoacetate was added dropwise over 30 minutes. The mixture was reacted at 130 ° C. for 3 hours. After cooling the reaction solution to room temperature, 200 mL of methyl isobutyl ketone was added, followed by separation with 1000 mL of pure water. Furthermore, the organic layer was washed twice with 500 mL of pure water, and the organic layer was recovered. After dehydration with anhydrous sodium sulfate, the solvent was distilled off with an evaporator. The residue was dissolved in 240 g of acetic acid, 72 g of an aqueous hydrobromic acid solution was added, and the mixture was stirred at 40 ° C. for 1 hour. After allowing to cool to room temperature, 150 g of 1N hydrochloric acid was added and the precipitated white powder was collected by filtration. The obtained white powder was further washed with 1N-hydrochloric acid and then with n-heptane, and then vacuum-dried to obtain 25.8 g of 4-methyl-7-cyclohexylbenzofuran-2-carboxylic acid as a white powder. The yield was 59% based on 3-cyclohexyl lu 6-methylsalicylaldehyde.

[Synthesis Example of Compound (69-a)]
To 125 g of chloroform, 22.2 g (145.0 mmol) of 2,5-dimethoxyaniline, 25.00 g (96.8 mmol) of 4-methyl-7-cyclohexylbenzofuran-2-carboxylic acid, and 9.79 g (96.8 mmol) of triethylamine were added. Dispersed. The obtained suspension was cooled in an ice bath, and then a mixture of 10.4-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride 20.4 g (107 mmol) and 100 g of chloroform was added over 4 hours. The reaction was allowed to proceed for 72 hours at room temperature. The obtained mixed solution was concentrated, and 400 g of a mixed solution of 1N hydrochloric acid and methanol (2 parts by volume of hydrochloric acid, 1 part by volume of methanol) and 150 g of heptane were added to the residue for crystallization. The resulting precipitate was collected by filtration, and a hydrochloric acid water-methanol mixed solution (hydrochloric acid water 2 parts by volume, methanol 1 part by volume) was added. The precipitated pale yellowish green precipitate was collected by filtration and further washed with a mixed solution of water and methanol (water 2 parts by volume, methanol 1 part by volume). The obtained pale yellowish green precipitate was washed with a 1N-KOH aqueous solution-methanol mixed solution (1 part by volume of potassium hydroxide aqueous solution, 2 parts by volume of methanol) and then 150 g of methanol and collected by filtration. Vacuum drying gave 12.3 g of compound (69-a) as a pale yellow powder. The yield was 32% based on 4-methyl-7-cyclohexylbenzofuran-2-carboxylic acid.

[Synthesis Example of Compound (69-b)]
Compound (69-a) 12.3 g (31 mmol), 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetan-2,4-disulfide (Lawson reagent) 7.6 g ( 19.0 mmol) and 120 g of toluene were mixed, and the resulting mixture was heated to 110 ° C. and reacted for 6 hours. After cooling, the toluene solution was washed with 500 mL of a 2N aqueous sodium hydroxide solution three times, and the organic layer was recovered and concentrated. Then, n-heptane was added, and the solvent was distilled off with an evaporator. The residue was crystallized by adding 50 g of methanol. The obtained bright yellow crystals were collected by filtration and vacuum dried to obtain 11.5 g of compound (69-b) as a bright yellow powder. The yield was 90% based on the compound (69-a).

[Synthesis Example of Compound (69-c)]
11.5 g of the compound (69-b) obtained in the previous item, 9.58 g (171 mmol) of potassium hydroxide and 182 g of water were mixed, and the resulting mixture was reacted under ice cooling. Subsequently, 28.09 g (85 mmol) of potassium ferricyanide was added to prepare a dispersion containing the compound (69-b). 40 g of methanol was added to the dispersion, and the mixture was reacted at 40 ° C. for 2 hours and at room temperature for 24 hours. The precipitated yellow precipitate was collected by filtration. The filtered precipitate was washed with water and then with hexane. Further, the mixture was dispersed in 400 ml of a toluene-heptane mixed solvent (1 part by volume of toluene, 2 parts by volume of heptane) to recover a pale yellow insoluble component. The obtained pale yellow was vacuum dried to obtain 4.5 g of a pale yellow solid containing the compound (69-c) as a main component. The yield was 36% based on the compound (69-a).

[Synthesis Example of Compound (69-d)]
Compound (69-c) 4.54 g (11.1 mmol) and pyridinium chloride 45.4 g (10-fold mass) were mixed, heated to 180 ° C. and reacted for 3 hours. The resulting mixture was added to ice and the resulting precipitate was collected by filtration. It was washed with water, washed with toluene, and vacuum-dried to obtain 3.4 g of an ocherous solid containing the compound (69-d) as a main component. The yield was 80% based on the compound (69-c).

[Synthesis Example of Compound (A69-1)]
Compound (69-d) 3.40 g (8.96 mmol), compound (A) 7.87 g (18.82 mmol), dimethylaminopyridine 0.11 g (0.90 mmol) and chloroform 40 mL were mixed. To the obtained mixture, 2.71 g (21.50 mmol) of N, N′-diisopropylcarbodiimide was added under ice cooling. The resulting reaction solution was reacted at room temperature overnight, filtered through silica gel, and then concentrated under reduced pressure. Methanol was added to the residue for crystallization. The crystals were collected by filtration, redissolved in chloroform, added with 0.3 g of activated carbon, and stirred at room temperature for 1 hour. The solution was filtered, and the filtrate was concentrated under reduced pressure to 1/3 with an evaporator. Methanol was added with stirring, and the resulting white precipitate was collected by filtration, washed with heptane, and dried under vacuum to obtain compound (A69-1). 4.84 g was obtained as an off-white powder. The yield was 45% based on the compound (69-d).

¹ H-NMR (CDCl ₃ ) of the compound (A69-1): δ (ppm) 1.45 to 1.87 (m, 34H), 2.34 to 2.54 (m, 11H), 2.65 2.85 (m, 4H), 3.10 to 3.14 (tt, 1H), 3.92 to 3.97 (t, 4H), 4.15 to 4.20 (t, 4H), 5. 79-5.84 (dd, 2H), 6.07-6.17 (m, 2H), 6.37-6.44 (m, 2H), 6.86-7.14 (m, 10H), 7.25 (s, 2H), 7.56 (s, 1H)

  The phase transition temperature of the obtained compound (A69-1) was confirmed by texture observation with a polarizing microscope. The compound (A69-1) exhibited a highly viscous phase from 207 ° C. when the temperature was raised, and was thermally polymerized at 220 ° C.

(Example 29)
<Synthesis Example of Compound (A70-1)>
Compound (A70-1) was synthesized according to the following scheme.

[Synthesis example of 3-propyl salicylaldehyde]
2-propylphenol 75g (551mmol), paraformaldehyde 41.3g (1377mmol), anhydrous magnesium chloride 78.7g (826.1mmol) was dispersed in tetrahydrofuran 900mL. After stirring in an ice bath for 30 minutes, 111.5 g (1101 mmol) of triethylamine was added dropwise over 2 hours. The mixture was reacted in a water bath for 8 hours and at room temperature for 96 hours. The reaction solution was acidified by adding 1500 mL of cold 5N hydrochloric acid, and extracted twice with 400 mL of ethyl acetate, and the organic layer was collected. The organic layer was dehydrated with anhydrous sodium sulfate and then concentrated under reduced pressure at 40 ° C. or lower with an evaporator. The residue was dissolved in 100 mL toluene and 600 mL n-heptane was added to the solution. 90 g of silica gel was added to the solution, and the solvent was removed with an evaporator. N-Heptane was added to the residue and extracted to distill off heptane, thereby obtaining 28.8 g of 3-propylsalicylaldehyde as a yellow liquid. The yield was 32% based on 2-propylphenol.

