TWI810264B - Composition and polarizing film - Google Patents

Abstract

This invention provides a composition including a polymerizable liquid crystal compound with sematic phase and a liquid crystal compound represented by formula (2).

[In the formulae, m represents an integer.

A¹ to A³ represent a divalent aromatic group.

L¹ to L² represent a single bond or an ester group, etc.

Z¹ represents a polymerizable group.

Z² represents a hydrogen atom or a polymerizable group.

Q¹ to Q² represent a group such as alkylene.

T¹ represents a single bond or an ester group, etc.

R^f and R^g represent a hydrogen atom or an alkyl group.]

Description

Composition and Polarizing Film

The present invention relates to compositions and the like used for manufacturing polarizing films.

In a flat panel display device (FPD), an optical film such as a polarizing plate or a retardation plate is used. As such a polarizing plate, an iodine PVA polarizing plate is widely used. The iodine PVA polarizing plate is composed of a polarizing layer and a protective film formed by adsorbing and aligning a dichroic dye with iodine on a polyvinyl alcohol-based resin film. In recent years, thin polarizers have been sought, and Patent Document 1 below discloses a thin polarizer composed of a polymerizable liquid crystal having a smectic phase and a dichroic dye. In addition, Patent Document 2 below describes a composition capable of producing a polarizing film excellent in temporal stability. In addition, the following Patent Document 3 describes a composition for producing a polarizing film having a high dichroic ratio.

[Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent No. 4719156.

[Patent Document 2] Japanese Patent Application Laid-Open No. 2011-246696.

[Patent Document 3] Japanese Patent Application Laid-Open No. 2013-101328.

The polarizing film produced from the composition of Patent Document 2 has a problem of low dichroism. In addition, the polarizing film produced by the composition of Patent Document 3 has a problem of high dichroism but insufficient durability.

The present invention provides a composition capable of producing a polarizing film with high dichroism and excellent durability.

That is, the present invention provides a composition comprising a polymerizable liquid crystal compound exhibiting a smectic phase, and a liquid crystal compound represented by formula (2).

[In formula (2), m represents an integer of 0 to 3.

A ¹ , A ² and A ³ each independently represent a divalent aromatic group which may have a substituent.

L ¹ and L ² each independently represent a single bond, -CH ₂ -, -CH ₂ CH ₂ -, -O-, -CH ₂ O-, -OCH ₂ -, -CO-, -COO-, -OCO- , -OCOO-, -CR ^c =CR ^d -, -C≡C-, -CR ^c =N-, -CONR ^c -, -NR ^c CO-, or -N=N-.

R ^c and R ^d each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbons.

Z ¹ represents a polymerizable group.

Z ² represents a hydrogen atom or a polymerizable group.

Q ¹ and Q ² each independently represent a straight-chain or branched chain alkylene group with 1 to 20 carbon atoms that may have a substituent, an alkenylene group with 1 to 20 carbon atoms that may have a substituent, or an optional substituent An alkynylene group having 1 to 20 carbon atoms, wherein -CH ₂ - contained in the alkylene, alkenylene or alkynylene group may be substituted by -O-, -S- or -NR ^e -.

R ^e represents a hydrogen atom or an alkyl group having 1 to 4 carbons.

T ¹ represents a single bond, -O-, -S-, -CO-, -COO-, -OCO-, -OCOO-, or -CONR ^f -, or -NR ^f CO-.

T ² represents a single bond, -O-, -S-, -CO-, -COO-, -OCO-, -OCOO-, -CONR ^f -, -NR ^f CO-, or, when Z ² is only a hydrogen atom In the case of -NR ^g -,

^Rf and ^Rg each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, but the alkyl group represented by ^Rg may form a ring with ^Q1 or ^Q2 .

Only A ¹ -(L ¹ -A ² ) _m -L ² -A ³ contains at least one represented by -A ^X1 -N=NA ^X2 - (where A ^X1 and A ^X2 each represent a divalent aromatic group) structure. And when T ² is the case of -NR ^g -, Z ² represents a hydrogen atom. ]

In addition, the present invention provides the following aspects.

In the above composition, the aforementioned polymerizable liquid crystal compound exhibiting a smectic phase is represented by formula (1).

