JP2009274984A - Compound, optical film and method for producing optical film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new compound giving an optical film capable of performing a uniform polarizing conversion in a wide wavelength range. <P>SOLUTION: This compound is expressed by formula (XA-1). By measuring the phase transition temperature of the compound (XA-1) with a texture observation by using a polarizing microscope, in the time of elevating temperature, it shows a smectic phase from 101 to 133°C, and also shows a nematic phase from 133 to 146°C. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a compound, an optical film, a method for producing the optical film, a polarizing plate using the same, a display device, and the like.

A flat panel display (FPD) includes members using optical films such as a polarizing plate and a retardation plate. Examples of the 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). The wavelength 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. According to the optical film having a wavelength dispersion characteristic with Re (λ) / Re (550)) close to 1, the wavelength dependence of the retardation value can be reduced, and uniform polarization conversion is possible in a wide wavelength range. It is known that
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>

  An object of the present invention is to provide a new compound that provides an optical film capable of uniform polarization conversion in a wide wavelength range.

［式（１）中、Ｘは、−Ｓ−、−Ｏ−、−ＣＨ_２−、−ＮＨ−、−Ｃ（＝Ｏ）−、−Ｓ（＝Ｏ）−または−Ｃ（＝Ｓ）−を表す。
Ｙは、−Ｃ（Ｒ）＝または−Ｎ＝を表す。Ｒは、水素原子、ハロゲン原子、−Ｃ≡Ｃ−Ｈ又は−Ｃ≡Ｃ−ＣＨ_３、炭素数１〜６のアルキル基、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のチオアルキル基、炭素数１〜６のアルキルアミノ基、炭素数１〜６のジアルキルアミノ基、シアノ基、ニトロ基、水酸基、メルカプト基を表す。
Ｚは、水素原子、ハロゲン原子、炭素数１〜６のアルキル基、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のチオアルキル基、シアノ基、ニトロ基、水酸基、メルカプト基、スルホン基、スルホキシド基、−ＮＲ^１Ｒ^２、−Ｃ（＝Ｏ）−Ｏ−Ｒ^１、−Ｏ−Ｃ（＝Ｏ）−Ｒ^１、−Ｃ（＝Ｓ）−Ｏ−Ｒ^１、−Ｏ−Ｃ（＝Ｓ）−Ｒ^１、−Ｃ（＝Ｏ）−ＮＲ^１Ｒ^２、−ＮＲ^１−Ｃ（＝Ｏ）−Ｒ^２、−Ｃ≡Ｃ−Ｒ^１、−Ｃ（＝Ｏ）−Ｒ^１、−Ｃ（＝Ｓ）−Ｒ^１、−ＣＲ^１＝ＮＲ^２、−Ｎ＝ＣＲ^１Ｒ^２、−ＣＲ^１＝ＣＲ^２Ｒ^３を表す。Ｒ^１、Ｒ^２およびＲ^３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。
Ｊ_１およびＪ_２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、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のチオアルキル基、シアノ基、ニトロ基、水酸基、メルカプト基、スルホン基、スルホキシド基、−ＮＲ^４Ｒ^５、−Ｃ（＝Ｏ）−Ｏ−Ｒ^４、−Ｏ−Ｃ（＝Ｏ）−Ｒ^４、−Ｃ（＝Ｓ）−Ｏ−Ｒ^４、−Ｏ−Ｃ（＝Ｓ）−Ｒ^４、−Ｃ（＝Ｏ）−ＮＲ^４Ｒ^５、−ＮＲ^４−Ｃ（＝Ｏ）−Ｒ^５、−Ｃ≡Ｃ−Ｒ^４、−Ｃ（＝Ｏ）−Ｒ^４、−Ｃ（＝Ｓ）−Ｒ^４、−ＣＲ^４＝ＮＲ^５、−Ｎ＝ＣＲ^４Ｒ^５、−ＣＲ^４＝ＣＲ^５Ｒ^６を表す。Ｒ^４、Ｒ^５およびＲ^６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。
Ｂ_１、Ｂ_２、Ｅ_１、Ｅ_２、Ｇ_１およびＧ_２は、それぞれ独立に、−ＣＲ^７Ｒ^８−、−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^７＝Ｎ−、−Ｎ＝ＣＲ^７−、−Ｃ（＝Ｏ）−ＮＲ^７−、−ＮＲ^７−Ｃ（＝Ｏ）−、−Ｏ−ＣＨ_２−、−Ｏ−ＣＦ_２−、−ＮＲ^７−、−ＣＨ_２−Ｏ−、−ＣＦ_２−Ｏ−、−Ｓ−ＣＨ_２−、−ＣＨ_２−Ｓ−、−ＣＨ＝ＣＨ−Ｃ（＝Ｏ）−Ｏ−、−Ｏ−Ｃ（＝Ｏ）−ＣＨ＝ＣＨ−または単結合を表す。Ｒ^７およびＲ^８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、ハロゲン原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、炭素数１〜４のフルオロアルキル基、炭素数１〜４のフルオロアルコキシ基、ニトロ基またはニトリル基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。
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、それぞれ独立に、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^９〜Ｒ^１３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。）］ According to the present invention, a compound represented by the formula (1) is provided.

[In the formula (1), X represents —S—, —O—, —CH ₂ —, —NH—, —C (═O) —, —S (═O) — or —C (═S) —. Represents.
Y represents -C (R) = or -N =. R is a hydrogen atom, a halogen atom, —C≡C—H or —C≡C—CH ₃ , an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, or an alkoxy having 1 to 6 carbon atoms. Group, a thioalkyl group having 1 to 6 carbon atoms, an alkylamino group having 1 to 6 carbon atoms, a dialkylamino group having 1 to 6 carbon atoms, a cyano group, a nitro group, a hydroxyl group, and a mercapto group.
Z is a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a thioalkyl group having 1 to 6 carbon atoms, a cyano group, or a nitro group. Group, hydroxyl group, mercapto group, sulfone group, sulfoxide group, —NR ¹ R ² , —C (═O) —O—R ¹ , —O—C (═O) —R ¹ , —C (═S) — O—R ¹ , —O—C (═S) —R ¹ , —C (═O) —NR ¹ R ² , —NR ¹ —C (═O) —R ² , —C≡C—R ¹ , ^{-C (= O) -R 1,} -C (= S) -R 1, -CR 1 = NR 2, -N = CR 1 R 2, represent a -CR 1 = ^CR 2 ^{R 3.} R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
J ₁ and J ₂ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms. Thioalkyl group, cyano group, nitro group, hydroxyl group, mercapto group, sulfone group, sulfoxide group, —NR ⁴ R ⁵ , —C (═O) —O—R ⁴ , —O—C (═O) —R ^4. , —C (═S) —O—R ⁴ , —O—C (═S) —R ⁴ , —C (═O) —NR ⁴ R ⁵ , —NR ⁴ —C (═O) —R ⁵ , ^{-C≡C-R 4, -C (=} O) -R 4, -C (= S) -R 4, -CR 4 = NR 5, -N = CR 4 R 5, -CR 4 = CR 5 R ⁶ is represented. R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
_{B 1, B 2, E 1} , E 2, G 1 and _{G 2} are each ^{independently, -CR 7 R 8 -, -} 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 7 = N -, - N = CR 7 —, —C (═O) —NR ⁷ —, —NR ⁷ —C (═O) —, —O—CH ₂ —, —O—CF ₂ —, —NR ⁷ —, —CH ₂ —O—, —CF ₂ —O—, —S—CH ₂ —, —CH ₂ —S—, —CH═CH—C (═O) —O—, —O—C (═O) —CH═CH— Represents a bond. R ⁷ and R ⁸ 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 a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or 1 carbon atom. It may be substituted with a -4 fluoroalkyl group, a C 1-4 fluoroalkoxy group, a nitro group or a nitrile group.
m and n each independently represent an integer represented by 1 to 3.
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 each independently 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 ^{9 to} R ¹³ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)]

