JP5453956B2 - Compound, optical film and method for producing optical film - Google Patents

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 is applied to a support substrate. 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.

［式（１）中、
Ｑ^１は、−ＣＲ^１ｂ＝又は−Ｎ＝を表す。
Ｔ^１及びＴ^２は、それぞれ独立に、−Ｏ−、−Ｓ−、−ＣＯ−又は−Ｎ（Ｒ^２ｂ）−を表す。
Ｒ^１ｂは、水素原子、ハロゲン原子又は炭素数１〜６のアルキル基を表す。
Ｒ^２ｂは、水素原子又は炭素数１〜６のアルキル基を表す。
Ｒ^１ａ〜Ｒ^３ａは、それぞれ独立に、水素原子、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、炭素数１〜６のアルキルスルフィニル基、炭素数１〜６のアルキルスルホニル基、カルボキシル基、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のアルキルチオ基、炭素数１〜６のＮ−アルキルアミノ基、炭素数２〜１２のＮ，Ｎ−ジアルキルアミノ基、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。
Ａ^１、Ａ^２及びＡ^３は、それぞれ独立に、単結合又は炭素数１〜４のアルキレン基を表し、該アルキレン基に含まれる水素原子は、ハロゲン原子又は炭素数１〜６のアルキル基で置換されていてもよく、該アルキレン基に含まれるメチレン基は、−Ｏ−、−Ｓ−、−ＣＯ−又は−Ｎ（Ｒ^３ｂ）−で置換されていてもよい。
Ｒ^３ｂは、水素原子又は炭素数１〜６のアルキル基を表す。
Ｂ^１、Ｂ^２及びＢ^３は、それぞれ独立に、２価の脂環式炭化水素基を表す。該脂環式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のフルオロアルキル基、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く、該脂環式炭化水素基に含まれるメチレン基は、−Ｏ−、−Ｓ−又は−Ｎ（Ｒ^４ｂ）−で置換されていてもよい。
Ｒ^４ｂは、水素原子又は炭素数１〜６のアルキル基を表す。
Ｘ^１、Ｘ^２及びＸ^３は、それぞれ独立に、有機基を表す。
ｍは、１又は２の整数を表す。］ That is, the present invention is the following invention.
1. The compound represented by Formula (1).

[In Formula (1),
Q ¹ represents -CR ^1b = or -N =.
T ¹ and T ² each independently represent —O—, —S—, —CO— or —N (R ^2b ) —.
R ^1b represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms.
R ^2b represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
R ^{1a to} R ^3a are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 6 carbon atoms, or an alkylsulfonyl having 1 to 6 carbon atoms. Group, carboxyl group, C1-C6 fluoroalkyl group, C1-C6 alkoxy group, C1-C6 alkylthio group, C1-C6 N-alkylamino group, C2-C12 Represents an N, N-dialkylamino group, an N-alkylsulfamoyl group having 1 to 6 carbon atoms, or an N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms.
A ¹ , A ² and A ³ each independently represent a single bond or an alkylene group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkylene group is a halogen atom or an alkyl group having 1 to 6 carbon atoms. The methylene group contained in the alkylene group may be substituted with —O—, —S—, —CO— or —N (R ^3b ) —.
R ^3b represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
B ¹ , B ² and B ³ 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 —N (R ^4b ) —.
R ^4b represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
X ¹ , X ² and X ³ each independently represents an organic group.
m represents an integer of 1 or 2. ]

［式（Ｘ１）、式（Ｘ２）及び式（Ｘ３）中、Ｄ^１、Ｄ^２及びＤ^３は、それぞれ独立に、単結合又は炭素数１〜４のアルキレン基を表し、該アルキレン基に含まれる水素原子は、ハロゲン原子又は炭素数１〜６のアルキル基で置換されていてもよく、該アルキレン基に含まれるメチレン基は、−Ｏ−、−Ｓ−、−ＣＯ−又は−Ｎ（Ｒ^５ｂ）−で置換されていてもよい。
Ｒ^５ｂは、水素原子又は炭素数１〜６のアルキル基を表す。
Ｅ^１、Ｅ^２及びＥ^３は、それぞれ独立に、置換基を有していてもよい脂環式炭化水素基又は置換基を有していてもよい芳香族炭化水素基を表し、該脂環式炭化水素基に含まれるメチレン基は、−Ｏ−、−Ｓ−又は−ＮＨ−で置換されていてもよく、該芳香族炭化水素基に含まれる＝Ｃ−は、＝Ｎ−で置換されていてもよい。
Ｇ^１、Ｇ^２及びＧ^３は、それぞれ独立に、単結合又は炭素数１〜４のアルキレン基を表し、該アルキレン基に含まれる水素原子は、ハロゲン原子又は炭素数１〜６のアルキル基で置換されていてもよく、該アルキレン基に含まれるメチレン基は、−Ｏ−、−Ｓ−、−ＣＯ−又は−Ｎ（Ｒ^６ｂ）−で置換されていてもよい。
Ｒ^６ｂは、水素原子又は炭素数１〜６のアルキル基を表す。
Ｊ^１、Ｊ^２及びＪ^３は、それぞれ独立に、置換基を有していてもよい炭素数１〜１２のアルキレン基を表す。該アルキレン基に含まれるメチレン基は、−Ｏ−又は−ＣＯ−で置換されていてもよい。
Ｐ^１、Ｐ^２及びＰ^３は、それぞれ独立に、水素原子又は重合性基を表す。ただし、Ｐ^１、Ｐ^２及びＰ^３のうち少なくとも１つが重合性基である。
ｋ^１、ｋ^２及びｋ^３は、それぞれ独立に、０〜３の整数を表す。］ 2. 1. X ¹ is a group represented by the formula (X1), X ² is a group represented by the formula (X2), and X ³ is a group represented by the formula (X3). The described compound.

[In Formula (X1), Formula (X2) and Formula (X3), D ¹ , D ² and D ³ each independently represent a single bond or an alkylene group having 1 to 4 carbon atoms, and are included in the alkylene group. The hydrogen atom may be substituted with a halogen atom or an alkyl group having 1 to 6 carbon atoms, and the methylene group contained in the alkylene group may be —O—, —S—, —CO— or —N (R ^5b ) ^optionally substituted ^by- .
R ^5b represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
E ¹ , E ² and E ³ each independently represents an alicyclic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group which may have a substituent, and the alicyclic ring The methylene group contained in the formula hydrocarbon group may be substituted with -O-, -S- or -NH-, and = C- contained in the aromatic hydrocarbon group is substituted with = N-. It may be.
G ¹ , G ² and G ³ each independently represent a single bond or an alkylene group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkylene group is a halogen atom or an alkyl group having 1 to 6 carbon atoms. The methylene group contained in the alkylene group may be substituted with —O—, —S—, —CO— or —N (R ^6b ) —.
R ^6b represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
J ¹ , J ² and J ³ each independently represent an alkylene group having 1 to 12 carbon atoms which may have a substituent. The methylene group contained in the alkylene group may be substituted with -O- or -CO-.
P ¹ , P ² and P ³ each independently represent a hydrogen atom or a polymerizable group. However, at least one of P ¹ , P ² and P ³ is a polymerizable group.
k ^{1, k 2} and ^{k 3} each independently represents an integer of 0 to 3. ]

3. 1. T ¹ and T ² are each independently —O— or —S—. Or 2. The described compound.

4). 1. Q ¹ is -C = ~ 3. The compound according to any one of

5. 1. B ¹ , B ² and B ³ are 1,4-cyclohexylene groups ~ 4. The compound in any one of these.

6). E ¹ , E ² and E ³ are each independently 1,4-phenylene group or 1,4-cyclohexylene group, and hydrogen contained in the 1,4-phenylene group and 1,4-cyclohexylene group The atom 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. ~ 5. The compound in any one of these.

7). P ¹ , P ² and P ³ are each independently a hydrogen atom, an acryloyloxy group or a methacryloyloxy group (provided that at least one of P ¹ , P ² and P ³ represents an acryloyloxy group or a methacryloyloxy group). 2). ~ 6. The compound in any one of these.

8). 1. ~ 7. A composition comprising the compound according to any one of the above.

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

10. 1. ~ 7. An optical film obtained by polymerizing the compound according to any one of the above.