[In the formula (1), X ¹ and X ² each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group, wherein, the divalent aromatic group or a divalent alicyclic hydrocarbon group The hydrogen atom contained in the group may be substituted by a halogen atom, an alkyl group having 1 to 4 carbons, a fluoroalkyl group having 1 to 4 carbons, an alkoxy group having 1 to 4 carbons, a cyano group or a nitro group. The carbon atoms constituting the divalent aromatic group or the divalent alicyclic hydrocarbon group may be substituted by an oxygen atom, a sulfur atom or a nitrogen atom. However, at least one of ^X1 and ^X2 is an optionally substituted 1,4-phenylene group or an optionally substituted cyclohexane-1,4-diyl group.

n is 1 to 3, and when n is 2 or more, X ¹ and X ² may be different from each other.

Y ¹ are each independently a single bond or a divalent linking group.

U ¹ represents a hydrogen atom or a polymerizable group.

U ² represents a polymerizable group.

W ¹ and W ² each independently represent a single bond or a divalent linking group.

V ¹ and V ² each independently represent an optionally substituted alkanediyl group having 1 to 20 carbon atoms, and -CH ₂ - constituting the alkanediyl group may be replaced by -O-, -CO-, -S- or NH-substituted. ]

The above-mentioned composition, wherein, when the above-mentioned ^U1 is a polymerizable group, the number of main chain atoms of ^V1 or the number of main chain atoms of ^V2 connected to the polymerizable group, and the number of main chain atoms of ^Q1 Or the difference between the number of main chain atoms of ^Q2 connected to the polymerizable group when ^Z2 is a polymerizable group is 3 or less.

As in the above composition, wherein U ¹ and Z ¹ and U ² and Z ² are the same polymerizable group, and the polymerizable group is an acryl group or a methacryl group.

The above composition, wherein the liquid crystal compound of the above formula (2) is a compound exhibiting dichroic light absorption in the visible light range.

The above composition, wherein the liquid crystal compound of the above formula (1) is a thermotropic liquid crystal and a compound having a smectic liquid crystal phase.

A polarizing film obtained by polymerizing the compound represented by formula (1) and the compound represented by formula (2) in the above composition in a molecular alignment state.

A polarizing film, which is obtained by polymerizing the compound represented by formula (1) and the compound represented by formula (2) in the above composition in a state of molecular alignment, and can be obtained in X-ray diffraction measurement Prague Peak.

A circular polarizing plate, which has the above-mentioned polarizing film and a quarter-wave plate, wherein the angle formed by the absorption axis of the above-mentioned polarizing film and the slow axis of the quarter-wave plate is 45±10°, and the four The one-wavelength plate satisfies the following formula (I).

100nm<Re(550)<160nm...(I)

(In the formula, Re(550) represents the in-plane retardation value with respect to light having a wavelength of 550 nm.)

A circular polarizing plate, which has the above-mentioned polarizing film and a quarter-wavelength plate, wherein the angle formed by the absorption axis of the above-mentioned polarizing film and the slow axis of the quarter-wavelength plate is 45±10°, in addition, the The quarter wave plate satisfies all of the following formulas (I), formula (II) and formula (III).

100nm<Re(550)<160nm...(I)

Re(450)/Re(550)≦1.0...(II)

1.00≦Re(650)/Re(550)…(III)

(where Re(450) represents the in-plane retardation value for light with a wavelength of 450nm, Re(550) represents the in-plane retardation value for light with a wavelength of 550nm, Re(650) represents the value for light with a wavelength of 650nm in-plane phase difference.)

An organic electroluminescent display device, which includes the above-mentioned circular polarizing plate.

According to the composition of the present invention, a polarizing film having high dichroism and excellent durability can be obtained.

