KR101952083B1 - Optical film and display device using the same - Google Patents

Abstract

The present invention relates to an optical film in which a polymerizable liquid crystal compound is oriented, wherein an absorbance A at 400 nm of a polymerizable liquid crystal compound measured using a solution (a) is 0.1 or less, orientation and order of the optical film at the maximum absorption wavelength of the polymerizable liquid crystal compound to be measured is also an object to provide an optical film which meets the S ₀ -0.50 <S ₀ <-0.15.
Solution (a): A solution obtained by dissolving a polymerizable liquid crystal compound in chloroform so as to have a concentration of 10 ^-4 mol / l.

Description

TECHNICAL FIELD [0001] The present invention relates to an optical film and a display device using the optical film.

The present invention relates to an optical film and a display device using the same.

A flat panel display (FPD) includes a member using an optical film such as a polarizing plate and a retardation plate. Japanese Patent Laying-Open No. 2010-31223 discloses an optical film obtained by coating a solution obtained by dissolving a polymerizable liquid crystal compound in a solvent on a support substrate and then polymerizing the polymerizable liquid crystal compound.

The present invention provides the following <1> to <9>.

&Lt; 1 > An optical film in which a polymerizable liquid crystal compound is aligned,

The absorbance A at 400 nm of the polymerizable liquid crystal compound measured by using the solution (a) is 0.1 or less,

Solution (a) orientation and order Figure S ₀ of the optical film in the maximum absorption wavelength of the liquid crystal in a polymerizable compound to be measured use is -0.50 <S ₀ <optical film to meet -0.15.

Solution (a): a solution prepared by dissolving the polymerizable liquid crystal compound in chloroform so as to have a concentration of 10 ^-4 mol / l;

&Lt; 2 > An optical film according to < 1 >, wherein the maximum absorption wavelength of the solution (a) is 300 nm or more and 400 nm or less;

<3> An optical film according to <1> or <2>, wherein the wavelength range satisfying -0.50 <S (λ) <- 0.15 is 40 nm or more;

[S (?) Represents the alignment order of the optical film at the wavelength? Nm.]

&Lt; 4 > The optical film according to any one of < 1 > to < 3 >, wherein the polymerizable liquid crystal compound is a compound represented by the formula (A)

L ¹ -G ¹ -D ¹ -Ar-D ² -G ² -L ² (A)

[In the above formula, Ar represents a divalent group having an aromatic ring, and the number of p-electrons contained in this aromatic ring is 12 or more and 22 or less.

D ¹ and D ² each independently represent a single bond, -CO-O-, -C (= S) -O-, -CR ¹ R ² -, -CR ¹ R ² -CR ³ R ⁴ - CR ¹ R ² -, -CO-O-CR ¹ R ² -, -O-CO-CR ¹ R ² -, -CR ¹ R ² -O-CR ³ R ⁴ -, -CR ¹ R ² -O- -CO-CR ³ R ⁴ -, -CR ¹ R ² -CO-O-CR ³ R ⁴ -, -NR ¹ -CR ² R ³ - or -CO-NR ¹ -.

R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.

G ¹ and G ² each independently represent a divalent aromatic hydrocarbon group having 5 to 8 carbon atoms which may have a substituent or a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms which may have a substituent and is included in the alicyclic hydrocarbon group -CH ₂ - may be substituted with -O-, -S- or -NH-, and -CH (-) - included in the alicyclic hydrocarbon group may be substituted with -N (-) -.

L ¹ represents a polymerizable group or a monovalent organic group.

L &lt; ² &gt; represents a polymerizable group.

<5> The optical film according to <4>, wherein G ¹ and G ² are each independently a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms;

<6> An optical element according to any one of <1> to <5>, which is obtained by applying a composition comprising a polymerizable liquid crystal compound to a substrate, orienting the polymerizable liquid crystal compound, and polymerizing the polymerizable component contained in the composition. film;

<7> A polarizing plate comprising the optical film and the polarizing film according to any one of <1> to <6>.

&Lt; 8 > A flat panel display device comprising the optical film according to any one of < 1 > to < 6 >;

<9> A color filter comprising the optical film according to any one of <1> to <6>.

1 is a cross-sectional view of an example of a polarizing plate of the present invention.
2 is a cross-sectional view of an example of a liquid crystal display device which is one of the flat panel display devices of the present invention.
3 is a cross-sectional view of an example of an organic EL display device which is one of the flat panel display devices of the present invention.
4 is a cross-sectional view of an example of the color filter of the present invention.

The optical film of the present invention is an optical film in which a polymerizable liquid crystal compound is oriented, wherein the absorbance A at 400 nm of the polymerizable liquid crystal compound measured using the solution (a) is 0.1 or less and the solution Is an optical film having an alignment order S ₀ of -0.50 &lt; S ₀ &lt; -0.15 in terms of the maximum absorption wavelength of the polymerizable liquid crystal compound. Here, the solution (a) is a solution in which the polymerizable liquid crystal compound is dissolved in chloroform so as to have a concentration of 10 ^-4 mol / l.

In the present specification, the alignment order S (?) Of the optical film at the wavelength? Nm is a value represented by the following equation (1).

_{S (λ) = (A p} -A v) / (A p + 2A v) (1)

[In the above formula, A _p represents the absorbance of light polarized in the direction parallel to the alignment direction of the polymerizable liquid crystal compound contained in the optical film. A _v represents the absorbance of light polarized in the direction perpendicular to the alignment direction of the polymerizable liquid crystal compound contained in the optical film.

The orientation order of the optical film S (?) Can be obtained by polarized absorption measurement.

When the molecules of the polymerizable liquid crystal compound contained in the optical film are completely uniaxially oriented, the alignment state of the optical film S (lambda) is 1. When the molecules of the liquid crystal compound are present in a random direction 0, and when the molecular length axis of this liquid crystal compound is distributed in the plane perpendicular to the orientation axis, it indicates -0.5.

If the solution (a) in a range between the alignment order is also S ₀ is larger than -0.50 -0.15 of the optical film at the maximum absorption wavelength of the polymerizable liquid crystal compound to be measured with, the optical film is capable of excellent optical compensation And decolorization is reduced.

The maximum absorption wavelength of the polymerizable liquid crystal compound measured by using the solution (a) is preferably in the range of 300 nm to 400 nm. When the maximum absorption wavelength is within the above range, the resulting optical film is less colored and has high transparency.

It is preferable that S (?) Of the optical film satisfies -0.50 <S (?) <- 0.15 in a wavelength range of 40 nm or more, and in a wavelength range of 40 nm or more of 300 nm to 400 nm, 0.50 &lt; S (?) &Lt; - 0.15. As the wavelength range satisfying -0.50 <S (?) <- 0.15 is wider, the discoloration of the optical film is further reduced.

The optical film of the present invention has birefringence because the polymerizable liquid crystal compound is aligned. When the optical film of the present invention is used as a? / 4 plate, the retardation value is adjusted to 113 nm to 163 nm, and when the? / 2 plate is used, the retardation value is adjusted to 250 nm to 300 nm, Can be further reduced.

The optical film of the present invention is formed using a composition comprising a polymerizable liquid crystal compound (hereinafter sometimes referred to as &quot; composition (A) &quot;).

The polymerizable liquid crystal compound is preferably a compound represented by the formula (A) [hereinafter sometimes referred to as &quot; compound (A) &quot;).

L ¹ -G ¹ -D ¹ -Ar-D ² -G ² -L ² (A)

[In the above formula (A), Ar represents a divalent group having an aromatic ring, and the number of p-electrons contained in the aromatic ring is 12 or more and 22 or less.

D ¹ and D ² each independently represent a single bond, -CO-O-, -C (= S) -O-, -CR ¹ R ² -, -CR ¹ R ² -CR ³ R ⁴ - CR ¹ R ² -, -CO-O-CR ¹ R ² -, -O-CO-CR ¹ R ² -, -CR ¹ R ² -O-CR ³ R ⁴ -, -CR ¹ R ² -O- -CO-CR ³ R ⁴ -, -CR ¹ R ² -CO-O-CR ³ R ⁴ -, -NR ¹ -CR ² R ³ - or -CO-NR ¹ -.

R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.

G ¹ and G ² each independently represent a divalent aromatic hydrocarbon group having 5 to 8 carbon atoms which may have a substituent or a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms which may have a substituent and is included in the alicyclic hydrocarbon group -CH ₂ - may be substituted with -O-, -S- or -NH-, and -CH (-) - included in the alicyclic hydrocarbon group may be substituted with -N (-) -.

L ¹ represents a polymerizable group or a monovalent organic group. L &lt; ² &gt; represents a polymerizable group.

D ¹ and D ² each independently represents a single bond, -CO-O-, -O-CO-, -C (═S) -O-, -OC (═S) -, -CR ¹ R ² -, - CR ¹ R ² -CR ³ R ⁴ -, -O-CR ¹ R ² -, -CR ¹ R ² -O-, -CR ¹ R ² -O-CR ³ R ⁴ -, -CR ¹ R ² -O -CO-CR ¹ R ² -, -CR ¹ R ² -O-CO-CR ³ R ⁴ -, -CR ¹ R ² -CO-O-CR ³ R ⁴ -, -NR ¹ -CR ² R ³ -, -CR ¹ R ² -NR ³ -, -CO-NR ¹ - or -NR ¹ -CO-. R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.

 Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group and a butyl group.

D ¹ and D ² are each independently of * -O-CO-, * -OC ( = S) -, * -O-CR 1 R 2 -, * -NR 5 -CR 1 R 2 - or * -NR ⁵ -CO- (* represents a bonding site with Ar). It is more preferable that D ¹ and D ² each independently represent * -O-CO-, * -OC (= S) - or * -NR ⁵ -CO- (* represents a bonding site with Ar). R ¹ , R ² , R ³ and R ⁴ are each independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group. R ⁵ is preferably a hydrogen atom, a methyl group or an ethyl group.

G ¹ and G ² are each independently a divalent aromatic hydrocarbon group having 5 to 8 carbon atoms or a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms. The aromatic hydrocarbon group and the alicyclic hydrocarbon group may have a halogeno group, an alkyl group having 1 to 4 carbon atoms, an alkyl fluoride group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group. -CH ₂ - included in the alicyclic hydrocarbon group may be substituted with -O-, -S- or -NH-, and -CH (-) - included in the alicyclic hydrocarbon group may be replaced with -N Or may be substituted.

Examples of the bivalent aromatic hydrocarbon group having 5 to 8 carbon atoms include a phenylene group and a naphthalenediyl group. Examples of the aromatic hydrocarbon group having a substituent include a chlorophenylene group, a methylphenylene group, a trifluoromethylphenylene group, a cyanophenylene group, a nitrophenylene group and a methoxynaphthalenediyl group.

There can be an alicyclic hydrocarbon group having a carbon number of 5 to 8 is the divalent represented by the following formula (g-1) to general formula _{(g-4), -CH 2} - is -O-, -S-, -NH- Include the groups represented by the following formulas (g-5) to (g-10).