11. 8). Or 9. An optical film obtained by polymerizing the composition described above.

12 9. For a λ / 4 plate having a retardation value (Re (550)) of 113 to 163 nm at a wavelength of 550 nm Or 11. The optical film as described.

12 9. For a λ / 2 plate having a retardation value (Re (550)) of 250 to 300 nm at a wavelength of 550 nm Or 11. The optical film as described.

14 10. -13. A polarizing plate comprising any one of the optical film and polarizing film.

15. 10. -13. A color filter obtained by forming the optical film according to any one of the above on an orientation polymer directly applied on a color filter substrate.

16. 15. A liquid crystal display device comprising the described color filter.

17. 14 A flat panel display comprising a liquid crystal panel comprising the polarizing plate described.

18. 14 An organic electroluminescence display provided with the organic electroluminescent panel containing the polarizing plate of description.

19. 1. ~ 7. 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.

20. 1. ~ 7. 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.

21. 19. Or 20. 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 the present invention (hereinafter sometimes referred to as “compound (1)”) is represented by the formula (1).

[In Formula (1),
Q ¹ represents —C (R ^1b ) ═ or —N═.
T ¹ and T ² each independently represent —O—, —S—, —CO— or —N (R ^2b ) —.
R ^1b represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms.
R ^2b represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
R ^{1a to} R ^3a are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 6 carbon atoms, or an alkylsulfonyl having 1 to 6 carbon atoms. Group, carboxyl group, C1-C6 fluoroalkyl group, C1-C6 alkoxy group, C1-C6 alkylthio group, C1-C6 N-alkylamino group, C2-C12 Represents an N, N-dialkylamino group, an N-alkylsulfamoyl group having 1 to 6 carbon atoms, or an N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms.
A ¹ , A ² and A ³ each independently represent a single bond or an alkylene group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkylene group is a halogen atom or an alkyl group having 1 to 6 carbon atoms. The methylene group contained in the alkylene group may be substituted with —O—, —S—, —CO— or —N (R ^3b ) —.
R ^3b represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
B ¹ , B ² and B ³ 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 —N (R ^4b ) —.
R ^4b represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
X ¹ , X ² and X ³ each independently represents an organic group.
m represents an integer of 1 or 2. ]

Examples of Q ¹ include -CH =, -CF =, -C (CH ₃ ) =, -C (C ₂ H ₅ ) = and -N =, and -CH = is preferred.

Examples of T ¹ and T ² include —O—, —S—, —CO—, —NH—, —N (CH ₃ ) — and —N (C ₂ H ₅ ) —. -S- is preferred.

R ^{1a to} R ^3a include a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, a carboxyl group, and carbon. C1-C6 fluoroalkyl group, C1-C6 alkoxy group, C1-C6 alkylthio group, C1-C6 N-alkylamino group, C2-C12 N, N-dialkyl Examples thereof include an amino group, an N-alkylsulfamoyl group having 1 to 6 carbon atoms, and an N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms.

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

  Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group and hexyl group. 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, hexyl group sulfinyl, and the like, an alkylsulfinyl group having 1 to 4 carbon atoms is preferable, an alkylsulfinyl group having 1 to 2 carbon atoms is more preferable, and a methylsulfinyl group is particularly 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 alkylthio group having 1 to 6 carbon atoms include methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, sec-butylthio group, tert-butylthio group, pentylthio group, and hexylthio group. , An alkylthio group having 1 to 4 carbon atoms is preferable, an alkylthio group having 1 to 2 carbon atoms is more preferable, and a methylthio 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 The N-alkylamino group of 2 is more preferable, and the 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, etc. are mentioned, and it has 2 to 8 carbon atoms. 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 and 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.

As A ¹ , A ² and A ³ , for example, —CO—O—, —O—CO—, —C (S) —O—, —O—C (S) —, —CR ⁵ R ⁶ —, ^{-CR 5 R 6 -CR 7 R 8} -, - O-CR 5 R 6 -, - CR 5 R 6 -O -, - CR 5 R 6 -O-CR 7 R 8 -, - CR 5 R 6 - O—CO—, —O—CO—CR ⁵ R ⁶ —, —CR ⁵ R ⁶ —O—CO—CR ⁷ R ⁸ —, —CR ⁵ R ⁶ —CO—O—CR ⁷ R ⁸ —, —NR ^{9 -CR 5 R 6 -, -} CR 5 R 6 -NR 9 -, - CO-NR 9 -, - NR 9 -CO -, - O -, - S -, - NR 9 -, - CR 5 = CR ^6- and the like. R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms. R ⁹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

A ¹ , A ² and A ³ are —O—CO— *, —O—C (═S) — *, —O—CR ⁵ R ⁶ — *, —NR ⁹ —CR ⁵ R ⁶ — * or — NR ⁹ —CO— * is preferable, and —O—CO— *, —O—C (═S) — *, or —NR ⁹ —CO— * is more preferable. However, * represents a bond with B ¹ , B ² or B ³ .
R ⁵ , R ⁶ , R ⁷ and R ⁸ are preferably a hydrogen atom, a methyl group or an ethyl group.
R ⁹ is preferably a hydrogen atom, a methyl group or an ethyl group.

Examples of B ¹ , B ^2, and B ³ include alicyclic hydrocarbon groups that may contain a hetero atom represented by the formula (g-1) to the formula (g-10), and a 5-membered ring or a 6-membered ring. The alicyclic hydrocarbon group is preferably.

  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; a methoxy group An alkoxy group having 1 to 4 carbon atoms such as ethoxy group; a fluoroalkyl group having 1 to 4 carbon atoms such as trifluoromethyl group; a fluoroalkoxy group having 1 to 4 carbon atoms such as 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.

B ¹ , B ² and B ³ are preferably groups represented by the formula (g-1), more preferably 1,4-cyclohexylene groups, and trans-1,4-cyclohexene. A xylene group is particularly preferred.

X ¹ , X ² and X ³ each independently represent an organic group, X ¹ is a group represented by the formula (X1), X ² is a group represented by the formula (X2), and X ³ is preferably a group represented by the formula (X3).

[In Formula (X1), Formula (X2) and Formula (X3), D ¹ , D ² and D ³ each independently represent a single bond or an alkylene group having 1 to 4 carbon atoms, and are included in the alkylene group. The hydrogen atom may be substituted with a halogen atom or an alkyl group having 1 to 6 carbon atoms, and the methylene group contained in the alkylene group may be —O—, —S—, —CO— or —N (R ^5b ) ^optionally substituted ^by- .
R ^5b represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
E ¹ , E ² and E ³ each independently represents an alicyclic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group which may have a substituent, and the alicyclic ring The methylene group contained in the formula hydrocarbon group may be substituted with -O-, -S- or -NH-, and = C- contained in the aromatic hydrocarbon group is substituted with = N-. It may be.
G ¹ , G ² and G ³ each independently represent a single bond or an alkylene group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkylene group is a halogen atom or an alkyl group having 1 to 6 carbon atoms. The methylene group contained in the alkylene group may be substituted with —O—, —S—, —CO— or —N (R ^6b ) —.
R ^6b represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
J ¹ , J ² and J ³ each independently represent an alkylene group having 1 to 12 carbon atoms which may have a substituent. The methylene group contained in the alkylene group may be substituted with -O- or -CO-.
P ¹ , P ² and P ³ each independently represent a hydrogen atom or a polymerizable group. However, at least one of P ¹ , P ² and P ³ is a polymerizable group.
k ^{1, k 2} and ^{k 3} each independently represents an integer of 0 to 3. ]

The D ^{1, D 2} and ^{D 3,} for _{^{example, -CR 10 R 11 -, -}} 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 ¹² —, —NR ¹² —CO—, — _{O-CH 2 -, - CH} 2 -O -, - S-CH 2 -, - CH 2 -S -, - NR 12 -, - CR 10 = CR 11 - , and the like. R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms. R ¹² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

D ¹ , D ² and D ³ are —CO—O—, —O—CO—, —O—CO—O—, —CO—NR ¹² —, —NR ¹² —CO—, —CH ₂ —O—. , —CH ₂ —S— or a single bond is preferable, and * —CO—O— is particularly preferable. However, * represents a bond with B ¹ , B ² or B ³ .