1‧‧‧Laminated body

2‧‧‧Supporting substrate

3‧‧‧Alignment film

4‧‧‧Polarizing film of the present invention

10‧‧‧LCD display device

11‧‧‧Anti-reflection film

12a, 12b‧‧‧Polarizing film of the present invention

13a, 13b‧‧‧retardation film

14a, 14b‧‧‧substrate

15‧‧‧color filter

16‧‧‧Transparent electrode

17‧‧‧LCD layer

18‧‧‧Interlayer insulating film

19‧‧‧Backlight unit

20‧‧‧Black Matrix

21‧‧‧Thin Film Transistor

22‧‧‧pixel electrode

23‧‧‧Spacer

24‧‧‧LCD display device

30‧‧‧EL display device

31‧‧‧Polarizing film of the present invention

32‧‧‧retardation film

33‧‧‧substrate

34‧‧‧Interlayer insulating film

35‧‧‧pixel electrode

36‧‧‧luminescent layer

37‧‧‧cathode electrode

38‧‧‧Desiccant

39‧‧‧Sealing cover

40‧‧‧Thin Film Transistor

41‧‧‧Convex

42‧‧‧Film sealing film

44‧‧‧EL display device

111‧‧‧Light source

112‧‧‧First lens array

112a‧‧‧Lens

113‧‧‧Second lens array

114‧‧‧polarization conversion element

115‧‧‧overlapping lens

121, 123, 132‧‧‧spectral filter

122‧‧‧reflector

140R, 140G, 140B‧‧‧LCD panel

142, 143‧‧‧Polarizing film of the present invention

150‧‧‧Cross splitter

170‧‧‧projection lens

180‧‧‧screen

Fig. 1 is a schematic diagram showing a laminate 1 including a polarizing film 4 made of the composition of the present invention.

FIG. 2 is a schematic diagram showing a liquid crystal display device 10, which is one of the display devices of the present invention.

FIG. 3 is a schematic diagram showing a liquid crystal display device 24, which is one of the display devices of the present invention.

Fig. 4 is a schematic diagram showing an EL display device 30, which is one of the display devices of the present invention.

Fig. 5 is a schematic diagram showing an EL display device 44, which is one of the display devices of the present invention.

Fig. 6 is a schematic diagram showing a projection type liquid crystal display device which is one of the display devices of the present invention.

The composition of the present invention provides a polymerizable liquid crystal compound exhibiting a smectic phase, and a liquid crystal compound represented by formula (2).

Among them, formula (2) is:

[In formula (2), m represents an integer of 0 to 3.

A ¹ , A ² and A ³ each independently represent a divalent aromatic group which may have a substituent.

L ¹ and L ² each independently represent a single bond, -CH ₂ -, -CH ₂ CH ₂ -, -O-, -CH ₂ O-, -OCH ₂ -, -CO-, -COO-, -OCO- , -OCOO-, -CR ^c =CR ^d -, -C≡C-, -CR ^c =N-, -CONR ^c -, -NR ^c CO-, or -N=N-.

R ^c and R ^d each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbons.

Z ¹ represents a polymerizable group.

Z ² represents a hydrogen atom or a polymerizable group.

Q ¹ and Q ² each independently represent a straight-chain or branched chain alkylene group with 1 to 20 carbon atoms that may have a substituent, an alkenylene group with 1 to 20 carbon atoms that may have a substituent, or may have a substitution An alkynylene group having 1 to 20 carbon atoms, wherein -CH ₂ - contained in the alkylene, alkenylene or alkynylene group may be substituted by -O-, -S- or -NR ^e -.

R ^e represents a hydrogen atom or an alkyl group having 1 to 4 carbons.

T ¹ represents a single bond, -O-, -S-, -CO-, -COO-, -OCO-, -OCOO- or -CONR ^f - or -NR ^f CO-, T ² represents a single bond, -O- , -S-, -CO-, -COO-, -OCO-, -OCOO-, -CONR ^f -, -NR ^f CO-, or -NR ^g - when Z ² is only a hydrogen atom.

^Rf and ^Rg each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, but the alkyl group represented by ^Rg may form a ring with ^Q1 or ^Q2 .

However, A ¹ -(L ¹ -A ² ) _m -L ² -A ³ contains at least one represented by -A ^X1 -N=NA ^X2 - (where A ^X1 and A ^X2 each represent a divalent aromatic group) representation structure. And when T ² is the case of -NR ^g -, Z ² represents a hydrogen atom. ] And in this composition, if necessary, contain a solvent.

In the present invention, the above-mentioned polymerizable liquid crystal compound exhibiting a smectic phase may be a polymerizable liquid crystal compound, but is preferably represented by formula (1).

[In formula (1), X ¹ and X ² each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group, wherein the divalent aromatic group or a divalent alicyclic hydrocarbon group The hydrogen atom contained in the hydrocarbon group may also be substituted by a halogen atom, an alkyl group with 1 to 4 carbons, a fluoroalkyl group with 1 to 4 carbons, an alkoxy group with 1 to 4 carbons, a cyano group or a nitro group . The carbon atoms constituting the divalent aromatic group or the divalent alicyclic hydrocarbon group may also be substituted by an oxygen atom, a sulfur atom or a nitrogen atom. However, at least one of ^X1 and ^X2 is an optionally substituted 1,4-phenylene group or an optionally substituted cyclohexane-1,4-diyl group.

n is 1 to 3, and when n is 2 or more, X ¹ and X ² may be different groups respectively.

