JP2009149754A - Polymerizable compound and optical film obtained by polymerizing the polymerizable compound - Google Patents

Abstract

【選択図】図１Disclosed is a novel polymerizable compound that provides an optical film having a large Δn.
A polymerizable compound represented by formula (1-a) or formula (1-b). _However, - for _{(B 1 -A 1) m -E} 1 -D 1 -G 1 -Q 1, - (B 2 -A 2) n -E 1 -D 2 -G 2 -Q 2 on the benzene ring The substitution position of is para or meta.

[Selection] Figure 1

Description

  The present invention relates to a polymerizable compound and an optical film containing a structural unit derived from the polymerizable compound.

The liquid crystal display device includes members using optical films such as a polarizing plate and a retardation plate. Recently, downsizing of liquid crystal display devices has been desired, and accordingly, optical films have been required to be thinned. Examples of the thinned optical film include an optical film obtained by polymerizing a solution obtained by dissolving a polymerizable compound in a solvent on a supporting substrate. It is known that the phase difference (Re (λ)) of the optical film given by the light of wavelength λnm is determined by the product of the birefringence Δn and the thickness d of the film (Re (λ) = Δn). Xd). That is, Δn should be increased in order to reduce the thickness of the optical film. When obtaining a predetermined phase difference, if Δn is large, there is an advantage that d can be reduced.
For example, LC242 (manufactured by BASF) is commercially available as the polymerizable compound (Non-Patent Document 1).

“Paliocolor”, [online], October 20, 2004, BASF, [Searched on December 5, 2007], Internet <http://www.inorganics.basf.com/p02/CAPortal/en_GB/ portal / Displaychemikalien / content / Produktgruppen / Displaychemikalien / Palicolor / Paliocolor>

  The subject of this invention is providing the new polymeric compound etc. which give the optical film with large (DELTA) n.

［式（１−ａ）および式（１−ｂ）中、Ｘ_１およびＸ_２は、それぞれ独立に、−ＣＨ＝ＣＨ−、−ＣＨ＝Ｃ（ＣＨ_３）−、−Ｃ（ＣＨ_３）＝ＣＨ−、−Ｃ（ＣＨ_３）＝Ｃ（ＣＨ_３）−、−ＣＨ＝Ｎ−、−Ｎ＝ＣＨ−、−Ｎ＝Ｃ（ＣＨ_３）−または−Ｃ（ＣＨ_３）＝Ｎ−を表す。
Ｙ_１およびＹ_２は、それぞれ独立に、６〜１８員環の芳香族炭化水素基または５〜１８員環の芳香族複素環基を表す。該芳香族炭化水素基および該芳香族複素環基に含まれる水素原子は、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基またはハロゲン原子に置換されていてもよい。
Ｂ_１、Ｂ_２、Ｇ_１およびＧ_２は、それぞれ独立に、−ＣＲ^１Ｒ^２−、−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−、−Ｏ−Ｃ（＝Ｓ）−、−Ｏ−Ｃ（＝Ｓ）−Ｏ−、−ＣＲ^１＝Ｎ−、−Ｎ＝ＣＲ^１−、−Ｃ（＝Ｏ）−ＮＲ^１−、−ＮＲ^１−Ｃ（＝Ｏ）−、−ＯＣＨ_２−、−ＯＣＦ_２−、−ＮＲ^１−、−ＣＨ_２Ｏ−、−ＣＦ_２Ｏ−、−ＳＣＨ_２−、−ＣＨ_２Ｓ−、−ＣＨ＝ＣＨ−Ｃ（＝Ｏ）−Ｏ−、−Ｏ−Ｃ（＝Ｏ）−ＣＨ＝ＣＨ−または単結合を表す。Ｒ^１およびＲ^２は、それぞれ独立に、水素原子または炭素数１〜６のアルキル基を表す。
Ａ_１およびＡ_２は、それぞれ独立に、６〜１８員環の芳香族炭化水素基、５〜１８員環の脂環式炭化水素基または５〜１８員環の複素環基を表す。該芳香族炭化水素基、該脂環式炭化水素基および該複素環基に含まれる水素原子は、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基またはハロゲン原子に置換されていてもよい。ｍおよびｎは、それぞれ独立に、１〜３で表される整数を表す。
Ｅ_１およびＥ_２は、それぞれ独立に、−ＣＲ^３Ｒ^４−、−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−、−Ｏ−Ｃ（＝Ｓ）−、−Ｏ−Ｃ（＝Ｓ）−Ｏ−、−ＣＲ^３＝Ｎ−、−Ｎ＝ＣＲ^３−、−Ｃ（＝Ｏ）−ＮＲ^３−、−ＮＲ^３−Ｃ（＝Ｏ）−、−ＯＣＨ_２−、−ＯＣＦ_２−、−ＮＲ^３−、−ＣＨ_２Ｏ−、−ＣＦ_２Ｏ−、−ＳＣＨ_２−、−ＣＨ_２Ｓ−、−ＣＨ＝ＣＨ−Ｃ（＝Ｏ）−Ｏ−、−Ｏ−Ｃ（＝Ｏ）−ＣＨ＝ＣＨ−、または単結合を表す。Ｒ^３およびＲ^４は、それぞれ独立に、水素原子または炭素数１〜６のアルキル基を表す。
Ｄ_１およびＤ_２は、それぞれ独立に、炭素数１〜１２のアルキレン基を表し、Ｄ_１およびＤ_２に含まれる水素原子は、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基又はハロゲン原子に置換されていてもよい。
Ｑ_１およびＱ_２は、水素原子または式（Ｑ−１）〜式（Ｑ−５）で表される基からなる群から選ばれる基である。

（式（Ｑ−１）〜式（Ｑ−５）中、Ｒ^５〜Ｒ^９はそれぞれ独立に、水素原子または炭素数１〜４のアルキル基を表す。）］ The present invention is a polymerizable compound represented by formula (1-a) or formula (1-b). _However, - for _{(B 1 -A 1) m -E} 1 -D 1 -G 1 -Q 1, - (B 2 -A 2) n -E 1 -D 2 -G 2 -Q 2 on the benzene ring The substitution position of is para or meta.

[In Formula (1-a) and Formula (1-b), X ₁ and X ₂ are each independently —CH═CH—, —CH═C (CH ₃ ) —, —C (CH ₃ ) = _{CH -, - C (CH 3} ) = C (CH 3) -, - CH = N -, - N = CH -, - N = C (CH 3) - or -C _(CH 3) = represents a N- .
Y ₁ and Y ₂ each independently represent a 6-18 membered aromatic hydrocarbon group or a 5-18 membered aromatic heterocyclic group. The hydrogen atom contained in the aromatic hydrocarbon group and the aromatic heterocyclic group may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom.
_{B 1,} B 2, _{G 1} and _{G 2} are each ^{independently, -CR 1 R 2 -, -} 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 -, - O-C (= S) -, - O-C (= S) -O -, - CR 1 = N -, - N = CR 1 -, - C (= O) —NR ¹ —, —NR ¹ —C (═O) —, —OCH ₂ —, —OCF ₂ —, —NR ¹ —, —CH ₂ O—, —CF ₂ O—, —SCH ₂ —, —CH ₂ S—, —CH═CH—C (═O) —O—, —O—C (═O) —CH═CH— or a single bond is represented. R ¹ and R ² each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
A ₁ and A ₂ each independently represents a 6-18 membered aromatic hydrocarbon group, a 5-18 membered alicyclic hydrocarbon group, or a 5-18 membered heterocyclic group. The hydrogen atom contained in the aromatic hydrocarbon group, the alicyclic hydrocarbon group and the heterocyclic group is substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a halogen atom. May be. m and n each independently represent an integer represented by 1 to 3.
E ₁ and _{E 2,} each ^{independently, -CR 3 R 4 -, -} 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 -, - O-C ( = S) -, - O-C (= S) -O -, - CR 3 = N -, - N = CR 3 -, - C (= O) -NR 3 - , —NR ³ —C (═O) —, —OCH ₂ —, —OCF ₂ —, —NR ³ —, —CH ₂ O—, —CF ₂ O—, —SCH ₂ —, —CH ₂ S—, —CH═CH—C (═O) —O—, —O—C (═O) —CH═CH—, or a single bond is represented. R ³ and R ⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
D ₁ and D ₂ each independently represent an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom contained in D ₁ and D ₂ is an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. It may be substituted with a group or a halogen atom.
Q ₁ and Q ₂ are a hydrogen atom or a group selected from the group consisting of groups represented by formula (Q-1) to formula (Q-5).