The divalent alicyclic hydrocarbon group or aromatic hydrocarbon group in E ¹ , E ² and E ³ is a 5-membered ring represented by the above formula (g-1) to formula (g-10) or 6 Examples thereof include alicyclic hydrocarbon groups composed of membered rings, and divalent aromatic hydrocarbon groups having about 6 to 20 carbon atoms represented by formulas (a-1) to (a-8).

  The hydrogen atom contained in the groups represented by the above formulas (a-1) to (a-8) has about 1 to 4 carbon atoms such as a methyl group, an ethyl group, an i-propyl group, or a t-butyl group. Alkyl group; alkoxy group having about 1 to 4 carbon atoms such as methoxy group or ethoxy group; trifluoromethyl group; trifluoromethyloxy group; cyano group; nitro group; halogen atom such as fluorine atom, chlorine atom or bromine atom May be substituted.

As E ¹ , E ² and E ³ , the same kind of group is preferable because the production of the compound (1) is easy. E ¹ , E ² and E ³ are preferably 1,4-phenylene group or 1,4-cyclohexylene group, and particularly preferably 1,4-phenylene group.

The G ^{1, G 2} and ^{G 3,} for _{^{example, -CR 10 R 11 -, -}} 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 ¹² —, —NR ¹² —CO _{-, - O-CH 2 -} , - CH 2 -O -, - S-CH 2 -, - CH 2 -S -, - NR 12 -, - CR 10 = CR 11 - , and the like. R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms. R ¹² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

G ¹ , G ² and G ³ are preferably the same kind of group because the production of the compound (1) is easy. G ¹ , G ² and G ³ are —CH ₂ —CH ₂ —, —O—, —CO—O—, —O—CO—, —O—CO—O—, —CO—NH—, —NH. It is preferably —CO—, —O—CH ₂ —, —CH ₂ —O— or a single bond, more preferably —CO—O— or —O—CO—.

k ¹ , k ² and k ³ each independently represents an integer of 0 to 3, preferably 0 to 2, and more preferably 1.

The J ^{1, J 2} and _{^{J 3, - (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 -are preferred. , — (CH ₂ ) ₄ — and — (CH ₂ ) ₆ — are more preferable.

P ¹ , P ² and P ³ each independently represent a hydrogen atom or a polymerizable group. At least one of P ¹ , P ² and P ³ is a polymerizable group, and when ^{two of} P ¹ , P ² and P ³ are polymerizable groups, the resulting optical film tends to have excellent hardness. preferably since ^there, the P 1, ^{P 2} and ^{P 3} is a polymerizable group, and more preferable. Furthermore, it is preferable that P ¹ , P ² and P ³ are the same polymerizable group because synthesis is easy.
The polymerizable group is a substituent capable of polymerizing the compound (1), and specifically includes a vinyl group, a p-stilbene group, an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, and a carboxyl group. , Methylcarbonyl group, hydroxyl group, amide group, alkylamino group having 1 to 4 carbon atoms, amino group, epoxy group, oxetanyl group, aldehyde group, isocyanate group, and thioisocyanate group. The polymerizable group is preferably a radical polymerizable group or a cationic polymerizable group suitable for photopolymerization, for example, and is preferably an acryloyloxy group or a methacryloyloxy group because it is easy to handle and easy to produce. An acryloyloxy group is more preferred.

Specific examples of -A ¹ -B ¹ -X ¹ , -A ² -B ² -X ² and -A ³ -B ³ -X ³ include those represented by formula (R-1) to formula (R-66). And the group represented.

  m represents an integer of 1 or 2, and is preferably 1.

The compound (1) is preferably a compound represented by the formula (1-1) or (1-2).

[In the formula (1), Q ¹ , T ¹ , T ² , R ^{1a to} R ^3a , A ¹ , A ² , A ³ , B ¹ , B ² , B ³ , X ¹ , X ² and X ³ are Represents the same meaning as above]

  Examples of compound (1) include compounds represented by formula (A1-1) to formula (A48-5). * Represents a bond. For example, the compound represented by the formula (A1-1) is a compound represented as follows.

A method for producing compound (1) will be described.
Compound (1) is a known organic synthesis reaction described in Methoden der Organischen Chemie, Organic Reactions, Organic Syntheses, Comprehensive Organic Synthesis, New Experimental Chemistry Course, etc. (for example, condensation reaction, esterification reaction, Williamson reaction, 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, A ¹ , A ^2, and A ³ are —O—CO— * (* represents a bond with B ¹ , B ^2, or B ³ ), and —B ¹ —X ¹ , —B ² — The compound (1) in which X ² and -B ³ -X ³ are the same group includes a compound represented by the formula (11-1) and a compound represented by the formula (11-2) having three or more equivalents. It can be produced by an esterification reaction.

[In formula (11-1), R ^1a , R ^2a , R ^3a , T ¹ , T ² , Q ¹ and m represent the same meaning as described above. ]

[In Formula (11-2), B ¹ and X ¹ represent the same meaning as described above. ]

  The reaction between the compound represented by formula (11-1) and the compound represented by formula (11-2) is preferably carried out in the presence of an esterifying agent.

  Examples of the esterifying agent (condensing agent) include 1-cyclohexyl-3- (2-morpholinoethyl) carbodiimide meth-p-toluenesulfonate, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide, 1- Ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (water-soluble carbodiimide: commercially available as WSC), bis (2,6-diisopropylphenyl) carbodiimide, bis (trimethylsilyl) carbodiimide, N, N′-diisopropyl Carbodiimides such as carbodiimide, 2-methyl-6-nitrobenzoic anhydride, 2,2′-carbonylbis-1H-imidazole, 1,1′-oxalyldiimidazole, diphenylphosphoryl azide, 1 (4-nitrobenze) Sulfonyl) -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 hexa Fluorophosphate, 2-bromo-1-ethylpyridinium tetrafluoroborate, 2-chloro-1,3-dimethylimidazolinium chloride, 2-chloro-1,3-dimethylimidazolinium hexafluorophosphate, 2-chloro- Examples thereof include 1-methylpyridinium iodide, 2-chloro-1-methylpyridinium-p-toluenesulfonate, 2-fluoro-1-methylpyridinium-p-toluenesulfonate, and trichloroacetic acid pentachlorophenyl ester. From the standpoint of reactivity, cost, and usable solvent, as the condensing agent, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride Bis (2,6-diisopropylphenyl) carbodiimide, bis (trimethylsilyl) carbodiimide, N, N′-diisopropylcarbodiimide, and 2,2′-carbonylbis-1H-imidazole are more preferable.

  The composition of the present invention (hereinafter sometimes referred to as “composition (1)”) includes compound (1). Furthermore, it is preferable to include a liquid crystal compound other than the compound (1) (hereinafter sometimes referred to as “liquid crystal compound”). As the liquid crystal compound, a compound represented by the formula (20) (hereinafter sometimes referred to as “compound (20)”) is preferable.

[In the formula (20), T ³ represents the same meaning as T ¹ .
R ^4a and R ^5a represent the same meaning as R ^1a .
A ⁴ and A ⁵ each independently represent the same meaning as A ¹ .
B ⁴ and B ⁵ each independently represent the same meaning as B ¹ .
D ⁴ and D ⁵ each independently represent the same meaning as D ¹ .
E ⁴ and E ⁵ each independently represent the same meaning as E ¹ .
G ⁴ and G ⁵ each independently represent the same meaning as G ¹ .
J ⁴ and J ⁵ each independently represent the same meaning as J ¹ .
P ⁴ and P ⁵ each independently represent the same meaning as P ¹ .
k ⁴ and ^{k 5} are each independently, represent the same meaning as ^{k 1.}
Y ¹ represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent. ]

The aromatic hydrocarbon group and aromatic heterocyclic group of Y ¹ are monocyclic aromatic hydrocarbon group, monocyclic aromatic heterocyclic group, polycyclic aromatic hydrocarbon group and polycyclic aromatic group. A heterocyclic group is mentioned.
Examples of the aromatic hydrocarbon group for Y ¹ include aromatic hydrocarbon groups having 6 to 20 carbon atoms such as a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and a biphenyl group, and a phenyl group or a naphthyl group is preferable. A phenyl group is more preferred. As the aromatic heterocyclic group, at least one hetero atom such as a furyl group, a pyrrolyl group, a thienyl group, a pyridinyl group, a thiazolyl group, a benzothiazolyl group, a benzofuryl group, a benzothienyl group, or the like And an aromatic heterocyclic group having 4 to 20 carbon atoms, and a furyl group, a thienyl group, a thiazolyl group, a benzothiazolyl group, a benzofuryl group, and a benzothienyl group are preferable.