Y ¹ are each independently a single bond or a divalent linking group.

U ¹ represents a hydrogen atom or a polymerizable group.

U ² represents a polymerizable group.

W ¹ and W ² each independently represent a single bond or a divalent linking group.

V ¹ and V ² each independently represent an optionally substituted alkanediyl group having 1 to 20 carbon atoms, and -CH ₂ - constituting the alkanediyl group may be replaced by -O-, -CO-, -S- or NH-substituted. ]

Hereinafter, the compound represented by formula (1) is demonstrated.

Compounds that can be represented by formula (1)

The composition of the present invention contains a compound represented by formula (1) (hereinafter, may be referred to as "compound (1)").

[In formula (1), X ¹ and X ² each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group, wherein the divalent aromatic group or a divalent alicyclic hydrocarbon group The hydrogen atom contained in the hydrocarbon group may also be substituted by a halogen atom, an alkyl group with 1 to 4 carbons, a fluoroalkyl group with 1 to 4 carbons, an alkoxy group with 1 to 4 carbons, a cyano group or a nitro group . The carbon atoms constituting the divalent aromatic group or the divalent alicyclic hydrocarbon group may also be substituted by an oxygen atom, a sulfur atom or a nitrogen atom. However, at least one of ^X1 and ^X2 is an optionally substituted 1,4-phenylene group or an optionally substituted cyclohexane-1,4-diyl group.

n is 1 to 3, and when n is 2 or more, X ¹ and X ² may be different groups respectively. From the viewpoint of liquid crystallinity, the case where n is 2 or more is preferable.

Y ¹ are each independently a single bond or a divalent linking group.

U ¹ represents a hydrogen atom or a polymerizable group.

U ² represents a polymerizable group.

W ¹ and W ² each independently represent a single bond or a divalent linking group.

V ¹ and V ² each independently represent an optionally substituted alkanediyl group having 1 to 20 carbon atoms, and -CH ₂ - constituting the alkanediyl group may be replaced by -O-, -CO-, -S- or NH-substituted. ]

Usually, in compound (1), W ¹ -(X ¹ -Y ¹ ) _n -X ² -W ³ does not have -A ^X1 -N=NA ^X2 -(A ^X1 and A ^X2 represent divalent aromatic Group group.) The structure represented.

In the compound (1), ^X1 and ^X2 are independent of each other, preferably a 1,4-phenylene group which may have a substituent, or a cyclohexane-1,4-diyl group which may have a substituent, and At least one of ^X1 and ^X2 is preferably a 1,4-phenylene group that may have a substituent, or a cyclohexane-1,4-diyl group that may have a substituent, trans-cyclohexane-1 ,4-diradical. Examples of the 1,4-phenylene group that may have a substituent or the cyclohexane-1,4-diyl group that may have a substituent include: C1-4 alkyl groups such as methyl and ethyl; group; and halogen atoms such as chlorine atom, fluorine atom, etc. Preferred is no substitute. In formula (1), when n is 2 or more and Y ¹ has the same structure, it is preferable that at least one of X ¹ and X ² has a different structure. When n is 2 or more and at least one of X ¹ and X ² has a different structure, smectic liquid crystallinity tends to be easily exhibited.

Y ¹ are independently a single bond or a divalent linking group. The preferred divalent linking groups are -CH ₂ CH ₂ -, -CH ₂ O-, -CH ₂ CH ₂ O-, -COO-, -OCOO-, -N=N-, -CR ^a =CR ^b -, -C≡C-, -CR ^a =N- or CO-NR ^a -. R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. More preferably, Y ¹ is -CH ₂ CH ₂ -, -COO- or a single bond. And Y ¹ is more preferably -CH ₂ CH ₂ - or CH ₂ O-. In formula (1), when n is 2 or more and both X ¹ and X ² have the same structure, Y ¹ is preferably a different bonding method. When n is 2 or more and Y ¹ is a different bonding method, smectic liquid crystallinity tends to be easily exhibited.