(In Formula (Q-1) to Formula (Q-5), R ^{5 to} R ⁹ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)]

（Ａ_１、Ａ_２、Ｂ_１、Ｂ_２、Ｅ_１、Ｅ_２、Ｄ_１、Ｄ_２、Ｇ_１、Ｇ_２、Ｑ_１、Ｑ_２、Ｘ_１、Ｘ_２、Ｙ_１、Ｙ_２、ｍおよびｎは、上記と同じ意味を表す。） In the present invention, the polymerizable compound represented by the formula (1-a) or the formula (1-b) is a compound represented by the formula (1-a-1) or the formula (1-b-1). It is a certain polymerizable compound.

_{(A 1, A 2, B} 1, B 2, E 1, E 2, D 1, D 2, G 1, G 2, Q 1, Q 2, X 1, X 2, Y 1, Y 2, m And n represent the same meaning as described above.)

The present invention is the above polymerizable compound, wherein X ₁ and X ₂ are each independently —CH═CH—, —CH═N— or —N═CH—.

The present invention, at least one of Q ₁ and Q _2, is the above polymerizable compound is a radical selected from the group consisting of groups represented by the formula (Q-1) ~ formula (Q-5).

The present invention, _-G 1 -Q ₁ and _-G 2 -Q ₂ is a the polymerizable compound is an acryloyl group or a methacryloyl group.

  Moreover, this invention is a composition containing the said polymeric compound and liquid crystal compounds (2) other than this polymeric compound.

In the present invention, the liquid crystal compound (2) other than the polymerizable compound is a compound represented by the formula (I), the formula (II), the formula (III), the formula (IV) or the formula (V). It is a composition.
P11-E11-B11-A11-B12-A12-B13-A13-B14-A14-B15-A15-B16-E12-P12 (I)
P11-E11-B11-A11-B12-A12-B13-A13-B14-A14-B15-E12-P12 (II)
P11-E11-B11-A11-B12-A12-B13-A13-B14-E12-P12 (III)
P11-E11-B11-A11-B12-A12-B13-A13-B14-F11 (IV)
P11-E11-B11-A11-B12-A12-B13-F11 (V)
(In the formulas (I) to (V), A11, A12, A13, A14, and A15 are each independently an aromatic hydrocarbon group, an alicyclic hydrocarbon group, a heterocyclic group, a fluorenyl group, or thiophenylene. A11 to A15 may be bonded to an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a nitrile group, a phenyl group, a dimethylamino group, or a halogen atom. .)
B11, B12, B13, B14, B15 and B16 are each _{independently, -CR 10 R 11 -, -} 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 -, - O-C (= S) -, - CH = N -, - N = CH -, - N = N -, - C (= O) -NR 10 -, - NR ₁₀ —C (═O) —, —OCH ₂ —, —OCF ₂ —, —NR ₁₀ —, —CH ₂ O—, —CF ₂ O—, —CH═CH—C (═O) —O— , -OC (= O) -CH = CH- or a single bond. R ₁₀ and R ₁₁ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms, and may be an alkylene group having 4 to 7 carbon atoms linked to R ₁₀ and R ₁₁ .
E11 and E12 each independently 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.
P11 and P12 each independently represents an acryloyloxy group, a methacryloyloxy group, or a vinyloxy group.
F11 represents a hydrogen atom, an alkyl group having 1 to 13 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, a nitrile group, a nitro group, a trifluoromethyl group, a dimethylamino group, or a halogen atom. )

  Moreover, this invention is an optical film containing the structural unit derived from the said polymeric compound.

  Moreover, this invention is an optical film formed by superposing | polymerizing the said composition.

  Moreover, this invention consists of said optical film, and is a (lambda) / 4 board whose phase difference value (Re (550)) in wavelength 550nm is 113-163 nm.

  Moreover, this invention consists of the said optical film, and is a (lambda) / 2 board whose retardation value (Re (550)) in wavelength 550nm is 250-300 nm.

  Moreover, this invention is a polarizing plate containing the said optical film and a polarizing film.

  Moreover, this invention is a liquid crystal display device provided with the said polarizing plate and a liquid crystal panel.

  Moreover, this invention is an organic electroluminescent display apparatus provided with the organic electroluminescent panel containing the said polarizing plate.

  Moreover, this invention is a manufacturing method of the unpolymerized film which apply | coats the solution containing the said polymeric compound to a support base material, and is dried.

  Moreover, this invention is a manufacturing method of the unpolymerized film which apply | coats the solution containing the said polymeric compound on the orientation film | membrane formed on the support base material, and dries.

  Moreover, this invention is a manufacturing method of the optical film which hardens | cures the unpolymerized film obtained by the manufacturing method of the said unpolymerized film by superposition | polymerization.

  According to the polymerizable compound of the present invention, an optical film having a large Δn can be produced.

中心ベンゼン環を介して−（Ｂ_１−Ａ_１）_ｍ−Ｅ_１−Ｄ_１−Ｇ_１−Ｑ_１および−（Ｂ_２−Ａ_２）_ｎ−Ｅ_１−Ｄ_２−Ｇ_２−Ｑ_２はできるだけ直線性を示した方が、分子配向が容易となるため、−（Ｂ_１−Ａ_１）_ｍ−Ｅ_１−Ｄ_１−Ｇ_１−Ｑ_１に対する、−（Ｂ_２−Ａ_２）_ｎ−Ｅ_１−Ｄ_２−Ｇ_２−Ｑ_２のベンゼン環への置換位置は、パラ位またはメタ位である。 The polymerizable compound of the present invention (hereinafter sometimes referred to as “polymerizable compound (1)”) is represented by formula (1-a) or formula (1-b).

Through the central benzene ring _{- (B 1 -A 1) m} -E 1 -D 1 -G 1 -Q 1 and _{- (B 2 -A 2) n} -E 1 -D 2 -G 2 -Q 2 is who possible show the linearity, the molecular orientation is _facilitated, - for _{(B 1 -A 1) m -E} 1 -D 1 -G 1 -Q 1, - (B 2 -A 2) n - The substitution position of E ₁ -D ₂ -G ₂ -Q _{2 on} the benzene ring is the para position or the meta position.

中心ベンゼン環を介して−（Ｂ_１−Ａ_１）_ｍ−Ｅ_１−Ｄ_１−Ｇ_１−Ｑ_１および−（Ｂ_２−Ａ_２）_ｎ−Ｅ_１−Ｄ_２−Ｇ_２−Ｑ_２はできるだけ直線性を示した方が、分子配向が容易となるため、−（Ｂ_１−Ａ_１）_ｍ−Ｅ_１−Ｄ_１−Ｇ_１−Ｑ_１に対する、−（Ｂ_２−Ａ_２）_ｎ−Ｅ_１−Ｄ_２−Ｇ_２−Ｑ_２のベンゼン環への置換位置は、パラ位であることが好ましい。 Among these, the polymerizable compound (1) is preferably represented by the formula (1-a-1) or the formula (1-b-1).

Through the central benzene ring _{- (B 1 -A 1) m} -E 1 -D 1 -G 1 -Q 1 and _{- (B 2 -A 2) n} -E 1 -D 2 -G 2 -Q 2 is who possible show the linearity, the molecular orientation is _facilitated, - for _{(B 1 -A 1) m -E} 1 -D 1 -G 1 -Q 1, - (B 2 -A 2) n - The substitution position of E ₁ -D ₂ -G ₂ -Q _{2 on} the benzene ring is preferably the para position.

In formula (1-a) and formula (1-b), X ₁ and X ₂ are each independently —CH═CH—, —CH═C (CH ₃ ) —, —C (CH ₃ ) ═CH _{-, - C (CH 3)} = C (CH 3) -, - CH = N -, - N = CH -, - N = C (CH 3) - or -C _(CH 3) = represents a N-.
These X ₁ and X ₂ can be easily produced by a Wittig reaction between the corresponding aldehyde and benzyltriphenylphosphine bromide (or chloride), or a Schiff base formation reaction between the corresponding aldehyde (or ketone) and an amine.
In view of relatively easy availability of raw materials, X ₁ and X ₂ are preferably each independently —CH═CH—, —CH═N— or —N═CH—.