[Synthesis example of 7-propylbenzofuran-2-carboxylic acid]
38.8 g (175 mmol) of 3-propylsalicylaldehyde and 59.3 g (429 mmol) of potassium carbonate were dispersed in 200 mL of N, N′-dimethylacetamide. After heating to 80 ° C., 34.2 g (175 mmol) of tert-butyl bromoacetate was added dropwise over 30 minutes. The mixture was reacted at 130 ° C. for 2 hours. After cooling the reaction solution to room temperature, 200 mL of methyl isobutyl ketone was added, followed by separation with 1000 mL of pure water. Furthermore, the organic layer was washed twice with 500 mL of pure water, and the organic layer was recovered. After dehydration with anhydrous sodium sulfate, the solvent was distilled off with an evaporator. The residue was dissolved in 150 g of acetic acid, 45 g of an aqueous hydrobromic acid solution was added, and the mixture was stirred at 40 ° C. for 1 hour. After allowing to cool to room temperature, 150 g of 1N hydrochloric acid was added and the precipitated white powder was collected by filtration. The obtained white powder was further washed with 1N-hydrochloric acid and then with n-heptane, and then vacuum-dried to obtain 28.1 g of 7-propylbenzofuran-2-carboxylic acid as a white powder. The yield was 78% based on 3-propyl salicylaldehyde.

[Synthesis Example of Compound (70-a)]
2,0.25 g (132.2 mmol) of 2,5-dimethoxyaniline, 18.0 g (88.1 mmol) of 7-propylbenzofuran-2-carboxylic acid, and 8.92 g (88.1 mmol) of triethylamine were dispersed in 90 g of chloroform. After cooling the obtained suspension in an ice bath, 18.6 g (97 mmol) of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and 100 g of chloroform were added over 4 hours. The reaction was allowed to proceed for 72 hours at room temperature. The obtained mixed solution was concentrated, and 400 g of a mixed solution of 1N hydrochloric acid and methanol (2 parts by volume of hydrochloric acid, 1 part by volume of methanol) and 150 g of heptane were added to the residue for crystallization. The resulting precipitate was collected by filtration and added to a mixed solution of hydrochloric acid water and methanol (hydrochloric acid water 2 parts by volume, methanol 1 part by volume). The pale yellowish green precipitate was collected by filtration, washed with a 1N-KOH aqueous solution-methanol mixed solution (1 part by volume of aqueous potassium hydroxide, 2 parts by volume of methanol) and collected by filtration. Vacuum drying gave 19.8 g of compound (70-a) as a pale yellow powder. The yield was 66% based on 7-propylbenzofuran-2-carboxylic acid.

[Synthesis Example of Compound (70-b)]
Compound (70-a) 19.8 g (58 mmol), 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetan-2,4-disulfide (Lawson reagent) 14.2 g ( 35.0 mmol) and 198 g of toluene were mixed, and the resulting mixture was heated to 110 ° C. and reacted for 6 hours. After cooling, the toluene solution was washed with 500 mL of 2N-sodium hydroxide aqueous solution three times, and the organic layer was recovered. The organic layer was concentrated and crystallized by adding n-heptane. The obtained bright yellow crystals were collected by filtration and vacuum dried to obtain 18.6 g of compound (70-b) as a bright yellow powder. The yield was 90% based on the compound (70-a).

[Synthesis Example of Compound (70-c)]
18.6 g of compound (70-b), 17.86 g (318 mmol) of potassium hydroxide and 320 g of water were mixed, and the resulting mixture was reacted under ice cooling. Subsequently, 52.41 g (159 mmol) of potassium ferricyanide was added to prepare a dispersion containing the compound (70-b). 70 g of methanol was added to the dispersion, and the mixture was reacted at 40 ° C. for 2 hours and at room temperature for 24 hours, and the deposited yellow precipitate was collected by filtration. The filtered precipitate was washed with water and then with methanol. Further, the yellow powder was washed with hot ethanol and collected by filtration. The obtained yellow color was vacuum-dried to obtain 15.8 g of a pale yellow solid mainly composed of compound (70-c). The yield was 76% based on the compound (70-a).

[Synthesis Example of Compound (70-d)]
Compound (70-c) 15.8 g (44.6 mmol) and pyridinium chloride 158 g (10 times mass) were mixed, heated to 180 ° 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, washing with toluene and vacuum drying were performed to obtain 13.6 g of an ocherous solid containing the compound (70-d) as a main component. The yield was 94% based on the compound (70-c).

[Synthesis Example of Compound (A70-1)]
Compound (70-d) 5.00 g (15.4 mmol), compound (A) 13.5 g (32.27 mmol), dimethylaminopyridine 0.19 g (1.54 mmol) and chloroform 60 mL were mixed. To the obtained mixture, 4.65 g (36.88 mmol) of N, N′-diisopropylcarbodiimide was added under ice cooling. The resulting reaction solution was reacted at room temperature overnight, filtered through silica gel, and then concentrated under reduced pressure. Methanol was added to the residue for crystallization. The crystals were collected by filtration, redissolved in chloroform, added with 0.3 g of activated carbon, and stirred at room temperature for 1 hour. The solution was filtered, and the filtrate was concentrated under reduced pressure to 1/3 with an evaporator. Methanol was added with stirring, and the resulting white precipitate was collected by filtration, washed with heptane, and dried under vacuum to obtain compound (A70-1). 8.38 g was obtained as an off-white powder. The yield was 48% based on the compound (70-d).

¹ H-NMR (CDCl ₃ ) of the compound (A70-1): δ (ppm) 1.01 to 1.06 (t, 3H), 1.45 to 1.84 (m, 26H), 2.34 to 2.48 (m, 8H), 2.63 to 2.71 (m, 4H), 2.94 to 3.00 (t, 2H), 3.92 to 3.97 (t, 4H), 4. 15-4.20 (t, 4H), 5.79-5.84 (dd, 2H), 6.07-6.17 (m, 2H), 6.36-6.44 (m, 2H), 6.87 to 6.98 (m, 8H), 7.22 to 7.24 (m, 4H), 7.52 to 7.53 (m, 2H)

  The phase transition temperature of the obtained compound (A70-1) was confirmed by texture observation with a polarizing microscope. The compound (A70-1) exhibits a highly viscous phase from 137 ° C. to 142 ° C. when the temperature is raised, and gives a clear nematic phase from 142 ° C. Furthermore, the compound (A70-1) exhibited a nematic phase up to 220 ° C. or higher, and crystallized by exhibiting a nematic phase up to 125 ° C. when the temperature was lowered.

(Examples 30 to 33, Comparative Example 1)
<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 subjected to a rubbing treatment, and the composition having the composition shown in Table 4 was applied to the surface subjected to the rubbing treatment by a spin coating method and dried at the drying temperature shown in Table 5 for 1 minute. . Next, while heating to the temperature at the time of light irradiation described in Table 5, the ultraviolet rays having the integrated light amount described in Table 5 were irradiated to form an optical film having the film thickness described in Table 6.
Table 4 shows the content rate (mass%) of each structural component with respect to the whole composition.

B1-1: Liquid crystal compound LC242 represented by the formula (B1-1): The same polymerization initiator as above: Irgacure 819 (manufactured by Ciba Japan Co., Ltd.)
Leveling agent: BYK361N (manufactured by Big Chemie Japan)
Solvent: cyclopentanone

<Measurement of optical properties>
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 d (micrometer) of the optical film was measured using the laser microscope (LEXT, Olympus company make). The results are shown in Table 6. Δn was calculated by dividing the value of Re (546.9) by the film thickness (Δn = Re (546.9) / d).

(Examples 34 to 39, Comparative Examples 2 to 7)
<< Thermal properties of the composition >>
<Preparation of composition>
A composition having the composition described in Table 7 was prepared.

光重合開始剤：イルガキュア８１９（チバ・ジャパン株式会社製）
レベリング剤：ＢＹＫ３６１Ｎ（ビックケミージャパン製）
溶剤：シクロペンタノン

Photopolymerization initiator: Irgacure 819 (manufactured by Ciba Japan Co., Ltd.)
Leveling agent: BYK361N (manufactured by Big Chemie Japan)
Solvent: cyclopentanone

<Thermophysical property observation>
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 dried by heating to form a film having a thickness of 89 nm. The surface of the film was rubbed to form an alignment film. The composition described in Table 8 was applied to the surface subjected to the rubbing treatment by a spin coating method. While heating the coated substrate with a hot stage polarizing microscope (hot stage: LTS350, manufactured by Linkam Co., Ltd., polarizing microscope: BX-51, manufactured by Olympus Co., Ltd.) at a temperature rising rate of 30 ° C./min The behavior of the composition was observed. When the temperature dropped, the behavior was observed by natural cooling. The results are shown in Table 8.