  Such an aromatic hydrocarbon group and aromatic heterocyclic group may have at least one substituent, such as a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, C1-C6 alkylsulfinyl group, C1-C6 alkylsulfonyl group, carboxyl group, C1-C6 fluoroalkyl group, C1-C6 alkoxy group, C1-C6 alkylthio group N-alkylamino group having 1 to 6 carbon atoms, N, N-dialkylamino group having 2 to 12 carbon atoms, N-alkylsulfamoyl group having 1 to 6 carbon atoms, N, N having 2 to 12 carbon atoms -Dialkyl sulfamoyl group etc. are mentioned, a halogen atom, a C1-C2 alkyl group, a cyano group, a nitro group, a C1-C2 alkylsulfonyl group, a C1-C2 fluoroalkyl group, carbon 1 to 2 alkoxy groups, 1 to 2 carbon alkylthio groups, 1 to 2 carbon atoms N-alkylamino groups, 2 to 4 carbon atoms N, N-dialkylamino groups, 1 to 2 carbon atoms alkylsulfur groups A famoyl group is preferred.

  Halogen atom, alkyl group having 1 to 6 carbon atoms, cyano group, nitro group, alkylsulfinyl group having 1 to 6 carbon atoms, alkylsulfonyl group having 1 to 6 carbon atoms, carboxyl group, fluoroalkyl group having 1 to 6 carbon atoms , An alkoxy group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, an N-alkylamino group having 1 to 6 carbon atoms, an N, N-dialkylamino group having 2 to 12 carbon atoms, and 1 to 6 carbon atoms Examples of the N-alkylsulfamoyl group and the N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms are the same as those described above.

  Examples of the monocyclic aromatic hydrocarbon group or monocyclic aromatic heterocyclic group include groups represented by the formula (Y-1) to the formula (Y-6), and the formula (Y-1) or the formula The group represented by (Y-3) is preferable.

[In formula (Y-1) to formula (Y-6), * represents a bond, Z ² represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, or 1 to carbon atoms. 6 alkylsulfinyl groups, alkylsulfonyl groups having 1 to 6 carbon atoms, carboxyl groups, fluoroalkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, thioalkyl groups having 1 to 6 carbon atoms, 1 carbon atom -6 N-alkylamino group, C2-C12 N, N-dialkylamino group, C1-C6 N-alkylsulfamoyl group or C2-C12 N, N-dialkylsulfa Represents a moyl group.
a ¹ is an integer of 0 to 5, a ² is an integer of 0 to 4, b ¹ is an integer of 0 to 3, b ² is an integer of 0 to 2, and R is a hydrogen atom or a methyl group. . ]

Z ² is preferably a halogen atom, methyl group, cyano group, nitro group, sulfone group, carboxyl group, trifluoromethyl group, methoxy group, thiomethyl group, N, N-dimethylamino group or N-methylamino group.
A group represented by formula (Y-1) or formula (Y-3) is preferable.

Examples of the polycyclic aromatic hydrocarbon group or the polycyclic aromatic heterocyclic group include groups represented by formulas (Y ¹ -1) to (Y ¹ -7), and more specifically, formulas Examples include groups represented by (Y ³ -1) to formula (Y ³ -6).

[In formulas (Y ¹ -1) to (Y ¹ -7), * represents a bond, Z ³ represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, or a carbon number. 1-6 alkylsulfinyl groups, C1-C6 alkylsulfonyl groups, carboxyl groups, C1-C6 fluoroalkyl groups, C1-C6 alkoxy groups, C1-C6 thioalkyl groups, carbon N-alkylamino group having 1 to 6 carbon atoms, N, N-dialkylamino group having 2 to 12 carbon atoms, N-alkylsulfamoyl group having 1 to 6 carbon atoms, or N, N-dialkyl having 2 to 12 carbon atoms Represents a sulfamoyl group.
V ¹ and V ² each independently represent —CO—, —S—, —NR ²¹ —, —O—, —Se— or —SO ₂ —.
W ^{1 to} W ⁵ each independently represent —C═ or —N═.
However, at least one of V ¹ , V ² and W ^{1 to} W ⁵ represents a group containing S, N, O or Se.
R ²¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
a represents the integer of 0-3 each independently.
b represents the integer of 0-2 each independently. ]

[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. ]

Z ³ includes a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, a carboxyl group, and 1 to 1 carbon atoms. 6 fluoroalkyl groups, alkoxy groups having 1 to 6 carbon atoms, alkylthio groups having 1 to 6 carbon atoms, N-alkylamino groups having 1 to 6 carbon atoms, N, N-dialkylamino groups having 2 to 12 carbon atoms, C1-C6 N-alkyl sulfamoyl group, C2-C12 N, N-dialkyl sulfamoyl group etc. are mentioned, A halogen atom, a methyl group, an ethyl group, an isopropyl group, sec-butyl group , Cyano group, nitro group, sulfone group, nitroxide group, carboxyl group, trifluoromethyl group, methoxy group, thiomethyl group, N, N-dimethylamino group or N-methyl group Mino group is preferred, halogen atom, methyl group, ethyl group, isopropyl group, sec-butyl group, cyano group, nitro group, trifluoromethyl group are more preferred, methyl group, ethyl group, isopropyl group, sec-butyl group, A pentyl group and a hexyl group are particularly preferred.

  A halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkylsulfinyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms An alkylthio group having 1 to 6 carbon atoms, an N-alkylamino group having 1 to 6 carbon atoms, an N, N-dialkylamino group having 2 to 12 carbon atoms, an N-alkylsulfamoyl group having 1 to 6 carbon atoms, and Examples of the N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms are the same as those described above.

V ₁ and V ₂ are preferably each independently —S—, —NR ²¹ — or —O—.
W ^{1 to} W ⁵ are preferably each independently -C = or -N =.
At least one of V ¹ , V ² and W ^{1 to} W ⁵ preferably represents a group containing S, N or O.
a is preferably 0 or 1. b is preferably 0.

  Examples of the compound (20) include compounds represented by the formulas (B1-1) to (B52-8). * Represents a bond.

As liquid crystal compounds, chapter 3 of the Liquid Crystal Handbook (Edited by the Liquid Crystal Handbook Editorial Board, published by Maruzen Co., Ltd., October 30, 2000) 3.2 Non-chiral rod-like liquid crystal molecules with molecular structure and liquid crystal properties, 3.3 Chiral Among the compounds described in the rod-like liquid crystal molecules, compounds having a polymerizable group can be mentioned.
A plurality of different compounds may be used in combination as the liquid crystal compound.

  As the liquid crystal compound, for example, a compound represented by the formula (30) (however, different from the compound (20), hereinafter may be referred to as “compound (30)”) is preferable.

^{P 11 -E 11 - (B 11} -A 11) t -B 12 -G (30)
[In the formula (30), 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 may be substituted with a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylamino group having 1 to 6 carbon atoms, a nitro group, a nitrile group, or a mercapto 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 represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms, and R ¹⁴ and R ¹⁵ are bonded to each other to form an alkylene 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 alkylene group having 1 to 12 carbon atoms. The hydrogen atom contained in the alkylene group may be substituted with an alkyl group having 1 to 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 alkylamino group having 1 to 13 carbon atoms, a nitrile group, It represents a polymerizable group that is a nitro group or bonded via an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom contained in the alkylene group is an alkyl group having 1 to 6 carbon atoms, or a carbon group having 1 to 6 carbon atoms. It may be substituted with an alkoxy group or a halogen atom.
t represents an integer of 1 to 5. ]

In particular, the polymerizable group in P ¹¹ and G may be any group that can be polymerized with the compound (1), and includes a vinyl group, a vinyloxy group, a p-stilbene group, an acryloyl group, an acryloyloxy group, a methacryloyl group, Methacryloyloxy group, carboxyl group, acetyl group, hydroxyl group, carbamoyl group, amino group, alkylamino group having 1 to 4 carbon atoms, epoxy group, oxetanyl group, formyl group, -N = C = O and -N = C = S Etc. Of these, a radically polymerizable group or a cationically polymerizable group is preferable in that it is suitable for photopolymerization, and an acryloyloxy group, a methacryloyloxy group, or a vinyloxy group is preferable in that it can be easily handled and manufactured.
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 (30), the compound represented by Formula (30-1) and Formula (30-2) is mentioned, for example.