In such a compound, X is preferably —S— or —O—, Y is preferably —N═ or —CH═, and X is —S—, Y is —N═. It is more preferable.
At least one of Q ₁ and Q ₂ is preferably a group selected from the group consisting of groups represented by the formula (Q-1) ~ formula (Q-5).
Furthermore, _-G 1 -Q ₁ and _-G 2 -Q ₂ preferably includes an acryloyl group or a methacryloyl group.

Moreover, according to this invention, the composition containing the compound mentioned above and the compound (however, it is not the same as the compound mentioned above) represented by Formula (2) is provided.
P11-E11- (B11-A11) _t- B12-G (2)
(In Formula (2), A11 represents an aromatic hydrocarbon group, an alicyclic hydrocarbon group, or a heterocyclic group, and these groups include a halogen atom, an alkyl group having 1 to 6 carbon atoms, and 1 to 1 carbon atoms. 6 alkoxy groups, C1-C6 alkylamino groups, nitro groups, nitrile groups, and mercapto groups may be substituted.
B11, B12 are each ^{independently, -CR 14 R 15 -, -} C≡C -, - CH = CH -, - CH 2 -CH 2 -, - O -, - S -, - C (= O) -, -C (= O) -O-, -OC (= O)-, -O-C (= O) -O-, -C (= S)-, -C (= S) -O. -, -OC (= S)-, -CH = N-, -N = CH-, -N = N-, -C (= O) -NR < ¹⁴ >-, -NR < ¹⁴ > -C (= O). —, —OCH ₂ —, —OCF ₂ —, —NR ¹⁴ —, —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 may be linked to form an alkylene group having 4 to 7 carbon atoms. Good.
E11 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 each independently 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 is an integer of 1 to 5)

According to this invention, the optical film containing the structural unit derived from the compound mentioned above is provided.
Furthermore, according to this invention, the optical film formed by superposing | polymerizing the composition mentioned above is provided.

  These optical films function as a λ / 4 plate having a retardation value (Re (550)) at a wavelength of 550 nm of light transmitted through the optical film of 113 to 163 nm or a λ / 2 plate having a wavelength of 250 to 300 nm. It is preferable that

According to this invention, the polarizing plate containing the optical film and polarizing film which were mentioned above is provided.
Furthermore, according to this invention, a liquid crystal display device provided with the polarizing plate mentioned above and a liquid crystal panel is provided.
Moreover, according to this invention, an organic electroluminescent display apparatus provided with the organic electroluminescent panel containing the polarizing plate mentioned above is provided.

  Furthermore, according to this invention, the manufacturing method of the unpolymerized film which apply | coats the solution containing the compound mentioned above on the support base material or the oriented film formed on the support base material, and dries is provided.

  According to this invention, the manufacturing method of the optical film which hardens | cures the unpolymerized film obtained by the manufacturing method of such an unpolymerized film by superposition | polymerization is provided.

  According to the compound of the present invention, an optical film capable of uniform polarization conversion in a wide wavelength range can be provided.

（式（１）中、各置換基の定義は上述したとおりである。） The compound of the present invention is a compound represented by the formula (1) (hereinafter sometimes referred to as “compound (1)”).

(In formula (1), the definition of each substituent is as above-mentioned.)

In the formula (1), examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group and the like. It is done.
Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, hexyloxy group, octyloxy group, 2-ethylhexyloxy group and the like.
Examples of the fluoroalkyl group include a trifluoromethyl group, a tetrafluoroethyl group, an n-fluoropropyl group, an isofluoropropyl group, an n-fluorobutyl group, a sec-fluorobutyl group, and a 2-fluoroethylhexyl group.

Examples of the fluoroalkoxy group include a trifluoromethoxy group, a tetrafluoroethoxy group, an n-fluoropropoxy group, an isofluoropropoxy group, an n-fluorobutoxy group, a sec-fluorobutoxy group, and a 2-fluoroethylhexoxy group. .
Examples of the thioalkyl group include thiomethyl, thioethyl, thiopropyl, thiobutyl and the like.
Examples of the alkylamino group include an N-methylamino group, an N-ethylamino group, an N-propylamino group, and an N-butylamino group.
Examples of the dialkylamino group include N, N-dimethylamino group, N, N-diethylamino group, N, N-dipropylamino group, N, N-dibutylamino group, N, N-methylethylamino group, N, N -An ethylpropylamino group etc. are mentioned.

等が挙げられる。 As an aromatic hydrocarbon group,

Etc.

等が挙げられる。
複素環基としては、

等が挙げられる。
アルキレン基としては、メチレン基、エチレン基、トリメチレン基、１−メチルエチレン基、２−メチルエチレン基、テトラメチレン基、１−メチルトリメチレン基、２−メチルトリメチレン基、３−メチルトリメチレン基、１−エチルエチレン基、２−エチルエチレン基等が挙げられる。 Examples of the alicyclic hydrocarbon group include cycloalkylene, that is, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, bicyclobutylene, bicycloheptylene, bicyclooctylene, and the like. In particular,

Etc.
As the heterocyclic group,

Etc.
As the alkylene group, methylene group, ethylene group, trimethylene group, 1-methylethylene group, 2-methylethylene group, tetramethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 3-methyltrimethylene group , 1-ethylethylene group, 2-ethylethylene group and the like.

  In the present specification, although different depending on the number of carbon atoms, unless otherwise specified, the above-described substituents are exemplified by the same ones in any chemical structural formula. Moreover, the thing which can take both a linear or branched includes both.

In the compound of the present invention, in particular, in formula (1), X is preferably —S— or —O—, and more preferably —S—.
Y is preferably -CH = and -N =, and more preferably -N =.
As a combination of X and Y, X is -S-, Y is -N =, X is -S-, Y is -CH =, X is -O-, and Y is -N =. Or X is —O— and Y is —CH═, more preferably X is —S— and Y is —N═.
Z is particularly a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, a cyano group, —NR ¹ R ² , —C (═O) —O—R ¹ , —C ( ═O) —NR ¹ R ² (R ¹ and R ² each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) and the like are preferable because of easy production.
J ₁ and J ₂ are particularly preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, or the like because production is easy.
B ₁ , B ₂ , E ₁ , E ₂ , G ₁ and G ₂ are preferably groups containing ether, ester, thioether, thioester and the like.
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.