Ｔ_ａ；結晶からネマチック相に相転移してモノドメイン構造を形成し始める温度。
Ｔ_ｂ；ネマチック相を高温で保持する温度。
Ｔ_ｃ；結晶化する温度。

T _a ; temperature at which a phase transition from _a crystal to a nematic phase starts to form a monodomain structure.
T _b : temperature at which the nematic phase is kept at a high temperature.
T _c : temperature for crystallization.

(Examples 34 to 39, Comparative Examples 2 to 8)
<Example of 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 dried by heating to form a film having a thickness of 89 nm. The surface of the film was rubbed to form an alignment film. The composition described in Table 7 was applied to the surface subjected to the rubbing treatment by spin coating, and dried at a temperature (T _d ) described in Table 9 for 1 minute. After leaving at the temperature (T _e ) described in Table 9 for 1 minute, a film was prepared by irradiating with an ultraviolet ray with an integrated light amount of 2400 mJ / cm ² . Here T _e without liquid crystallizes, the temperature required to produce with good reproducibility a uniform film monodomain, the more T _e is low, indicating that can be produced an optical film at a low temperature.

(Example 40)
<Synthesis Example of Compound (A71-1)>
Compound (A71-1) was synthesized according to the following scheme.

[Synthesis Example of 5-Chloro-4,6-dimethylsalicylaldehyde]
4-chloro-3,5-dimethylphenol 100 g (639 mmol), paraformaldehyde 47.94 g (1597 mmol) and anhydrous magnesium chloride 91.19 g (958 mmol) were dispersed in acetonitrile 800 mL. After stirring in an ice bath for 30 minutes, 129.23 g (1277 mmol) of triethylamine was added dropwise over 2 hours. The mixture was reacted in a water bath for 3 hours and at 50 ° C. for 18 hours. Cold 2N-hydrochloric acid was added to the reaction solution to neutralize it, and the mixture was extracted twice with 600 mL of ethyl acetate to collect the organic layer. The organic layer was dehydrated with anhydrous sodium sulfate, 3 g of activated carbon was added and stirred, and then filtered through Celite, and the filtrate was concentrated under reduced pressure at 40 ° C. or lower using an evaporator. To the residue was added 1000 mL of heptane, and insoluble matters were removed by filtration. The filtrate was collected and recrystallized to obtain 20.00 g of 5-chloro-4,6-dimethylsalicylaldehyde as a pale yellow powder. The yield was 17% based on 4-chloro-3,5-dimethylphenol.

[Synthesis example of 5-chloro-4,6-dimethylbenzofuran-2-carboxylic acid]
20.00 g (108 mmol) of 5-chloro-4,6-dimethylsalicylaldehyde and 36.68 g (265 mmol) of potassium carbonate were dispersed in 150 mL of N, N′-dimethylacetamide. After heating to 80 ° C., 21.13 g (108 mmol) of tert-butyl bromoacetate was added dropwise over 10 minutes. The mixture was reacted at 130 ° C. for 3 hours. After cooling the reaction solution to room temperature, 200 mL of methyl isobutyl ketone was added, followed by separation with 1000 mL of pure water. Further, the organic layer was washed twice with 300 mL of pure water to recover the organic layer. After dehydration with anhydrous sodium sulfate, the solvent was distilled off with an evaporator. The residue was dissolved in 60 g of acetic acid, 20 g of trifluoroacetic acid was added, and the mixture was stirred at 60 ° C. for 1 hour. After cooling to room temperature, 10 g of 1N aqueous hydrochloric acid was added and the precipitated white powder was collected by filtration. The obtained white powder was further washed with 1N-hydrochloric acid water and then with n-heptane, and then vacuum-dried to obtain 19.37 g of white powder as 5-chloro-4,6-dimethylbenzofuran-2-carboxylic acid. Obtained. The yield was 80% based on 5-chloro-4,6-dimethylsalicylaldehyde.

[Synthesis Example of Compound (71-a)]
19.43 g (127 mmol) of 2,5-dimethoxyaniline and 19.00 g (84.6 mmol) of 5-chloro-4,6-dimethylbenzofuran-2-carboxylic acid were dispersed in 200 g of chloroform. The resulting suspension was cooled in an ice bath, and then a mixture of 17.64 g (93.0 mmol) of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and 80 g of chloroform was added over 6 hours. In addition, the reaction was allowed to proceed at room temperature for 24 hours. An additional 0.2 g of 2,5-dimethoxyaniline was added to the reaction solution and reacted for 48 hours. The obtained mixed solution was concentrated, and 400 g of a mixed solution of 1N-hydrochloric acid and methanol (hydrochloric acid water 2 parts by volume, methanol 1 part by volume) was added to the residue for crystallization. The resulting pale yellow powder was washed with methanol and then with toluene and collected by filtration. Vacuum drying gave 13.68 g of compound (71-a) as a pale yellow powder. The yield was 45% based on 5-chloro-4,6-dimethylbenzofuran-2-carboxylic acid.

[Synthesis Example of Compound (71-b)]
Compound (71-a) 13.63 g (38 mmol), 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetan-2,4-disulfide (Lawson reagent) 9.19 g ( 23 mmol) and 150 g of toluene were mixed, and the resulting mixture was heated to 110 ° C. and reacted for 6 hours. After cooling, a 1N sodium hydroxide aqueous solution was added. The organic layer was collected and crystallized by adding 100 mL of heptane. The red crystals were collected by filtration and dried to obtain 14.24 g of compound (71-b) as an orange powder. Although it was contaminated with impurities from Lawson reagent, it was used in the next step as it was.

[Synthesis Example of Compound (71-c)]
14.24 g (38 mmol) of the compound (71-b), 11.60 g (207 mmol) of potassium hydroxide and 220 g of water were mixed, and the resulting mixture was reacted under ice cooling. Subsequently, 34.03 g (103 mmol) of potassium ferricyanide was added under ice cooling, and then 44 g of methanol was added for reaction. After reacting at room temperature for 12 hours, the reaction was allowed to proceed at 80 ° C for 8 hours. The precipitated pale yellow precipitate was collected by filtration. The collected precipitate was washed with water, methanol and ethanol, and a pale yellow precipitate was collected by filtration. The obtained pale yellow powder was vacuum-dried to obtain 10.3 g of a pale yellow solid containing the compound (71-c) as a main component. The yield was 73% based on the compound (71-a) in two steps.

[Synthesis Example of Compound (71-d)]
Compound (71-c) 10.00 g (27 mmol) and pyridinium chloride 100 g (10 times mass) were mixed, heated to 190 ° C. and reacted for 2 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 chloroform and dried in vacuo to obtain 7.20 g of a yellow solid mainly composed of compound (71-d). The yield was 78% based on the compound (71-c).

[Synthesis Example of Compound (A71-1)]
1.00 g (2.89 mmol) of the compound (71-d), 2.54 g (6.07 mmol) of the compound (A), 0.04 g (0.29 mmol) of dimethylaminopyridine, and 40 mL of chloroform were mixed. To the resulting mixture, 0.88 g (6.94 mmol) 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. Ethanol was added to the residue for crystallization. The crystals were collected by filtration, redissolved in chloroform, added with 0.3 g of activated carbon, and stirred at room temperature for 1 hour. The solution was filtered, and the filtrate was concentrated under reduced pressure to 1/3 with an evaporator. Methanol was added with vigorous stirring, and the resulting white precipitate was collected by filtration, washed with heptane, and dried in vacuo to give compound (A71-1). Was obtained as an off-white powder. The yield was 78% based on the compound (71-d).

¹ H-NMR (CDCl ₃ ) of the compound (A71-1): δ (ppm) 1.45 to 1.83 (m, 24H), 2.35 to 2.85 (m, 18H), 3.93 to 3.98 (t, 4H), 4.15 to 4.20 (t, 4H), 5.80 to 5.84 (dd, 2H), 6.07 to 6.18 (m, 2H), 6. 37-6.44 (m, 2H), 6.87-7.01 (m, 8H), 7.25 (s, 1H), 7.32 (s, 1H), 7.52 (d, 1H)

  The phase transition temperature of the obtained compound (A71-1) was confirmed by texture observation with a polarizing microscope. Compound (A71-1) exhibits a highly viscous phase from 148 ° C. to 154 ° C. when the temperature is raised, and gives a clear nematic phase from 154 ° C. Furthermore, the compound (A71-1) exhibited a nematic phase up to 160 ° C. or higher, and crystallized by exhibiting a nematic phase up to 127 ° C. when the temperature was lowered.