^{P 11 -E 11 - (B 11} -A 11) t1 -B 12 -E 12 -P 12 (30-1)
^{P 11 -E 11 - (B 11} -A 11) t2 -B 12 -F 11 (30-2)
[In formula (30-1) and formula (30-2), P ¹¹ , E ¹¹ , B ¹¹ , A ¹¹ and B ¹² have the same meanings 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 alkylamino group having 1 to 13 carbon atoms, or a nitrile group. Or represents a nitro group.
E ¹² has ^the same meaning as ^{E 11.}
P ¹² has ^the same meaning as ^{P 11.}
t ¹ and ^{t 2} have the same meanings as t. ]

  Further, the compounds represented by the formulas (30-1) and (30-2) 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 (30-1), formula (30-2), formula (I), formula (II), formula (III), formula (IV) and formula (V), P ¹¹ It is preferable that both are bonded via an ether bond or an ester bond by appropriately selecting a combination of E ¹¹ and E ¹¹ and further selecting a combination of P ¹² and E ¹² as appropriate.

  Specific examples of the compound (30) include a compound represented by the following formula, for example. However, k represents the integer of 1-11 in a formula.

  The content of the liquid crystal compound is, for example, 90 parts by weight or less with respect to 100 parts by weight in total of the compound (1) and the liquid crystal compound.

  The composition (1) preferably further contains a polymerization initiator. The polymerization initiator is preferably a photopolymerization initiator.

  Examples of the polymerization initiator include benzoins, benzophenones, benzyl ketals, α-hydroxyketones, α-aminoketones, iodonium salts, sulfonium salts, and the like. More specifically, Irgacure 907, IRGACURE 184, IRGACURE 651, IRGACURE 819, IRGACURE 250, IRGACURE 369 (all manufactured by Ciba Japan Co., Ltd.), Seiko All BZ, Seiko All Z, Seiko All BEE (all the above manufactured by Seiko Chemical Co., Ltd.), Kayacure BP100 (Manufactured by Nippon Kayaku Co., Ltd.), Kayacure UVI-6992 (manufactured by Dow), Adeka optomer SP-152 and Adeka optomer SP-170 (all of which are manufactured by ADEKA Corporation).

  Moreover, the usage-amount of a polymerization initiator is 0.1 weight part-30 weight part with respect to a total of 100 weight part of a compound (1) and a liquid crystal compound, for example, Preferably, 0.5 weight part-10 weight part Part.

  The composition (1) preferably further contains a polymerization inhibitor, a photosensitizer, a leveling agent, an organic solvent, and the like.

(Polymerization inhibitor)
Examples of the polymerization inhibitor include hydroquinones having a substituent such as hydroquinone and alkyl ether, catechol having a substituent such as alkyl ether such as butylcatechol, pyrogallol, 2,2,6,6-tetramethyl-1 -Radical scavengers such as piperidinyloxy radical, thiophenols, β-naphthylamines, β-naphthols and the like.

  By using a polymerization inhibitor, the polymerization of the compound (1) can be controlled, and the stability of the obtained optical film can be improved. The amount of the polymerization inhibitor used is, for example, 0.1 to 30 parts by weight, preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the total of the compound (1) and the liquid crystal compound. It is.

[Photosensitizer]
Examples of the photosensitizer include xanthones such as xanthone and thioxanthone, anthracene having a substituent such as anthracene or alkyl ether, phenothiazine, and rubrene.

  By using a photosensitizer, the polymerization of the compound (1) or the like can be made highly sensitive. Moreover, as the usage-amount of a photosensitizer, it is 0.1 weight part-30 weight part with respect to a total of 100 weight part of a compound (1) and a liquid crystal compound, Preferably it is 0.5 weight part-10 weight part. Parts by weight.

(Leveling agent)
As a leveling agent, for example, an additive for radiation-curing coatings (by Big Chemie Japan: BYK-352, BYK-353, BYK-361N), coating additives (by Toray Dow Corning Co., Ltd .: SH28PA, DC11PA, ST80PA), Paint additives (manufactured by Shin-Etsu Chemical Co., Ltd .: KP321, KP323, X22-161A, KF6001) and fluorine-based additives (Dainippon Ink Chemical Industries, Ltd .: F-445, F-470, F-479), etc. Can be mentioned.

  By using a leveling agent, the optical film can be smoothed. Furthermore, in the production process of the optical film, the fluidity of the composition (1) can be controlled, or the crosslinking density of the optical film obtained by polymerizing the compound (1) or the like can be adjusted. Moreover, the usage-amount of a leveling agent is 0.1 weight part-30 weight part with respect to a total of 100 weight part of a compound (1) and a liquid crystal compound, for example, Preferably it is 0.5 weight part-10 weight part. is there.

〔Organic solvent〕
The organic solvent is an organic solvent that can dissolve the compound (1) and the like, and may be any solvent that is inert to the polymerization reaction. Specifically, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl Alcohols such as cellosolve, butyl cellosolve or propylene glycol monomethyl ether; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, gamma-butyrolactone, propylene glycol methyl ether acetate or ethyl lactate; acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone Ketone solvents such as methyl amyl ketone or methyl isobutyl ketone; non-chlorine aliphatic hydrocarbon solvents such as pentane, hexane or heptane; , Non-chlorinated aromatic hydrocarbon solvents such as xylene or phenol, nitrile solvents such as acetonitrile; and the like; chlorinated solvents such as chloroform or chlorobenzene; an ether solvent such as tetrahydrofuran or dimethoxyethane. These organic solvents may be used alone or in combination. The composition (1) is excellent in compatibility and can be dissolved in alcohol, ester solvents, ketone solvents, non-chlorine aliphatic hydrocarbon solvents, non-chlorine aromatic hydrocarbon solvents, etc. Even without using a chlorinated solvent, it can be dissolved and applied.

  The viscosity of the composition (1) is preferably adjusted to, for example, 10 Pa · s or less, and preferably about 0.1 to 7 Pa · s so as to be easily applied.

  Moreover, the density | concentration of solid content in a composition (1) is 5 to 50 weight%, for example. When the solid content is 5% or more, the optical film does not become too thin, and there is a tendency that a birefringence index necessary for optical compensation of the liquid crystal panel is provided. Moreover, since the viscosity of a composition (1) is low as it is 50% or less, since there exists a tendency for the nonuniformity to arise in the film thickness of an optical film, it is preferable.

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

  The wavelength dispersion characteristic of the optical film of the present invention can be determined by the content of the structural unit derived from the compound (1) in the optical film. When the content of the structural unit derived from the compound (1) in the optical film is increased, flatter wavelength dispersion characteristics and further reverse wavelength dispersion characteristics are exhibited.

  Specifically, about the composition (1), about 2 to 5 types of compositions having different content of structural units derived from the compound (1) are prepared, and the same film thickness as described later for each composition. The retardation value of the optical film obtained by producing the optical film was obtained, and from the result, the correlation between the content of the structural unit derived from the compound (1) and the retardation value of the optical film was obtained and obtained. What is necessary is just to determine content of the structural unit derived from the compound (1) required in order to give a desired retardation value to the optical film in the said film thickness from correlation.

The manufacturing method of the optical film of this invention is demonstrated below.
First, an additive such as a liquid crystal compound, a polymerization initiator, a polymerization inhibitor, a photosensitizer, a leveling agent, or an organic solvent is added to the compound (1) as necessary to prepare the composition (1). . In particular, it is preferable to include an organic solvent that facilitates film formation during film formation, and it is preferable to include a polymerization initiator because it functions to cure the obtained optical film.

  Subsequently, the composition (1) is applied to a supporting substrate, dried and polymerized, and a desired optical film can be obtained on the supporting substrate.