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. Further, it is preferable because phase separation after polymerization is avoided. It is further preferred that Q ₁ and Q ₂ are groups represented by formula (Q-1) to formula (Q-5). This is because the film hardness of the optical film obtained using the compound (1) tends to be excellent.
-G ₁ -Q ₁ and -G ₂ -Q ₂ are substituents capable of polymerizing the compound (1) or contain such substituents, specifically vinyl groups, vinyloxy groups, p -Stilbene group, acryloyl group, acryloyloxy group, methacryloyl group, methacryloyloxy group, carboxyl group, methylcarbonyl group, hydroxyl group, amide group, amino group, C1-C4 alkylamino group, epoxy group, oxetanyl group, Examples thereof include aldehyde groups, isocyanate groups, thioisocyanate groups, and the like. Of these, an acryloyl group or a methacryloyl group is preferable because it is easy to handle during photopolymerization and is easy to produce, and an acryloyl group is particularly preferable.

Examples of the compound of the formula (1) include the following. However, r shows the integer of 1-12 in a formula.

  The compound (1) of the present invention comprises Wittig reaction, Schiff base formation reaction, condensation reaction, esterification reaction, Williamson reaction, Ullmann reaction, benzylation reaction, Sonogashira reaction, Suzuki-Miyaura reaction, Negishi reaction, Kumada reaction, It can be produced according to a known synthesis method such as Kashiyama reaction, Buchwald-Hartwig reaction, Friedel-Craft reaction, Heck reaction or aldol reaction. The synthetic methods include, for example, Houben Wyle (Methoden der Organischen Chemie, Georg Thieme Verlag, Stuttgart), Organic Reactions (Organic Reactions, John Wily & Sons Inc.), Organic Syntheses (Johnson) Synthesize by properly combining the synthesis methods in organic chemistry described in Wily & Sons Inc., Comprehensive Organic Synthesis, Pergamon Press, New Experimental Chemistry Course (Maruzen), etc. Can do.

  The optical film of the present invention is substantially formed by a composition containing the above-mentioned compound (1), that is, formed by including a structural unit derived from the compound (1). May be formed by a composition comprising one or more different compounds. That is, the structural unit derived from 1 or more types of compounds different from a compound (1) may be included. By including one or more compounds different from the compound (1), the composition ratio of the two can be changed, and the birefringence Δn and wavelength dispersion characteristics of the resulting optical film can be controlled. it can.

  Examples of compounds different from compound (1) include, for example, Chapter 3 of Liquid Crystal Handbook (Edited by Liquid Crystal Handbook Editorial Committee, published by Maruzen Co., Ltd., October 30, 2000). Among the compounds described in Liquid Crystal Molecules, 3.3 Chiral Rod-like Liquid Crystal Molecules, compounds having a polymerizable group are exemplified.

Examples of such a compound include a compound represented by the formula (2).
P11-E11- (B11-A11) _t- B12-G (2)
(In Formula (2), the definition of each substituent is as above-mentioned.)
In particular, the polymerizable group in P11 and G may be any group that can be polymerized with the compound (1), and examples thereof include a vinyl group, a vinyloxy group, a p-stilbene group, an acryloyl group, an acryloyloxy group, and a methacryloyl group. And methacryloyloxy group, carboxyl group, methylcarbonyl group, hydroxyl group, amide group, amino group, alkylamino group having 1 to 4 carbon atoms, epoxy group, oxetanyl group, aldehyde group, isocyanate group or thioisocyanate group The Of these, an acryloyloxy group, a methacryloyloxy group, and a vinyloxy group are preferable because they are easy to handle during photopolymerization and easy to produce. In particular, it is preferable that both P11 and G are an acryloyloxy group, a methacryloyloxy group, a vinyloxy group, or contain these groups.
Moreover, C3-C18 is mentioned for the aromatic hydrocarbon group of A11, an alicyclic hydrocarbon group, and a heterocyclic group, C5-C12 is suitable, C5-C6 is the most preferable.

Examples of the compound (2) include compounds represented by the formula (2-1) and the formula (2-2).
P11-E11- (B11-A11) _t1 -B12-E12-P12 (2-1)
P11-E11- (B11-A11) _t2 -B12-F11 (2-2)
(In the formula, P11, E11, B11, A11, and B12 are as defined above.
F11 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, Represents a nitro group.
E12 is synonymous with E11.
P12 is synonymous with P11.
t1 and t2 are synonymous with t. )

Further, the compounds represented by the formulas (2-1) and (2-2) are represented by the formula (I), the formula (II), the formula (III), the formula (IV), or the formula (V). Contains compounds.
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 formula, A12 to A15 are synonymous with A11, and B13 to B16 are synonymous with B11).
In the compounds represented by formula (2-1), formula (2-2), formula (I), formula (II), formula (III), formula (IV) and formula (V), P11 and It is preferable that both are bonded via an ether bond or an ester bond by appropriately selecting a combination with E11 and further selecting a combination of P12 and E12 as appropriate.

Specific examples of the 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 may be formed unpolymerized or polymerized using, for example, a composition containing the compound (1) and / or a composition containing a compound different from the compound (1). it can.
In this case, the structural unit derived from the compound (1) and / or a compound different from the compound (1) (for example, the compound (2)) is 1 for every 100 parts by weight of all the structural units constituting the optical film. It is preferable to contain at least about parts by weight and / or about 0 to 20 parts by weight.

(Preparation of composition solution)
A method for polymerizing and producing the optical film of the present invention will be described below.
First, a composition containing the compound (1) of the present invention or a composition containing a compound different from the compound (1) (for example, the compound (2)), optionally, a polymerization initiator, a polymerization inhibitor, A composition solution in which one or more additives such as a photosensitizer, a leveling agent, an organic solvent, and a crosslinking agent are mixed is prepared. In particular, the organic solvent is preferably contained because film formation is facilitated and the polymerization initiator has a function of curing the obtained optical film. Such a composition preferably exhibits a liquid crystal phase such as a nematic phase. Thereby, it can have birefringence by monodomain orientation.

(Polymerization initiator)
The composition solution can be fixed without impairing the alignment form in the liquid crystal state by once heating to the liquid crystal phase expression temperature and then cooling while maintaining the alignment state. Moreover, after heating the composition which added the polymerization initiator to the composition solution to liquid crystal phase expression temperature, it superposes | polymerizes and can cool, and the orientation state of a liquid crystal state can be fixed. In order to fix the alignment state, the latter polymerization reaction is preferably performed.
Generally, the polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator, a photopolymerization reaction using a photopolymerization initiator, a polymerization reaction by electron beam irradiation, etc., but the supporting base material is deformed by heat, In order to prevent alteration, a photopolymerization reaction or a polymerization reaction by electron beam irradiation is preferred. Therefore, it is particularly preferable to use a photopolymerization initiator.