U ² is a polymerizable group. ^U1 is a hydrogen atom or a polymerizable group, preferably a polymerizable group. It is preferable that U ¹ and U ² are both polymerizable groups, and both are preferably free radical polymerizable groups. Examples of polymerizable groups include vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, acryloxy, methacryloxy, oxiranyl, Oxetanyl, etc. Among them, acryloxy, methacryloxy, ethyleneoxy, oxiranyl and oxetanyl are preferred, and acryloxy is more preferred. The polymerizable group represented by ^U1 and the polymerizable group represented by ^U2 may be different from each other, but are preferably the same type of group. In addition, the polymerizable group may be in a polymerized state or an unpolymerized state, but is preferably in an unpolymerized state.

W ¹ and W ² are each independently a single bond or a divalent linking group. W ¹ and W ² are preferably -O-, -S-, -COO- or OCOO-, more preferably a single bond or -O-.

V ¹ and V ² each independently represent an alkanediyl group having 1 to 20 carbon atoms that may have a substituent, and -CH ₂ - constituting the alkanediyl group may be replaced by -O-, -CO-, -S- or NH -replace. Examples of the alkanediyl group include: methylene group, ethylidene group, propane-1,3-diyl group, butan-1,3-diyl group, butan-1,4-diyl group, pentane-1,5-diyl group, Base, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, decane-1,10-diyl, tetradecane-1,14- Diyl and eicosan-1,20-diyl, etc. V ¹ and V ² are preferably an alkanediyl group having 2 to 12 carbons, more preferably an alkanediyl group having 6 to 12 carbons.

Examples of the substituent that the alkanediyl group optionally has include a cyano group, a halogen atom, and the like. The alkanediyl group is preferably unsubstituted, more preferably an unsubstituted linear alkanediyl group.

Compound (1) includes, for example, compounds represented by formula (1-1) to formula (1-25). When the compound (1) has a cyclohexane-1,4-diyl group, the cyclohexane-1,4-diyl group is preferably a trans isomer.

Wherein, preferably be selected from formula (1-2), formula (1-3), formula (1-4), formula (1-5), formula (1-6), formula (1-7), In the group consisting of compounds represented by formula (1-8), formula (1-13), formula (1-14), formula (1-15), formula (1-16) and formula (1-17) at least one of them. Compound (1) may be used alone or in combination of two or more.

For example, Compound (1) can be produced by a known method described in Lub et al., Recl. Trav. Chim. Pays-Bas, Vol. 115, pp. 321 to 328 (1996) or Japanese Patent No. 4719156.

The content of the compound (1) is preferably from 70 to 99.99% by mass, more preferably from 90 to 99.9% by mass, relative to the solid content of the composition. Within the above range, the alignment of the compound (1) tends to be high. Here, the solid content refers to the total amount of components in the composition after deducting the solvent.

Compounds represented by formula (2)

The composition of the present invention contains a liquid crystal compound represented by formula (2) (hereinafter sometimes referred to as "compound (2)"). Compound (2) is preferably a liquid crystal compound exhibiting dichroism in the visible light range. Dichroism refers to the property that the absorbance in the direction of the long axis of a molecule is different from the absorbance in the direction of the short axis.

[In formula (2), m represents an integer of 0 to 3.]

A ¹ , A ² and A ³ each independently represent a divalent aromatic group which may have a substituent.

L ¹ and L ² each independently represent a single bond, -CH ₂ -, -CH ₂ CH ₂ -, -O-, -CH ₂ O-, -OCH ₂ -, -CO-, -COO-, -OCO- , -OCOO-, -CR ^c =CR ^d -, -C≡C-, -CR ^c =N-, -CONR ^c -, -NR ^c CO-, or -N=N-.

R ^c and R ^d each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbons.

Z ¹ represents a polymerizable group.

Z ² represents a hydrogen atom or a polymerizable group.

Q ¹ and Q ² each independently represent a straight-chain or branched chain alkylene group with 1 to 20 carbon atoms that may have a substituent, an alkenylene group with 1 to 20 carbon atoms that may have a substituent, or may have a substitution Alkynylene groups with 1 to 20 carbon atoms, wherein -CH ₂ - contained in the alkylene, alkenylene or alkynylene groups may also be substituted by -O-, -S- or -NR ^e - .

R ^e represents a hydrogen atom or an alkyl group having 1 to 4 carbons.

T ¹ represents a single bond, -O-, -S-, -CO-, -COO-, -OCO-, -OCOO-, or -CONR ^f - or -NR ^f CO-.