[Unpolymerized film preparation process]
When the composition (1) is applied onto a supporting substrate and dried, an unpolymerized film is obtained. When the unpolymerized film exhibits a liquid crystal phase such as a nematic phase, the obtained optical film has birefringence due to monodomain alignment. Since the unpolymerized film is oriented at a low temperature of about 0 to 120 ° C., preferably 25 to 80 ° C., a supporting substrate that is not necessarily sufficient with respect to heat resistance as exemplified above can be used as the orientation film. Moreover, even if it cools to about 30-10 degreeC after orientation, since it does not crystallize, handling is easy.

  In addition, a film thickness can be adjusted so that a desired phase difference may be given by adjusting the application quantity and density | concentration of a composition (1) suitably. In the case of the composition (1) in which the amount of the compound (1) is constant, the retardation value (retardation value, Re (λ)) of the obtained optical film is determined as shown in the formula (7). In order to obtain a desired Re (λ), the film thickness d may be adjusted.

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.)
The chromatic dispersion characteristic is usually represented by a value (Re (λ) / Re (550)) obtained by dividing the phase difference value Re (λ) at a certain wavelength λ by the phase difference value Re (550) at 550 nm. (Λ) / Re (550)) is close to 1, and [Re (450) / Re (550)] <1 and [Re (650) / Re (550)]> 1. In the wavelength range shown, uniform polarization conversion is possible.

  Examples of the application method 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, and a spin coater, etc. are mentioned.

  As said support base material, glass, a plastic sheet, a plastic film, and 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, and polyphenylene oxide film.

  For example, even a process that requires the strength of the optical film, such as a bonding process, a transport process, and a storage process of the optical film of the present invention, can be easily handled without tearing by using the support substrate.

  Moreover, it is preferable to form an alignment film on a support substrate and to apply the composition (1) on the alignment film. The alignment film has a solvent resistance that does not dissolve in the composition (1) when the composition (1) is applied, has heat resistance during the removal of the solvent and the heat treatment of the alignment of the liquid crystal, and friction during rubbing. It is preferable that peeling due to the above does not occur, and it is preferable to contain a polymer.

  Examples of the 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, polyoxazole, which are hydrolysates thereof. Mention may be made of polymers such as polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid and polyacrylic acid esters. These polymers may be used alone, or two or more of them 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.

  Further, these polymers can be applied after being dissolved in a solvent. The solvent is not particularly limited, but specifically water; alcohol such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl cellosolve, butyl cellosolve or propylene glycol monomethyl ether; ethyl acetate, butyl acetate, ethylene glycol Ester solvents such as methyl ether acetate, gamma-butyrolactone, propylene glycol methyl ether acetate or ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone or methyl isobutyl ketone; pentane, hexane or heptane Non-chlorinated aliphatic hydrocarbon solvents; non-chlorinated aromatic hydrocarbon solvents such as toluene or xylene, acetonitrile, etc. Chlorinated solvents such as chloroform or chlorobenzene; tolyl solvent; ether solvent such as tetrahydrofuran or dimethoxyethane, and the like. These organic solvents may be used alone or in combination.

  In order to form the alignment film, a commercially available alignment film material may be used 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).

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

  As a method for forming an alignment film on the support substrate, for example, a commercially available alignment film material or a compound serving as an alignment film material is applied as a solution on the support substrate, and then annealed, An alignment film can be formed on the support substrate.

  The thickness of the alignment film thus obtained is, for example, 10 nm to 10000 nm, preferably 10 nm to 1000 nm. If it is the said range, a compound (1) etc. can be orientated on a desired angle on this alignment film.

  Further, these alignment films can be rubbed or irradiated with polarized UV rays as necessary. With these, the compound (1) and the like can be oriented in a desired direction.

  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 placed on a stage and brought into contact with the alignment film being conveyed can be used.

  As described above, in the unpolymerized film preparation step, the unpolymerized film (liquid crystal layer) is laminated on the alignment film laminated on the support substrate. Therefore, the production cost can be reduced as compared with a method of manufacturing a liquid crystal cell and injecting a liquid crystal compound into the liquid crystal cell. Furthermore, it is possible to produce a film using a roll film.

  The solvent may be dried while the polymerization proceeds, but it is preferable from the viewpoint of film formability that most of the solvent is dried before the polymerization.

  Examples of the solvent drying method include natural drying, ventilation drying, and vacuum drying. The specific heating temperature is preferably 10 to 120 ° C, more preferably 25 to 80 ° 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.

[Unpolymerized film polymerization process]
In the unpolymerized film polymerization step, the unpolymerized film obtained in the unpolymerized film preparation step is polymerized and cured. Thereby, a film in which the orientation of the compound (1) is fixed, that is, a polymerized film is obtained. Therefore, it is possible to produce a polymer film having a small change in refractive index in the plane direction of the film and a large change in refractive index in the normal direction of the film.

  The method for polymerizing the unpolymerized film is determined according to the type of the compound (1). If the polymerizable group contained in the compound (1) is photopolymerizable, the unpolymerized film can be polymerized by photopolymerization, and if the polymerizable group is thermally polymerizable, the unpolymerized film can be polymerized by thermal polymerization. In the present invention, it is particularly preferable to polymerize an unpolymerized film by photopolymerization. According to photopolymerization, an unpolymerized film can be polymerized at a low temperature, so that the range of selection of the support substrate is widened in terms of heat resistance. In addition, it is easy to manufacture industrially. Photopolymerization is also preferred from the viewpoint of film formability. Photopolymerization is performed by irradiating an unpolymerized film with visible light, ultraviolet light, or laser light. From the viewpoint of handleability, ultraviolet light is particularly preferable. The light irradiation may be performed while heating to a temperature at which the compound (1) takes a liquid crystal phase. At this time, the polymerized film can be patterned by masking or the like.

  The optical film of the present invention is easy to manufacture because the adhesion between the alignment film and the optical film is good. The optical film of the present invention is a thin film as compared with a stretched film that gives a phase difference by stretching a polymer.

  In the manufacturing method of the optical film of this invention, the process of peeling a support base material may be included following the said process. By setting it as such a structure, the laminated body obtained becomes a film which consists of an oriented film and an optical film. Moreover, in addition to the process of peeling the said support base material, the process of peeling an alignment film may be further included. By setting it as such a structure, an optical film can be obtained.

  The optical film thus obtained is excellent in transparency and used as various display films. As described above, the thickness of the layer to be formed varies depending on the retardation value of the obtained optical film. In the present invention, the thickness is preferably 0.1 to 10 μm, and more preferably 0.5 to 3 μm from the viewpoint of reducing photoelasticity.

  In the case where the alignment film is used and has birefringence, for example, the retardation value 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.

  In order to use the optical film of the present invention as a broadband λ / 4 plate or λ / 2 plate, the content of the structural unit derived from the compound (1) is 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.

  In order to use the optical film of the present invention as an optical film for a VA (vertical alignment) mode, the content of the structural unit derived from the compound (1) is appropriately selected. The film thickness may be adjusted so that Re (550) is preferably 40 to 100 nm, more preferably about 60 to 80 nm.

  By adding a small amount of compound (1), 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 used for an antireflection film such as an anti-reflection (AR) film, a polarizing film, a retardation film, an elliptically polarizing film, a viewing angle widening film, and an optical compensation film for compensating a viewing angle of a transmissive liquid crystal display. can do. Moreover, although the optical film of this invention shows the outstanding optical characteristic even if it is 1 sheet, you may laminate | stack several sheets.

  Moreover, you may combine with another film. Specifically, an elliptically polarizing plate in which the optical film of the present invention is bonded to a polarizing film, a broadband circularly polarizing plate in which the optical film of the present invention is further bonded to the elliptical polarizing plate as a broadband λ / 4 plate, and the like. It is done.

  Since the optical film of the present invention can be formed by coating on an alignment film and polymerization by ultraviolet irradiation, as shown in FIG. A λ / 2 plate 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 manufacturing method of the color filter 1 having the above configuration will be described. First, an alignment polymer is printed on the color filter layer 4 and a rubbing process is performed to form the alignment film 3.
Next, the composition (1) is prepared on the alignment film 3 obtained so as to have a desired wavelength dispersion characteristic, and is applied while adjusting the thickness so that a desired retardation value is obtained. Form.