Examples of the photopolymerization initiator include benzoins, benzophenones, benzyl ketals, α-hydroxyketones, α-aminoketones, iodonium salts, sulfonium salts, and the like, and more specifically, Irgacure 907. , Irgacure 184, Irgacure 651, Irgacure 250, Irgacure 369 (all manufactured by Ciba Japan Co., Ltd.), SEIKO ALL BZ, SEIKO ALL Z, SEIKO ALL BEE (all manufactured by Seiko Chemical Co., Ltd.), kayacure BP100 (Japan) Kayaku UVI-6992 (manufactured by Dow), Adeka optomer SP-152 or Adeka optomer SP-170 (all of which are ADEKA Co., Ltd.) and the like.
The usage-amount of a polymerization initiator is 0.1 to 30 weight part normally with respect to a total of 100 weight part of a compound (1) and a compound (2), Preferably, 0.5 to 10 weight part is preferable. Parts by weight. If it is in the said range, a composition can be polymerized, without disturbing the orientation of a composition.

(Polymerization inhibitor)
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. Examples include radical scavengers such as -1-piperidinyloxy radical, thiophenols, β-naphthylamines, β-naphthols, and the like.
By containing a polymerization inhibitor, the polymerization of the compound (1) and the compound (2) can be controlled, and the stability of the resulting optical film and the composition before coating can be improved. Moreover, the usage-amount of a polymerization inhibitor is 0.1 to 30 weight part normally with respect to a total of 100 weight part of a compound (1) and a compound (2), Preferably, it is 0.5 weight part. -10 parts by weight. If it is in the said range, it can superpose | polymerize, without disturbing the orientation of the composition which comprises this optical film.

[Photosensitizer]
Examples of the photosensitizer include xanthones such as xanthone or thioxanthone, anthracene having a substituent such as anthracene or alkyl ether, phenothiazine, or rubrene.
By using the photosensitizer, the polymerization of the compound (1) and the compound (2) can be made highly sensitive. The photosensitizer is used in an amount of usually 0.1 to 30 parts by weight, preferably 0.5 parts by weight based on a total of 100 parts by weight of the compound (1) and the compound (2). Parts to 10 parts by weight. If it is in the said range, a compound (1) can be polymerized, without disturbing the orientation of the composition which comprises an optical film, especially a compound (2).

[Crosslinking agent]
The crosslinking agent is not particularly limited, and examples thereof include those known in the art, such as polyacrylates, polymethacrylates, urethane acrylates, polyisocyanates, epoxy compounds, oxetane compounds and the like. More specifically, triacrylates (manufactured by Shin-Nakamura Chemical Co., Ltd .: CBX-1N, CBX-0, A-TMPT-3EO, A-TMPT-6EO, A-TMPT-9EO, A-TMM-3, A-TMM-3L, A-TMM-3LMN, A-GLY-3E, A-GLY-6E, A-GLY-9E, A-GLY-20E, TM-4EL, manufactured by SARTOMER: SR499, SR502, SR9035, SR368), tetraacrylates (manufactured by Shin-Nakamura Chemical Co., Ltd .: ATM-4E, ATM-35E), pentaacrylates (manufactured by Shin-Nakamura Chemical Co., Ltd .: A-9530, manufactured by SARTOMER: SR399E), hexaacrylates (Shin Nakamura Chemical Co., Ltd .: A-DPH-6E, A-DPH-12E, A-DPH-6P, Kyoeisha Chemical Co., Ltd. Formula company made: UA-306H, UA-306I, manufactured by Nippon Kayaku Co., Ltd.: DPCA-60, DPCA-120), and the like.

By using a crosslinking agent, the crosslinking density of the optical film can be adjusted.
The amount of the crosslinking agent used is usually 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 compound (1) and compound (2). Part. By using a crosslinking agent, the compound (1) and the compound (2) can be crosslinked by photopolymerization. Therefore, the influence of changes in birefringence due to heat can be reduced.

(Leveling agent)
As the leveling agent, for example, various compounds such as silicone-based, fluorine-based, polyether-based, acrylic acid copolymer-based or titanate-based compounds can be used. Chemie Japan make: 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) and the like.
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 can be controlled, and the crosslinking density of the optical film obtained by polymerizing the compound (1) and the compound (2) can be adjusted. Moreover, the usage-amount of a leveling agent is 0.1 to 30 weight part normally with respect to a total of 100 weight part of a compound (1) and a compound (2), Preferably, 0.5 weight part- 10 parts by weight. If it is in the said range, a compound (1) can be polymerized, without disturbing the orientation of the composition which comprises this optical film, especially a compound (2).

[Organic solvent]
As an organic solvent, what is necessary is just an organic solvent which can melt | dissolve the compound etc. which are contained in an optical film. Specifically, alcohols such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl cellosolve or butyl cellosolve; ester systems such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, gamma-butyrolactone or propylene glycol methyl ether acetate Solvent; Ketone solvent such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone or methyl isobutyl ketone; Aliphatic hydrocarbon solvent such as pentane, hexane or heptane; Aromatic hydrocarbon solvent such as toluene, xylene or chlorobenzene , Acetonitrile, propylene glycol monomethyl ether, tetrahydrofuran, dimethoxyethane Ethyl lactate, chloroform or phenol, and the like. These organic solvents may be used alone or in combination. Especially, it is excellent in compatibility with the composition constituting the optical film, and can be dissolved in alcohol, ester solvent, ketone solvent, non-chlorine aliphatic hydrocarbon solvent, non-chlorine aromatic hydrocarbon solvent, etc. Therefore, it can be dissolved and applied without using a halogenated hydrocarbon such as chloroform.

The viscosity of the mixed solution containing the above-described composition is usually adjusted to 10 Pa · s or less, preferably about 0.1 to 7 Pa · s so that it can be easily applied.
Moreover, the density | concentration of the solid content in a mixed solution is 5-50 weight% normally. By setting the solid content concentration within this range, the film thickness of the optical film is less likely to be uneven, making it easy to adjust the film thickness to an appropriate thickness, and providing the optical anisotropy necessary for optical compensation of the liquid crystal panel. Can be given.

[Preparation of support substrate]
Any material may be used as the supporting base material as long as it can form an alignment film on the surface thereof. For example, glass, a plastic sheet, a plastic film, a translucent film, etc. can be mentioned. As the translucent film, for example, polyolefin film such as polyethylene, polypropylene, norbornene polymer, polyvinyl alcohol film, polyethylene terephthalate film, polymethacrylate film, polyacrylate film, cellulose ester film, polyethylene naphthalate film, Examples thereof include a polycarbonate film, a polysulfone film, a polyethersulfone film, a polyetherketone film, a polyphenylene sulfide film, and a polyphenylene oxide film.
Since the optical film obtained from the above composition may require strength such as bonding, transportation, storage, etc., use of the supporting substrate does not break the film and facilitates handling.
In addition, although the solution of the said composition may be applied directly on a support base material, in order to obtain a more uniform orientation, it is preferable to apply on the orientation film | membrane formed on the support base material.

  The alignment film has solvent resistance that does not dissolve due to application of a solution containing the above composition, etc., has heat resistance due to solvent removal, liquid crystal alignment heat treatment, and peeling due to rubbing due to rubbing, etc. And the like, and can be formed by a composition containing a polymer and optionally a solvent.

  Examples of the polymer that forms the alignment film 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, Examples thereof include polymers such as acrylamide, polyoxazole, polyethyleneimine, polystyrene, polyvinyl pyrrolidone, polyacrylic acid, and polyacrylic acid esters. These polymers may be used alone, or two or more kinds may be mixed and copolymerized. These polymers can be easily obtained by polycondensation such as dehydration or deamination, chain polymerization such as radical polymerization, anionic polymerization, and cationic polymerization, coordination polymerization, or ring-opening polymerization.