Examples of the groups represented by the formulas (g-1) to (g-10) include an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an isopropyl group or a tert- An alkoxy group having 1 to 4 carbon atoms such as methoxy group and ethoxy group; A fluorinated alkyl group having 1 to 4 carbon atoms such as a trifluoromethyl group; A fluoroalkoxy group having 1 to 4 carbon atoms such as a trifluoromethoxy group; Cyano; A nitro group; Or a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom.

G ¹ and G ² are preferably a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, more preferably an alicyclic hydrocarbon group having 5 or 6 ring members, more preferably a cyclohexane-1,4-diyl group , and trans-cyclohexane-1,4-diyl group. When G ¹ and G ² are the above-mentioned groups, decolorization tends to be reduced.

Ar is a divalent group having an aromatic ring, and the aromatic ring is at least one selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle. The number of? Electrons included in the aromatic ring is 12 or more and 22 or less, and preferably 13 or more and 22 or less.

Examples of Ar include a group represented by the following formulas (Ar-1) to (Ar-13), and preferably a group represented by the formula (Ar-6).

[In the formulas (Ar-1) to (Ar-13), Z ¹ is each independently a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 6 carbon atoms, An alkylsulfonyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylsulfanyl group having 1 to 6 carbon atoms, an N-alkylamino group having 1 to 6 carbon atoms, An N, N-dialkylamino group, an N-alkylsulfamoyl group having 1 to 6 carbon atoms or an N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms.

Q ¹ and Q ³ each independently represent -CR ⁹ R ¹⁰ -, -S-, -NR ⁹ -, -CO- or -O-.

R ⁹ and R ¹⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

Y ¹ , Y ² and Y ³ each independently represent an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent.

W ^a and W ^b each independently represent a hydrogen atom, a cyano group, a methyl group or a halogen atom.

m represents an integer of 0 to 6; and n represents an integer of 0 to 2.]

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

Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, More preferably an alkyl group having 1 to 2 carbon atoms, and a methyl group is particularly preferable.

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

Examples of the alkylsulfonyl group having 1 to 6 carbon atoms include methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, An alkylsulfonyl group having 1 to 4 carbon atoms is preferable, an alkylsulfonyl group having 1 to 2 carbon atoms is more preferable, and a methylsulfonyl group is particularly preferable.

Examples of the fluoroalkyl group having 1 to 6 carbon atoms include a fluoromethyl group, a trifluoromethyl group, a fluoroethyl group, a pentafluoroethyl group, a heptafluoropropyl group and a nonafluorobutyl group, and a fluoroalkyl group having 1 to 4 carbon atoms An alkyl group is preferable, a fluoroalkyl group having 1 to 2 carbon atoms is more preferable, and a trifluoromethyl group is particularly preferable.

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

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

Examples of the N-alkylamino group having 1 to 6 carbon atoms include N-methylamino, N-ethylamino, N-propylamino, N-isopropylamino, N-butylamino, N-isobutylamino, An N-tert-butylamino group, an N-pentylamino group and an N-hexylamino group, preferably an N-alkylamino group having 1 to 4 carbon atoms, more preferably an N-alkylamino group having 1 to 2 carbon atoms, Methylamino groups are particularly preferred.

Examples of the N, N-dialkylamino group having 2 to 12 carbon atoms include N, N-dimethylamino group, N-methyl-N-ethylamino group, N, N-diethylamino group, Diisopropylamino group, N, N-dibutylamino group, N, N-diisobutylamino group, N, N-dipentylamino group and N, N-dihexylamino group, -Dialkylamino group is preferable, an N, N-dialkylamino group having 2 to 4 carbon atoms is more preferable, and an N, N-dimethylamino group is particularly preferable.

Examples of the N-alkylsulfamoyl group having 1 to 6 carbon atoms include N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N- An N-sec-butylsulfamoyl group, an N-tert-butylsulfamoyl group, an N-pentylsulfamoyl group and an N-hexylsulfamoyl group, and includes N-alkyl Sulfamoyl group is preferable, N-alkyl sulfamoyl group having 1 to 2 carbon atoms is more preferable, and N-methyl sulfamoyl group is particularly preferable.

Examples of the N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms include N, N-dimethylsulfamoyl group, N-methyl-N-ethylsulfamoyl group, N, N, N-diisopropylsulfamoyl, N, N-diisopropylsulfamoyl, N, N-diisopropylsulfamoyl, N, N-dialkylsulfamoyl group having 2 to 8 carbon atoms is preferable, and N, N-dialkylsulfamoyl group having 2 to 4 carbon atoms is more preferable, and N, N- Particularly preferred is a dimethylsulfamoyl group.

Z ¹ represents a halogen atom, a methyl group, a cyano group, a nitro group, a carboxy group, a methylsulfonyl group, a trifluoromethyl group, a methoxy group, a methylsulfanyl group, an N-methylamino group, Or an N, N-dimethylsulfamoyl group.

Examples of the alkyl group having 1 to 4 carbon atoms for R ⁹ and R ¹⁰ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group and a tert-butyl group. And a methyl group is more preferable.

Q ¹ is preferably -S-, -CO-, -NH- or -N (CH ₃ ) -, and Q ³ is preferably -S- or -CO-.

Examples of the aromatic hydrocarbon group and aromatic heterocyclic group represented by Y ¹ , Y ² and Y ³ include an aromatic hydrocarbon group or an aromatic heterocyclic group.

Examples of the aromatic hydrocarbon group for Y ¹ , Y ² and Y ³ include an aromatic hydrocarbon group having 6 to 20 carbon atoms such as a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group and a biphenyl group, and a phenyl group and a naphthyl group are preferable And a phenyl group is more preferable. Examples of the aromatic heterocyclic group include a nitrogen atom such as a furyl group, a pyrrolyl group, a thienyl group, a pyridyl group, a thiazolyl group, a benzothiazolyl group, a benzofuryl group and a benzothienyl group, a hetero atom such as an oxygen atom, Or an aromatic heterocyclic group having 4 to 20 carbon atoms, and is preferably a furyl group, a thienyl group, a thiazolyl group, a benzothiazolyl group, a benzofuryl group or a benzothienyl group.

The aromatic hydrocarbon group and the aromatic heterocyclic group may have one or more substituents. Examples of the substituent include a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 6 carbon atoms, A fluoroalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylsulfanyl group having 1 to 6 carbon atoms, an N-alkylamino group having 1 to 6 carbon atoms, an N , An N-dialkylamino group, an N-alkylsulfamoyl group having 1 to 6 carbon atoms and an N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms. Examples of the halogen atom include an alkyl group having 1 to 2 carbon atoms, , A nitro group, an alkylsulfonyl group having 1 to 2 carbon atoms, a fluoroalkyl group having 1 to 2 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, an alkylthio group having 1 to 2 carbon atoms, an N-alkylamino group having 1 to 2 carbon atoms, N, N-dialkylamino groups having 2 to 4 carbon atoms and alkylsulfamoyl groups having 1 to 2 carbon atoms are preferable .

A halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, a carboxy group, a fluoroalkyl group having 1 to 6 carbon atoms, An alkylsulfanyl group having 1 to 6 carbon atoms, an N-alkylamino group having 1 to 6 carbon atoms, an N, N-dialkylamino group having 2 to 12 carbon atoms, an N-alkylsulfamoyl group having 1 to 6 carbon atoms, Examples of the N, N-dialkylsulfamoyl group of 12 include the same ones as described above.

Examples of the monocyclic aromatic hydrocarbon group or aromatic heterocyclic group include groups represented by the following formulas (Y-1) to (Y-6).

In the formulas (Y-1) to (Y-6), each Z ² independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkyl sulfinyl group having 1 to 6 carbon atoms, An alkylsulfonyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylsulfanyl group having 1 to 6 carbon atoms, an N-alkylamino group having 1 to 6 carbon atoms, An N, N-dialkylamino group, an N-alkylsulfamoyl group having 1 to 6 carbon atoms or an N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms.

a1 represents an integer of 0 to 5, a2 represents an integer of 0 to 4, b1 represents an integer of 0 to 3, b2 represents an integer of 0 to 2, and R represents a hydrogen atom or a methyl group.

Z ² each independently is preferably a halogen atom, a methyl group, a cyano group, a nitro group, a sulfo group, a carboxyl group, a trifluoromethyl group, a methoxy group, a methylsulfanyl group, an N, N-dimethylamino group or an N-methylamino group.

Y ¹ , Y ² and Y ³ are each independently a group represented by the formula (Y-1) or (Y-3) in terms of the production process and cost.

Examples of the polycyclic aromatic hydrocarbon group or aromatic heterocyclic group include groups represented by the following formulas (Y ¹ -1) to (Y ¹ -7).

In the formulas (Y ¹ -1) to (Y ¹ -7), Z ³ is independently selected from the group consisting of a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, a nitroso group, A fluoroalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylsulfanyl group having 1 to 6 carbon atoms, an N, N-dialkylamino group having 2 to 8 carbon atoms, or an alkylsulfonyl group having 1 to 6 carbon atoms, 4 &lt; / RTI &gt;

V ¹ and V ² each independently represent -CO-, -S-, -NR ¹¹ -, -O-, -Se- or -SO ₂ -.

W ^{1 to} W ⁵ each independently represent -CR ¹¹ = or -N =.

Provided that at least one of V ¹ , V ² and W ^{1 to} W ⁵ represents a group containing S, N, O or Se.

R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

a represents independently an integer of 0 to 3; b each independently represent an integer of 0 to 2.]

Y ¹ , Y ² and Y ³ are preferably groups represented by the following formulas (Y ³ -1) to (Y ³ -6).

In the above formulas (Y ³ -1) to (Y ³ -6), *, Z ³ , a, b, V ¹ , V ² and W ¹ have the same meanings as above.

Z ³ represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, a carboxy group, a fluoroalkyl group having 1 to 6 carbon atoms, An alkylsulfanyl group having 1 to 6 carbon atoms, an N-alkylamino group having 1 to 6 carbon atoms, an N, N-dialkylamino group having 2 to 12 carbon atoms, an N-alkylsulfamoyl group having 1 to 6 carbon atoms And N, N-dialkylsulfamoyl groups having 2 to 12 carbon atoms, and examples thereof include a halogen atom, a methyl group, an ethyl group, an isopropyl group, a sec-butyl group, a cyano group, a nitro group, a sulfo group, Methyl, ethyl, n-propyl, isopropyl, sec-butyl, cyano, nitro, and tri A fluoromethyl group is more preferable, and a methyl group, an ethyl group, an isopropyl group, a sec-butyl group , Pentyl group and hexyl group are particularly preferable.

A halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkylsulfinyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, Alkylsulfanyl group, an N-alkylamino group having 1 to 6 carbon atoms, an N, N-dialkylamino group having 2 to 12 carbon atoms, an N-alkylsulfamoyl group having 1 to 6 carbon atoms and an N, Examples of the sulfamoyl group include the same ones as described above.

V ¹ and V ² are each independently -S-, -NR ¹¹ - or -O-.