Y ₁ and Y ₂ each independently represent a 6-18 membered aromatic hydrocarbon group or a 5-18 membered aromatic heterocyclic group.
The aromatic hydrocarbon group and aromatic heterocyclic group have an aromatic hydrocarbon group or aromatic heterocyclic group in the molecule, and these may be monocyclic or condensed. Examples of Y ₁ and Y ₂ include groups represented by the following formulas.

Moreover, the hydrogen atom contained in this aromatic hydrocarbon group and this aromatic heterocyclic group may be substituted by a C1-C4 alkyl group, a C1-C4 alkoxy group, or a halogen atom.
Specific examples of the substituent include, for example, an alkyl group having about 1 to 4 carbon atoms such as a methyl group, an ethyl group, an i-propyl group or a t-butyl group; an about 1 to 4 carbon atoms such as a methoxy group or an ethoxy group. Examples include alkoxy groups; trifluoromethyl groups; trifluoromethyloxy groups; nitrile groups; nitro groups; halogen atoms such as fluorine atoms, chlorine atoms, or bromine atoms.
Further, examples of Y ₁ and Y ₂ include groups listed in the following formulae.

_{B 1,} B 2, _{G 1} and _{G 2} are each ^{independently, -CR 1 R 2 -, -} 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 -, - O-C (= S) -, - O-C (= S) -O -, - CR 1 = N -, - N = CR 1 -, - C (= O) —NR ¹ —, —NR ¹ —C (═O) —, —OCH ₂ —, —OCF ₂ —, —NR ¹ —, —CH ₂ O—, —CF ₂ O—, —SCH ₂ —, —CH ₂ S—, —CH═CH—C (═O) —O—, —O—C (═O) —CH═CH— or a single bond is represented. R ¹ and R ² each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
B ₁ and B ₂ , and G ₁ and G ₂ are preferably the same type of group because of easy production.
B ₁ , B ₂ , G ₁ and G ₂ are, among others, from the viewpoint of ease of production of the polymerizable compound (1), —C (═O) —, —C (═O) —O—, —O It is preferable that -C (= O)-, -OC (= O) -O-, -CR = N-, or -N = CR-. According to these, since the liquid crystallinity is further improved, the molecular alignment is further facilitated.

A ₁ and A ₂ each independently represents a 6-18 membered aromatic hydrocarbon group, a 5-18 membered alicyclic hydrocarbon group, or a 5-18 membered heterocyclic group.
As A ₁ and A ₂ , a divalent aromatic hydrocarbon group represented by the following formula,

A divalent alicyclic hydrocarbon group represented by the following formula,

該芳香族炭化水素基、該脂環式炭化水素基および該複素環基に含まれる水素原子は、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基またはハロゲン原子に置換されていてもよい。
置換基の具体例としては、たとえばメチル基、エチル基、ｉ−プロピル基またはｔ−ブチル基などの炭素数１〜４程度のアルキル基；メトキシ基またはエトキシ基などの炭素数１〜４程度のアルコキシ基；トリフルオロメチル基；トリフルオロメチルオキシ基；ニトリル基；ニトロ基；フッ素原子、塩素原子または臭素原子などのハロゲン原子などが挙げられる。 Examples thereof include a divalent heterocyclic group represented by the following formula.

The hydrogen atom contained in the aromatic hydrocarbon group, the alicyclic hydrocarbon group and the heterocyclic group is substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a halogen atom. May be.
Specific examples of the substituent include, for example, an alkyl group having about 1 to 4 carbon atoms such as a methyl group, an ethyl group, an i-propyl group or a t-butyl group; an about 1 to 4 carbon atoms such as a methoxy group or an ethoxy group. Examples include alkoxy groups; trifluoromethyl groups; trifluoromethyloxy groups; nitrile groups; nitro groups; halogen atoms such as fluorine atoms, chlorine atoms, or bromine atoms.

Among them, it is preferable that A ₁ and A ₂ are the same type of group because production is easy. In particular, as A ₁ and A ₂ , a 1,4-phenylene group, a 1,4-cyclohexylene group, or a 3-methyl-1,4-phenylene group is preferable because of easy production.

  m and n are each independently an integer represented by 1 to 3. From the viewpoint of improving the orientation of the resulting polymerizable compound (1), m and n are preferably 2 or 3.

E ₁ and _{E 2,} each ^{independently, -CR 3 R 4 -, -} 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 -, - O-C ( = S) -, - O-C (= S) -O -, - CR 3 = N -, - N = CR 3 -, - C (= O) -NR 3 - , —NR ³ —C (═O) —, —OCH ₂ —, —OCF ₂ —, —NR ³ —, —CH ₂ O—, —CF ₂ O—, —SCH ₂ —, —CH ₂ S—, —CH═CH—C (═O) —O—, —O—C (═O) —CH═CH—, or a single bond is represented. R ³ and R ⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
D ₁ and D ₂ each independently represent an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom contained in D ₁ and D ₂ is an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. It may be substituted with a group or a halogen atom.

式（Ｑ−１）〜式（Ｑ−５）中、Ｒ^５〜Ｒ^９はそれぞれ独立に、水素原子または炭素数１〜４のアルキル基を表す。
Ｑ_１およびＱ_２の少なくとも一方が、式（Ｑ−１）〜式（Ｑ−５）で表される基からなる群から選ばれる基であると、得られる光学フィルムの膜硬度が優れる傾向があることから好ましい。Ｑ_１およびＱ_２がいずれも式（Ｑ−１）〜式（Ｑ−５）で表される基であると、さらに好ましい。
−Ｇ_１−Ｑ_１および−Ｇ_２−Ｑ_２は、本発明の重合性化合物（１）を重合させることのできる置換基であり、具体的にはビニル基、ｐ−スチルベン基、アクリロイル基、メタクロイル基、カルボキシル基、メチルカルボニル基、水酸基、アミド基、炭素数１〜４のアルキルアミノ基、アミノ基、エポキシ基、オキセタニル基、アルデヒド基、イソシアネート基またはチオイソシアネート基などが例示される。
中でも光重合させる際の取り扱いが容易な上、製造も容易であることからアクリロイル基またはメタクロイル基が好ましく、特にアクリロイル基が好ましい。
本発明の光学フィルムにおいて、異なる複数の種類の重合性化合物（１）を用いてもよい。 Q ₁ and Q ₂ are a hydrogen atom or a group selected from the group consisting of groups represented by formula (Q-1) to formula (Q-5).

In formula (Q-1) to formula (Q-5), R ^{5 to} R ⁹ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
When at least one of Q ₁ and Q ₂ is a group selected from the group consisting of groups represented by formula (Q-1) to formula (Q-5), the film hardness of the resulting optical film tends to be excellent. This is preferable. It is further preferred that Q ₁ and Q ₂ are groups represented by formula (Q-1) to formula (Q-5).
-G ₁ -Q ₁ and -G ₂ -Q ₂ are substituents capable of polymerizing the polymerizable compound (1) of the present invention, specifically, vinyl group, p-stilbene group, acryloyl group, Examples include methacryloyl group, 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 or thioisocyanate group.
Among them, an acryloyl group or a methacryloyl group is preferable because it is easy to handle during photopolymerization and easy to produce, and an acryloyl group is particularly preferable.
In the optical film of the present invention, a plurality of different types of polymerizable compounds (1) may be used.

As a method for producing the polymerizable compound (1), in addition to the Wittig reaction and the Schiff base production reaction,-(B ₁ -A ₁ ) _m -E ₁ -D ₁ -G ₁ -Q ₁ is added to the central benzene ring. And-(B ₂ -A ₂ ) _n -E ₂ -D ₂ -G ₂ -Q ₂ structural units are condensed, esterified, Williamson reaction, Ullmann reaction, benzylation reaction, Sonogashira It can be produced by bonding by reaction, Suzuki-Miyaura reaction, Negishi reaction, Kumada reaction, Kashiyama reaction, Buchwald-Heart wig reaction, Friedel-Craft reaction, Heck reaction or aldol reaction. Examples of synthetic methods include Houben Wyle (Methoden der Organischen Chemie, Georg Thieme Verlag, Stuttgart), Organic Reactions (Organic Reactions, John Wily & Sons Inc.), Organic Syntheses (Johnson). Synthesize by combining organic synthesis methods described in Wily & Sons Inc., Comprehensive Organic Synthesis, Pergamon Press, New Experimental Chemistry Course (Maruzen), etc. Can do.
A polymerizable compound (1) is synthesized by a condensation reaction between a dihydroxy compound having X ₁ -Y ₁ and HOOC-A _1- (B ₁ -A ₁ ) _m-1- E ₁ -D ₁ -G ₁ -Q _1. can do. In the condensation reaction, for example, a method using an esterifying agent such as DCC, HOOC-A _1- (B ₁ -A ₁ ) _m-1- E ₁ -D ₁ -G ₁ -Q ₁ is converted to acid chloride or There is a method of performing a condensation reaction with a dihydroxy compound after mesitylation.