  The solvent is not particularly limited, and specifically, alcohol such as water, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl cellosolve, butyl cellosolve; ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, gamma-butyrolactone Ester solvents such as propylene glycol methyl ether acetate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone, and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane, and heptane; toluene, Aromatic hydrocarbon solvents such as xylene and chlorobenzene, acetonitrile, propylene glycol monomethyl ether, tetrahydrofuran, dimethoxyethane, Ethyl, it can be used such as various chloroform. These organic solvents may be used alone or in combination.

  Further, in order to form the alignment film, a commercially available alignment film material may be used as it is. Examples of commercially available alignment films include those obtained by subjecting photosensitive polyimide to polarized UV treatment, such as Sunever (registered trademark, manufactured by Nissan Chemical Industries), Optomer (registered trademark, manufactured by JSR), etc. Examples include POVAL (registered trademark, manufactured by Kuraray).

As a method for forming an alignment film on a support substrate, for example, a commercially available alignment film material, the above-described polymer or a constituent monomer as an alignment film material, and optionally a solvent are applied on the support substrate. Then, the method of annealing is mentioned.
The thickness of the obtained alignment film is usually about 10 nm to 10000 nm, and preferably about 10 nm to 1000 nm. If it is the said range, in the unpolymerized film manufacturing process mentioned later, the film formed from the composition of this invention can be oriented at a desired angle on an oriented film.
Moreover, these alignment films can be rubbed or irradiated with polarized ultraviolet rays as required. Thereby, the film formed from the composition of this invention 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 brought into contact with the alignment film placed and transported on the stage can be used.
As described above, by using the alignment film, it is possible to easily obtain a desired alignment such as a homogeneous alignment, a homeotropic alignment, a hybrid alignment, and the like, so that it is not necessary to control the refractive index by stretching. Therefore, it becomes an optical film excellent in uniformity with small in-plane variation of birefringence. As a result, it is possible to form a large optical film that can cope with an increase in the size of the FPD on the support substrate.

[Production of unpolymerized film]
The solution of the composition described above is applied directly to the support substrate or on the alignment film and dried. In particular, by forming the unpolymerized film by applying the composition solution on the alignment film formed on the support substrate, it becomes possible to produce a film with a roll film, and to improve the production efficiency. It is preferable because production costs can be reduced.
Examples of the method for applying the solution of the composition onto the support substrate or 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, you may apply | coat using coaters, such as a dip coater, a bar coater, and a spin coater.
In the case of photopolymerization, in the case of photopolymerization, the composition coated on the support substrate or the alignment film is preferably dried by almost drying the solvent before photopolymerization to obtain an unpolymerized film. In the case of thermal polymerization, the polymerization may usually proceed with drying. However, it is preferable to dry most of the solvent before the polymerization and then perform the polymerization because the film formability tends to be excellent. .

Examples of the solvent drying method include natural drying, ventilation drying, and vacuum drying. A specific heating temperature is suitably about 10 to 120 ° C, and preferably about 25 to 80 ° C. The heating time is suitably about 10 seconds to 60 minutes, preferably about 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.
Since the obtained unpolymerized film is oriented at a low temperature of about 0 to 120 ° C., preferably 25 to 100 ° C., a supporting substrate that is not necessarily sufficient in terms of heat resistance can be used.

[Polymerization of unpolymerized film]
The unpolymerized film described above may be polymerized and cured. Thereby, the orientation of the film having a structural unit derived from the composition of the present invention can be fixed. 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.
If the polymerizable group of the compound contained in the composition described above is photopolymerizable, the polymerization can be cured by irradiation with light such as visible light, ultraviolet light, or laser light. If these polymerizable groups are thermopolymerizable, they can be polymerized by heating.
In particular, it is preferable to polymerize an unpolymerized film by photopolymerization. Thereby, an unpolymerized film can be polymerized at a low temperature, and the selection range of the heat resistance of the support substrate is expanded. Moreover, it becomes easy to manufacture industrially. Furthermore, by cross-linking by photopolymerization, it becomes difficult to be affected by changes in birefringence due to heat in subsequent processes and the like. From the viewpoint of handleability, polymerization with ultraviolet light is particularly preferable.

  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.

Thus, by using the composition containing the compound (1) of the present invention, an optical film can be produced without using a liquid crystal polymer.
In addition, the optical film obtained by the above-described production method has good adhesion between the support substrate and the alignment film and / or the alignment film and the optical film, and the adhesion between the support substrate and the optical film. The surface treatment agent such as a surfactant does not need to be used separately.
Furthermore, the optical film of the present invention can be a thin film as compared with a stretched film having an equivalent retardation value.

[Optical film]
The optical film of the present invention is excellent in transparency, has a single layer or a laminated structure (for example, about 2 to 4 layers), and has various uses with the above-described support substrate and / or alignment film or various optical films. Can be used. In addition, when laminating | stacking two or more layers, the same film may be sufficient and you may use it combining a different thing. Here, the optical film refers to a film that can transmit light and has an optical function, and the optical function refers to refraction, birefringence, and the like.

Examples of such an optical film include an optical film having excellent wavelength dispersion characteristics, such as an antireflection film such as an antireflection (AR) film, a polarizing film, a retardation film, an elliptically polarizing film, a viewing angle widening film, and a transmission film. Examples thereof include an optical compensation film for compensating the viewing angle of a liquid crystal display. Moreover, these uses are illustrated as a use of the optical film of this invention.
For example, the film of the present invention can be bonded to a polarizing film and used as an elliptically polarizing plate. Further, the film of the present invention can be further bonded to this elliptical polarizing plate as a broadband λ / 4 plate and used as a broadband circular polarizing plate.

In particular, in order to use the optical film of the present invention as a broadband λ / 4 plate or λ / 2 plate, it contains a structural unit derived from the compound (1) and a different compound (for example, the compound (2)). The amount may be adjusted appropriately, the film thickness of the film may be adjusted, and the retardation value may be adjusted.
Specifically, in the case of a λ / 4 plate, Re (550) of the obtained film may be adjusted to 113 to 163 nm, preferably 135 to 140 nm, more preferably about 137.5 nm. In the case of a λ / 2 plate, Re (550) of the obtained film may be adjusted to 250 to 300 nm, preferably 273 to 277 nm, more preferably about 275 nm.

  In addition, in order to use the optical film of the present invention as an optical film for VA (Vertical Aimment) mode, the content of the structural unit derived from the compound (1) of the present invention or a compound different therefrom is appropriately adjusted, What is necessary is just to adjust the film thickness of a film. Specifically, the film thickness may be adjusted so that Re (550) is, for example, about 40 to 100 nm, preferably about 60 to 80 nm.

  That is, in the above composition, by changing the content of the compound (1) or a compound different from this, the wavelength dependency of the refractive index of the film obtained, wavelength dispersion characteristics, etc. can be arbitrarily controlled, By adjusting the amount of the composition applied and the concentration of the organic solvent, etc., and adjusting the film thickness of the resulting film, the retardation value can be controlled, or the retardation layer can be laminated. Can be omitted.