W ^{1 to} W ⁵ are each independently preferably -CR ¹¹ = or -N =.

It is preferable that at least one of V ¹ , V ² and W ^{1 to} W ⁵ is a group containing S, N or O.

a is preferably 0 or 1. b is preferably 0.

Specific examples of the group represented by the formulas (Ar-1) to (Ar-4) include groups represented by the following formulas (ar-1) to (ar-29). In the following formulas, * represents a bonding position.

Specific examples of the group represented by the formula (Ar-5) include groups represented by the following formulas (ar-30) to (ar-39).

Specific examples of the group represented by the formula (Ar-6) or (Ar-7) include groups represented by the following formulas (ar-40) to (ar-99).

Specific examples of the group represented by the formula (Ar-8) or (Ar-9) include groups represented by the following formulas (ar-100) to (ar-109).

Specific examples of the group represented by the formula (Ar-10) include groups represented by the following formulas (ar-110) to (ar-129).

Specific examples of the group represented by the formula (Ar-11) include groups represented by the following formulas (ar-130) to (ar-139).

Specific examples of the group represented by the formula (Ar-12) include groups represented by the following formulas (ar-140) to (ar-159).

Specific examples of the group represented by the formula (Ar-13) include groups represented by the following formulas (ar-160) to (ar-169).

In the compound (A), it is preferable that L ¹ is a group represented by the following formula (D) and L ² is a group represented by the following formula (E).

P ¹ -F ¹ - (B ¹ -A ¹ ) _k -E ¹ - (D)

P ² -F ² - (B ² -A ² ) ₁ -E ² - (E)

In formula (D), B ¹ , B ² , E ¹ and E ² are each independently -CR ⁵ R ⁶ -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O -, -O-CO-O-, -C (= S) -O-, -OC (= S) -O-, -CO-NR 5 -, -O-CH 2 -, -S-CH 2 - Or a single bond.

R ⁵ and R ⁶ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.

A ¹ and A ² each independently represent a divalent aromatic hydrocarbon group having 6 to 8 carbon atoms which may have a substituent or a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms which may have a substituent and the aliphatic hydrocarbon group contained in the alicyclic hydrocarbon group -CH ₂ - may be substituted with -O-, -S- or -NH-, and -CH (-) - included in the alicyclic hydrocarbon group may be substituted with -N (-) -.

k and l each independently represent an integer of 0 to 3;

F ¹ and F ² represent a divalent aliphatic hydrocarbon group having 1 to 12 carbon atoms.

P ¹ represents a polymerizable group.

And P ² represents a hydrogen atom or a polymerizable group.

A ¹ and A ² each independently represent a divalent aromatic hydrocarbon group having 6 to 8 carbon atoms or a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms. The aromatic hydrocarbon group and the alicyclic hydrocarbon group may be substituted with a halogeno group, an alkyl group having 1 to 4 carbon atoms, an alkyl fluoro group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkoxy fluoro group having 1 to 4 carbon atoms, . -CH ₂ - included in the alicyclic hydrocarbon group may be substituted with -O-, -S- or -NH-, and -CH (-) - included in the alicyclic hydrocarbon group may be replaced with -N Or may be substituted.

Examples of the bivalent aromatic hydrocarbon group represented by A ¹ and A ² include groups represented by the following formulas (a-1) to (a-8), and examples of the bivalent alicyclic hydrocarbon group include the above- ) To (g-10).

When A ¹ and A ² are the same kind of groups, the compound (A) is preferable because of easy production. The 1,4-phenylene group or the cyclohexane-1,4-diyl group is preferable as A ¹ and A ² , and the 1,4-phenylene group is more preferable since the compound (A) is easily produced.

B ¹ , B ² , E ¹ and E ² are each independently -CR ⁵ R ⁶ -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO-O -, -C (= S) -O-, -OC (= S) -O-, -CO-NR ⁵ -, -O-CH ₂ -, -S-CH ₂ - or a single bond. These groups may be combined in either direction.

When B ¹ and B ² are the same kind of groups, the production of the compound (A) is preferable because it is easy.

B ² bonded only to B ¹ and A ² which are bonded to A ¹ alone are each independently -CH ₂ -CH ₂ -, -CO-O-, -CO-NH-, -O-CH ₂ - and, B ² is also bonded to B ¹ and F ^2, which is coupled to the F ¹ each independently represent -O-, -CO-O-, -O- CO-O-, -CO-NH- or a single bond . With these groups, the preparation of the compound (A) is easy.

In addition, B ² that is bonded only to B ¹ and A ² are bonded only when A ¹ is -CO-O-, because they tend to exhibit a high liquid crystallinity, is more preferred.

E ¹ and E ² are preferably -CO-O-, -O-, -O-CO-O-, and single bond.

k and l are each independently an integer of 0 to 3; k and l are each independently preferably an integer of 0 to 3 from the viewpoint of liquid crystallinity, and more preferably k and l are 0 to 2. The sum of k and l is preferably 5 or less, more preferably 4 or less.

P ¹ is a polymerizable group, and P ² is a hydrogen atom or a polymerizable group. The polymerizable group means a group capable of participating in the polymerization reaction of the compound (A). When both P ¹ and P ² are polymerizable groups, the resulting optical film tends to have a higher hardness.

Examples of the polymerizable group include vinyl group, vinyloxy group, styryl group, p- (2-phenylethenyl) phenyl group, acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, carboxy group, acetyl group, A hydroxy group, a carbamoyl group, an N-alkylamino group having 1 to 4 carbon atoms, an amino group, an oxiranyl group, an oxetanyl group, a formyl group, an isocyanate group and an isothiocyanate group. Among them, a radically polymerizable group and a cationic polymerizable group are preferable from the standpoint of being suitable for photopolymerization, and acryloyloxy group and methacryloyloxy group are preferable because of ease of handling and easy production of compound (A) More preferably an acryloyloxy group is particularly preferable.

-D ¹ -G ¹ -E ¹ - (A ¹ -B ¹ ) _k -F ¹ -P ¹ and -D ² -G ² -E ² - (A ² -B ² ) ₁ -F ² -P ² Specific examples thereof include groups represented by the following formulas (R-1) to (R-134). * Represents a bonding site with Ar. In the formulas (R-1) to (R-134), n represents an integer of 2 to 12.

Examples of the compound (A) include the following compounds (i) to (xxvi). R 1 in Table 1 represents -D ¹ -G ¹ -E ¹ - (A ¹ -B ¹ ) _k -F ¹ -P ¹ , and R ² represents -D ² -G ² -E ² - (A ² -B ² ) ₁ -F ² -P ² .

In the compound (xxv) and the compound (xxvi), either the group represented by R 1 or the group represented by the formula R 2 is any one of (R-57) to (R-131).

In the above Table 1, the compound (xv) is a compound wherein Ar is a group represented by the formula (ar-74), Ar is a group represented by the formula (ar-75) Or a mixture of a group represented by the formula (ar-75) and a group represented by the formula (ar-75).

The compounds (i), (ii), (iv), (v), (vi), (ix), (x), (xvi) Representative structural formulas of compound (xviii), compound (xx), compound (xxi), compound (xxii), compound (xxii), compound (xxiv), compound (xxv) and compound (xxvi) are shown below. As the polymerizable liquid crystal compound used in the production of the optical film of the present invention, the compound (A) may be used alone or in combination of two or more different kinds.

Examples of the compound (A) include compounds represented by the following formulas (A1-1) to (A64-8). * Represents a bonding site. For example, the compound represented by the formula (A1-1) is a compound represented by the following formula.

The production method of the compound (A) is described below.

The compound (A) can be synthesized by a known organic synthesis reaction (for example, condensation reaction, esterification reaction, Williamson reaction, Ullmann reaction, Biotin reaction, etc.) described in Methoden der Organischen Chemie, Organic Reactions, Organic Syntheses, Comprehensive Organic Synthesis, A Buchwald-Hartwig reaction, a Friedel-Crafts reaction, a Schiff base reaction, a Schiff base reaction, a benzylation reaction, a Sonogashira reaction, a Suzuki-Miyaura reaction, a Negishi reaction, Heck reaction, aldol reaction, etc.), depending on the structure thereof.

For example, in the case of compound (A) wherein D ¹ and D ² are * -O-CO- (* represents a bonding site with Ar), a compound represented by the following formula (1-1) (1-3) is obtained by reacting a compound represented by the following formula (1-3) with a compound represented by the following formula (1-4) by reacting a compound represented by the following formula .

(In the above formula, Ar has the same meaning as described above.)

(Wherein G ¹ , E ¹ , A ¹ , B ¹ , F ¹ , P ¹ and k have the same meanings as defined above.)

(Wherein Ar, G ¹ , E ¹ , A ¹ , B ¹ , F ¹ , P ¹ and k have the same meanings as defined above.)

Wherein G ² , E ² , A ² , B ² , F ² , P ² and l have the same meanings as defined above.

The reaction between the compound represented by the formula (1-1) and the compound represented by the formula (1-2) and the reaction between the compound represented by the formula (1-3) and the compound represented by the formula (1-4) It is preferably carried out in the presence of a condensing agent.

Examples of the condensing agent include 1-cyclohexyl-3- (2-morpholinoethyl) carbodiimide metho-para-toluenesulfonate, dicyclohexylcarbodiimide, 1- Bis (2,6-diisopropylphenyl) carbodiimide, bis (2,6-diisopropylphenyl) carbodiimide hydrochloride (some water-soluble carbodiimide: commercially available as WSC) (Trimethylsilyl) carbodiimide and bisisopropylcarbodiimide, carbodiimides such as 2-methyl-6-nitrobenzoic anhydride, 2,2'-carbonylbis-1H-imidazole, Salicyldiimidazole, diphenylphosphoryl azide, 1- (4-nitrobenzenesulfonyl) -1H-1,2,4-triazole, 1H-benzotriazol-1-yloxytripyrrolidinophosphonium hexa (N, N, N ', N'-tetramethyl-O- (N-dimethylamino) phosphonium hexafluorophosphate, (1,2,2,2-tetrachloroethoxycarbonyloxy) succinimide, N-carbobenzylsuccinimide, O- (6-chloro N, N ', N'-tetramethyluronium tetrafluoroborate, O- (6-chlorobenzotriazol-1-yl) -N, N'-tetramethyluronium hexafluorophosphate, 2-bromo-1-ethylpyridinium tetrafluoroborate, 2-chloro-1,3-dimethylimidazolinium chloride, 2- Dimethylimidazolinium hexafluorophosphate, 2-chloro-1-methylpyridinium iodide, 2-chloro-1-methylpyridinium paratoluenesulfonate, 2-fluoro-1-methylpyridinium para- toluenesulfo And trichloroacetic acid pentachlorophenyl esters. Examples of the condensing agent in terms of reactivity, cost and usable solvent include dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide, 1-ethyl- ) Carbodiimide hydrochloride, bis (2,6-diisopropylphenyl) carbodiimide, bis (trimethylsilyl) carbodiimide, bisisopropyl carbodiimide, 2,2'-carbonylbis-1H-imidazole Is more preferable.