(Example 41)
<Synthesis Example of Compound (A21-1)>
Compound (A21-1) was synthesized according to the following scheme.

[Synthesis Example of Compound (21-a)]
12.82 g (83.7 mmol) of 2,5-dimethoxyaniline and 10.00 g (55.8 mmol) of benzothiazole-2-carboxylic acid were dispersed in 100 g of chloroform. After cooling the resulting suspension in an ice bath, a mixture of 11.77 g (61.4 mmol) of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and 70 g of chloroform was added over 4 hours. In addition, the reaction was allowed to proceed at room temperature for 24 hours. To the reaction solution, 0.5 g of 2,5-dimethoxyaniline was further added and reacted for 48 hours. The obtained mixed solution was concentrated, and 400 g of a mixed solution of 1N hydrochloric acid and methanol (2 parts by volume of hydrochloric acid, 1 part by volume of methanol) and 150 g of heptane were added to the residue for crystallization. The resulting precipitate was collected by filtration, and a hydrochloric acid water-methanol mixed solution (hydrochloric acid water 2 parts by volume, methanol 1 part by volume) was added. The bright yellow precipitate thus deposited was collected by filtration and further washed with a mixed solution of water and methanol (water 2 parts by volume, methanol 1 part by volume). The obtained bright yellow precipitate was washed with 1N-KOH aqueous solution-methanol mixed solution (1 part by volume of potassium hydroxide aqueous solution, 2 parts by volume of methanol) and then 150 g of water and collected by filtration. Vacuum drying gave 8.47 g of compound (21-a) as a yellow powder. The yield was 48% based on benzothiazole-2-carboxylic acid.

[Synthesis Example of Compound (21-b)]
Compound (21-a) 8.47 g (27 mmol), 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetan-2,4-disulfide (Lawson reagent) 6.54 g ( 16 mmol) and 85 g of toluene were mixed, and the resulting mixture was heated to 110 ° C. and reacted for 6 hours. After cooling, a 1N sodium hydroxide aqueous solution was added. The organic layer was collected and crystallized by adding 100 mL of heptane. The orange crystals were collected by filtration and dried in vacuo to give compound (21-b) as a bright yellow powder. Although it was contaminated with impurities from Lawson reagent, it was used in the next step as it was.

[Synthesis Example of Compound (21-c)]
Compound (21-b) 8.90 g (27 mmol), potassium hydroxide 8.25 g (147 mmol) and water 156 g were mixed, and the resulting mixture was reacted under ice cooling. Subsequently, 24.19 g (73 mmol) of potassium ferricyanide was added under ice cooling, and then 30 g of methanol was added for reaction. The reaction was carried out at room temperature for 12 hours and at 50 ° C. for 12 hours, and the precipitated pale yellow precipitate was collected by filtration. The collected precipitate was washed with water, methanol and ethanol, and a pale yellow precipitate was collected by filtration. The obtained pale yellow powder was vacuum-dried to obtain 7.40 g of a pale yellow solid mainly containing the compound (21-c). The yield was 84% based on the compound (21-a).

[Synthesis Example of Compound (21-d)]
7.00 g (21 mmol) of the compound (21-c) and 105 g (15 times mass) of pyridinium chloride were mixed, heated to 190 ° C. and reacted for 3 hours. The resulting mixture was added to ice and the resulting precipitate was collected by filtration. After washing with water, washing with toluene and vacuum drying, 6.00 g of a yellow solid containing compound (21-d) as a main component was obtained. The yield was 94% based on the compound (21-c).

[Synthesis Example of Compound (A21-1)]
Compound (21-d) 1.00 g (3.33 mmol), compound (A) 2.93 g (6.99 mmol), dimethylaminopyridine 0.04 g (0.33 mmol) and chloroform 50 mL were mixed. To the obtained mixture, 1.01 g (7.99 mmol) 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, redissolved in chloroform, added with 0.3 g of activated carbon, and stirred at room temperature for 1 hour. The solution was filtered, and the filtrate was concentrated under reduced pressure to 1/3 with an evaporator. Methanol was added with vigorous stirring, and the resulting white precipitate was collected by filtration, washed with heptane, and dried in vacuo to give compound (A21-1). Was obtained as an off-white powder. The yield was 74% based on the compound (21-d).

¹ H-NMR (CDCl ₃ ) of the compound (A21-1): δ (ppm) 1.45 to 1.83 (m, 24H), 2.32 to 2.50 (m, 8H), 2.62 to 2.84 (m, 4H), 3.93 to 3.98 (t, 4H), 4.15 to 4.20 (t, 4H), 5.80 to 5.84 (dd, 2H), 6. 07-6.18 (m, 2H), 6.37-6.44 (m, 2H), 6.87-7.03 (m, 8H), 7.25-7.32 (2d, 2H), 7.50 to 7.59 (m, 2H), 7.97 to 8.00 (dd, 1H), 8.14 to 8.17 (dd, 1H)

  The phase transition temperature of the obtained compound (A21-1) was confirmed by texture observation with a polarizing microscope. Compound (A21-1) exhibits a highly viscous phase from 137 ° C. to 155 ° C. when the temperature is raised, and gives a clear nematic phase from 155 ° C. Further, the compound (A21-1) exhibited a nematic phase up to 170 ° C. or higher, and crystallized with a nematic phase up to 121 ° C. when the temperature was lowered.

(Examples 42 to 43, Comparative Example 1)
<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 subjected to a rubbing treatment, and the composition having the composition shown in Table 10 was applied to the surface subjected to the rubbing treatment by a spin coating method and dried at the drying temperature shown in Table 5 for 1 minute. . Next, while heating up to the temperature at the time of light irradiation described in Table 11, ultraviolet rays having an accumulated light amount described in Table 11 were irradiated to form an optical film having a film thickness described in Table 12.
Table 10 shows the content rate (mass%) of each structural component with respect to the whole composition.

LC242: same polymerization initiator as above: Irgacure 819 (manufactured by Ciba Japan Co., Ltd.)
Leveling agent: BYK361N (manufactured by Big Chemie Japan)
Solvent: cyclopentanone

<Measurement of optical properties>
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 450.9 nm, 549.4 nm, and 627.8 nm, respectively, and [Re (450.9) / Re (549.4)] (referred to as α). And [Re (627.8) / Re (549.4)] (referred to as β). Moreover, the film thickness d (micrometer) of the optical film was measured using the laser microscope (LEXT, Olympus company make). The results are shown in Table 6. Δn was calculated by dividing the value of Re (549.4) by the film thickness (Δn = Re (549.4) / d).

In the optical films of Examples 12 to 24, Examples 30 to 33, and Examples 42 to 43, the value of [Re (447.3) / Re (546.9)] (α in the table) was 1 or less. It was. In addition, the value of [Re (627.8) / Re (546.9)] (β in the table) was 1 or more. That is, since the wavelength dependency of the refractive index indicates so-called reverse wavelength dispersion, uniform polarization conversion is possible in a wide wavelength range.
If the film of an Example is utilized for a liquid crystal panel, it has the characteristic excellent in optical compensation. Furthermore, from Examples 20 to 24 and Examples 32 to 33, it was revealed that wavelength dispersion can be freely controlled from positive wavelength dispersion to reverse wavelength dispersion simply by mixing the compound of the present invention with a liquid crystal compound. .
Further, when Examples 34 to 39 and Comparative Examples 2 to 7 are compared, the temperature of the monodomain structure is shifted to the low temperature side by mixing the compound of the present invention and the liquid crystal compound, and the retardation film is produced at a lower temperature. It was found that can be manufactured.

(Examples 44 to 45)
<Example of optical film production>
In the same manner as in Examples 42 to 43 and Comparative Example 1, a composition having the composition shown in Table 13 was applied by spin coating, dried at 140 ° C. for 1 minute, and then heated at 80 ° C. for 2400 mJ of accumulated light. Irradiation formed an optical film.