For example, since the values of [Re (450) / Re (550)] and [Re (650) / Re (550)] of compound (1) are close to 1 or less than 1, the content of compound (1) is reduced. By increasing the value, Re (450) / Re (550) or the like can be changed, that is, a desired wavelength dispersion characteristic (for example, a value close to 1) can be obtained, such as reducing the wavelength dispersion. In other words, the value of Re (450) / Re (550) in the optical film can be reduced by adding a small amount of compound (1), and as a result, uniform polarization conversion is possible in a wide wavelength range. A simple optical film can be produced by a simple method.
Moreover, the composition can be oriented in the film direction by increasing the content of the compound different from the compound (1).

In the case of a mixed solution in which the compound (1) is constant, the retardation value (retardation value, Re (λ)) of the film is determined as shown in Equation (3), so that a desired Re (λ) is obtained. For this purpose, the film thickness d is adjusted.
Re (λ) = d × Δn (λ) (3)
(In the formula, 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.)
Therefore, the film thickness may be increased to increase the phase difference value, and the film thickness may be decreased to decrease the phase difference value.

The film thickness of the optical film of the present invention is about 0.1 to 100 μm, preferably about 0.1 to 10 μm, and preferably 0.5 to 3 μm from the viewpoint of reducing photoelasticity.
When the alignment film is used and has birefringence, the retardation value is usually about 50 to 500 nm, preferably 100 to 300 nm.
Thus, the optical film of the present invention can be a thin film as compared with a stretched film having an equivalent retardation value. In addition, the wavelength dependence of the phase difference value can be reduced.

〔Polarizer〕
As a specific embodiment of the optical film of the present invention, a polarizing plate constituted by laminating the optical film of the present invention and a polarizing film will be described.
The polarizing plate 1a is obtained by directly bonding the optical film 2 of the present invention and a film having a polarizing function, that is, the polarizing film 3 (FIG. 1 (a)), and the optical film 2 includes a supporting substrate 4 and an alignment film. 5 and the optically anisotropic layer 6. The polarizing plate 1a is laminated | stacked in order of the support base material 4, the alignment film 5, the optically anisotropic layer 6, and the polarizing film 3. FIG.

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 ′. Are pasted together.

Instead of the optical film 2 and the optical film 2 ′, a film composed only of the optically anisotropic layer 6 containing a structural unit derived from the compound (1), in which the supporting substrate 4 and the alignment film 5 are peeled from the optical film 2. Alternatively, a film made of the alignment film 5 and the optically anisotropic layer 6 in which the support substrate 4 is peeled 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 may be, for example, a film having a polarizing function, such as a film obtained by adsorbing iodine or a dichroic dye on a polyvinyl alcohol film, or a film obtained by stretching a polyvinyl alcohol film, and an iodine or dichroic dye. The film etc. which adsorb | sucked are mentioned.
The adhesive 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.

[Flat panel display]
Further, the optical film of the present invention functions in any position, in any manner, and in any manner in a flat panel display (FPD) such as a reflective liquid crystal display and an organic electroluminescence (EL) display. It may be provided as a thing.
For example, a liquid crystal display device (LCD) including a liquid crystal panel in which the above-described polarizing plate and a liquid crystal panel are bonded together, and an organic electroluminescence display device including an organic electroluminescence panel in which the above-described polarizing plate and a light-emitting layer are bonded together (EL) Furthermore, LCD and EL provided with the optical film of this invention as a phase difference plate, LCD, EL provided with a color filter, etc. are mentioned.
Thus, by using the optical film of the present invention having optical characteristics, all FPDs can be optically compensated with a thin film.

[LCD]
As LCD, for example, as shown in FIG. 2, the polarizing plate 1 of the present invention and the liquid crystal panel 11 are constituted by a bonded product 10 formed by bonding through an adhesive layer 12.
According to this configuration, by applying a voltage to the liquid crystal panel using an electrode (not shown), the liquid crystal molecules can be driven and the optical shutter effect can be exhibited.

[Organic EL]
As the EL, for example, as shown in FIG. 3, an organic EL panel 13 in which the polarizing plate 1 of the present invention and the light emitting layer 14 are bonded via an adhesive layer 15 can be mentioned. In this organic EL panel, the polarizing plate 1 functions as a broadband circular polarizing plate. The light emitting layer 14 is composed of 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 following description, “%” and “parts” are by weight and parts by weight unless otherwise specified.
<Production Example of Compound (XA-1)>
Synthesized according to the following scheme. The raw material monotetrahydropyranyl protected hydroquinone (a) was synthesized by the method described in the patent document (Japanese Patent Application Laid-Open No. 2004-262848).

(Synthesis Example of Compound (b))
100.1 g (515 mmol) of monotetrahydropyranyl protected hydroquinone (a), 97.1 g (703 mmol) of potassium carbonate and 64 g (468 mmol) of 6-chlorohexanol were taken and dissolved and dispersed in dimethylacetamide. The mixture was stirred at 90 ° C. in a nitrogen atmosphere and then at 100 ° C. Thereafter, the mixture was cooled to room temperature, pure water and methyl isobutyl ketone were added, and the collected organic layer was dehydrated after washing with an aqueous sodium hydroxide solution and pure water, and concentrated under reduced pressure after filtration. Methanol was added to the residue, and the resulting precipitate was filtered and then vacuum dried to obtain 126 g (428 mmol) of compound (b). The yield was 91% based on 6-chlorohexanol.

(Synthesis Example of Compound (c))
126 g (428 mmol) of compound (b), 1.40 g (6.42 mmol) of 3,5-ditertiarybutyl-4-hydroxytoluene (hereinafter referred to as BHT), 116.7 g (963 mmol) of N, N-dimethylaniline, 1 , 3-dimethyl-2-imidazolidinone 1.00 g was taken and dissolved in chloroform. Under a nitrogen atmosphere and ice cooling, 58.1 g (642 mmol) of aquiroyl chloride was added dropwise, and pure water was further added and stirred. The collected organic layer was washed with aqueous hydrochloric acid, a saturated aqueous sodium carbonate solution and pure water. The organic layer was dried and filtered, and 1 g of BHT was added and concentrated under reduced pressure to obtain compound (c).

(Synthesis Example of Compound (d))
To the compound (c), 200 ml of tetrahydrofuran (hereinafter referred to as THF) was added, chloroform was distilled off, and then 200 ml of THF was added. Hydrochloric acid and concentrated hydrochloric acid were added thereto, and the mixture was stirred at 60 ° C. in a nitrogen atmosphere. 500 ml of saturated brine was added to the reaction solution and stirred, and the collected organic layer was dehydrated, filtered and concentrated under reduced pressure. Hexane was further added, and the mixture was stirred under ice-cooling. The precipitated powder was filtered and dried under vacuum to obtain 90 g (339 mmol) of compound (d). The yield was 79% based on the compound (c).