  On the other hand, if the color filter 1 is used, a thin liquid crystal display device with a reduced number of optical films 2 can be manufactured. As an example, there is a thin liquid crystal display device formed on the liquid crystal layer side of at least one substrate in a liquid crystal display element in which a liquid crystal layer is sandwiched and formed between a pair of substrates as 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 via an adhesive, and a color filter layer 4 ′ formed on the substrate 7. An optical film 2 ′ is formed thereon via an alignment film 3 ′. Further, a counter electrode 8 is formed on the optical film 2 ′, and a liquid crystal layer 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 can reduce the number of optical films as compared with a conventional liquid crystal display device, and enables the manufacture of a thinner liquid crystal display device.

Below, an example of the manufacturing method of the liquid crystal display device 5 in which color filter 1 'was formed in the liquid crystal layer side of one board | substrate is described. 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 is formed, and thereafter, P, B, etc. are doped in the regions on both sides of the gate electrode to form n-channel and p-channel TFTs. By further forming an insulating film made of SiO _2, the backlight side of the substrate is obtained. 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'. The composition (1) is applied onto the alignment film 3 ', and polymerized and optical film 2' is formed 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 layer 9 is formed, and finally the liquid crystal display device 5 is manufactured by assembling together with the substrate on the backlight side. Further, the value of [Re (450) / Re (550)] and [Re (650) / Re (550)] of the compound (1) of the present invention is close to 1 or less than 1, so that the composition is changed. Thus, desired wavelength dispersion characteristics can be obtained, and the retardation value can be controlled from the film thickness, so that the lamination of the optical film can also be omitted.

  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.

Thus, the film according to the present invention can be used in a wide range of applications. For example, a polarizing plate formed by laminating the optical film and the polarizing film according to the present invention and an FPD including the polarizing plate will be described below. The polarizing plate according to the present invention is a film having a polarizing function, that is, one side of the polarizing film. Alternatively, it is obtained by laminating the optical film directly on both sides or using an adhesive or a pressure-sensitive adhesive. In the following description of FIGS. 3 to 5, the adhesive and the pressure-sensitive adhesive may be collectively referred to as an adhesive.

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 adsorbing iodine or a dichroic dye on a polyvinyl alcohol film and drawn, or a film obtained by drawing 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. As such an adhesive, for example, an acrylic, epoxy, or urethane adhesive is used.

  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 film of the present invention and a liquid crystal panel are bonded, and the polarizing film of the present invention And an organic EL display device including an organic EL panel on which a light emitting layer is bonded.

  As embodiments of a flat panel display device according to the present invention, a liquid crystal display device and an organic EL display device will be described in detail below.

[Liquid Crystal Display]
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 according to the present invention.

  As a liquid crystal display device, a liquid crystal display device provided with the bonding product 21 of the liquid crystal panel 20 and the polarizing plate 30 as shown, for example in FIG. 2 is mentioned. 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 an optical shutter effect is produced.

[Organic EL display device]
FIG. 5 is a schematic view showing an organic EL panel 23 of the organic EL display device according to the present invention.

  Examples of the organic EL display device include an organic EL display device including the organic EL panel 23 shown in FIG. 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. In the examples, “%” and “parts” are by weight and parts by weight unless otherwise specified.

Example 1
<Synthesis Example of Compound (A13-1)>
Compound (A13-1) was synthesized according to the following scheme.

[Synthesis Example of Compound (13-a)]
17.93 g (117.0 mmol) of 2,5-dimethoxyaniline, 15.00 g (78.1 mmol) of 7-methoxybenzofuran-2-carboxylic acid, 0.95 g (7.8 mmol) of N, N′-dimethylaminopyridine and 75.0 g of dehydrated chloroform was mixed. After cooling the obtained solution in an ice bath, 16.46 g (85.9 mmol) of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride was added and reacted at room temperature for 72 hours. 1N hydrochloric acid aqueous solution and methanol mixed solution (hydrochloric acid water 2 parts by volume, methanol 1 part by volume) were added to the obtained mixed liquid 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 19.1 g of compound (13-a) as a white powder. The yield was 75% based on 7-methoxybenzofuran-2-carboxylic acid.

[Synthesis Example of Compound (13-b)]
Compound (13-a) 15.0 g (46 mmol), 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetan-2,4-disulfide (Lawson reagent) 11.12 g ( 27 mmol) and 150 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 and partitioned with a 1N sodium hydroxide aqueous solution. The organic layer was collected and crystallized by adding 100 mL of heptane. The yellow precipitate was collected by filtration and dried in vacuo to obtain 15.7 g as a yellow powder containing compound (13-b) as the main component. The yield was 99% based on the compound (13-a).

[Synthesis Example of Compound (13-c)]
15.7 g of the mixture containing the compound (13-b) obtained in the previous item, 18.72 g (334 mmol) of potassium hydroxide and 250 g of water were mixed, and the resulting mixture was reacted under ice cooling. Subsequently, 105 mL of an aqueous solution containing 54.93 g (167 mmol) of potassium ferricyanide and 20 mL of methanol were added and reacted under ice cooling. 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 water, toluene, and methanol. The obtained yellow powder was collected by filtration and dried in vacuo to obtain 11.5 g of a yellow powder mainly containing compound (13-c). The yield was 55% based on the compound (13-b).

[Synthesis Example of Compound (13-d)]
Compound (13-c) 10.0 g (29 mmol) and pyridinium chloride 150.0 g (15 times mass) 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 hang-washing with water, washing with toluene and vacuum drying were performed to obtain 8.57 g of an ocherous solid mainly composed of compound (13-d). The yield was 98% based on the compound (13-c).

[Synthesis Example of Compound (A13-1)]
Compound (13-d) 5.00 g (16.71 mmol), compound (A) 23.07 g (55.13 mmol), dimethylaminopyridine 0.20 g (1.67 mmol) and chloroform 120 mL were mixed. N, N′-diisopropylcarbodiimide (7.59 g, 60.14 mmol) 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 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. Ethanol was added with stirring, and the resulting pale yellow precipitate was collected by filtration, washed with heptane, and dried in vacuo to give compound (A13-1). Was obtained as a white powder. The yield was 80% based on the compound (13-d).

¹ H-NMR (CDCl ₃ ) of the compound (A13-1): δ (ppm) 1.47 to 1.91 (m, 36H), 2.34 to 2.42 (m, 12H), 2.61 2.81 (2tt, 6H), 3.89-3.95 (m, 6H), 4.15-4.20 (t, 6H), 5.79-5.84 (dd, 3H), 6. 07-6.17 (m, 3H), 6.37-6.44 (m, 3H), 6.79-7.01 (m, 12H), 7.16-7.34 (m, 4H), 7.56-7.59 (m, 2H)

  The phase transition temperature of the obtained compound (A13-1) was confirmed by texture observation with a polarizing microscope. Compound (A13-1) melted at 209 ° C. at the time of temperature rise and exhibited a viscous phase. It showed a highly viscous phase up to 300 ° C., and it was difficult to distinguish the liquid crystal phase.

(Example 2)
<Synthesis Example of Compound (B41-1)>
Compound (B41-1) was synthesized according to the following scheme.

[Synthesis Example of Compound (B41-a)]
48.30 g (315 mmol) of 2,5-dimethoxyaniline, 63.82 g (631 mmol) of triethylamine and 500 g of dehydrated chloroform were mixed. To the resulting solution, 50.00 g (315 mmol) of 4-fluorobenzoic acid chloride was added dropwise under ice cooling, and the resulting solution was reacted in an ice bath for 3 hours. Water (500 mL) was added to the obtained mixed solution to separate it, and the organic layer was recovered. Further, the organic layer was separated with 1N-hydrochloric acid (333 mL), and the organic layer was recovered. Furthermore, the organic layer was washed with 666 mL of water, and the organic layer was collected and dried over anhydrous sodium sulfate. The solution was concentrated with an evaporator, and the precipitated crystals were collected by filtration and vacuum dried to obtain 87.0 g of compound (B41-a) as an off-white powder. The yield was 100% based on 2,5-dimethoxyaniline.

[Synthesis Example of Compound (B41-b)]
Compound (B41-a) 60.0 g (218 mmol), 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetan-2,4-disulfide (Lawson reagent) 52.9 g ( 131 mmol) and 600 g of toluene were mixed, and the resulting mixture was heated to 80 ° C. and reacted for 3 hours. After cooling, the mixture was concentrated, and the resulting crystals were collected by filtration. The crystals were washed with 300 mL of methanol, collected by filtration and dried in vacuo to obtain 63.5 g of a yellow powder mainly containing compound (B41-b). The yield was 100% based on the compound (B41-a).