Polymerization initiator:
* 1): Irgacure 369 (Ciba Japan Co., Ltd.) (acetophenone compound)
* 2): Irgacure 819 (Ciba Japan Co., Ltd.) (acylphosphine oxide compound)
Leveling agent: BYK361N (manufactured by Big Chemie Japan)
Solvent: cyclopentanone

<Heat resistance test of optical film>
The optical films obtained in Example 44 and Example 45 were kept in an oven at a temperature of 85 ° C. and a humidity of 0% for 1000 hours to conduct a heat resistance test. The optical characteristics before and after the test were measured, and a value obtained by subtracting the initial α value from the α value after the test was defined as a change amount Δα. If Δα is −0.2 or more and +0.2 or less, it can be determined that the change in optical characteristics is small. The results are shown in Table 15.

<Moisture and heat resistance test of optical film>
The optical film obtained in Example 44 and Example 45 was kept in an oven at a temperature of 60 ° C. and a humidity of 90% for 1000 hours, and a moisture and heat resistance test was performed. The optical characteristics before and after the test were measured, and a value obtained by subtracting the initial α value from the α value after the test was defined as a change amount Δα. If Δα is −0.2 or more and +0.2 or less, it can be determined that the change in optical characteristics is small. The results are shown in Table 16.

表１５及び表１６に示しているように、本発明の光学フィルムは、耐熱性試験及び耐湿熱性試験において、△αが−０．２以上＋０．２以下であることから、ともに良好な耐熱性及び耐湿熱性を示すことがわかる。また、表１６に示しているように、実施例４４の光学フィルムが、耐湿熱性においてより小さい△αを示すことから、開始剤としてアセトフェノン化合物を用いると、さらに良好な耐湿熱性すなわち良好な耐久性を示すことがわかる。

As shown in Table 15 and Table 16, the optical film of the present invention has good heat resistance because Δα is −0.2 or more and +0.2 or less in the heat resistance test and the moist heat resistance test. It can also be seen that it exhibits resistance to moist heat. Further, as shown in Table 16, since the optical film of Example 44 shows a smaller Δα in wet heat resistance, when an acetophenone compound is used as an initiator, even better wet heat resistance, that is, good durability. It can be seen that

(Example 46)
<Synthesis Example of Compound (A72-1)>
Compound (A72-1) was synthesized according to the following scheme.

[Synthesis example of 4,5,6-trimethylsalicylaldehyde]
10.00 g of 3,4,5-trimethylphenol, 5.51 g of paraformaldehyde, and 10.49 g of anhydrous magnesium chloride were dispersed in 60 mL of acetonitrile. After stirring in an ice bath for 30 minutes, 14.86 g of triethylamine was added dropwise over 2 hours. The mixture was reacted at 50 ° C. for 8 hours and at room temperature for 24 hours. After adding 400 mL of ethyl acetate and 100 mL of pure water to the reaction solution, 1N-hydrochloric acid was added to make it acidic, and then the organic layer was collected. The organic layer was dehydrated with anhydrous sodium sulfate and then concentrated under reduced pressure at 40 ° C. or lower with an evaporator. The residue was purified by column chromatography using ethyl acetate / heptane (1: 3 volume ratio) as an eluent to obtain 8.10 g of 4,5,6-trimethylsalicylaldehyde as a yellow powder. The yield was 67% based on 3,4,5-trimethylphenol.

[Synthesis example of 4,5,6-trimethylbenzofuran-2-carboxylic acid]
4.10 g of 4,5,6-trimethylsalicylaldehyde and 16.36 g of potassium carbonate were dispersed in 50 mL of N, N′-dimethylacetamide. After heating to 80 ° C., 9.62 g of tertiary butyl bromoacetate was added dropwise over 30 minutes. The mixture was reacted at 135 ° C. for 2 hours. After cooling the reaction solution to room temperature, 200 mL of methyl isobutyl ketone was added and filtered. The filtrate was collected and separated with 1000 mL of pure water. Furthermore, the organic layer was washed twice with 500 mL of pure water, and the organic layer was recovered. After dehydration with anhydrous sodium sulfate, the solvent was distilled off with an evaporator. The residue was dissolved in 150 g of acetic acid, 45 g of an aqueous hydrobromic acid solution was added, and the mixture was stirred at 40 ° C. for 1 hour. After allowing to cool to room temperature, 150 g of 1N hydrochloric acid was added, and the precipitated light red powder was collected by filtration. The obtained light red powder was further washed with 1N-hydrochloric acid and then with toluene, and then vacuum-dried to obtain 6.34 g of 4,5,6-trimethylbenzofuran-2-carboxylic acid as a light red powder. The yield was 63% based on 4,5,6-trimethylsalicylaldehyde.

[Synthesis Example of Compound (72-a)]
7.13 g of 2,5-dimethoxyaniline and 6.34 g of 4,5,6-trimethylbenzofuran-2-carboxylic acid were dispersed in 30 g of chloroform. The obtained suspension was cooled in an ice bath, and then a mixture of 6.55 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and 100 g of chloroform was added over 4 hours, and then at room temperature for 48 hours. Reacted. The obtained mixture was concentrated under reduced pressure, and 400 g of a mixed solution of 1N-hydrochloric acid and methanol (hydrochloric acid water 2 parts by volume, methanol 1 part by volume) was added to the residue for crystallization. The resulting precipitate was collected by filtration and added to a mixed solution of hydrochloric acid water and methanol (hydrochloric acid water 2 parts by volume, methanol 1 part by volume). The pale orange precipitate was collected by filtration, washed with a 1N-KOH aqueous solution-methanol mixed solution (1 part by volume of potassium hydroxide aqueous solution, 2 parts by volume of methanol) and collected by filtration. Vacuum drying gave 9.39 g of the compound (72-a) as a pale yellow powder. The yield was 89% based on 4,5,6-trimethylbenzofuran-2-carboxylic acid.

[Synthesis Example of Compound (72-b)]
9.39 g of the compound (72-a), 6.71 g of 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetan-2,4-disulfide (Lawson reagent) and 95 g of toluene. The resulting mixture was heated to 110 ° C. and reacted for 4 hours. After cooling, 500 mL of 2N sodium hydroxide aqueous solution and 100 g of heptane were added to the toluene solution, and the yellow precipitate that had precipitated was collected by filtration. The obtained precipitate was further washed with heptane, 2N-sodium hydroxide aqueous solution, and vacuum dried to obtain 9.83 g of compound (72-b) as a bright yellow powder. Compound (72-b) contained 3% degradation product of Lawson reagent, but was used as it was in the next step.

[Synthesis Example of Compound (72-c)]
9.83 g of compound (72-b), 8.47 g of potassium hydroxide and 400 g of water were mixed, and the resulting mixture was reacted under ice cooling. Subsequently, 24.84 g of potassium ferricyanide was added to prepare a dispersion containing the compound (72-b). 70 g of methanol was added to the dispersion and reacted at 60 ° C. for 48 hours, and the deposited yellow precipitate was collected by filtration. The filtered precipitate was washed with water and then with methanol. Further, the yellow powder was recrystallized with hot toluene. The produced pale yellow crystals were collected by filtration and dried in vacuo to obtain 4.60 g of a pale yellow solid containing the compound (72-c) as a main component. The yield was 47% based on the compound (72-a).

[Synthesis Example of Compound (72-d)]
4.60 g of compound (72-c) and 64.4 g of pyridinium chloride were mixed, heated to 180 ° C. and reacted for 3 hours. The resulting mixture was added to ice and the resulting precipitate was collected by filtration. After washing with water, washing with toluene and vacuum drying, 4.10 g of a yellowish green solid containing compound (72-d) as a main component was obtained. The yield was 97% based on the compound (72-c).

[Synthesis Example of Compound (A72-1)]
Compound (72-d) 1.10 g, compound (A) 2.97 g, dimethylaminopyridine 0.04 g, chloroform 20 mL and toluene 20 mL were mixed. To the obtained mixture, 1.02 g of N, N′-diisopropylcarbodiimide was added under ice cooling. The resulting reaction solution was allowed to react overnight at room temperature. To the reaction solution, 4 g of silica gel and 200 mg of activated carbon were added, stirred for 1 hour at room temperature, and filtered through celite. The filtrate was concentrated under reduced pressure to remove chloroform, and methanol was added to the solution for crystallization. The off-white powder was collected by filtration, further washed twice with ethanol, washed with heptane, and dried under vacuum to obtain 2.95 g of compound (A72-1) as an off-white powder. The yield was 78% based on the compound (72-d).