A composition comprising a polymerizable liquid crystal compound (hereinafter sometimes referred to as "composition (A)") is a liquid crystal compound further having a polymerizable group and different from the compound (A) [hereinafter referred to as "liquid crystal compound May be included. Specific examples of the liquid crystal compound (A1) include three chiral liquid crystal molecules, 3.2 chiral chiral rod-like liquid crystal molecules of 3.3 molecular structure and 3.3 chiral liquid crystal molecules of 3.3 (published by Marunen Co., Ltd., A compound having a polymerizable group among the compounds described in the chiral rod-like liquid crystal molecule, and the like.

Examples of the liquid crystal compound (A1) include a compound represented by the following formula (F) [hereinafter sometimes referred to as "compound (F)").

P ¹¹ -E ¹¹ - (B ¹¹ -A ¹¹ ) _t -B ¹² -G (F)

[In the above formula (F), A ¹¹ independently represents a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 18 carbon atoms, and the aromatic hydrocarbon group and the alicyclic hydrocarbon group included in the alicyclic hydrocarbon group The hydrogen atom may be substituted with a halogen atom, an alkyl group having 1 to 6 carbon atoms which may have a fluoro group, an alkoxy group having 1 to 6 carbon atoms which may have a fluoro group, a nitro group, a cyano group or the like.

B ¹¹ and B ¹² each independently represent -C≡C-, -CH═CH-, -CH ₂ -CH ₂ -, -O-, -S-, -C (═O) -, -C ) -O-, -OC (= O) -, -OC (= O) -O-, -CH = N-, -N = CH-, -N = N-, -C (= O) -NR 16 -, -NR ¹⁶ -C (= O) -, -OCH ₂ -, -OCF ₂ -, -CH ₂ O-, -CF ₂ O-, -CH = CH-C OC (= O) or a single bond. R ¹⁶ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

G represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 13 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, a fluoroalkyl group having 1 to 13 carbon atoms, an N-alkylamino group having 1 to 13 carbon atoms, a cyano group, ¹² -P ¹² .

E ¹¹ and E ^{12 each} represent an alkanediyl group having 1 to 18 carbon atoms, the hydrogen atom contained in the alkanediyl group may be substituted with a halogen atom, and -CH ₂ - included in the alkanediyl group may be replaced by -O- or -CO-.

P ¹¹ and P ¹² represent a polymerizable group. t represents an integer of 1 to 5]

P ¹¹ and P ¹² are the same groups as P ¹ and P ² of the compound (A). (P-1) can be used because it is easy to handle, and the preparation of the compound (F) is also easy, because a radical polymerizable group or a cationic polymerizable group is preferable, To (P-5) are preferable, and a vinyl group, an isopropenyl group, an oxiranyl group, a 3-methyloxiran-2-yl group, a 3-methyloxetan- A methacryloyloxy group is more preferable, and acryloyloxy group and methacryloyloxy are particularly preferable.

In the formulas (P-1) to (P-5), R ¹⁷ to R ²¹ each independently represent an alkyl group having 1 to 6 carbon atoms or a hydrogen atom. * Represents a bonding site with B ^11. ]

The number of carbon atoms of the aromatic hydrocarbon group and the alicyclic hydrocarbon group of A ¹¹ is, for example, 3 to 18, preferably 5 to 12, and particularly preferably 5 or 6. A ¹¹ is preferably a cyclohexane-1,4-diyl group or a 1,4-phenylene group.

As E ¹¹ and E ¹² , an alkanediyl group having 1 to 18 carbon atoms is preferable, and an alkanediyl group having 1 to ¹² carbon atoms and having one straight-chain or branched-chain group is preferable. -CH ₂ - included in the alkanediyl group may be substituted with -O- or -CO-.

Specific examples thereof include a methylene group, an ethylene group, a propanediyl group, a butanediyl group, a pentanediyl group, a hexanediyl group, a heptanediyl group, an octanediyl group, a nonanediyl group, a decanediyl group, a undecanediyl group, _{-CH 2 -CH 2 -O-CH 2} -CH 2 -, -CH 2 -CH 2 -O-CH 2 -CH 2 -O-CH 2 -CH 2 - and -CH ₂ -CH ₂ -O-CH _{2 -CH 2 -O-CH 2 -CH} 2 -O-CH 2 -CH 2 - may be mentioned.

Specific examples of the compound (F) wherein t is 4 and G is -E ¹² -P ¹² include compounds represented by the formulas (I-1) to (I-4). In the following formulas, k1 and k2 in the formula represent an integer of 2 to 12. These liquid crystal compounds are easily synthesized and commercially available, and are easily available.

Specific examples of the compound (F) wherein t is 4 and G is a group other than -E ¹² -P ¹² include compounds represented by the formulas (II-1) to (II-4).

Specific examples of the compound (F) wherein t is 3 and G is -E ¹² -P ¹² include compounds represented by the formulas (III-1) to (III-26).

Specific examples of the compound (F) wherein t is 3 and G is a group other than -E ¹² -P ¹² include compounds represented by the formulas (IV-1) to (IV-19).

Specific examples of the compound (F) wherein t is 2 and G is -E ¹² -P ¹² include compounds represented by the formulas (V-1) and (V-2) , And specific examples of the compound (F) wherein G is a group other than -E ¹² -P ¹² include the compounds represented by the formulas (VI-1) to (VI-6).

The content of the compound (A) in the composition (A) is preferably 10 to 100 parts by mass, more preferably 30 to 100 parts by mass, per 100 parts by mass of the total amount of the liquid crystal compound (A1) and the compound (A) Preferably 60 to 100 parts by mass. The content of the liquid crystal compound (A1) is preferably from 0 to 90 parts by mass, more preferably from 0 to 70 parts by mass, and still more preferably from 0 to 90 parts by mass, per 100 parts by mass of the total amount of the liquid crystal compound (A1) To 40 parts by mass. When the content of the compound (A) and the liquid crystal compound (A1) is within the above range, excellent polarization conversion can be achieved.

In the optical film of the present invention, discoloration is reduced as the content of the structural unit derived from the compound (A) is increased.

The composition (A) preferably contains a polymerization initiator. The polymerization initiator is a compound capable of generating a radical or an acid by the action of light or heat and capable of initiating polymerization of the polymerizable liquid crystal compound contained in the composition (A). The polymerization initiator is preferably a photopolymerization initiator in that polymerization reaction can be carried out at a low temperature, and more preferably a photopolymerization initiator that generates radicals upon irradiation of light. By containing a polymerization initiator, the durability of the optical film is improved.

Examples of the thermal polymerization initiator include azo initiators such as 2,2'-azobis (isobutyronitrile) and 4,4'-azobis (4-cyanovaleric acid), and peroxides such as benzoyl peroxide.

Examples of the photopolymerization initiator include benzoins such as benzoin, benzoin methyl ether and benzoin ethyl ether; Benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone and the like Benzophenones; Benzyl ketalation such as benzyl ketal; 2-methyl-1-phenylpropan-1-one, 1,2-diphenyl-2,2-dimethoxy-1-ethanone, 2-hydroxy- Hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1-one, 1-hydroxycyclohexyl phenyl ketone, ) Phenyl] propan-1-one; 1-one, 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan- Amino ketones, iodonium salts, sulfonium salts and the like. Irgacure 907, Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369 (all manufactured by BASF Japan), Sheikol BZ, Sheikol Z and Sheikol BEE [ (All manufactured by Seiko Kagaku Co., Ltd.), Kayacure BP100 (manufactured by Nippon Kayaku), Kayacure UVI-6992 (manufactured by Daiso), Adeka Optomer SP-152 A commercially available photopolymerization initiator such as ADEKA OPTOMER SP-170 (manufactured by ADEKA) may be used.

The content of the polymerization initiator is preferably 0.1 part by mass to 30 parts by mass, more preferably 0.5 part by mass to 10 parts by mass, per 100 parts by mass of the total amount of the compound (A) and the liquid crystal compound (A1). Within the above range, the alignment of the polymerizable liquid crystal compound such as the compound (A) or the liquid crystal compound (A1) can be polymerized without clutter.

The composition (A) may contain a photosensitizer. Examples of the photosensitizer include xanthene compounds such as xanthone or thioxanthone (for example, 2,4-diethylthioxanthone and 2-isopropylthioxanthone), anthracene compounds having substituents such as anthracene and alkyl ethers Compounds (e.g., dibutoxyanthracene and the like), phenothiazine, and rubrene.

By using a photosensitizer, the polymerization of the polymerizable liquid crystal compound can be highly sensitized. The content of the photosensitizer is preferably 0.1 parts by mass to 30 parts by mass, more preferably 0.5 parts by mass to 10 parts by mass, per 100 parts by mass of the total amount of the compound (A) and the liquid crystal compound (A1). Within the above range, the alignment of the polymerizable liquid crystal compound can be polymerized without clogging.

The composition (A) may contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone having a substituent such as hydroquinone or alkyl ether, catechol having a substituent such as alkyl ether such as butyl catechol, pyrogallol, 2,2,6,6-tetramethyl-1-piper And radical supplements such as pyridyloxy radical, thiophenols,? -Naphthyl amines and? -Naphthols.

By using the polymerization inhibitor, the polymerization of the polymerizable liquid crystal compound can be controlled, and the stability of the composition can be further improved.

The content of the polymerization inhibitor is preferably 0.1 part by mass to 30 parts by mass, more preferably 0.5 parts by mass to 10 parts by mass, per 100 parts by mass of the total amount of the compound (A) and the liquid crystal compound (A1). Within the above range, the alignment of the polymerizable liquid crystal compound can be polymerized without clogging.

The composition (A) preferably contains a solvent. The solvent is not particularly limited as long as it dissolves the components constituting the composition (A) and is not involved in the polymerization of the polymerizable liquid crystal compound. Specific examples include alcohol solvents such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether and propylene glycol monomethyl ether; Ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate,? -Butyrolactone, propylene glycol methyl ether acetate and ethyl lactate; Ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and methyl isobutyl ketone; Chlorinated aliphatic hydrocarbon solvents such as pentane, hexane and heptane; Non-chlorinated aromatic hydrocarbon solvents such as toluene and xylene; Nitrile solvents such as acetonitrile; Ether solvents such as tetrahydrofuran and dimethoxyethane; And chlorine-containing solvents such as chloroform and chlorobenzene. These solvents may be used alone or in combination of two or more. Such a solvent may contain water.

The content of the solvent is preferably 50 to 95% by mass with respect to the composition (A).

The viscosity of the composition (A) is preferably 10 mPa · s or less, and more preferably 0.1 to 7 mPa · s. When the viscosity is within the above range, the optical film of the present invention can be easily adjusted to a desired film thickness. The viscosity can be adjusted by the content of the solvent.