T ² represents a single bond, -O-, -S-, -CO-, -COO-, -OCO-, -OCOO-, -CONR ^f -, -NR ^f CO-, or, when Z ² is only a hydrogen atom In the case of , it means -NR ^g -.

^Rf and ^Rg each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, but the alkyl group represented by ^Rg may form a ring with ^Q1 or ^Q2 .

However, A ¹ -(L ¹ -A ² ) _m -L ² -A ³ contains -A ^X1 -N=NA ^X2 - (wherein A ^X1 and A ^X2 each represent a divalent aromatic group) structure. And when T ² is the case of -NR ^g -, Z ² represents a hydrogen atom. ]

m represents an integer of 0 to 3, and m is preferably 1 to 3.

A ¹ , A ² and A ³ each independently represent a divalent aromatic group which may have a substituent.

Examples of the divalent aromatic group include a 1,4-phenylene group, a naphthalene-1,4-diyl group, and a divalent heterocyclic group which may have a substituent. Examples of the divalent heterocyclic group include groups obtained by removing two hydrogen atoms from quinoline, thiazole, benzothiazole, thienothiazole, imidazole, benzimidazole, oxazole, and benzoxazole. When ^A is a divalent heterocyclic group, it is preferably a structure in which the molecular bonding angle is substantially 180°, more specifically, a thienothiazole structure in which two five-membered ring systems are condensed .

The substituents that the divalent aromatic group may have include, for example: alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, and butyl; and alkyl groups having 1 to 4 carbon atoms such as methoxy, ethoxy, and butoxy groups. Alkoxy groups to 4; fluorinated alkyl groups with 1 to 4 carbon atoms such as trifluoromethyl; cyano group; nitro group; halogen atoms such as chlorine atom and fluorine atom; amino group, diethylamino group and pyrrolidinyl group and other substituted or unsubstituted amino groups (wherein the substituted amino group is an amino group having one or two alkyl groups with 1 to 6 carbon numbers, or an alkyl group with one or two carbon numbers of 2 to 8 Diradical cyclic amino groups. Unsubstituted amino groups refer to —NH ₂ ). In addition, examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group and the like. Examples of alkanediyl groups having 2 to 8 carbon atoms include: ethane-1,2-diyl, propane-1,3-diyl, butan-1,3-diyl, butan-1,4-diyl, pentane Alkane-1,5-diyl, hexa-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, etc.

Specifically, the divalent aromatic group that may have a substituent is preferably an unsubstituted group or a 1,4-phenylene group in which hydrogen is substituted with a methyl or methoxy group, or the above-mentioned divalent aromatic group valent heterocyclic group.

L ¹ and L ² each independently represent a single bond, -CH ₂ -, -CH ₂ CH ₂ -, -O-, -CH ₂ O-, -OCH ₂ -, -CO-, -COO-, -OCO- , -OCOO-, -CR ^c =CR ^d -, -C≡C-, -CR ^c =N-, -CONR ^c -, -NR ^c CO-, or -N=N-. The aforementioned R ^c and R ^d each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbons. The alkyl group having 1 to 4 carbon atoms is the same as above, and examples thereof include methyl, ethyl, propyl, and butyl groups. L ¹ and L ² are preferably -COO-, -CH=CH-, -C≡C-, -CONH- or -N=N-, wherein, more preferably -COO-, -OCO- or -N =N-.

Z ¹ is a polymerizable group, and Z ² is a hydrogen atom or a polymerizable group. Here, the polymerizable group refers to the group that can participate in the polymerization reaction by the active free radical or acid generated by the polymerization initiator, and the so-called photopolymerizable group refers to the group that can be generated by the photopolymerization initiator. Active free radicals or acids that participate in the polymerization reaction. When Z ¹ and Z ² are both polymerizable groups, Z ¹ and Z ² are preferably the same type of polymerizable groups, more preferably the same polymerizable groups. The polymerizable group may be in a polymerized state or an unpolymerized state, but is preferably in an unpolymerized state.

Examples of polymerizable groups include vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, acryloxy, methacryloxy, oxiranyl, Oxetanyl, etc. Among them, acryloxy, methacryloxy, ethyleneoxy, oxiranyl and oxetanyl are preferred, and acryloxy is more preferred.

Q ¹ and Q ² each independently represent a straight-chain or branched chain alkylene group with 1 to 20 carbon atoms that may have a substituent, an alkenylene group with 1 to 20 carbon atoms that may have a substituent, or may have The substituent is an alkynylene group having 1 to 20 carbon atoms, and the -CH ₂ - contained in the alkylene, alkenylene or alkynylene group may be substituted by -O-, -S- or -NR ^e -.