¹ H-NMR (CDCl ₃ ) of the compound (A72-1): δ (ppm) 1.45 to 1.84 (m, 24H), 2.27 to 2.50 (m, 17H), 2.62 to 2.84 (m, 4H), 3.93 to 3.97 (t, 4H), 4.16 to 4.20 (t, 4H), 5.79 to 5.84 (dd, 2H), 6. 07 to 6.17 (m, 2H), 6.37 to 6.45 (m, 2H), 6.87 to 7.02 (m, 8H), 7.22 to 7.23 (2s, 3H), 7.54 (s, 1H)

  The phase transition temperature of the obtained compound (A72-1) was confirmed by texture observation with a polarizing microscope. Compound (A72-1) exhibits a highly viscous phase from 136 ° C. to 148 ° C. when the temperature is raised, and gives a clear nematic phase from 148 ° C. Furthermore, the compound (A72-1) exhibited a nematic phase up to 170 ° C. or higher, and crystallized by exhibiting a nematic phase up to 120 ° C. when the temperature was lowered.

(Example 47)
<Synthesis Example of Compound (A73-1)>

[Synthesis example of 6-methylbenzofuran-2-carboxylic acid]
4-methyl salicylaldehyde (20.0 g) and potassium carbonate (48.73 g) were dispersed in N, N′-dimethylacetamide (100 mL). After heating to 70 ° C., 28.65 g of tertiary butyl bromoacetate was added dropwise over 30 minutes. The mixture was reacted at 135 ° C. for 2 hours. After cooling the reaction solution to room temperature, 200 mL of methyl isobutyl ketone was added, followed by separation with 1000 mL of pure water. Furthermore, the organic layer was washed twice with 500 mL of pure water, and the organic layer was recovered. After dehydration with anhydrous sodium sulfate, the solvent was distilled off with an evaporator. The residue was dissolved in 150 g of acetic acid, 45 g of an aqueous hydrobromic acid solution was added, and the mixture was stirred at 40 ° C. for 1 hour. After allowing to cool to room temperature, 150 g of 1N hydrochloric acid was added and the precipitated white powder was collected by filtration. The obtained white powder was further washed with 1N-hydrochloric acid, then with heptane and toluene, and then vacuum-dried to obtain 20.58 g of 6-methylbenzofuran-2-carboxylic acid as a white powder. The yield was 80% based on 4-methylsalicylaldehyde.

[Synthesis Example of Compound (73-a)]
26.09 g of 2,5-dimethoxyaniline and 20.00 g of 6-methylbenzofuran-2-carboxylic acid were dispersed in 100 g of chloroform. After cooling the obtained suspension in an ice bath, a mixture of 23.94 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and 120 g of chloroform was added over 4 hours, and at room temperature for 48 hours. Reacted. The obtained mixture was concentrated, and 400 g of 1N-hydrochloric acid / methanol mixed solution (hydrochloric acid water 2 parts by volume, methanol 1 part by volume) was added to the residue for crystallization. The resulting precipitate was collected by filtration and added to a mixed solution of hydrochloric acid water and methanol (hydrochloric acid water 2 parts by volume, methanol 1 part by volume). The pale yellowish green precipitate was collected by filtration, washed with a 1N-KOH aqueous solution-methanol mixed solution (1 part by volume of aqueous potassium hydroxide, 2 parts by volume of methanol) and collected by filtration. Vacuum drying gave 31.26 g of compound (73-a) as a pale yellow powder. The yield was 89% based on 6-methylbenzofuran-2-carboxylic acid.

[Synthesis Example of Compound (73-b)]
Compound (73-a) 31.26 g, 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetan-2,4-disulfide (Lawson reagent) 24.73 g and toluene 300 g. The resulting mixture was heated to 110 ° C. and reacted for 6 hours. After cooling, the toluene solution was washed with 500 mL of 2N aqueous sodium hydroxide solution three times, and the organic layer was recovered, and then n-heptane was added for crystallization. The obtained bright yellow crystals were collected by filtration and dried in vacuo to give compound (73-b) as a bright yellow powder. The entire amount of the obtained compound (73-b) was used in the next step as it was.

[Synthesis Example of Compound (73-c)]
35.69 g of compound (73-b), 33.37 g of potassium hydroxide and 630 g of water were mixed. Subsequently, 97.91 g of potassium ferricyanide was added to prepare a dispersion containing the compound (73-b). 126 g of methanol was added to the dispersion, and the mixture was reacted at 40 ° C. for 2 hours and at room temperature for 24 hours. The precipitated pale yellow precipitate was collected by filtration. The filtered precipitate was washed with water and then with methanol. Further, the yellow powder was washed with hot methanol and collected by filtration. The obtained pale yellow was vacuum-dried to obtain 23.31 g of a pale yellow solid containing the compound (73-c) as a main component. The yield was 66% based on the compound (73-a).

[Synthesis Example of Compound (73-d)]
Compound (73-c) 23.31 g and pyridinium chloride 233.1 g were mixed, heated to 180 ° C., and reacted for 3 hours. The resulting mixture was added to ice and the resulting precipitate was collected by filtration. After washing with water, washing with toluene, the mixture was dispersed in a saturated sodium nithionite aqueous solution and chloroform and stirred at room temperature for 2 hours. The dispersion was filtered, and the precipitate was washed with pure water and then vacuum dried to obtain 21.2 g of a yellow solid containing compound (73-d) as a main component. The yield was 100% based on the compound (73-c).

[Synthesis Example of Compound (A73-1)]
1.00 g of compound (73-d), 2.96 g of compound (A), 0.04 g of dimethylaminopyridine, 20 mL of chloroform, and 20 mL of toluene were mixed. To the obtained mixture, 1.02 g of N, N′-diisopropylcarbodiimide was added under ice cooling. The resulting reaction solution was allowed to react overnight at room temperature. To the reaction solution, 4 g of silica gel and 200 mg of activated carbon were added, stirred for 1 hour at room temperature, and filtered through celite. The filtrate was concentrated under reduced pressure to remove chloroform, and methanol was added to the solution for crystallization. The off-white powder was collected by filtration, further washed twice with ethanol, washed with heptane, and dried under vacuum to obtain 2.11 g of compound (A73-1) as an off-white powder. The yield was 57% based on the compound (73-d).

¹ H-NMR (CDCl ₃ ) of the compound (A73-1): δ (ppm) 1.45 to 1.85 (m, 24H), 2.36 to 2.87 (m, 15H), 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), 6.87-6.99 (m, 8H), 7.13-7.16 (d, 1H), 7.23 (s, 2H), 7.38 ( s, 1H), 7.51 (s, 1H), 7.57 (d, 1H).

  The phase transition temperature of the obtained compound (A73-1) was confirmed by texture observation with a polarizing microscope. Compound (A73-1) exhibits a highly viscous phase from 82 ° C. to 141 ° C. when the temperature is raised, and gives a clear nematic phase from 141 ° C. Further, the compound (A73-1) exhibited a nematic phase up to 180 ° C. or higher, and gradually crystallized with a nematic phase up to 84 ° C. when the temperature was lowered.

(Example 48)
<Synthesis Example of Compound (A63-1)>

[Synthesis example of 3,4,6-trimethylsalicylaldehyde]
2,0.005 g of 2,3,5-trimethylphenol, 11.03 g of paraformaldehyde and 20.97 g of anhydrous magnesium chloride were dispersed in 120 g of acetonitrile. After stirring at room temperature for 30 minutes, 29.72 g of triethylamine was added dropwise over 2 hours. The mixture was reacted in a water bath for 8 hours and at room temperature for 96 hours. The reaction solution was poured into a mixed solvent consisting of 200 mL of ethyl acetate and 400 mL of n-heptane, and 400 mL of pure water was added. After adding cold 2N-hydrochloric acid to make it acidic, the organic layer was recovered. The organic layer was dehydrated with anhydrous sodium sulfate, 20 g of silica gel and 2 g of activated carbon were added, and the mixture was gently stirred for 30 minutes, and the dispersion was filtered through celite. The filtrate was concentrated under reduced pressure at 40 ° C. or lower with a 3 evaporator to obtain 24.69 g of 3,4,6-trimethylsalicylaldehyde as a pale yellow viscous liquid. The yield was 102% based on 2,3,5-trimethylphenol.