The composition (A) may contain a leveling agent. Examples of the leveling agent include additives for radiation curing paints (e.g., BYK-352, BYK-353, BYK-361N; manufactured by Beck Chemie Japan), paint additives (for example, SH28PA, DC11PA, ST80PA; Dow Corning Co., Ltd.), paint additives (e.g., KP321, KP323, X22-161A, KF6001; (For example, F-445, F-470, F-477, and F-479 manufactured by Shinetsu Kagaku Kogyo Co., DIC Co., Ltd.].

By using the leveling agent, the optical film of the present invention can be smoothed. Further, the flowability of the composition (A) may be controlled, or the crosslinking density of the optical film of the present invention may be adjusted. The content of the leveling agent is 0.1 part by mass to 30 parts by mass, preferably 0.5 parts by mass to 10 parts by mass, based on 100 parts by mass of the total amount of the liquid crystal compound (A1) and the compound (A). Within the above range, the alignment of the polymerizable liquid crystal compound can be polymerized without clogging.

The method for producing the optical film of the present invention will be described.

The optical film of the present invention can be obtained by applying the composition (A) to a substrate, removing the solvent, and polymerizing the polymerizable component such as the polymerizable liquid crystal compound contained in the composition in an aligned state.

As a coating method on the substrate, extrusion coating method, direct gravure coating method, reverse gravure coating method, CAP coating method and die coating method can be mentioned. In addition, a coating method such as a dip coater, a bar coater, and a spin coater may be used.

Examples of the substrate include glass, a plastic sheet, a plastic film, and a light-transmitting film. It may be a plate type or a film type. Examples of the light transmitting film include a polyolefin film (such as polyethylene, polypropylene, and norbornene-based polymer), a polyvinyl alcohol film, a polyethylene terephthalate film, a polymethacrylic acid ester film, a polyacrylic acid ester film, a cellulose ester film, Film, polycarbonate film, polysulfone film, polyethersulfone film, polyether ketone film, polyphenylene sulfide film and polyphenylene oxide film.

When the substrate is used, the optical film of the present invention can be easily handled without being damaged when it is manufactured, transported, or stored.

When the optical film of the present invention is produced, it is preferable that an alignment film is formed on the substrate. Preferably, after the alignment film is formed on the substrate, the composition (A) is preferably applied on the alignment film. It is preferable that the alignment film has solvent resistance that is not dissolved by application of the composition (A) or the like. Further, it is preferable that heat resistance is provided in the heat treatment for removing the solvent or aligning the liquid crystal. In addition, it is preferably an alignment film which does not cause peeling or the like due to rubbing due to rubbing. Such an orientation film is preferably composed of a composition containing an orienting polymer or an orienting polymer. By using the orientation film, the alignment of the polymerizable liquid crystal compound is facilitated, and the in-plane variation of the birefringence of the resulting optical film is reduced. In addition, it is easy to control the alignment, and various orientations such as horizontal alignment, vertical alignment, hybrid alignment, and oblique alignment can be obtained.

Examples of the orienting polymer include polyamides and gelatins having amide bonds in the molecule, polyimides having imide bonds in the molecule, and polyamic acids, polyvinyl alcohols, alkyl modified polyvinyl alcohols, polyacrylamides, poly And polymers such as oxazole, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid, and polyacrylic acid esters. These polymers may be used alone, or two or more of them may be mixed or copolymerized. These polymers can be easily obtained by chain polymerization, coordination polymerization or ring-opening polymerization such as polycondensation by dehydration or deamination, radical polymerization, anion polymerization and cation polymerization.

The oriented polymer can be applied by dissolving in a solvent. The solvent is not particularly limited, but specifically includes water; Alcohol solvents such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether and propylene glycol monomethyl ether; Ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate,? -Butyrolactone, propylene glycol methyl ether acetate and ethyl lactate; Ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and methyl isobutyl ketone; Non-chlorinated aliphatic hydrocarbon solvents such as pentane, hexane or heptane; Non-chlorinated aromatic hydrocarbon solvents such as toluene and xylene; Nitrile solvents such as acetonitrile; Ether solvents such as tetrahydrofuran and dimethoxyethane; Chlorine-containing solvents such as chloroform and chlorobenzene, and the like. These solvents may be used alone or in combination of two or more.

In addition, a commercially available alignment film material may be used to form an alignment film. Examples of commercially available alignment film materials include "SunEver" (registered trademark, manufactured by Nissan Chemical Industries, Ltd.) and "Optomer" (registered trademark, manufactured by JSR Corporation).

An alignment film can be formed on the substrate by applying a commercially available alignment film material, a composition containing an orientation polymer or an orientation polymer, and then annealing. As a method of applying a composition containing a commercially available orientation film material, an orientation polymer or an orientation polymer to a substrate, the same method as that described above can be mentioned as a method of applying the composition (A) to a substrate.

The thickness of the alignment film thus obtained is, for example, 10 nm to 10,000 nm, preferably 10 nm to 1000 nm. Within this range, the polymerizable liquid crystal compound can be oriented at a desired angle on the alignment film.

Further, rubbing or polarized UV irradiation can be performed on the alignment film as needed. By this, the polymerizable liquid crystal compound can be oriented in a desired direction.

As a method for rubbing the alignment film, there is a method in which a rubbing roll in which a rubbing cloth is wound and rotated is brought into contact with an alignment film on a substrate carried on a stage. When rubbing or polarized UV irradiation is performed, an optical film having a pattern can be produced by masking.

The retardation value Re (?) For light with a wavelength? Nm is represented by the product of the birefringence? N and the thickness d of the optical film of the present invention (Re (?) =? Nxd). In the optical film of the present invention, the retardation value (Re ()) is determined by appropriately selecting the content of the structural unit derived from the compound (A) contained in the optical film of the present invention, (d), the desired value can be obtained. The retardation value Re ([lambda]) may be suitably selected in the range of 30 nm to 300 nm, depending on the application.

Specifically, in order to adjust the retardation value, two to five kinds of compositions having different contents of the compound (A) are prepared, and the optical films of the present invention having the same film thickness are prepared for each composition, From the result, a correlation between the content of the compound (A) in the composition and the retardation value of the optical film of the present invention was determined, and from the obtained correlation, a desired retardation value was given to the optical film of the present invention at the film thickness It is possible to determine the content of the compound (A) necessary for the reaction.

The retardation value can also be adjusted by appropriately changing the thickness (d) of the obtained optical film with respect to the composition in which the content of the compound (A) is determined.

When the optical film of the present invention is used as a retarder, the thickness d is preferably 0.1 to 10 mu m, and more preferably 0.5 to 3 mu m in terms of reducing photoelasticity.

When used as a lambda / 4 plate, Re (550) of the resulting retardation plate is adjusted to 113 nm to 163 nm, preferably 130 nm to 150 nm, and when used as a lambda / 2 plate, (550) of 250 nm to 300 nm, preferably, 265 nm to 285 nm.

When the optical film of the present invention is used as an optical film for a VA (Vertical Alignment) mode, the Re (550) may be adjusted to be, for example, 40 nm to 100 nm, preferably 60 nm to 80 nm.

The method for producing the optical film of the present invention will be described in more detail.

After the composition (A) is applied to the substrate, the solvent is removed. Examples of the method for removing the solvent include natural drying, air drying, and vacuum drying. The temperature at which the solvent is removed is preferably 10 ° C to 150 ° C, more preferably 25 ° C to 120 ° C. The time for removing the solvent is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes. If the temperature for removing and the time for removing are within the above range, the optical film of the present invention can also be produced by using a substrate having low heat resistance and an alignment film.

The coating film on which the composition (A) is formed is oriented at a temperature of from 0 캜 to 150 캜, preferably from 25 캜 to 120 캜, of the polymerizable liquid crystal compound. The polymerizable liquid crystal compound having a mono domain orientation has birefringence. This polymerizable liquid crystal compound is aligned and polymerized at a temperature at which the polymerizable liquid crystal compound is oriented in a monodomain. When the polymerizable liquid crystal compound is aligned by heating, the solvent may be removed at the same time, or the solvent may be removed and then further heated and oriented.

The optical film of the present invention can be obtained by polymerizing a polymerizable liquid crystal compound or the like in a coating film while the polymerizable liquid crystal compound is oriented. By polymerizing, the orientation of the polymerizable liquid crystal compound is fixed, and therefore birefringence of the optical film is hardly changed by heat.

The method of polymerizing the polymerizable liquid crystal compound may be selected depending on the type of the polymerizable group of the polymerizable liquid crystal compound. When the polymerizable group of the polymerizable liquid crystal compound is a photopolymerizable group, a photopolymerization method is used, and if the polymerizable group is a heat-polymerizable group, a thermal polymerization method is used. According to the photopolymerization method, a polymerizable liquid crystal compound having a photopolymerizable group can be used because it can polymerize a polymerizable liquid crystal compound at a low temperature, broadens the selection of heat resistance of the substrate, and is industrially easy to manufacture . The photopolymerization reaction is carried out by irradiating visible light, ultraviolet light or laser light to a film obtained by applying the composition (A) and orienting the polymerizable liquid crystal compound. Ultraviolet light is particularly preferable in terms of handling.

The optical film of the present invention may be used as a single layer, or may be laminated with a substrate and / or an alignment film. When a plurality of layers of the optical film of the present invention are laminated, they may be the same or different.

The optical film of the present invention is used for an antireflection film such as an anti-reflection (AR) film, a polarizing film, a retardation film, an elliptically polarizing film, a viewing angle enlarging film and an optical compensation film for compensating a viewing angle of a transmission type liquid crystal display.

It is preferably used as a polarizing plate comprising the optical film and the polarizing film of the present invention. By joining the optical film and the polarizing film of the present invention, an elliptically polarizing plate can be obtained. By further bonding the optical film of the present invention to this elliptically polarizing plate, a wide-band? / 4 plate can be obtained.

In the following description of the drawings, the optical film of the present invention may be the optical film of the present invention, or the optical film of the present invention and the orientation film may be laminated, and the optical film of the present invention, It may be that it is.

The polarizing plate of the present invention includes (1) to (5) as shown in Figs. 1 (a) to 1 (e). Here, the adhesive is generically referred to as an adhesive and / or an adhesive.

(1) The polarizing plate 4a (FIG. 1 (a)) directly laminated with the optical film 1 of the present invention and the polarizing film layer 2,

(2) The polarizing plate 4b (Fig. 1 (b)) in which the optical film 1 of the present invention and the polarizing film layer 2 are bonded to each other through the adhesive layer 3,

(3) A polarizing plate 4c (in which the optical film 1 of the present invention and the optical film 1 'of the present invention are laminated and the optical film 1' of the present invention and the polarizing film layer 2 are further laminated) 1 (c)),

(4) The optical film 1 of the present invention and the optical film 1 'of the present invention are bonded to each other through the adhesive layer 3, and the polarizing film layer 2 is formed on the optical film 1' A polarizing plate 4d (Fig. 1 (d)) which is further laminated, and

(5) The optical film (1) of the present invention and the optical film (1 ') of the present invention are bonded to each other through the adhesive layer (3), and the optical film (1') and the polarizing film layer And a polarizing plate 4e (Fig. 1 (e)) bonded further through the layer 3 '.