Examples of alkylene groups with carbon numbers from 1 to 20 include: polymethyl groups with carbon numbers from 1 to 20, namely: methylene, ethylidene, propylidene, butylene, pentyl, hexylene, and heptylene Base, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, Heptadecyl, octadecyl, nonadecyl and eicosyl, etc. Preferred are propyl, butyl, pentyl, hexyl, heptyl, octyl, nonylene, decyl, undecyl, dodecyl, and tridecyl Butyl, tetradecyl, etc.; particularly preferred are butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl base, tridecyl, etc.

Examples of alkenyl groups with a carbon number of 1 to 20 include: vinyl, propenyl, butenyl, pentenyl, hexenyl, heptyl, heptyl, alkynyl, alkynyl, alkene Decyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, heptadecenyl, octadecenyl, nonadecenyl and eicosynyl, etc.; preferably propenyl, butenyl, pentenyl, hexenyl, heptyl, octenyl, nonenyl, decyl, undecenyl alkenyl, dodecenyl, tridecenyl, tetradecenyl, etc.; particularly preferred are butenyl, pentenyl, hexenyl, heptenyl, octenyl, Nonylene, decylene, undecylene, dodecylene, tridecylene and the like.

Examples of alkynyl groups with 1 to 20 carbon atoms include: ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl , Decynyl, Undecynyl, Dodecynyl, Tridecynyl, Tetradecynyl, Pentadecynyl, Hexadeynyl, Heptadeynyl, Decynyl Octynyl, nonadeynyl, eicosynyl, etc.; preferably propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, Nonynyl, Decynyl, Undecynyl, Dodecynyl, Tridecynyl, Tetradecynyl, etc.; butynyl, pentynyl, hexynyl are particularly preferred Alkynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl, dodecynyl, tridecynyl, etc.

Examples of substituents that the above-mentioned alkylene, alkenylene or alkynylene may have include cyano; fluorine, chlorine, bromine and other halogen groups.

The above-mentioned alkylene, alkenylene or alkynylene is preferably an unsubstituted alkylene, alkenylene or alkynylene, and more preferably an unsubstituted linear chain alkylene or alkenylene or alkynyl.

The above R ^e represents a hydrogen atom or an alkyl group having 1 to 4 carbons. Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl and butyl.

T ¹ represents a single bond, -O-, -S-, -CO-, -COO-, -OCO-, -OCOO-, or -CONR ^f - or -NR ^f CO-.

T ² represents a single bond, -O-, -S-, -CO-, -COO-, -OCO-, -OCOO-, -CONR ^f -, -NR ^f CO-, or when Z ² is only a hydrogen atom -NR ^g- .

T ¹ and T ² are preferably functional groups bonded parallel to the long axis direction of the compound when Z ¹ and Z ² of the respective terminal groups are polymerizable groups. In this case, a single bond, -O-, -COO- is preferred.

^Rf and ^Rg each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, but the alkyl group represented by ^Rg may form a ring with ^Q1 or ^Q2 .

In formula (2), A ¹ -(L ¹ -A ² ) _m -L ² -A ³ contains at least one -A ^X1 -N=NA ^X2 - (where A ^X1 and A ^X2 each represent a divalent aromatic The structure represented by the family group). When T ² is the case of -NR ^g -, Z ² represents a hydrogen atom. The divalent aromatic groups represented by ^AX1 and ^AX2 include the same groups as the divalent aromatic groups represented by ^A1 and ^A2 above.

Compound (2) includes compounds represented by formula (2-1) to formula (2-115). Compound (2) preferably contains a structure represented by -A ^X1 -N=NA ^X2 -N=NA ^X3 - (where A ^X1 and A ^X2 are as defined above, and A ^X3 represents a divalent aromatic group) By. In addition, examples of the divalent aromatic group represented by A ^X3 include the same groups as A ^X1 and A ^X2 . Examples of A ^X1 , A ^X2 and A ^X3 are preferably a divalent aromatic hydrocarbon group having 6 to 12 carbons, or a divalent aromatic heterocyclic group having a sulfur atom or a nitrogen atom having 6 to 12 carbons. More preferably, at least one of A ^X1 , A ^X2 and A ^X3 is a divalent aromatic hydrocarbon group having 6 to 12 carbons such as phenylene and aryl alkenylene.