(Synthesis Example of Compound (e))
24.68 g (118 mmol) of transcyclohexanedicarboxylic acid was dispersed in toluene, 74.91 g (590 mmol) of oxalyl dichloride and 0.5 mL of dimethylformamide were added, and the mixture was stirred under a nitrogen atmosphere. Toluene and oxalyl dichloride were removed under reduced pressure, and chloroform was added to the liquid (crude product of cyclohexanedicarboxylic acid dichloride) obtained by dissolution. On the other hand, 12 g (45.4 mmol) of the compound (d) was dissolved in chloroform. A solution of the compound (d) and 12.6 g (159 mmol) of pyridine were added dropwise to a solution containing a crude purified product of cyclohexanedicarboxylic acid dichloride under ice cooling. The precipitate obtained by stirring the reaction solution under a nitrogen atmosphere was removed by filtration and then concentrated under reduced pressure. This was dropped into a mixed solvent of water / methanol (1/1 by volume), and the resulting precipitate was pulverized, washed with pure water, filtered and vacuum dried. The obtained powder was pulverized again, dispersed in n-heptane, stirred and dissolved in toluene. Insoluble components were filtered off, and the filtrate was concentrated under reduced pressure and reprecipitated in n-heptane. The precipitate was vacuum dried to obtain 7.8 g of compound (e). The yield was 40% based on the compound (d).

(Synthesis Example of Compound (A-1))
In a container, 50.0 g (256 mmol) of 2-acetamido-1,4-dimethoxybenzene, 2,4-bis (4-methoxyphenyl) -1,3-dithia 2,4-diphosphatan-2,4-disulfide (Lawson reagent) ) 53.9 g (133 mmol) and 579 g of toluene were added, and the mixture was heated to 80 ° C. and stirred. The reaction solution was concentrated to obtain a solid containing the compound (A-1) as a main component. The compound (A-1) was used in the next step as it was without purification.

(Synthesis Example of Compound (A-2))
In a container, a solid mainly composed of the compound (A-1) obtained in the previous step, 159 g (3975 mmol) of sodium hydroxide, and 880 g of water were mixed and stirred well under ice cooling. Subsequently, a solution prepared by dissolving 238.5 g (724 mmol) of potassium ferricyanide in 477 g of water was added under ice cooling and stirred. The precipitated solid was separated by filtration and washed well with cold water and heptane to obtain 22.8 g of a solid mainly composed of compound (A-2). The yield of the two steps combined with the previous step was 44% based on 2-acetamido-1,4-dimethoxybenzene.

(Synthesis Example of Compound (A-3))
3.0 g (14.4 mmol) of compound (A-2) and 15.0 g (5 times mass) of pyridinium chloride were put in a container, and the temperature was raised to 160 ° C. to melt and stir the solid. After cooling, 210 g of water was added, and the resulting precipitate was filtered off and washed well with water and chloroform to obtain 2.5 g of a solid containing compound (A-3) as the main component. The yield was 95% based on the compound (A-2).

化合物（ＸＡ−１）の^１Ｈ−ＮＭＲ（ＣＤＣｌ_３）：δ（ｐｐｍ）１．４−１．５（４Ｈｋ＋４Ｈｌ）、１．６−１．８（４Ｈｊ＋４Ｈｍ＋４Ｈｆ＋４Ｈｇ）、２．３−２．４（４Ｈｆ＋４Ｈｇ）、２．６（２Ｈｅ＋２Ｈｈ）、２．８（３Ｈｒ）、３．９（４Ｈｎ）、４．２（４Ｈｉ）、５．８（２Ｈｑ）、６．１（２Ｈｏ）、６．４（２Ｈｐ）、６．９（４Ｈｄ）、７．０（４Ｈｃ），７．２（Ｈａ＋Ｈｂ） (Synthesis Example of Compound (XA-1))
In a container, 2.2 g (12.0 mmol) of compound (A-3), 10.6 g (25.2 mmol) of compound (e), 0.31 g (2.5 mmol) of 4-dimethylaminopyridine, and 84 g of chloroform Then, 6.2 g (30.2 mmol) of N, N′-dicyclohexylcarbodiimide (DCC) was dissolved in 21 g of chloroform, added dropwise, and stirred at room temperature. After separating the precipitated solid by filtration, the chloroform solution was separated and washed twice with 105 g of 2N hydrochloric acid, and the organic layer was taken out. The solvent was distilled off from the organic layer under reduced pressure, and methanol was added to obtain a solid. The obtained solid was washed with methanol to obtain 5.9 g of compound (XA-1). The yield was 50% based on the compound (A-3).

¹ H-NMR (CDCl ₃ ) of compound (XA-1): δ (ppm) 1.4-1.5 (4Hk + 4Hl), 1.6-1.8 (4Hj + 4Hm + 4Hf + 4Hg), 2.3-2.4 ( 4Hf + 4Hg), 2.6 (2He + 2Hh), 2.8 (3Hr), 3.9 (4Hn), 4.2 (4Hi), 5.8 (2Hq), 6.1 (2Ho), 6.4 (2Hp) ), 6.9 (4Hd), 7.0 (4Hc), 7.2 (Ha + Hb)

  The phase transition temperature of the obtained compound (XA-1) was measured by texture observation with a polarizing microscope. As the temperature was raised, the crystal phase changed to a smectic phase around 101 ° C., and further changed to a nematic phase around 133 ° C. As the temperature was further increased, thermal polymerization occurred at around 146 ° C. That is, it was found that the compound (XA-1) exhibited a smectic phase from 101 ° C. to 133 ° C. and a nematic phase from 133 ° C. to 146 ° C. when the temperature was raised.

Example 1
<Example of optical film production>
After applying a 2% by weight aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified type, manufactured by Wako Pure Chemical Industries, Ltd.) to a glass substrate, a film having a thickness of 89 nm was obtained after drying by heating. 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. Then, it dried for 1 minute on a 110 degreeC hotplate, and irradiated the ultraviolet ray of 2000 mJ / cm < ² >, heating the 110 degreeC hotplate, and created the optical film.
In Table 1, the compound (1) is the compound (XA-1) produced above, the compound (2) is LC242 (a liquid crystal compound obtained from BASF), and the photopolymerization initiator is Irgacure 819 ( Ciba Specialty Chemicals), the leveling agent used was BYK361N (manufactured by Big Chemie Japan), and the solvent was chloroform. Further, in Table 1, “% by weight” in the tables other than the solvent means “% by weight” of the solid content with the coating solution being 100% by weight.

<Measurement of optical characteristics>
About the created optical film, the phase difference value in wavelength 547nm was measured using the measuring machine (KOBRA-WR, Oji Scientific Instruments company make). Moreover, the film thickness derived from the polymeric compound of an optical film was measured using the laser microscope (LEXT, Olympus Corporation make). Δn was calculated from the retardation value and the film thickness at a wavelength of 547 nm. Similarly, retardation values at wavelengths of 447 nm and 628 nm were measured, and wavelength dispersion characteristics Re (447) / Re (547) and Re (628) / Re (547) were calculated. The results are shown in Table 2.

(Example 2)
An optical film was prepared in the same manner as in Example 1 using the coating liquid shown in Table 1. About the obtained optical film, the phase difference value was measured like Example 1 using the measuring machine (KOBRA-WR, Oji Scientific Instruments company make). The results are shown in Table 2.