The polarizing film layer may be a film having a polarizing function. For example, a film obtained by adsorbing iodine or a dichroic dye to a polyvinyl alcohol-based film and a film obtained by stretching a polyvinyl alcohol-based film to adsorb an iodine or a dichroic dye . Further, the polarizing film layer may be provided with a film to be a protective film, if necessary.

Examples of the protective film include a polyolefin film such as polyethylene, polypropylene and norbornene polymer, a polyethylene terephthalate film, a polymethacrylic acid ester film, a polyacrylic acid ester film, a cellulose ester film, a polyethylene naphthalate film, a polycarbonate film, Sulfone film, polyethersulfone film, polyether ketone film, polyphenylene sulfide film and polyphenylene oxide film.

The adhesive used for the adhesive layer 3 and the adhesive layer 3 'is preferably an adhesive having high transparency and excellent heat resistance. As such an adhesive, for example, an acrylic adhesive, an epoxy adhesive or a urethane adhesive is used.

Further, in the polarizing film, as shown in Figs. 1C to 1E, two or more optical films of the present invention may be bonded directly or through an adhesive layer.

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 the optical film and the liquid crystal panel of the present invention, the optical film of the present invention and the organic electroluminescence , &Quot; EL &quot;) panel.

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

[Liquid crystal display device]

Examples of the liquid crystal display device include a liquid crystal display device as shown in Figs. 2A and 2B. The liquid crystal display 10 shown in Figure 2 (a) is obtained by bonding the polarizing plate 4 and the liquid crystal panel 6 of the present invention via an adhesive layer 5, and Figure 2 (b) The liquid crystal display 10b shown in the figure is obtained by bonding the polarizing plate 4 of the present invention and the polarizing plate 4 'of the present invention to both surfaces of the liquid crystal panel 6 through the adhesive layer 5 and the adhesive layer 5' . According to the above configuration, by changing the orientation of the liquid crystal molecules to a voltage applied to the liquid crystal panel from a driving circuit (not shown), the liquid crystal display device can be displayed in black and white. The liquid crystal panel is formed by bonding an array substrate and a color filter, and injecting and sealing liquid crystal therebetween.

[Organic EL display device]

Examples of the organic EL display device include the organic EL display device shown in Fig. The organic EL display device includes an organic EL display device 11 formed by bonding a polarizing plate 4 of the present invention and an organic EL panel 7 through an adhesive layer 5. The organic EL panel 7 is at least one layer made of a conductive organic compound. According to the above configuration, a luminous compound included in the organic EL panel is emitted by a voltage to be applied to the organic EL panel from a driving circuit (not shown), so that the organic EL display can be displayed in black and white. The organic EL panel is formed by stacking an organic layer such as a light emitting layer, a pixel electrode, a switching element, and the like.

Further, in the organic EL display device 11, it is preferable that the polarizing plate 4 functions as a broadband circularly polarizing plate. It is possible to prevent reflection of external light on the surface of the organic EL display device 11 as long as it functions as a wide-band circularly polarizing plate.

[Color Filter]

4 is a schematic view showing a color filter 14 including the optical film of the present invention.

The color filter 14 is a color filter formed by forming a color filter layer 13 on the optical film 12 of the present invention. The color filter layer is a layer having a function of absorbing specific light in the visible light region and is, for example, a layer for converting white light into light such as red, blue, and green.

An example of a method of manufacturing the color filter 14 will be described. First, an alignment film material is coated on a supporting substrate and rubbed or polarized UV treatment is performed to form an alignment film. Next, the composition (A) is coated on the obtained alignment film while adjusting the thickness so that the resulting optical film has a desired retardation value, thereby forming a film. The color filter layer 13 is formed on the optical film 12 of the present invention obtained by orienting the polymerizable liquid crystal compound contained in the film. The optical film (12) of the present invention may be a patterned optical film having a plurality of regions in which the direction in which the polymerizable liquid crystal compound is oriented is different. The patterned optical film can be obtained by performing the rubbing treatment or the polarizing UV treatment through a mask.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples. In the following examples, "% " and " part " are by weight and parts by weight unless otherwise specified.

Synthesis Example 1 &Lt; Synthesis Example of Compound (A11-1) >

(1) Synthesis Example of 4,6-dimethylbenzofuran

25 g of 3,5-dimethylphenol was dissolved in 150.0 g of N, N'-dimethylacetamide. After the solution was cooled by an ice bath (ice bath), sodium hydroxide 9.82 was added. The mixture was stirred at room temperature for 1 hour, and 25.49 g of chloroacetaldehyde dimethylacetal was added dropwise. The mixture was stirred at 100 DEG C for 15 hours, and the reaction solution was added to 1000 mL of water and 400 mL of methyl isobutyl ketone and the liquid was separated. The organic layer was recovered, washed twice with 500 ml of 1N-sodium hydroxide aqueous solution, and further washed twice with 800 ml of pure water. The organic layer was collected, dehydrated with anhydrous sodium sulfate, and concentrated under reduced pressure using an evaporator to obtain a pale red viscous liquid. On the other hand, 400 g of toluene and 3.01 g of orthophosphoric acid were mixed and heated to 110 캜. To this solution was added dropwise a solution of a light red viscous liquid dissolved in 100 ml of toluene. After stirring for 3 hours at &lt; RTI ID = 0.0 &gt; 110 C &lt; / RTI &gt; The reaction solution was washed once with 1N aqueous sodium hydrogencarbonate solution and finally washed with 500 ml of pure water. The organic layer was collected, dehydrated with anhydrous sodium sulfate, concentrated under reduced pressure using an evaporator, and vacuum dried to obtain 16.5 g of 4,6-dimethylbenzofuran as a pale red viscous liquid. The yield was 55% based on 3,5-dimethylphenol.

(2) Synthesis Example of 2-formyl-4,6-dimethylbenzofuran

21.62 g of 4,6-dimethylbenzofuran was dissolved in 28.4 g of N, N'-dimethylformamide. After the solution was cooled by a water bath, 25 g of phosphorus oxychloride was added dropwise. The pink solution was stirred at room temperature for 1 hour and then at 100 ° C for 10 hours. The reaction solution was allowed to cool to room temperature, 100 ml of pure water was added, and the mixture was stirred for 1 hour and neutralized with 1N sodium hydrogen carbonate. After the pH was adjusted to 8, the solution was separated from toluene. The organic layer was recovered, and 2.6 g of activated carbon was added thereto, followed by filtration. Concentrated under reduced pressure with an evaporator, and the residue was dissolved in chloroform and crystallized with heptane. The crystals were collected by filtration and vacuum dried to obtain 19.5 g of 2-formyl-4,6-dimethylbenzofuran as a pale yellow powder. The yield was 76% based on 4,6-dimethylbenzofuran.

(3) Synthesis of 4,6-dimethylbenzofuran-2-carboxylic acid

19.50 g of 2-formyl-4,6-dimethylbenzofuran and 13.04 g of amide sulfuric acid were mixed with 100 ml of pure water. Cooled with an ice bath, and a solution of sodium chlorite (12.15 g) in water (100 ml) was added dropwise. And reacted for 36 hours in a water bath. 100 ml of toluene and 25 g of potassium hydroxide were added to the reaction solution to adjust the pH to 12. The aqueous layer was recovered, and the aqueous layer was further washed with 200 ml of toluene. The aqueous layer was recovered, the pH was adjusted to 2 with 2N-hydrochloric acid, and 400 ml of toluene was added to separate the layers. The organic layer was collected, dehydrated with anhydrous sodium sulfate, concentrated under reduced pressure using an evaporator, and dried in vacuo to obtain 14.27 g of 4,6-dimethylbenzofuran-2-carboxylic acid as a yellow powder. The yield was 67% based on 2-formyl-4,6-dimethylbenzofuran.

(5) Synthesis Example of Compound (11-a)

11.49 g of 2,5-dimethoxyaniline, 14.27 g of 4,6-dimethylbenzofuran-2-carboxylic acid, 7.59 g of triethylamine, 1.83 g of N, N'-dimethylaminopyridine, Acetamide were mixed. After the obtained solution was cooled with an ice bath, 34.85 g of BOP reagent was added and reacted at room temperature for 24 hours. A mixed solution of water and methanol (2 parts by volume of water and 1 part by volume of methanol) was added to the resulting mixture to crystallize the mixture. The obtained precipitate was filtered off, washed with a mixed solution of water and methanol (3 parts by volume of water, 2 parts by volume of methanol) and vacuum-dried to obtain 16.2 g of a compound (11-a) as a pale yellow powder. The yield was 66% based on 2,5-dimethoxy aniline.

(6) Synthesis Example of Compound (11-b)

16.0 g of the compound (11-a), 9.2 g of 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetane- And 100 g of toluene were mixed, and the resulting mixture was heated to 80 DEG C and reacted for 12 hours. After cooling, the solution was concentrated to obtain a red-tinged solid containing the decomposition product of compound (11-b) and Lawson's reagent as a main component.

(7) Synthesis Example of Compound (11-c)

A mixture containing the compound (11-b) obtained in the preceding step, 11.8 g of sodium hydroxide and 250 g of water were mixed, and the resulting mixture was reacted under ice-cooling. Subsequently, an aqueous solution containing 44.17 g of potassium ferricyanide was added and reacted under ice-cooling. The reaction was carried out at 60 DEG C for 12 hours, and the precipitated yellow precipitate was collected by filtration. The precipitate taken by filtration was washed with water, then with hexane, and crystallized with toluene. The obtained yellow color was vacuum-dried to obtain 4.1 g of an ocher-colored solid containing the compound (11-c) as a main component. The yield was 25% based on the compound (11-a).

(8) Synthesis Example of Compound (11-d)

4.0 g of the compound (11-c) and 40.0 g of pyridinium chloride were mixed, and the mixture was heated to 180 DEG C and reacted for 3 hours. The obtained mixture was added to ice, and the resultant precipitate was collected by filtration. Washed with water, washed with toluene and vacuum dried to obtain 3.4 g of an ocher-colored solid containing the compound (11-d) as a main component. The yield was 93% based on compound (11-c).

(9) Synthesis Example of Compound (A11-1)

3.00 g of the compound (11-d), 8.47 g of the compound (A), 0.12 g of dimethylaminopyridine and 40 ml of chloroform were mixed. To the obtained mixture, 2.92 g of N, N'-diisopropylcarbodiimide was added under ice-cooling. The resulting reaction solution was reacted at room temperature overnight, filtered through silica gel, and then concentrated under reduced pressure. Methanol was added to the residue to crystallize. The crystals were collected by filtration, redissolved in chloroform, and 0.3 g of activated carbon was added thereto, followed by stirring at room temperature for 1 hour. The solution was filtered and the filtrate was concentrated under reduced pressure to 1/3 with an evaporator. Methanol was added while stirring, and the resulting white precipitate was collected by filtration. The filtrate was washed with heptane and vacuum dried to obtain 7.60 g of Compound (A11-1) Powder. The yield was 71% based on compound (11-d).