  The polymerizable compound (1) of the present invention has a large Δn, is easily soluble in general-purpose organic solvents and has good coating properties, and is an antireflection film such as an antireflection (AR) film, a polarizing film, and a retardation film. An optical film having excellent optical properties such as an elliptically polarizing film and a viewing angle widening film is provided by a simple method. The optical film of the present invention can be used in flat panel display devices (FPD) such as liquid crystal display devices (LCD) and organic electroluminescence (EL).

  The composition of the present invention comprises a polymerizable compound (1), a polymerizable compound different from the polymerizable compound (1) and exhibiting liquid crystallinity (hereinafter sometimes referred to as “liquid crystal compound (2)”). Containing. When the liquid crystal compound (2) is contained, the orientation of the optical film obtained by polymerizing the composition is increased, and the retardation value tends to increase, which is preferable.

Specific examples of the liquid crystal compound (2) include the liquid crystal handbook (edited by the Liquid Crystal Handbook Editorial Committee, published by Maruzen Co., Ltd., October 30, 2000). Among the compounds described in Molecule, 3.3 Chiral rod-like liquid crystal molecule, there are compounds having a polymerizable group.
A plurality of different types of liquid crystal compounds (2) may be used in combination as the liquid crystal compound (2).

Examples of the liquid crystal compound (2) include compounds represented by the formula (I), the formula (II), the formula (III), the formula (IV), or the formula (V).
P11-E11-B11-A11-B12-A12-B13-A13-B14-A14-B15-A15-B16-E12-P12 (I)
P11-E11-B11-A11-B12-A12-B13-A13-B14-A14-B15-E12-P12 (II)
P11-E11-B11-A11-B12-A12-B13-A13-B14-E12-P12 (III)
P11-E11-B11-A11-B12-A12-B13-A13-B14-F11 (IV)
P11-E11-B11-A11-B12-A12-B13-F11 (V)
In formulas (I) to (V), A11, A12, A13, A14, and A15 are each independently an aromatic hydrocarbon group, an alicyclic hydrocarbon group, a heterocyclic group, a fluorenyl group, or a thiophenylene group. Represents. A11 to A15 may be bonded to an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a nitrile group, a phenyl group, a dimethylamino group, or a halogen atom.
B11, B12, B13, B14, B15 and B16 are each _{independently, -CR 10 R 11 -, -} 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 -, - O-C (= S) -, - CH = N -, - N = CH -, - N = N -, - C (= O) -NR 10 -, - NR ₁₀ —C (═O) —, —OCH ₂ —, —OCF ₂ —, —NR ₁₀ —, —CH ₂ O—, —CF ₂ O—, —CH═CH—C (═O) —O— , -OC (= O) -CH = CH- or a single bond. R ₁₀ and R ₁₁ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms, and may be an alkylene group having 4 to 7 carbon atoms linked to R ₁₀ and R ₁₁ .
E11 and E12 each independently 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.
P11 and P12 each independently represent a polymerizable group such as an acryloyloxy group, a methacryloyloxy group, or a vinyloxy group.
F11 represents a hydrogen atom, an alkyl group having 1 to 13 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, a nitrile group, a nitro group, a trifluoromethyl group, a dimethylamino group, or a halogen atom.

Specific examples of the liquid crystal compound (2) include, for example, the following formulas (I-1) to (I-5), (II-1) to (I-6), (III-1) to (III-19). , (IV-1) to (IV-14), and compounds represented by (V-1) to (V-5). However, in the formula, k independently represents an integer represented by 1 to 11.

The optical film of the present invention contains a structural unit derived from the polymerizable compound (1). Although it may contain only a structural unit derived from the polymerizable compound (1), it may further contain a structural unit derived from the liquid crystal compound (2). Including a structural unit derived from the liquid crystal compound (2) is preferred because the orientation is increased and the retardation value tends to increase.
At this time, the polymerizable group of -G ₁ -Q ₁ or -G ₂ -Q ₂ contained in the polymerizable compound (1) is copolymerized with the polymerizable compound (1) and the liquid crystal compound (2). The polymerizable group of the liquid crystal compound (2) is a polymerizable group capable of reacting with each other, and particularly preferably an acryloyl group with each other because it can be easily photopolymerized.
Moreover, Δn of the obtained optical film is controlled by changing the content of the structural unit derived from the polymerizable compound (1) contained in the optical film and the content of the structural unit derived from the liquid crystal compound (2). Can do. That is, even if the liquid crystal compound (2) has a small Δn, the Δn of the obtained optical film can be increased by adding the polymerizable compound (1).
These liquid crystal compounds are preferred because they are easy to synthesize and are commercially available.

<Method for producing optical film>
A method for producing an optical film containing the structural unit derived from the polymerizable compound (1) of the present invention and the structural unit derived from the liquid crystal compound (2) will be described below.
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.

[Mixed solution adjustment process]
First, an additive such as a polymerization initiator, a polymerization inhibitor, a photosensitizer, a leveling agent, or a crosslinking agent is added to the polymerizable compound (1), the liquid crystal compound (2), and the organic solvent as necessary. Prepare the solution. In particular, the organic solvent is preferably contained at the time of film formation because the film formation becomes easy, and the polymerization initiator is preferable because it has a function of curing the obtained optical film.

(Polymerization initiator)
In preparing the optical film of the present invention, a polymerization initiator for polymerizing the polymerizable compound (1) and the liquid crystal compound (2) is generally used. A preferred embodiment of the method for producing an optical film of the present invention includes a method of photopolymerizing the polymerizable compound (1) and the liquid crystal compound (2). Therefore, the polymerization initiator is preferably a photopolymerization initiator.
Examples of the photopolymerization 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 250, IRGACURE 369 (all manufactured by Ciba Specialty Chemicals Co., Ltd.), SEIKO ALL BZ, SEIKO ALL Z, SEIKO ALL BEE (all manufactured by Seiko Chemical Co., Ltd.), kayacure BP100 ( Nippon Kayaku Co., Ltd.), Kayacure UVI-6992 (Dow), Adekaoptomer SP-152 or Adekaoptomer SP-170 (all asahi Denka Kogyo Co., Ltd.).
The amount of the polymerization initiator used is, for example, 0.1 to 30 parts by weight, preferably 0.5 parts by weight with respect to a total of 100 parts by weight of the polymerizable compound (1) and the liquid crystal compound (2). -10 parts by weight. Within the above range, the polymerizable compound (1) can be polymerized without disturbing the orientation of the liquid crystal compound (2).

(Polymerization inhibitor)
In preparing the optical film of the present invention, a polymerization inhibitor may be used. Examples of the polymerization inhibitor include hydroquinones having a substituent such as hydroquinone or alkyl ether, catechols having a substituent such as alkyl ether such as butylcatechol, pyrogallols, 2,2,6,6-tetramethyl-1 -Radical scavengers such as piperidinyloxy radicals, thiophenols, β-naphthylamines, β-naphthols and the like.
By using a polymerization inhibitor, the polymerization of the polymerizable compound (1) and the liquid crystal compound (2) 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 parts by weight based on 100 parts by weight of the total of the polymerizable compound (1) and the liquid crystal compound (2). -10 parts by weight. Within the above range, the polymerizable compound (1) can be polymerized without disturbing the orientation of the liquid crystal compound (2).

[Photosensitizer]
Moreover, when preparing the optical film of this invention, you may use a photosensitizer. Examples of the photosensitizer include xanthone such as xanthone or thioxanthone, anthracene having a substituent such as anthracene or alkyl ether, phenothiazine, or rubrene.
By using a photosensitizer, the polymerization of the polymerizable compound (1) and the liquid crystal compound (2) can be made highly sensitive. The amount of the photosensitizer used is, for example, 0.1 to 30 parts by weight, preferably 0.5 to 100 parts by weight in total of the polymerizable compound (1) and the liquid crystal compound (2). Parts by weight to 10 parts by weight. Within the above range, the polymerizable compound (1) can be polymerized without disturbing the orientation of the liquid crystal compound (2).