[Synthesis example of 4,6,7-trimethylbenzofuran-2-carboxylic acid]
24,11 g of 3,4,6-trimethylsalicylaldehyde and 48.71 g of potassium carbonate were dispersed in 130 mL of N, N′-dimethylacetamide. After heating to 80 ° C., 28.64 g of tertiary butyl bromoacetate was added dropwise over 30 minutes. The mixture was reacted at 140 ° C. for 2 hours. After cooling the reaction solution to room temperature, 200 mL of methyl isobutyl ketone was added, followed by separation with 1000 mL of pure water. Further, the organic layer was washed twice with 500 mL of 1N hydrochloric acid water to recover the organic layer. After dehydration with anhydrous sodium sulfate, the solvent was distilled off with an evaporator. The residue was dissolved in 150 g of acetic acid, 45 g of an aqueous hydrobromic acid solution was added, and the mixture was stirred at 40 ° C. for 1 hour. After allowing to cool to room temperature, 150 g of 1N hydrochloric acid was added and the precipitated white powder was collected by filtration. The obtained white powder was further washed with 1N-hydrochloric acid, then with heptane and toluene, and then vacuum-dried to obtain 14.6 g of 4,6,7-trimethylbenzofuran-2-carboxylic acid as an off-white powder. . The yield was 50% based on 3,4,6-trimethylsalicylaldehyde.

[Synthesis Example of Compound (63-a)]
16.75 g (109.4 mmol) of 2,5-dimethoxyaniline and 14.89 g (72.9 mmol) of 4,6,7-trimethylbenzofuran-2-carboxylic acid were dispersed in 75 mL of chloroform. After cooling the obtained suspension in an ice bath, a mixture of 15.37 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and 100 g of chloroform was added over 4 hours, and 72 hours at room temperature. Reacted. The obtained mixture was concentrated, and the residue was crystallized by adding 400 g of a mixed solution of 1N hydrochloric acid and methanol (hydrochloric acid water 2 parts by volume, methanol 1 part by volume) and heptane 150 g. The resulting precipitate was collected by filtration and added to a mixed solution of hydrochloric acid water and methanol (hydrochloric acid water 2 parts by volume, methanol 1 part by volume). The pale yellowish green precipitate was collected by filtration, washed with a 1N-KOH aqueous solution-methanol mixed solution (1 part by volume of aqueous potassium hydroxide, 2 parts by volume of methanol) and collected by filtration. It vacuum-dried and obtained 22.71g of compounds (63-a) as pale yellow powder. The yield was 92% based on 6-methylbenzofuran-2-carboxylic acid.

[Synthesis Example of Compound (63-b)]
22.71 g of compound (63-a), 16.24 g of 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetan-2,4-disulfide (Lawson reagent) and 228 g of toluene The resulting mixture was heated to 110 ° C. and reacted for 6 hours. After cooling, the toluene solution was washed with 500 mL of 2N-sodium hydroxide aqueous solution three times, and the organic layer was recovered. The organic layer was concentrated and crystallized by adding n-heptane. The obtained pale orange crystals were collected by filtration and vacuum dried to obtain 23.78 g of compound (63-b) as a bright yellow powder. Compound (63-b) contained a decomposition product of Lawson reagent, but the entire amount was used as it was in the next step.

[Synthesis Example of Compound (63-c)]
23.78 g of compound (63-b), 20.48 g of potassium hydroxide and 389 g of water were mixed. Subsequently, 60.09 g of potassium ferricyanide was added to prepare a dispersion containing the compound (63-b). 77.83 g of methanol was added to the dispersion and reacted at 50 ° C. for 4 hours and at room temperature for 24 hours, and the deposited yellow precipitate was collected by filtration. The filtered precipitate was washed with water and then with methanol. Further, the yellow powder was washed with hot ethanol and collected by filtration. The obtained yellow color was vacuum-dried to obtain 20.14 g of a pale yellow solid mainly composed of compound (63-c). The yield was 86% based on the compound (63-a).

[Synthesis Example of Compound (63-d)]
20.14 g of compound (63-c) and 200.1 g of pyridinium chloride were mixed, heated to 180 ° C. and reacted for 3 hours. The resulting mixture was added to ice and the resulting precipitate was collected by filtration. After washing with water, washing with toluene, the mixture was dispersed in a saturated sodium nithionite aqueous solution and chloroform and stirred at room temperature for 2 hours. The dispersion was filtered, and the precipitate was further washed with pure water and then vacuum dried to obtain 18.9 g of an orange solid mainly composed of compound (73-d). The yield was 102% based on the compound (63-c).

[Synthesis Example of Compound (A63-1)]
Compound (63-d) 1.10 g, compound (A) 2.97 g, dimethylaminopyridine 0.04 g, chloroform 20 mL and toluene 20 mL were mixed. To the obtained mixture, 1.02 g of N, N′-diisopropylcarbodiimide was added under ice cooling. The resulting reaction solution was allowed to react overnight at room temperature. To the reaction solution, 4 g of silica gel and 200 mg of activated carbon were added, stirred for 1 hour at room temperature, and filtered through celite. The filtrate was concentrated under reduced pressure to remove chloroform, and methanol was added to the solution for crystallization. The off-white powder was collected by filtration, further washed twice with ethanol, washed with heptane, and dried under vacuum to obtain 2.65 g of compound (A63-1) as an off-white powder. The yield was 70% based on the compound (63-d).

¹ H-NMR (CDCl ₃ ) of the compound (A63-1): δ (ppm) 1.47 to 1.82 (m, 24H), 2.36 to 2.52 (m, 17H), 2.52 2.85 (m, 4H), 3.93 to 3.97 (t, 4H), 4.16 to 4.20 (t, 4H), 5.79 to 5.84 (dd, 2H), 6. 07-6.17 (m, 2H), 6.37-6.45 (m, 2H), 6.87-7.05 (m, 9H), 7.23 (s, 2H), 7.53 ( s, 1H).

  The phase transition temperature of the obtained compound (A63-1) was confirmed by texture observation with a polarizing microscope. Compound (A63-1) exhibits a highly viscous phase from 136 ° C. to 139 ° C. when the temperature is raised, and gives a clear nematic phase from 139 ° C. Furthermore, the compound (A63-1) exhibited a nematic phase up to 180 ° C. or higher, and crystallized by exhibiting a nematic phase up to 125 ° C. when the temperature was lowered.

(Examples 49 to 51 and Comparative Example 1)
<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 subjected to a rubbing treatment, and the composition having the composition shown in Table 17 was applied to the surface subjected to the rubbing treatment by a spin coating method, followed by drying at a drying temperature shown in Table 18 for 1 minute. . Next, while heating to the temperature at the time of light irradiation described in Table 5, the ultraviolet light having the integrated light amount described in Table 18 was irradiated to form an optical film having a film thickness described in Table 19.

ＬＣ２４２：上記と同じ
重合開始剤：イルガキュア８１９（チバ・ジャパン株式会社製）
レベリング剤：ＢＹＫ３６１Ｎ（ビックケミージャパン製）
溶剤：シクロペンタノン

LC242: same polymerization initiator as above: Irgacure 819 (manufactured by Ciba Japan Co., Ltd.)
Leveling agent: BYK361N (manufactured by Big Chemie Japan)
Solvent: cyclopentanone

<Measurement of optical properties>
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 d (micrometer) of the optical film was measured using the laser microscope (LEXT, Olympus company make). The results are shown in Table 19. Δn was calculated by dividing the value of Re (546.9) by the film thickness (Δn = Re (546.9) / d).

  According to the compound of this invention, the optical film which performs uniform polarization conversion in a wide wavelength range can be manufactured.

DESCRIPTION OF SYMBOLS 1,1 'Color filter 2,2' Optical film 3,3 'Orientation 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' Laminated body 15 Polarizing film 16, 16 'Supporting substrate 17, 17' Alignment film 18, 18 'Optical film 19, 19 ', 22, 25 Adhesive layer 20 Liquid crystal panel 21 Bonded product 23 Organic EL panel 24 Light emitting layer

Claims (25)

A compound having a divalent group represented by formula (1-1) or formula (1-2).