Compound ¹ H-NMR (CDCl ₃₎ of (A11-1): δ (ppm) 1.45~1.85 (m, 24H), 2.36~2.87 (m, 18H), 3.93~3.97 (t, 4H), 4.15~4.20 (m, 2H), 6.87-7.01 (m, 9H), 7.20 (s, 1H), 7.23 (s, 2 H), 7.53 (s, 1 H)

The phase transition temperature of the resulting compound (A11-1) was confirmed by a texture observation by a polarizing microscope. Compound (A11-1) exhibited a highly viscous intermediate phase at 105 캜 to 137 캜 at the time of heating. Although discrimination of the liquid crystal phase was difficult, a clear nematic liquid crystal phase was exhibited at 137 DEG C or higher. It exhibited a nematic liquid crystal phase at 180 ° C or higher and showed a nematic phase up to 61 ° C at the time of temperature lowering and crystallized.

Synthesis Example 2 &Lt; Synthesis Example of Compound (A5-1) >

(1) Synthesis Example of Compound (5-a)

18.9 g of 2,5-dimethoxyaniline, 20.0 g of benzofuran-2-carboxylic acid and 125.0 g of dehydrated chloroform were mixed and reacted. To the resulting mixture was added 1.51 g of N, N-dimethylaminopyridine. The resultant mixture was cooled with an ice bath, 28.0 g of N, N'-dicyclohexylcarbodiimide was added, and the mixture was reacted for 1 hour. Thereafter, the mixture was returned to room temperature and reacted overnight. The resulting mixture was filtered through silica gel to remove white precipitate and brownish components, which were then concentrated under reduced pressure. An ethyl acetate / heptane solution (v / v = 1/2) was added to the residue to crystallize. The precipitated crystals were collected by filtration and vacuum-dried to obtain 14.4 g of a compound (5-a) as a pale yellow powder. The yield was 39% based on 2,5-dimethoxy aniline.

(2) Synthesis Example of Compound (5-b)

13.0 g of the compound (5-a), 9.2 g of 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetane- And 100 g of toluene were mixed, and the resulting mixture was heated to 80 DEG C and reacted for 5 hours. After cooling, the solution was concentrated to obtain a red-tinged solid containing the decomposition product of compound (5-b) and Lawson's reagent as a main component.

(3) Synthesis Example of Compound (5-c)

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

(4) Synthesis Example of Compound (5-d)

7.0 g of the compound (5-c) and 35.0 g of pyridinium chloride were mixed, and the mixture was heated to 180 캜 and reacted for 2 hours. The resulting mixture was cooled, water was added, and the obtained precipitate was collected by filtration and washed with water and hexane to obtain 6.5 g of a solid containing the compound (5-d) as a main component. The yield was 100% based on the compound (5-c).

(5) Synthesis Example of Compound (A5-1)

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

Compound ¹ H-NMR (CDCl ₃₎ of (A5-1): δ (ppm) 1.45~1.91 (m, 24H), 2.35~2.83 (m, 12H), 3.92~3.97 (t, 4H), 4.15~4.20 2H), 7.37-6.44 (m, 2H), 6.87-7.01 (m, 8H), 7.25 (s, 2H), 7.31 1H), 7.40-7.42 (t, 1H), 7.55-7.60 (m, 2H), 7.68-7.71 (d,

The phase transition temperature of the obtained compound (A5-1) was confirmed by a texture observation by a polarizing microscope. The compound (A5-1) exhibited a nematic phase at 139 ° C at 180 ° C or higher and a nematic phase at 93 ° C at the time of temperature decrease to crystallize.

Synthesis Example 3 &Lt; Synthesis Example of Compound (A10-1) >

(1) Synthesis Example of 5-isobutylbenzofuran

40 g of 4-isopropylphenol was dissolved in 240.0 g of N, N-dimethylacetamide. After the obtained solution was cooled by an ice bath, 10.9 g of sodium hydride was added in divided portions of 10 times. The mixture was stirred at room temperature for 1 hour. When hydrogen evolution was completed, 33.17 g of chloroacetaldehyde dimethylacetal was added dropwise. The mixture was stirred at 80 ° C for 5 hours, and when the completion of the reaction was confirmed, the reaction mixture was added to water (1000 ml) and methyl isobutyl ketone (400 ml) and the liquid was separated. The organic layer was recovered and the organic layer was washed twice with 800 ml of pure water. The organic layer was recovered, dehydrated with anhydrous sodium sulfate, and concentrated under reduced pressure using an evaporator to obtain a red viscous liquid. On the other hand, 400 g of toluene and 2.61 g of orthophosphoric acid were mixed and heated to 110 캜. To this solution was added dropwise a solution of a red viscous liquid dissolved in 100 ml of toluene. After stirring for 3 hours at &lt; RTI ID = 0.0 &gt; 110 C &lt; / RTI &gt; The reaction solution was washed twice with 1N aqueous sodium hydrogencarbonate solution and finally washed with 500 ml of pure water. The organic layer was recovered, dehydrated with anhydrous sodium sulfate, concentrated under reduced pressure, and vacuum-dried to obtain 41.9 g of 5-isobutylbenzofuran as a pale red viscous liquid. The yield was 90% based on 4-isopropylphenol.

(2) Synthesis Example of 2-formyl-5-isobutylbenzofuran

25.77 g of 5-isobutylbenzofuran was dissolved in 28.4 g of N, N'-dimethylformamide. After the solution was cooled by a water bath, 25 g of phosphorus oxychloride was added dropwise. The pink solution was stirred at room temperature for 1 hour and then at 100 ° C for 10 hours. The reaction solution was allowed to cool to room temperature, 100 ml of pure water was added, and the mixture was stirred for 1 hour and neutralized with 1N sodium hydrogen carbonate. After the pH was adjusted to 8, the solution was separated from toluene. The organic layer was recovered, and 2.6 g of activated carbon was added thereto, followed by filtration. The residue was dissolved in chloroform and treated with silica gel column chromatography (eluent: chloroform / heptane = 1/1 (v / v) -> chloroform 100 vol%). The leading components were taken, concentrated by an evaporator and vacuum dried to obtain 8.5 g of 2-formyl-5-isobutylbenzofuran as a pale red viscous liquid. The yield was 28% based on 5-isobutylbenzofuran.

(3) Synthesis of 5-isobutylbenzofuran-2-carboxylic acid

16.40 g of 2-formyl-5-isobutylbenzofuran and 9.43 g of amide sulfuric acid were mixed with 60 ml of pure water. Cooled with an ice bath, and a solution of sodium chlorite (8.78 g) in water (50 ml) was added dropwise. And reacted for 36 hours in a water bath. 100 ml of toluene and 5 g of potassium hydroxide were added to the reaction solution to adjust the pH to 12. And the aqueous layer was recovered, and the aqueous layer was further washed with 300 ml of toluene. The aqueous layer was recovered, the pH was adjusted to 2 with 2N-hydrochloric acid, and 300 ml of toluene was added to separate the layers. The organic layer was collected, dehydrated with anhydrous sodium sulfate, concentrated under reduced pressure using an evaporator, and dried under vacuum to obtain 6.7 g of 5-isobutylbenzofuran-2-carboxylic acid as a pale red viscous liquid. The yield was 38% based on 2-formyl-5-isobutylbenzofuran.

(4) Synthesis Example of Compound (10-a)

4.71 g of 2,5-dimethoxyaniline, 8.71 g of 5-isobutylbenzofuran-2-carboxylic acid, 3.11 g of triethylamine, 0.75 g of N, N'-dimethylaminopyridine and 0.75 g of dehydrated N, N'-dimethylacetate Amide were mixed. The obtained solution was cooled with an ice bath, 14.28 g of BOP reagent was added, and the reaction was allowed to proceed at room temperature for 24 hours. A mixed solution of water and methanol (2 parts by volume of water, 1 part by volume of methanol) was added to the resulting mixture, followed by crystallization. The resulting precipitate was filtered off, washed with a mixed solution of water and methanol (1 part by volume of water, 1 part by volume of methanol) and vacuum-dried to obtain 5.7 g of compound (10-a) as a pale yellow powder. The yield was 53% based on 2,5-dimethoxy aniline.

(5) Synthesis Example of Compound (10-b)

, 9.2 g of 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetane-2,4-disulfide (Lawson's reagent) And 100 g of toluene were mixed, and the resulting mixture was heated to 80 DEG C and reacted for 5 hours. After cooling and concentration, a red-tinged solid containing the compound (10-b) and a decomposition product of Lawesson's reagent as a main component was obtained.

(6) Synthesis Example of Compound (10-c)

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

(7) Synthesis Example of Compound (10-d)

2.5 g of the compound (10-c) and 12.5 g of pyridinium chloride were mixed, and the mixture was heated to 180 DEG C and reacted for 2 hours. The resulting mixture was cooled, water was added, and the resulting precipitate was collected by filtration and washed with water, toluene and hexane to obtain 1.8 g of a solid containing the compound (10-d) as a main component. The yield was 77% based on compound (10-c).

(8) Synthesis Example of Compound (A10-1)

1.80 g of the compound (10-d), 4.92 g of the compound (A), 0.07 g of dimethylaminopyridine and 30 ml of chloroform were mixed. To the obtained mixture, 1.70 g of N, N'-diisopropylcarbodiimide was added under ice-cooling. The resulting reaction solution was reacted at room temperature overnight, filtered through silica gel, and then concentrated under reduced pressure. The residue was crystallized by the addition of methanol. The crystals were filtered off and redissolved in chloroform. Methanol was added to the resulting solution while stirring. The resultant white precipitate was collected by filtration. The filtrate was washed with ethanol, and the first component eluted with chloroform 80 vol% -acetone 20 vol% was recovered by silica gel column chromatography and concentrated under reduced pressure using an evaporator And then crystallized with cold methanol. The resulting pale yellow powder was collected by filtration and dried in vacuo to give 4.60 g of the compound (A10-1) as a white powder. The yield was 72% based on compound (10-d).

Compound ¹ H-NMR (CDCl ₃₎ of (A10-1): δ (ppm) 0.81~0.87 (t, 3H), 1.29~1.31 (d, 3H), 1.48~1.79 (m, 26H), 2.35~2.47 (m, 2H), 2.63-2.83 (m, 5H), 3.93-3.97 (m, 4H), 4.15-4.20 (t, 4H), 5.79-5.84 (dd, 2H), 6.07-6.17 , 6.37-6.44 (m, 2H), 6.87-7.02 (m, 8H), 7.23 (m, 3H), 7.48-7.50

The phase transition temperature of the resulting compound (A10-1) was confirmed by a texture observation by a polarizing microscope. Compound (A10-1) exhibited a viscous phase at 144 캜 at the time of temperature elevation, and showed a transparent point at 169 캜. At the time of lowering the temperature, a definite nematic phase was observed at 167 ° C, and a nematic phase was observed up to 105 ° C to crystallize.