(Leveling agent)
Furthermore, a leveling agent may be used when preparing the optical film of the present invention. As the leveling agent, various compounds such as silicone-based, fluorine-based, polyether-based, acrylic acid copolymer-based or titanate-based compounds can be used. For example, an additive for radiation curable coatings (by BYK Japan: BYK- 352, BYK-353, BYK-361N), paint additive (Toray Dow Corning Co., Ltd .: SH28PA, DC11PA, ST80PA), or paint additive (Shin-Etsu Chemical Co., Ltd .: KP321, KP323, X22-161A, KF6001).
By using a leveling agent, the optical film can be smoothed. Furthermore, the crosslink density of the optical film obtained by controlling the fluidity of the mixed solution containing the polymerizable compound (1) or polymerizing the polymerizable compound (1) and the liquid crystal compound (2) during the production process of the optical film. Can be adjusted. Moreover, the specific numerical value of 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 polymeric compound (1) and liquid crystal compound (2), for example, Preferably it is 0. .5 to 10 parts by weight. Within the above range, the polymerizable compound (1) can be polymerized without disturbing the orientation of the liquid crystal compound (2).

[Organic solvent]
The organic solvent used for the preparation of the mixed solution containing the polymerizable compound (1) and the liquid crystal compound (2) is an organic solvent capable of dissolving the polymerizable compound (1) and the liquid crystal compound (2). Specifically, alcohols such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol or methyl cellosolve or butyl cellosolve; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, gamma-butyrolactone or propylene glycol methyl ether acetate; Ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone, methyl isobutyl ketone or N-methyl-2-pyrrolidone; pentane, hexane Or an aliphatic hydrocarbon solvent such as heptane; an aromatic hydrocarbon solvent such as toluene, xylene, chlorobenzene, methoxybenzene or 1,2-dimethoxybenzene; an ether solvent such as tetrahydrofuran, 1,4-dioxane or dimethoxyethane; Examples thereof include phenol, acetonitrile, butyronitrile, propylene glycol monomethyl ether, N, N-dimethylacetamide, ethyl lactate, and chloroform. These organic solvents may be used alone or in combination. Among them, the composition of the present invention is excellent in compatibility and can be dissolved in alcohols, ester solvents, ketone solvents, non-chlorine aliphatic hydrocarbon solvents, non-chlorine aromatic hydrocarbon solvents, etc., such as chloroform. Even if the halogenated hydrocarbon is not used, it can be dissolved and applied.

The viscosity of the mixed solution containing the polymerizable compound (1) and the liquid crystal compound (2) is adjusted to, for example, 10 Pa · s or less, preferably about 0.1 to 7 Pa · s so as to be easily applied.
Moreover, the density | concentration of the solid content in the said mixed solution is 5 to 50 weight%, for example. When the solid content is 5% or more, the optical film does not become too thin, and the optical anisotropy necessary for optical compensation of the liquid crystal panel tends to be provided. Moreover, since the viscosity of the said mixed solution 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.

[Alignment film forming step]
The support base material should just be what can form an oriented film on this support base material. For example, glass, a plastic sheet, a plastic film, or a translucent film can be mentioned. Examples of the translucent film include polyolefin films such as polyethylene, polypropylene and norbornene polymers, polyvinyl alcohol films, polyethylene terephthalate films, polymethacrylate films, polyacrylate films, cellulose ester films, and polyethylene naphthalate films. Polycarbonate film, polysulfone film, polyethersulfone film, polyetherketone film, polyphenylene sulfide film or polyphenylene oxide film.
In general, the optical film obtained from the polymerizable compound (1) and the liquid crystal compound (2) is a thin film. For example, the strength of the film such as a bonding process using the film of the present invention, a process of transporting and storing the film, etc. Can be handled easily without tearing by using a supporting substrate.

In the method for producing an optical film of the present invention, preferably, after forming an alignment film on a support substrate, the mixed solution is applied. The alignment film has a solvent resistance that does not dissolve by application of a mixed solution containing the polymerizable compound (1), etc., has heat resistance due to solvent removal or heat treatment of liquid crystal alignment, friction due to rubbing, etc. It is necessary to prevent peeling due to, and the like, and it is a polymer or a composition containing 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, and the hydrolyzate thereof. Mention may be made of polymers such as polyethyleneimine, polyacrylic acid or polyacrylates. These polymers may be used alone, in combination of two or more, or may be used after copolymerization. These polymers can be easily obtained by polycondensation such as dehydration and deamination, chain polymerization such as radical polymerization, anion polymerization, and cation polymerization, coordination polymerization, and ring-opening polymerization.

  These alignment film materials can be applied after being dissolved in a solvent. The solvent is not particularly limited, and specifically, water; alcohol such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl cellosolve or butyl cellosolve; ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, gamma Ester solvents such as butyrolactone or propylene glycol methyl ether acetate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone or methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane or heptane; toluene , Aromatic hydrocarbon solvents such as xylene or chlorobenzene, acetonitrile, propylene glycol monomethyl ether, tetra Dorofuran, dimethoxyethane, and the like ethyl lactate or chloroform. These organic solvents may be used alone or in combination.

As the alignment film, a commercially available alignment film may be used as it is. Examples of the commercially available alignment film include Sanever (registered trademark, manufactured by Nissan Chemical Industries, Ltd.) or Optmer (registered trademark, manufactured by JSR Corporation), etc., as a modified polyimide subjected to polarized UV treatment. Examples of the alcohol include Poval (registered trademark, manufactured by Kuraray Co., Ltd.).
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, there is an effect that it is possible to provide a large optical film that can cope with an increase in the size of the FPD on the support substrate.

As a method for forming an alignment film on the support substrate, for example, an alignment film is formed on the support substrate by applying an alignment film material on the support substrate and then annealing. it can.
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, or a spin coater, etc. are mentioned.

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 polymeric compound (1), a liquid crystal compound, etc. can be aligned at a desired angle on the said alignment film.
Further, these alignment films can be rubbed or irradiated with polarized UV rays as necessary. By these, the polymerizable compound (1), the liquid crystal compound (2) and the like can be aligned 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.

[Unpolymerized film preparation process]
If an alignment film is formed on the support substrate, an unpolymerized film is obtained by applying a mixed solution containing the polymerizable compound (1) and the liquid crystal compound (2) onto the alignment film and drying. . When this unpolymerized film exhibits a liquid crystal phase such as a nematic phase, it has birefringence due to monodomain alignment. Since this 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, After orientation, even if it is further cooled to about 30 to 10 ° C., it does not crystallize.
Examples of the coating method on the alignment film include an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a CAP coating method, and a die coating method. Moreover, the method of apply | coating using coaters, such as a dip coater, a bar coater, or a spin coater, etc. are mentioned.

[Unpolymerized film drying process]
In the case of photopolymerization, in order to improve the film formability, it is preferable to dry the solvent before photopolymerization to obtain an unpolymerized film. In the case of thermal polymerization, polymerization may proceed with drying, but a method of obtaining a non-polymerized film by drying the solvent prior to polymerization is preferred because it tends to be excellent in film formability.
Examples of the solvent drying method include natural drying, ventilation drying, and reduced pressure 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. Thus, a film in which the orientation of the polymerizable compound (1) and the liquid crystal compound (2) 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 to irradiate light such as visible light, ultraviolet light or laser light if the polymerizable group contained in the polymerizable compound (1) and the liquid crystal compound (2) is photopolymerizable. When cured, if the polymerizable group is thermally polymerizable, it is polymerized by heating. In the present invention, it is particularly preferable to polymerize an unpolymerized film by photopolymerization. According to this, since the unpolymerized film can be polymerized at a low temperature, the selection range of the heat resistance of the supporting substrate is expanded. In addition, it is easy to manufacture industrially. From the viewpoint of handleability, polymerization with ultraviolet light is particularly preferable.
The optical film thus obtained can be produced without using a liquid crystal polymer.

In the unpolymerized film polymerization step, the polymerizable compound (1) and the liquid crystal compound can be crosslinked by photopolymerization. Therefore, there is an effect that it is not easily affected by the change in birefringence due to heat.
Moreover, it is not necessary to use surface treating agents, such as surfactant, for the obtained optical film. That is, since the alignment film used for the optical film of the present invention has good adhesion between the supporting substrate and the alignment film and adhesion between the alignment film and the optical film, the production of the optical film is easy.
Furthermore, the optical film of the present invention is a thin film as compared with a stretched film having an equivalent retardation value.