[Synthesis Example of Compound (B41-c)]
63.5 g of a mixture containing the compound (B41-b) obtained in the previous section, 171.45 g (4286 mmol) of sodium hydroxide, 171.45 g (521 mmol) of potassium ferricyanide, and 952 g of water were mixed, and the resulting mixture was mixed at room temperature. It was made to react with. The reaction solution was reacted at room temperature for 2 hours, and the deposited yellow precipitate was collected by filtration. The precipitate collected by filtration was washed with water and toluene. The obtained yellow powder was vacuum-dried to obtain 33.5 g of a yellow solid containing compound (B41-c) as a main component. The yield was 53% based on the compound (B41-a).

[Synthesis Example of Compound (B41-d)]
Compound (B41-c) 30.0 g (104 mmol) and pyridinium chloride 150.0 g (5 times mass) were mixed, heated to 200 ° 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 acetone, ethyl acetate, and toluene, and dried under vacuum to obtain 12.13 g of an ocher solid containing the compound (B41-d) as a main component. The yield was 45% based on the compound (B41-c).

[Synthesis Example of Compound (B41-1)]
Compound (B41-d) 3.14 g (12 mmol), compound (A) 12.55 g (30 mmol), dimethylaminopyridine 0.37 g (3.0 mmol) and chloroform 120 mL were mixed. 9.28 g (45 mmol) of N, N′-dicyclohexylcarbodiimide was added to the obtained mixture under ice cooling. The resulting reaction solution was allowed to react at room temperature overnight, and after white precipitation filtration, the filtrate was washed twice with 100 mL of 1N aqueous hydrochloric acid to recover the organic layer. The organic layer was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure. Methanol was added to the residue for crystallization. The crystals were collected by filtration, redissolved in chloroform, the solution was filtered, the filtrate was concentrated under reduced pressure to 1/3 with an evaporator, methanol was added with stirring, the resulting white precipitate was collected by filtration, washed with heptane, Vacuum drying gave 6.80 g of compound (B41-1) as an off-white powder. The yield was 54% based on the compound (B41-d).

¹ H-NMR (CDCl ₃ ) of the compound (B41-1): δ (ppm) 1.44 to 1.90 (m, 24H), 2.34 to 2.81 (m, 12H), 3.92 to 4.00 (t, 4H), 4.15 to 4.20 (t, 4H), 5.79 to 5.84 (m, 2H), 6.07 to 6.18 (m, 2H), 6. 36 to 6.44 (m, 2H), 6.86 to 7.02 (m, 8H), 7.14 to 7.21 (m, 4H), 8.00 to 8.07 (m, 2H)

  The phase transition temperature of the compound (B41-1) was measured by texture observation with a polarizing microscope. As the temperature was raised, it changed to a nematic phase around 95 ° C. When the temperature was further increased, it changed to an isotropic phase around 212 ° C. When the temperature was lowered from here, it changed to a nematic phase around 212 ° C., and changed to a crystal around 86 ° C. That is, it was found that the compound (B41-1) exhibited a nematic phase from 95 ° C. to 212 ° C. when the temperature was raised, and a nematic phase from 212 ° C. to 86 ° C. when the temperature was lowered.

(Examples 3 and 4, Comparative Examples 1 and 2)
<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, followed by drying at the drying temperature shown in Table 2 for 1 minute. . 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 prepare an optical film having a film thickness described in Table 3.
In Table 1, “%” means “% by weight” based on 100% by weight of the composition.

LC242: Liquid crystal compound polymerization initiator of the following formula commercially available from BASF: Irgacure 819 (manufactured by Ciba Specialty Chemicals)
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).

In the optical films of Examples 3 and 4, the value of [Re (447.3) / Re (546.9)] (α in the table) decreased and approached 1 as compared with Comparative Example 1. That is, since the wavelength dependence of the refractive index can be made closer to reverse chromatic dispersion, uniform polarization conversion is possible in a wider wavelength range.
If the optical film of an Example is utilized for a liquid crystal panel, it has the characteristic excellent in optical compensation. Moreover, it became clear that the wavelength dispersion of the optical film obtained can be controlled by mixing the compound (1) with a liquid crystal compound.

  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 (19)

The compound represented by Formula (1).

[In Formula (1),
Q ¹ represents -CR ^1b = or -N =.
T ¹ and T ² each independently represent —O—, —S—, —CO— or —N (R ^2b ) —.
R ^1b represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms.
R ^2b represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
R ^{1a to} R ^3a are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 6 carbon atoms, or an alkylsulfonyl having 1 to 6 carbon atoms. Group, carboxyl group, C1-C6 fluoroalkyl group, C1-C6 alkoxy group, C1-C6 alkylthio group, C1-C6 N-alkylamino group, C2-C12 Represents an N, N-dialkylamino group, an N-alkylsulfamoyl group having 1 to 6 carbon atoms, or an N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms.
A ¹ , A ² and A ³ each independently represent —O—CO— *, —O—C (═S) — * or —NR ⁹ —CO— *. However, * represents a bond with B ¹ , B ² or B ³ .
R ⁹ represents a hydrogen atom, a methyl group or an ethyl group.
B ¹ , B ² and B ³ 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 —N (R ^4b ) —.
R ^4b represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
X ¹ is a group represented by the formula (X1), X ² is a group represented by the formula (X2), and X ³ is a group represented by the formula (X3).

[In Formula (X1), Formula (X2), and Formula (X3), D ¹ , D ^2, and D ³ are each independently —CO—O—, —O—CO—, —O—CO—O—, , —CO—NR ¹² —, —NR ¹² —CO—, —CH ₂ —O—, —CH ₂ —S— or a single bond. R ¹² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
E ¹ , E ² and E ³ each independently represents an alicyclic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group which may have a substituent, and the alicyclic ring The methylene group contained in the formula hydrocarbon group may be substituted with -O-, -S- or -NH-, and = C- contained in the aromatic hydrocarbon group is substituted with = N-. It may be.
G ¹ , G ² and G ³ are each independently —CH ₂ —CH ₂ —, —O— , —CO —O—, —O—CO—, —O—CO—O—, —CO—NH. -, - NH-CO -, - O-CH 2 -, - represents a CH 2 -O- or a single bond.
J ¹ , J ² and J ³ each independently represent an alkylene group having 1 to 12 carbon atoms which may have a substituent. The methylene group contained in the alkylene group may be substituted with -O- or -CO-.
P ¹ , P ² and P ³ are each independently a hydrogen atom, an acryloyloxy group or a methacryloyloxy group (provided that at least one of P ¹ , P ² and P ³ represents an acryloyloxy group or a methacryloyloxy group). Express).
k ^{1, k 2} and ^{k 3} each independently represents an integer of 0 to 3. ]
m represents an integer of 1 or 2. ] The compound according to claim ^1, wherein T ¹ and T ² are each independently —O— or —S—. The compound according to claim 1 or 2, wherein Q ¹ is -C =. B ^{1, B 2} and ^{B 3} A compound according to any one of claims 1 to 3 is a 1,4-cyclohexylene group. E ¹ , E ² and E ³ are each independently 1,4-phenylene group or 1,4-cyclohexylene group, and hydrogen contained in the 1,4-phenylene group and 1,4-cyclohexylene group The compound according to any one of claims 1 to 4 , wherein the atom 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. The composition for optical films containing the compound in any one of Claims 1-5 . Furthermore , the composition for optical films of Claim 6 containing a polymerization initiator. The optical film obtained by polymerizing a compound according to any of claims 1-5. The optical film formed by superposing | polymerizing the composition for optical films of Claim 6 or 7 . The optical film according to claim 8 or 9 , wherein the optical film 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 8 or 9, 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 8-11 . A color filter, wherein the optical film according to claim 8 is formed on an orientation polymer directly applied on a color filter substrate. A liquid crystal display device comprising the color filter according to claim 13 . A flat panel display comprising a liquid crystal panel comprising the polarizing plate according to claim 12 . An organic EL display device comprising an organic electroluminescence panel comprising the polarizing plate according to claim 12 . The manufacturing method of the unpolymerized film which apply | coats the solution containing the compound in any one of Claims 1-5 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 1-5 on the orientation film 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 17 or 18 by superposition | polymerization.

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