Synthesis Example 4 &Lt; Synthesis Example of Compound (z-1) >

(1) Synthesis Example of Compound (z-a)

52.3 g of 2,5-dimethoxyaniline, 69.0 g of triethylamine and 365.7 g of dehydrated chloroform were mixed. The resulting mixture was stirred and then 50.0 g of 3-thiophenecarboxylic acid chloride was added. After stirring the mixture obtained under ice-cooling, the mixture was poured into water. The separated organic layer was washed with water and hydrochloric acid. The obtained organic layer was concentrated under reduced pressure, and the resulting solid was washed with hexane to obtain 82.1 g of a solid containing the compound (z-a) as a main component. The yield was 91% based on 2,5-dimethoxy aniline.

(2) Synthesis Example of Compound (z-b)

81.0 g of the compound (za), 64.7 g of 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphatane-2,4-disulfide (Lawesson's reagent) g, and the resulting mixture was heated to 80 DEG C and stirred. After cooling, the solution was concentrated to obtain a red-tinged solid containing the decomposition product of compound (z-b) and Lawson's reagent as a main component.

(3) Synthesis Example of Compound (z-c)

A mixture containing the compound (z-b) obtained in the preceding step, 73.8 g of sodium hydroxide and 750 g of water were mixed, and the resulting mixture was stirred under ice-cooling. Subsequently, an aqueous solution containing 257.8 g of potassium ferricyanide was added under ice-cooling, and the reaction was carried out at room temperature for 24 hours. The precipitated yellow precipitate was filtered off. The precipitate obtained by filtration was washed with water and ethanol, dissolved by heating and refluxing, and allowed to stand overnight with an ice bath. The resulting pale yellow powder was collected by filtration and vacuum-dried to obtain 49.1 g of a yellowish green solid containing the compound (z-c) as a main component. The yield was 58% based on compound (z-a).

(4) Synthesis Example of Compound (z-d)

40.0 g of the compound (z-c) and 200 g of pyridinium chloride were mixed, and the mixture was heated to 180 占 폚 and reacted for 6 hours. The resulting mixture was cooled, water was added, and the resulting precipitate was collected by filtration and washed with water, toluene and hexane to obtain 36.4 g of a solid containing the compound (z-d) as a main component.

(5) Synthesis Example of Compound (z-1)

3.00 g of the compound (z-d), 12.09 g of the compound (A), 0.15 g of dimethylaminopyridine and 181 g of chloroform were mixed. To the obtained mixture, 5.07 g of N, N'-diisopropylcarbodiimide was added at room temperature. The resulting mixture was reacted at room temperature for 2 hours, and then methanol was added to the reaction mixture for crystallization. The crystals were filtered off and redissolved in chloroform. Ethanol was added to the resulting solution while stirring, and the resulting solid was collected by filtration and vacuum dried to obtain 6.97 g of a compound (z-1) as a white powder. The yield was 55% based on the compound (z-d).

Compound ¹ H-NMR (CDCl ₃₎ of (z-1): δ ( ppm) 1.43~1.83 (m, 24H), 2.29~2.82 (m, 12H), 3.92~3.97 (t, 4H), 4.15~4.20 (m, 2H), 6.86-7.03 (m, 8H), 7.12 (dt, 1H), 7.19 (s, 2H), 7.44 (dd, IH), 7.62 (dd, IH), 7.98

The phase transition temperature of the obtained compound (z-1) was determined by texture observation by a polarizing microscope. The compound (z-1) exhibited a smectic phase from 111 ° C to 125 ° C at elevated temperature, a nematic phase from 125 ° C to 242 ° C, and a nematic phase at 242 ° C to 82 ° C .

Synthesis Example 5 &Lt; Synthesis Example of Compound (z-2) >

The procedure of Synthesis Example 4 was repeated, except that the compound (za) was replaced by the compound (z-2a) obtained by the reaction of 2,5-dimethoxyaniline and 4-fluorobenzoyl chloride , And compound (z-2). The yield was 46% based on the compound (z-2a).

Compound ¹ H-NMR (CDCl ₃₎ of the (z-2): δ ( ppm) 1.44~1.90 (m, 24H), 2.34~2.81 (m, 12H), 3.92~4.00 (t, 4H), 4.15~4.20 (m, 2H), 6.36-6.44 (m, 2H), 6.86-7.02 (m, 8H), 7.14-7.21 (m, 4H) , 8.00-8.07 (m, 2H)

The phase transition temperature of the obtained compound (z-2) was determined by a texture observation by a polarizing microscope. The compound (z-2) exhibited a smectic phase from 137 ° C to 146 ° C at elevated temperature, a nematic phase from 146 ° C to 170 ° C or higher, exhibited a nematic phase at 78 ° C during cooling, Respectively.

&Lt; Preparation of composition >

Each of the components listed in Table 2 was mixed, and the resulting mixture was stirred at 80 DEG C for 1 hour and then cooled to room temperature to prepare compositions 1 to 6, respectively.

A polymerizable liquid crystal compound;

(A11-1): The compound obtained in Synthesis Example 1

(A5-1): The compound obtained in Synthesis Example 2

(A10-1): The compound obtained in Synthesis Example 3

LC242: a compound represented by the following formula [Poliocolor (registered trademark of BASF Corporation) LC242]

(z-1): The compound obtained in Synthesis Example 4

(z-2): The compound obtained in Synthesis Example 5

A polymerization initiator;

Family cure 369; 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one (BASF Japan)

Ilgueur cure 819; Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (BASF Japan)

Leveling agents; BYK361N (manufactured by Beck Chemie Japan)

Solvent: Cyclopentanone

<Absorption measurement>

The polymerizable liquid crystal compounds shown in Table 2 were each dissolved in chloroform to prepare a solution having a concentration of 10 ^-4 mol / l. The absorbance of the solution was measured in a range of 300 nm to 800 nm by using an ultraviolet visible infrared spectrophotometer (UV-3150, manufactured by Shimadzu Seisakusho) into a quartz cell (10 mm square cell). The absorbance at 400 nm is shown in Table 2.

Table 3 shows the maximum absorption wavelength? ₀ of the polymerizable liquid crystal compound.

Examples 1 to 3 and Comparative Examples 1 to 3

&Lt; Production of optical film &

A 2% by mass aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 fully saponified type, manufactured by Wako Pure Chemical Industries, Ltd.) was applied to the glass substrate, and then the glass substrate was heated and dried at 120 캜 for 60 minutes to form a film having a thickness of 89 nm Of polyvinyl alcohol film was obtained. Subsequently, the surface of the polyvinyl alcohol film was rubbed to obtain a laminate of an alignment film and a glass substrate. On the surface of the resulting laminate subjected to the rubbing treatment, a solution having the composition shown in Table 1 was applied by spin coating. The solution-applied laminate was dried on a hot plate for 1 minute, and then irradiated with ultraviolet light of 2400 mJ / cm 2 while heating to obtain an optical film.

&Lt; Measurement of alignment order S ()

The obtained optical film was placed in a sample holder (manufactured by Shimadzu Corporation) equipped with a polarizer in an ultraviolet visible infrared spectrophotometer (UV-3150, manufactured by Shimadzu Corporation), and an optical film The sample holder was set. Subsequently, the absorbance A _p when the alignment direction of the polymerizable liquid crystal compound included in the optical film and the polarization direction of the polarized light were parallel, and the absorbance A _v when the alignment direction and the polarization direction of the polarized light were perpendicular were measured. From the measured absorbance A _p and the absorbance A _v , the orientation order S (?) Was also calculated using the equation (1). Further, a wavelength range satisfying -0.50 <S (?) <- 0.15 was calculated. The results are shown in Table 3.

In Table 3, " *) " means that no wavelength satisfies -0.50 <S (?) <- 0.15.

&Lt; Fabrication of phase difference plate (? / 2 plate)

The film thickness was adjusted so that the retardation value of the resulting retardation plate was 270 ± 5 nm, and a retardation film (λ / 2 plate) was produced in the same manner as in the production of the optical film. The front retardation value at a wavelength of 550 nm of the produced retardation plate was measured using a spectroscopic ellipsometer (M-220 type, manufactured by Nihon Bunko K.K.). Further, the film thickness of the composition layer was measured using a laser microscope (LEXT OLS3000, manufactured by Olympus Corporation). The results are shown in Table 4.

<Evaluation of discoloration>

The prepared retardation plate was set in parallel sample holder (Shimadzu Seisakusho) equipped with a polarizer attached to an ultraviolet visible infrared spectrophotometer (UV-3150, manufactured by Shimadzu Seisakusho) to measure transmittance Was set to 100%, and the transmittance measured by inserting a shield plate was set in the background. The transmittance was measured by providing a phase difference plate made in the sample holder such that the direction of vibration of incident polarized light and the direction of alignment of the polymerizable liquid crystal compound contained in the retardation plate were 45 °. The chromaticity values a ^* and b ^{* in} the L ^* a ^* b ^* (CIE) colorimetric system and their absolute values | a ^* | and b ^* are calculated from the values obtained by subtracting the background values from the measured transmittances, And | b ^* | were calculated. | a ^* | And &quot; b ^* &quot; are smaller, it can be determined that discoloration is less. The results are shown in Table 4.

As shown in Table 3 and Table 4, the alignment order is also an optical film of S ₀ are met, the -0.5 <S ₀ <-0.15 It can be seen that the discoloration is reduced.

INDUSTRIAL APPLICABILITY The optical film of the present invention is suitable for a polarizing plate or a flat panel display device because the discoloration is reduced.

1, 1 ', 12: Optical film of the present invention
2, 2 ': polarizing film layer
3, 3 ', 3 ": adhesive layer
4a, 4b, 4c, 4d, 4e, 4, 4 ': The polarizing plate
5, 5 ': adhesive layer
6: liquid crystal panel
10, 10b: liquid crystal display
7: Organic EL panel
11: organic EL display device
13: Color filter layer
14: Color filter

Claims (9)

As the optical film in which the polymerizable liquid crystal compound is oriented,
The absorbance A at 400 nm of the polymerizable liquid crystal compound measured using the following solution (a) is 0.1 or less,
Solution (a) and the alignment order of the optical film according to the polymerizable liquid crystal compound of the maximum absorption wavelength is measured by using also the S ₀ is satisfied -0.50 <S ₀ <-0.15,
Wherein the maximum absorption wavelength of the solution (a) is from 302 nm to 400 nm.
Solution (a): A solution obtained by dissolving a polymerizable liquid crystal compound in chloroform so as to have a concentration of 10 ^-4 mol / l. delete The optical film according to claim 1, wherein the wavelength range satisfying -0.50 <S (?) <-0.15 [S (?) Indicates the order of orientation of the optical film at wavelength? Nm) is 40 nm or more. delete delete The optical film according to any one of claims 1 to 3, which is obtained by applying a composition comprising a polymerizable liquid crystal compound to a substrate, orienting the polymerizable liquid crystal compound, and polymerizing the polymerizable component contained in the composition. A polarizing plate comprising the optical film and the polarizing film according to any one of claims 1 to 3. A flat panel display device comprising the optical film according to claim 1 or 3. 4. A color filter comprising the optical film according to claim 1 or 3.

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