  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 film obtained becomes a film which consists of an oriented film and an optically anisotropic layer. 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, the film obtained becomes a film which consists only of an optically anisotropic layer.

The film thickness can be adjusted to give a desired phase difference by appropriately adjusting the amount of the coating solution of the mixed solution and the concentration of the coating solution. In the case of a mixed solution in which the polymerizable compound (1) is constant, the retardation value (retardation value, Re (λ)) of the obtained optical film is determined as shown in Equation (3). In order to obtain (λ), the film thickness d may be adjusted.
Re (λ) = d × Δn (λ) (3)
(In formula (3), Re (λ) represents a retardation value at a wavelength λnm, d represents a film thickness, and Δn (λ) represents a refractive index anisotropy at a wavelength λnm.)

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 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.
As described above, in the unpolymerized film preparation step, the unpolymerized film (liquid crystal layer) is laminated on the alignment film laminated on an arbitrary 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 roll film.
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 an optical film which is a thin film and exhibits reverse wavelength dispersion characteristics 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, by appropriately selecting the content of the structural unit derived from the polymerizable compound (1), according to the formula (3), When the retardation value is 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 the case of a λ / 2 plate, the film thickness may be adjusted so that the 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 polymerizable compound (1) is appropriately selected according to the formula (3). What is necessary is just to adjust a film thickness so that the retardation value of the optical film obtained may be Re (550), Preferably it is 40-100 nm, More preferably, it is about 60-80 nm.

The optical film of the present invention can be widely used with an optical film having excellent optical properties. Examples of the optical film include 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, or an optical compensation film for compensating a viewing angle of a transmissive liquid crystal display. be able to. Moreover, although the optical film of the invention shows excellent optical characteristics even with one sheet, a plurality of sheets may be laminated.
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.
Furthermore, the film concerning this invention can be utilized also for FPD provided with the phase difference plate of a reflection type liquid crystal display and an organic EL display, and the said phase difference plate and the said 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 an optical film and a polarizing film according to the present invention and a flat panel display device including the polarizing plate will be described below. A polarizing plate according to the present invention is a film having a polarizing function, that is, polarizing It is obtained by laminating the optical film directly on one side or both sides of the film or using an adhesive or a pressure-sensitive adhesive. In the following description of FIGS. 1 to 3, the adhesive and the pressure-sensitive adhesive may be collectively referred to as an adhesive.

Fig.1 (a)-FIG.1 (e) are schematic which shows the polarizing plate 1 which concerns on this invention.
In the polarizing plate 1a shown in FIG. 1A, an optical film 2 and a polarizing film 3 are directly bonded, and the optical film 1a is composed of a support substrate 4, an alignment film 5, and an optically anisotropic layer 6. . The optical film 1 a is laminated in the order of the support substrate 4, the alignment film 5, the optical anisotropic layer 6, and the polarizing film 3.
In the polarizing plate 1 b shown in FIG. 1B, the optical film 2 and the polarizing film 3 are bonded together with an adhesive layer 7 interposed therebetween.
In the polarizing plate 1c shown in FIG. 1C, the optical film 2 and the optical film 2 ′ are directly bonded, and the optical film 2 ′ and the polarizing film 3 are directly bonded.
In the polarizing plate 1d shown in FIG. 1 (d), the optical film 2 and the optical film 2 ′ are bonded via the adhesive layer 7, and the polarizing film 3 is directly bonded on the optical film 2 ′.
In the polarizing plate 1e shown in FIG. 1 (e), the optical film 2 and the optical film 2 ′ are bonded via the adhesive layer 7, and the optical film 2 ′ and the polarizing film 3 are further bonded via the adhesive layer 7 ′. To show the configuration.

The polarizing plate of the present invention is a laminate of a polarizing film and the optical film of the present invention. Instead of the optical film 2 and the optical film 2 ′, only the optically anisotropic layer 6 containing the structural unit derived from the polymerizable compound (1), in which the supporting substrate 4 and the alignment film 5 are peeled off from the optical film 2, is used. The film which consists of the orientation film 5 and the optically anisotropic layer 6 which peeled the support base material 4 from the optical film 2 may be used.
The polarizing plate of the present invention may be formed by laminating a plurality of optical films, and the plurality of optical films may be the same or may be used in combination with different films described above.

The polarizing film 3 may be a film having a polarizing function. For example, a film obtained by stretching a polyvinyl alcohol film by adsorbing iodine or a dichroic dye, or a film obtained by stretching a polyvinyl alcohol film to obtain iodine or a dichroic dye. Examples include adsorbed films.
The adhesive used for the adhesive layer 7 and the adhesive layer 7 ′ 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. 2 is a schematic view showing a bonded product 10 between the liquid crystal panel 11 and the polarizing plate 1 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 10 of the liquid crystal panel 11 and the polarizing plate 1 as shown, for example in FIG. 2 is mentioned. The bonded product 10 is obtained by bonding the polarizing plate 1 of the present invention and the liquid crystal panel 11 through an adhesive layer 12. By applying a voltage to the liquid crystal panel 11 using an electrode (not shown), the liquid crystal molecules are driven to produce an optical shutter effect.

[Organic EL display device]
FIG. 3 is a schematic view showing an organic EL panel 13 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 13 shown in FIG. The organic EL panel 13 is formed by laminating the polarizing film 1 of the present invention and the light emitting layer 14 via an adhesive layer 15.
In the organic EL panel, the polarizing film 4 functions as a broadband circularly polarizing plate. The light emitting layer 7 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.
<Production Example of Polymerizable Compound (1-1)>
The polymerizable compound (1-1) was synthesized according to the following scheme.

(Synthesis example of ethyl 4- (6-hydroxyhexyloxy) benzoate (PG-a))
150 g (0.90 mol) of ethyl 4-hydroxybenzoate, 186 g (1.35 mol) of potassium carbonate and 750 g of N, N-dimethylacetamide were added, and the temperature was raised to 80 ° C. Subsequently, 244 g (1.24 mol) of 6-bromohexanol was added dropwise and then stirred at 80 ° C. After cooling, ethyl acetate was added, washed with water, and the solvent was distilled off to obtain 312 g of a white solid mainly composed of (PG-a).

(Synthesis example of 4- (6-hydroxyhexyloxy) benzoic acid (PG-b))
312 g of a white solid mainly composed of (PG-a) obtained in the previous item was dissolved in methanol. Subsequently, a methanol solution containing potassium hydroxide (potassium hydroxide 328 g (5.85 mol)) was added dropwise and stirred at about 70 ° C. After cooling, hydrochloric acid was added, and the precipitated white solid was washed with water, filtered, and dried under reduced pressure at 50 ° C. to obtain 195 g (0.82 mol) of a white solid mainly composed of (PG-b). The yield was 91% based on (PG-a).

(Synthesis example of 4- (6-acryloxyhexyloxy) benzoic acid (PG-c))
After replacing the inside of the container containing 195 g of white solid (PG2) (0.82 mol as (PG-b)) and 208 g of N, N-dimethylaniline obtained in the previous section with nitrogen, Dissolved with 4-dioxane. The temperature of the reaction solution was raised to 70 ° C., and 148 g (1.64 mol) of acrylic acid chloride was added dropwise and stirred. After cooling, ethyl acetate was added, washed with water, and the solvent was distilled off to obtain 120 g (0.41 mol) of a white solid mainly composed of (PG-c). The yield was 50% based on (PG-b).

(Synthesis example of 4-hydroxybenzoic acid ethoxymethyl ester (PG-d))
166 g (1.2 mol) of 4-hydroxybenzoic acid, 121 g (1.2 mol) of triethylamine and 1193 g of chloroform were placed in a container and stirred. At room temperature, a mixed solution of 113 g (1.2 mol) of chloromethyl ethyl ether and 298 g of chloroform was added dropwise and further stirred. After cooling, the reaction solution was washed with water, an aqueous hydrochloric acid solution and an aqueous sodium carbonate solution in this order, and the solvent was distilled off to obtain 251 g of a yellow liquid mainly composed of (PG-d).