(Example 3)
Using the coating solution of Table 1, applying by spin coating, drying on a 150 ° C. hot plate for 1 minute, and irradiating with ultraviolet rays while heating on a 150 ° C. hot plate, the same as in Example 1, An optical film was created. About the obtained optical film, the phase difference value was measured like Example 1 using the measuring machine (KOBRA-WR, Oji Scientific Instruments company make). The results are shown in Table 2.

(Comparative Example 1)
An optical film was prepared in the same manner as in Example 1 except that the coating solution shown in Table 1 was applied by spin coating, dried on a 45 ° C. hot plate for 1 minute, and irradiated with ultraviolet rays at room temperature. About the obtained optical film, the phase difference value was measured like Example 1 using the measuring machine (KOBRA-WR, Oji Scientific Instruments company make). The results are shown in Table 2.

The optical films obtained in Examples 1 to 3 contain [Re (450) / Re (550)] and [Re (650) / Re as compared with Comparative Example 1 by containing the compound (XA-1). The value of (550)] is closer to 1 and has excellent wavelength dispersion.

  According to the compound of the present invention, an optical film capable of uniform polarization conversion in a wide wavelength range can be provided.

It is the schematic which shows the polarizing plate of this invention. It is the schematic which shows the bonding product of the liquid crystal panel of the liquid crystal display device of this invention, and the polarizing plate 1. FIG. It is the schematic which shows the organic electroluminescent panel of the organic electroluminescent display apparatus of 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 ′ optically anisotropic layer 7, 7 ′, 12 , 15 Adhesive layer 10 Bonded product 11 Liquid crystal panel 13 Organic EL panel 14 Light emitting layer

Claims (16)

The compound represented by Formula (1).

[In the formula (1), X represents —S—, —O—, —CH ₂ —, —NH—, —C (═O) —, —S (═O) — or —C (═S) —. Represents.
Y represents -C (R) = or -N =. R is a hydrogen atom, a halogen atom, —C≡C—H or —C≡C—CH ₃ , an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, or an alkoxy having 1 to 6 carbon atoms. Group, a thioalkyl group having 1 to 6 carbon atoms, an alkylamino group having 1 to 6 carbon atoms, a dialkylamino group having 1 to 6 carbon atoms, a cyano group, a nitro group, a hydroxyl group, and a mercapto group.
Z is a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a thioalkyl group having 1 to 6 carbon atoms, a cyano group, or a nitro group. Group, hydroxyl group, mercapto group, sulfone group, sulfoxide group, —NR ¹ R ² , —C (═O) —O—R ¹ , —O—C (═O) —R ¹ , —C (═S) — O—R ¹ , —O—C (═S) —R ¹ , —C (═O) —NR ¹ R ² , —NR ¹ —C (═O) —R ² , —C≡C—R ¹ , ^{-C (= O) -R 1,} -C (= S) -R 1, -CR 1 = NR 2, -N = CR 1 R 2, represent a -CR 1 = ^CR 2 ^{R 3.} R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
J ₁ and J ₂ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms. Thioalkyl group, cyano group, nitro group, hydroxyl group, mercapto group, sulfone group, sulfoxide group, —NR ⁴ R ⁵ , —C (═O) —O—R ⁴ , —O—C (═O) —R ^4. , —C (═S) —O—R ⁴ , —O—C (═S) —R ⁴ , —C (═O) —NR ⁴ R ⁵ , —NR ⁴ —C (═O) —R ⁵ , ^{-C≡C-R 4, -C (=} O) -R 4, -C (= S) -R 4, -CR 4 = NR 5, -N = CR 4 R 5, -CR 4 = CR 5 R ⁶ is represented. R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
_{B 1, B 2, E 1} , E 2, G 1 and _{G 2} are each ^{independently, -CR 7 R 8 -, -} 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 7 = N -, - N = CR 7 —, —C (═O) —NR ⁷ —, —NR ⁷ —C (═O) —, —O—CH ₂ —, —O—CF ₂ —, —NR ⁷ —, —CH ₂ —O—, —CF ₂ —O—, —S—CH ₂ —, —CH ₂ —S—, —CH═CH—C (═O) —O—, —O—C (═O) —CH═CH— Represents a bond. R ⁷ and R ⁸ 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. Hydrogen atoms contained in the aromatic hydrocarbon group, the alicyclic hydrocarbon group, and the heterocyclic group are a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and 1 carbon atom. It may be substituted with a -4 fluoroalkyl group, a C 1-4 fluoroalkoxy group, a nitro group or a nitrile group.
m and n each independently represent an integer represented by 1 to 3.
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 each independently 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 ^{9 to} R ¹³ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)]   The compound according to claim 1, wherein X is -S- or -O-, and Y is -N = or -CH =.   The compound according to claim 1, wherein X is -S- and Y is -N =. The compound according to any one of claims 1 to 3, 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 compound according to any one of claims 1 to 4, wherein -G ₁ -Q ₁ and -G ₂ -Q ₂ contain an acryloyl group or a methacryloyl group. The composition containing the compound in any one of Claims 1-5, and the compound (however, it is not the same as the compound in any one of Claims 1-5) represented by Formula (2).
P11-E11- (B11-A11) _t- B12-G (2)
(In Formula (2), A11 represents an aromatic hydrocarbon group, an alicyclic hydrocarbon group, or a heterocyclic group, and these groups include a halogen atom, an alkyl group having 1 to 6 carbon atoms, and 1 to 1 carbon atoms. 6 alkoxy groups, C1-C6 alkylamino groups, nitro groups, nitrile groups, and mercapto groups may be substituted.
B11, B12 are each ^{independently, -CR 14 R 15 -, -} C≡C -, - CH = CH -, - CH 2 -CH 2 -, - O -, - S -, - C (= O) -, -C (= O) -O-, -OC (= O)-, -O-C (= O) -O-, -C (= S)-, -C (= S) -O. -, -OC (= S)-, -CH = N-, -N = CH-, -N = N-, -C (= O) -NR < ¹⁴ >-, -NR < ¹⁴ > -C (= O). —, —OCH ₂ —, —OCF ₂ —, —NR ¹⁴ —, —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 may be linked to form an alkylene group having 4 to 7 carbon atoms. Good.
E11 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 each independently 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 is an integer of 1 to 5)   The optical film containing the structural unit derived from the compound in any one of Claims 1-5.   An optical film obtained by polymerizing the composition according to claim 6.   The optical film according to claim 7 or 8, which functions as a λ / 4 plate having a retardation value (Re (550)) at a wavelength of 550 nm of light transmitted through the optical film of 113 to 163 nm.   The optical film according to claim 7 or 8, which functions as a λ / 2 plate having a retardation value (Re (550)) at a wavelength of 550 nm of light transmitted through the optical film of 250 to 300 nm.   A polarizing plate comprising the optical film according to claim 7 or 9 and a polarizing film.   A liquid crystal display comprising the polarizing plate according to claim 11 and a liquid crystal panel.   An organic electroluminescence display device comprising an organic electroluminescence panel including the polarizing plate according to claim 11.   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 | membrane formed on the support base material, and dries.   The manufacturing method of the optical film which hardens the unpolymerized film obtained by the manufacturing method of the unpolymerized film of Claim 14 or 15 by superposition | polymerization.

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