[In Formula (1-1) and Formula (1-2), Z ¹ and Z ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, or a carbon number. An alkylsulfinyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, a carboxy group, a fluoroalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylsulfanyl group having 1 to 6 carbon atoms, C1-C6 N-alkylamino group, C2-C12 N, N-dialkylamino group, C1-C6 N-alkylsulfamoyl group or C2-C12 N, N- Represents a dialkylsulfamoyl group.
Q ¹ and Q ² each independently represent —CR ¹ R ² —, —S—, —NR ² —, —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 a substituted or unsubstituted polycyclic aromatic hydrocarbon group or a substituted or unsubstituted polycyclic aromatic heterocyclic group.
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, an alkyl group having 1 to 4 carbon atoms, carbon The optionally substituted fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group, and —CH ₂ — contained in the alicyclic hydrocarbon group is —O—, -S- or -NH- may be substituted. ] The compound of Claim 1 containing the bivalent group represented by Formula (2-1) or Formula (2-2).

[In Formula (2-1) and Formula (2-2), Z ¹ , Z ² , Q ¹ , Q ² , Y ¹ , D ¹ , D ² , G ¹ and G ² represent the same meaning as described above. .
E ¹ and E ² each independently represents a single bond or a divalent linking group.
B ¹ and B ² each independently represent a single bond or a divalent linking group.
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, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group. The hydrogen atom contained in the alkyl group having 1 to 4 carbon atoms and the alkoxy group having 1 to 4 carbon atoms may be substituted with a fluorine atom.
k and l each independently 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 being the same or different. ] The compound of Claim 1 or 2 represented by Formula (3-1) or Formula (3-2).

[In Formula (3-1) and Formula (3-2), Z ¹ , Z ² , Q ¹ , Q ² , Y ¹ , D ¹ , D ² , G ¹ , G ² , E ¹ , E ² , B ¹ , B ² , A ¹ , A ² , k and l represent the same meaning as described above.
F ¹ and F ² each independently represents an alkanediyl group having 1 to 12 carbon atoms, and the hydrogen atom contained in the alkanediyl group is an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms. It may be substituted with a group or a halogen atom, and —CH ₂ — contained in the alkanediyl group may be replaced with —O— or —CO—.
P ¹ and P ² each independently represent a hydrogen atom or a polymerizable group. ] Y ¹ has the formula ^(Y 1 -1) or formula ^(Y 1 -4) is a group represented by a compound according to any one of claims 1 to 3.

[In formulas (Y ¹ -1) and (Y ¹ -4), * represents a linking part, and Z ³ each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, or nitro. Group, nitroso group, alkylsulfonyl group having 1 to 6 carbon atoms, alkylsulfinyl group having 1 to 6 carbon atoms, carboxy group, fluoroalkyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, carbon number 1 -6 alkylsulfanyl group, N, N-dialkylamino group having 2 to 8 carbon atoms, N-alkylamino group having 1 to 4 carbon atoms, sulfamoyl group, N-alkylsulfamoyl group having 1 to 6 carbon atoms, or An N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms is represented.
V ¹ represents —CO—, —S—, —NR ³ —, —O—, —Se— or —SO ₂ —.
W ¹ to ^W-5 each independently represent a -CR ³ = or -N =.
However, at least one of V ¹ and W ^{1 to} W ⁵ represents a group containing S, N, O, or Se.
R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
a represents the integer of 0-3 each independently. when a is an integer of 2 or more, a plurality of Z ³ may be the being the same or different. ] The compound according to any one of claims 1 to 4, wherein Y ¹ is a group represented by the formula (Y ³ -1) or the formula (Y ³ -3).

[In Formula (Y ³ -1) and Formula (Y ³ -3), Z ³ , a, V ¹ and W ¹ represent the same meaning as described above. ] V ₁ is, -S -, - NR ³ - or -O- and is claim 4 or 5 compounds according. The compound according to any one of claims 1 to 6, wherein G ₁ and G ₂ are trans-1,4-cyclohexanediyl groups. A ¹ and A ² are each independently a 1,4-phenylene group or a 1,4-cyclohexanediyl group, and the hydrogen atoms contained in the 1,4-phenylene group and the 1,4-cyclohexanediyl group are , A halogen atom, an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, a cyano group or a nitro group, may be substituted. ^{B 2} that is bonded only to ^{B 1} and ^{A 2} are bonded only to A ¹ are each _{independently, -CH 2 -CH 2 -, -} CO-O -, - O-CO -, - CO- NH—, —NH—CO—, —O—CH ₂ —, —CH ₂ —O— or a single bond,
B ¹ bonded to F ¹ and B ² bonded to F ² are each independently —O—, —CO—O—, —O—CO—, —O—CO—O—, — The compound according to any one of claims 2 to 8, which is CO-NH-, -NH-CO-, or a single bond. P ¹ and P ² are each independently a hydrogen atom, an acryloyloxy group or a methacryloyloxy group (wherein at least one of P ¹ and P ² represents an acryloyloxy group or a methacryloyloxy group). The compound in any one of 3-9. The composition containing the compound in any one of Claims 1-10, and the compound represented by Formula (20).
^{P 11 -E 11 - (B 11} -A 11) t -B 12 -G (20)
[In the formula (20), A ¹¹ each independently represents a divalent aromatic hydrocarbon group, a divalent alicyclic hydrocarbon group or a divalent heterocyclic group, and the aromatic hydrocarbon group, The hydrogen atom contained in the alicyclic hydrocarbon group and the heterocyclic group is a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an N-alkylamino having 1 to 6 carbon atoms. Group, a C2-C12 N, N-dialkylamino group, a nitro group, a cyano group or a sulfanyl group may be substituted.
B ¹¹ and ^{B 12} are each ^{independently, -CR 14 R 15 -, -} C≡C -, - CH = CH -, - CH 2 -CH 2 -, - O -, - S -, - C (= O)-, -C (= O) -O-, -O-C (= O)-, -O-C (= O) -O-, -C (= S)-, -C (= S). -O-, -OC (= S)-, -CH = N-, -N = CH-, -N = N-, -C (= O) -NR < ¹⁶ >-, -NR < ¹⁶ > -C (= O) —, —OCH ₂ —, —OCF ₂ —, —NR ¹⁶ —, —CH ₂ O—, —CF ₂ O—, —CH═CH—C (═O) —O—, —O—C ( = O) -CH = CH- 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, or R ¹⁴ and R ¹⁵ are connected to each other to represent an alkanediyl group having 4 to 7 carbon atoms. R ¹⁶ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
E ¹¹ represents an alkanediyl group having 1 to 12 carbon atoms, and a hydrogen atom contained in the alkanediyl group is substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogen atom. It may be.
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, carbon The N, N-dialkylamino group of 2 to 26, a cyano group, a nitro group, or a C1-18 alkyl group having a polymerizable group, and the hydrogen atom contained in the alkyl group has a carbon number It may be substituted with 1 to 6 alkoxy groups or halogen atoms.
t represents an integer of 1 to 5. If t is an integer of 2 or more, a plurality of A ¹¹ and B ¹¹ may be the being the same or different. ]   Furthermore, the composition of Claim 11 containing a polymerization initiator.   The composition according to claim 12, wherein the polymerization initiator is a polymerization initiator containing an acetophenone compound.   The optical film obtained by superposing | polymerizing the compound in any one of Claims 1-10.   The optical film obtained by superposing | polymerizing the composition in any one of Claims 11-13.   The optical film according to claim 14 or 15, which is for a λ / 4 plate having a retardation value (Re (550)) of 113 to 163 nm at a wavelength of 550 nm.   The optical film according to claim 14 or 15, which is for a λ / 2 plate having a retardation value (Re (550)) of 250 to 300 nm at a wavelength of 550 nm.   The polarizing plate containing the optical film and polarizing film in any one of Claims 14-17.   A color filter comprising the optical film according to claim 14 formed on an alignment film coated on a color filter substrate.   A liquid crystal display device comprising the color filter according to claim 19.   A flat panel display comprising a liquid crystal panel comprising the polarizing plate according to claim 18.   An organic EL display device comprising an organic electroluminescence panel comprising the polarizing plate according to claim 18.   The manufacturing method of the unpolymerized film which apply | coats the solution containing the compound in any one of Claims 1-10 on a support base material, and is dried.   The manufacturing method of the unpolymerized film which apply | coats the solution containing the compound in any one of Claims 1-10 on the orientation film | membrane formed on the support base material, and dries.   The manufacturing method of the optical film which hardens the unpolymerized film obtained by the manufacturing method of the unpolymerized film of Claim 23 or 24.

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