(Synthesis example of 4- (4- (6-acryloyloxyhexyloxy) benzyloxy) benzoic acid (PG-e))
To 124 g of the yellow liquid mainly composed of (PG-d) obtained in the previous section, 147 g (0.50 mol) of white solid of (PG-c), 7.7 g (63 mmol) of 4-dimethylaminopyridine, and 824 g of chloroform were added. added. Subsequently, 123 g (0.60 mol) of N, N′-dicyclohexylcarbodiimide (DCC) was dissolved in 165 g of chloroform, added dropwise and stirred. Thereafter, the organic layer obtained by filtering to remove the solid was washed with hydrochloric acid, and the solvent was distilled off to obtain 237 g of a pale yellow liquid.
474 g of ethanol and 12.7 g (50 mmol) of paratoluenesulfonic acid pyridinium salt were added to the obtained liquid, and the mixture was stirred at 60 ° C. for 3 hours. The reaction solution was cooled to room temperature, the obtained crystal was filtered, the solid was washed with ethanol, and dried to obtain 180 g of (PG-e). The yield was 86% based on (PG-c).

(Synthesis example of (T-01))
In a container, 7.8 g (56.5 mmol) of 2,5-dihydroxybenzaldehyde, 24.5 g (56.5 mmol) of benzyltriphenylphosphine bromide, 1,8-diazabicyclo [5.4.0] -7-undecene8. 9 g (58.4 mmol) and 83 g of acetonitrile were mixed and stirred at reflux. After cooling, the solvent was distilled off, and the resulting solid was dissolved in chloroform, washed in turn with water and aqueous hydrochloric acid, the solvent was distilled off, and purification was performed by silica column chromatography to obtain 3.9 g of (T-01). Got. The yield was 32% based on 2,5-dihydroxybenzaldehyde.

(Synthesis example of polymerizable compound (1-1))
In a container, 1.91 g (9.0 mmol) of (T-01), 7.79 g (18.9 mmol) of 4- (4- (6-acryloyloxyhexyloxy) benzyloxy) benzoic acid (PG-e) 4-Dimethylaminopyridine (0.23 g, 1.9 mmol) and chloroform (249 g) were mixed, and N, N′-dicyclohexylcarbodiimide (DCC) (5.85 g, 28.4 mmol) was dissolved in chloroform (62 g). Added dropwise and stirred at room temperature. The precipitated solid was separated by filtration, washed with hydrochloric acid, the solvent was distilled off, and methanol was added to obtain a solid. The obtained solid was washed with methanol to obtain 7.54 g of a polymerizable compound (1-1) as a white solid. The yield was 85% based on (T-01).
The polymerizable compound (1-1) exhibited a transition from a crystal phase to a nematic liquid crystal phase at 118 ° C. and was thermally polymerized at 268 ° C.

<Production Example of Polymerizable Compound (1-2)>
The polymerizable compound (1-2) was synthesized according to the following scheme.

(Synthesis example of (T-02))
A solution prepared by dissolving 4.0 g (29.0 mmol) of 2,5-dihydroxybenzaldehyde in 20 g of ethanol and a solution prepared by dissolving 3.42 g (29.0 mmol) of 4-aminobenzonitrile in 27 g of ethanol were mixed and stirred. . The deposited precipitate was filtered and washed with ethanol to obtain 5.9 g of (T-02) as an orange solid. The yield was 58% based on 2,5-dihydroxybenzaldehyde.

(Synthesis example of polymerizable compound (1-2))
In a container, 3.10 g (13.0 mmol) of (T-02), 11.3 g (27.3 mmol) of 4- (4- (6-acryloyloxyhexyloxy) benzyloxy) benzoic acid (PG-e) , 4-dimethylaminopyridine (0.33 g, 2.73 mmol) and chloroform (360 g) were mixed, and N, N′-dicyclohexylcarbodiimide (DCC) (5.63 g, 27.3 mmol) was dissolved in chloroform (90 g). The solution was added dropwise and stirred at room temperature for 26 hours. After the precipitated solid was filtered off, triethylamine was added to the chloroform solution, and the solvent was distilled off to about 1/3. Methanol containing triethylamine was added to this solution to obtain a solid. The obtained solid was washed with methanol containing triethylamine and then with hexane. 8.24 g of polymerizable compound (1-2) as a white solid was obtained. The yield was 62% based on (T-02).
The polymerizable compound (1-2) exhibited a transition from a crystal phase to a nematic liquid crystal phase at 135 ° C., and was thermally polymerized at 250 ° C.

Example 1
<Example of optical film production>
A 2% 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 a film was obtained after heat drying. Subsequently, after rubbing the surface, a coating solution (mixed solution) having the composition shown in Table 1 was applied to the surface subjected to the rubbing treatment by a spin coating method. Subsequently, an ultraviolet ray of 1200 mJ / cm ² was irradiated while heating on a 110 ° C. hot plate to produce an optical film having a thickness of 0.940 μm.
In Table 1, Irgacure 907 (manufactured by Ciba Specialty Chemicals Co., Ltd.) was used as the photopolymerization initiator, BYK361N (manufactured by BYK Japan) was used as the leveling agent, and cyclopentanone was used as the solvent. Further,% in the table other than the solvent means% of solid content with the coating solution as 100%.

光重合性開始剤：イルガキュア９０７（チバ・スペシャルティ・ケミカルズ株式会社製）
溶媒：シクロペンタノン

Photopolymerizable initiator: Irgacure 907 (Ciba Specialty Chemicals)
Solvent: cyclopentanone

<Measurement of optical characteristics>
About the produced optical film, the front phase difference value Re (550) and the tilt angle at a measurement wavelength of 550 nm were measured using a measuring machine (KOBRA-WR, manufactured by Oji Scientific Instruments). Moreover, the film thickness derived from the polymeric compound of an optical film was measured using the laser microscope (LEXT, Olympus Corporation make). When the above measurements were performed, it was found that the front phase difference value was 169.2 nm, the tilt angle was 5.5 degrees, and Δn was 0.180. The results are shown in Table 2.

(Example 2)
Using the coating solution of Table 1, an optical film was produced in the same manner as in Example 1 except that 2400 mJ / cm ² of ultraviolet rays were irradiated while heating at 130 ° C., and an optical film having a thickness of 0.802 μm was produced. . When the front retardation value and tilt angle of the obtained optical film were measured using a measuring instrument (KOBRA-WR, manufactured by Oji Scientific Instruments), the front retardation value was 151.6 nm and the tilt angle was 8.2. Degree, Δn was found to be 0.189. The results are shown in Table 2.

(Comparative Example 1)
Using the coating liquid of Table 1, an optical film was produced in the same manner as in Example 1, and an optical film having a thickness of 1.09 μm was produced. When the front retardation value and tilt angle of the obtained optical film were measured using a measuring instrument (KOBRA-WR, manufactured by Oji Scientific Instruments), the front retardation value was 156.0 nm and the tilt angle was 1.7. Degree, Δn was found to be 0.143. The results are shown in Table 2.

  From the results of Example 1 and Example 2, the polymerizable compound (1-1) and the polymerizable compound (1-2) are easily soluble in a general-purpose organic solvent and have good coatability. Δn was a large value. On the other hand, from the results of Comparative Example 1, LC242 was able to prepare a coating solution, but Δn was a small value.

(Example 3)
<Example of optical film production>
A 2% 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 a film was obtained after heat drying. Subsequently, the surface was subjected to rubbing treatment, and then a coating solution (mixed solution) having the composition shown in Table 3 was applied to the surface subjected to rubbing treatment by a spin coating method. Subsequently, the film was dried on a 45 ° C. hot plate for 1 minute, air-cooled at room temperature for 1 minute, and then irradiated with ultraviolet rays of 1200 mJ / cm ² to produce an optical film having a thickness of 0.79 nm.
In Table 3, LC242 is a liquid crystal compound obtained from BASF, the photopolymerization initiator is Irgacure 907 (Ciba Specialty Chemicals), the leveling agent is BYK361N (Bicchemy Japan), Cyclopentanone was used as the solvent. In Table 3, all the examples have the same molar ratio of the compound added to LC242, and% in the table other than the solvent means% of the solid content with the coating solution being 100%.

液晶化合物：ＬＣ２４２（ＢＡＳＦ社製）
光重合性開始剤：イルガキュア９０７（チバ・スペシャルティ・ケミカルズ株式会社製）
溶媒：シクロペンタノン

Liquid crystal compound: LC242 (manufactured by BASF)
Photopolymerizable initiator: Irgacure 907 (Ciba Specialty Chemicals Co., Ltd.)
Solvent: cyclopentanone

<Measurement of optical characteristics>
The retardation value at 550 nm of the produced optical film was measured using a measuring device (KOBRA-WR, manufactured by Oji Scientific Instruments), and Δn was calculated from the film thickness. The results are shown in Table 4.

Example 4
Using the coating liquid of Table 3, an optical film was produced in the same manner as in Example 1, and an optical film having a thickness of 0.81 μm was produced. About the obtained optical film, the phase difference value was measured using the measuring machine (KOBRA-WR, Oji Scientific Instruments company make). The results are shown in Table 4.

  According to the polymerizable compound of the present invention, an optical film having a large Δn can be produced.

It is the schematic which shows the polarizing plate 1 which concerns on this invention. It is the schematic which shows the bonding product 10 of the liquid crystal panel 11 and the polarizing plate 1 of the liquid crystal display device which concerns on this invention. It is the schematic which shows the organic electroluminescent panel 13 of the organic electroluminescent display apparatus which concerns on this invention.

Explanation of symbols

1, 1a, 1b, 1c, 1d, 1e Polarizing plate 2, 2 'Optical film 3 Polarizing film 4, 4' Support substrate 5, 5 'Alignment film 6, 6' Optical anisotropic layer 7, 7 ', 12 , 15 Adhesive layer 10 Bonded product 11 Liquid crystal panel 13 Organic EL panel 14 Light emitting layer

Claims (17)

A polymerizable compound represented by formula (1-a) or formula (1-b). _However, - for _{(B 1 -A 1) m -E} 1 -D 1 -G 1 -Q 1, - (B 2 -A 2) n -E 1 -D 2 -G 2 -Q 2 on the benzene ring The substitution position of is para or meta.

[In Formula (1-a) and Formula (1-b), X ₁ and X ₂ are each independently —CH═CH—, —CH═C (CH ₃ ) —, —C (CH ₃ ) = _{CH -, - C (CH 3} ) = C (CH 3) -, - CH = N -, - N = CH -, - N = C (CH 3) - or -C _(CH 3) = represents a N- .
Y ₁ and Y ₂ each independently represent a 6-18 membered aromatic hydrocarbon group or a 5-18 membered aromatic heterocyclic group. The hydrogen atom contained in the aromatic hydrocarbon group and the aromatic heterocyclic group may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom.
_{B 1,} B 2, _{G 1} and _{G 2} are each ^{independently, -CR 1 R 2 -, -} 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 -, - O-C (= S) -, - O-C (= S) -O -, - CR 1 = N -, - N = CR 1 -, - C (= O) —NR ¹ —, —NR ¹ —C (═O) —, —OCH ₂ —, —OCF ₂ —, —NR ¹ —, —CH ₂ O—, —CF ₂ O—, —SCH ₂ —, —CH ₂ S—, —CH═CH—C (═O) —O—, —O—C (═O) —CH═CH— or a single bond is represented. R ¹ and R ² each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
A ₁ and A ₂ each independently represents a 6-18 membered aromatic hydrocarbon group, a 5-18 membered alicyclic hydrocarbon group, or a 5-18 membered heterocyclic group. The hydrogen atom contained in the aromatic hydrocarbon group, the alicyclic hydrocarbon group and the heterocyclic group is substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a halogen atom. May be. m and n each independently represent an integer represented by 1 to 3.
E ₁ and _{E 2,} each ^{independently, -CR 3 R 4 -, -} 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 -, - O-C ( = S) -, - O-C (= S) -O -, - CR 3 = N -, - N = CR 3 -, - C (= O) -NR 3 - , —NR ³ —C (═O) —, —OCH ₂ —, —OCF ₂ —, —NR ³ —, —CH ₂ O—, —CF ₂ O—, —SCH ₂ —, —CH ₂ S—, —CH═CH—C (═O) —O—, —O—C (═O) —CH═CH—, or a single bond is represented. R ³ and R ⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
D ₁ and D ₂ each independently represent an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom contained in D ₁ and D ₂ is an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. It may be substituted with a group or a halogen atom.
Q ₁ and Q ₂ are a hydrogen atom or a group selected from the group consisting of groups represented by formula (Q-1) to formula (Q-5).

(In Formula (Q-1) to Formula (Q-5), R ^{5 to} R ⁹ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)] The polymerizable compound represented by formula (1-a) or formula (1-b) is a compound represented by formula (1-a-1) or formula (1-b-1). Polymerizable compound.

(A ₁ , A ₂ , B ₁ , B ₂ , E ₁ , E ₂ , D ₁ , D ₂ , G ₁ , G ₂ , Q ₁ , Q ₂ , X ₁ , X ₂ , Y ₁ , Y ₂ , m And n represent the same meaning as described above.) The polymerizable compound according to claim 1, wherein X ₁ and X ₂ are each independently —CH═CH—, —CH═N— or —N═CH—. The polymerizable compound according to claim 1, wherein at least one of Q ₁ and Q ₂ is a group selected from the group consisting of groups represented by formula (Q-1) to formula (Q-5). . The polymerizable compound according to any one of claims 1 to 4, wherein -G ₁ -Q ₁ and -G ₂ -Q ₂ are an acryloyl group or a methacryloyl group.   The composition containing the polymeric compound in any one of Claims 1-5, and liquid crystal compounds (2) other than this polymeric compound. The composition according to claim 6, wherein the liquid crystal compound (2) other than the polymerizable compound is a compound represented by the formula (I), the formula (II), the formula (III), the formula (IV) or the formula (V). object.
P11-E11-B11-A11-B12-A12-B13-A13-B14-A14-B15-A15-B16-E12-P12 (I)
P11-E11-B11-A11-B12-A12-B13-A13-B14-A14-B15-E12-P12 (II)
P11-E11-B11-A11-B12-A12-B13-A13-B14-E12-P12 (III)
P11-E11-B11-A11-B12-A12-B13-A13-B14-F11 (IV)
P11-E11-B11-A11-B12-A12-B13-F11 (V)
(In the formulas (I) to (V), A11, A12, A13, A14, and A15 are each independently an aromatic hydrocarbon group, an alicyclic hydrocarbon group, a heterocyclic group, a fluorenyl group, or thiophenylene. A11 to A15 may be bonded to an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a nitrile group, a phenyl group, a dimethylamino group, or a halogen atom. .)
B11, B12, B13, B14, B15 and B16 are each _{independently, -CR 10 R 11 -, -} 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 -, - O-C (= S) -, - CH = N -, - N = CH -, - N = N -, - C (= O) -NR 10 -, - NR ₁₀ —C (═O) —, —OCH ₂ —, —OCF ₂ —, —NR ₁₀ —, —CH ₂ O—, —CF ₂ O—, —CH═CH—C (═O) —O— , -OC (= O) -CH = CH- or a single bond. R ₁₀ and R ₁₁ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms, and may be an alkylene group having 4 to 7 carbon atoms linked to R ₁₀ and R ₁₁ .
E11 and E12 each independently 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.
P11 and P12 each independently represents an acryloyloxy group, a methacryloyloxy group, or a vinyloxy group.
F11 represents a hydrogen atom, an alkyl group having 1 to 13 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, a nitrile group, a nitro group, a trifluoromethyl group, a dimethylamino group, or a halogen atom. )   The optical film containing the structural unit derived from the polymeric compound in any one of Claims 1-5.   An optical film obtained by polymerizing the composition according to claim 6 or 7.   A λ / 4 plate comprising the optical film according to claim 8 or 9 and having a retardation value (Re (550)) of 113 to 163 nm at a wavelength of 550 nm.   A λ / 2 plate comprising the optical film according to claim 8 or 9, and having a retardation value (Re (550)) of 250 to 300 nm at a wavelength of 550 nm.   A polarizing plate comprising the optical film according to claim 8 or 9 and a polarizing film.   A liquid crystal display device comprising the polarizing plate according to claim 12 and a liquid crystal panel.   An organic electroluminescence display device comprising an organic electroluminescence panel including the polarizing plate according to claim 12.   The manufacturing method of the unpolymerized film which apply | coats the solution containing the polymeric 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 polymeric 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 | cures the unpolymerized film obtained by the manufacturing method of the unpolymerized film of Claim 15 or 16 by superposition | polymerization.

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