The compound (2) can be obtained by the known organic synthesis reactions (condensation reaction, esterification reaction, Williamson synthesis method, Uzbekistan synthesis method, etc. Germann reaction, Witty reaction, Schiff base formation reaction, benzylation reaction, Soto coupling reaction, Suzuki-Miyaura reaction, Negishi coupling reaction, Kumata coupling reaction, Nozaki-Hinoki-Kishi reaction, Buchwald reaction -Hartwig reaction, Friedel-Crafts reaction, Heck reaction, aldol reaction, etc.) are manufactured by appropriately combining these reactions according to the structure.

In the present invention, compound (1) and compound (2) are preferably those satisfying the following requirements. That is, when the above-mentioned ^U1 is a polymerizable group, the number of main chain atoms of ^V1 connected to the polymerizable group, or the number of main chain atoms of ^V2 , and the number of main chain atoms of ^Q1 , or when Z ² is a polymerizable group and the difference in the number of main chain atoms of Q ² connected to the polymerizable group is 3 or less. Among them, any one of U ¹ -V ¹ -, U ² -V ² -, Z ¹ -Q ¹ - and Z ² -Q ² - is preferably acrylalkyl or methacrylalkyl, And the carbon number difference of the alkyl group is 3 or less.

The content of the compound (2) is preferably from 0.01 to 30% by mass, more preferably from 0.1 to 10% by mass, relative to the solid content of the composition. Within the above range, since compound (1) and compound (2) can be polymerized without interfering with the alignment of compound (1), the dichroic ratio of the polarizing film tends to become high. Compound (2) may be used alone or in combination of two or more.

The dichromatic ratio refers to the light incident on the polarizing film, and the absorption intensity ratio of two linearly polarized lights that oscillate perpendicularly to each other. This is defined as the ratio of the absorbance (AV) along the extinction axis (measured at normal incidence) relative to the absorbance (AH) along the transmission axis (AV/AH). The transmission axis (polarization axis) refers to the polarization direction of the components that pass through the polarizing film among the incident light incident on the polarizing film, and the extinction axis (absorption axis) refers to the incident light incident on the polarizing film, absorbed by the polarizing film The polarization direction of the component.

Generally, when a liquid crystal compound having a polymerizable group is polymerized after being aligned, the alignment tends to be easily disturbed, but since compound (2) itself has liquid crystallinity, even if compound (1) and compound (2) are mixed, , the obtained composition also tends to show a liquid crystal phase stably. In addition, since compound (1) and compound (2) can be polymerized without disturbing the alignment of compound (1) and compound (2), the resulting polarizing film tends to have a high dichroic ratio.

polymerization initiator

The composition of the present invention is preferably a composition further containing a polymerization initiator. The polymerization initiator is a compound that initiates the polymerization of compound (1) and compound (2), and is preferably a photopolymerization initiator that generates acid or free radicals by light irradiation, and is more preferably a photopolymerization initiator that generates acid or free radicals by light irradiation. Free radical photopolymerization initiator.

Examples of photopolymerization initiators include benzoin compounds, benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, tricompounds, iodine salts, and sulfur salts.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Examples of benzophenone compounds include: benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl diphenyl sulfide, 3,3',4,4'-Tetrakis(tertiary butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc.

Acetophenone compounds include: diethoxyacetophenone, 2-methyl-2-morpholinyl-1-(4-methylthiophenyl)propan-1-one, 2-benzyl-2- Dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1,2-diphenyl-2 ,2-Dimethoxyethane-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl Phenyl ketone, an oligomer of 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one, and the like.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and the like.

化合物可列舉：2,4-雙(三氯甲基)-6-(4-甲氧基苯基)-1,3,5-三

、2,4-雙(三氯甲基)-6-(4-甲氧基萘基)-1,3,5-三

、2,4-雙(三氯甲基)-6-(4-甲氧基苯乙烯基)-1,3,5-三

、2,4-雙(三氯甲基)-6-[2-(5-甲基呋喃-2-基)乙烯基]-1,3,5-三

、2,4-雙(三氯甲基)-6-[2-(呋喃-2-基)乙烯基]-1,3,5-三

、2,4-雙(三氯甲基)-6-[2-(4-二乙胺基-2-甲基苯基)乙烯基]-1,3,5-三

、2,4-雙(三氯甲基)-6-[2-(3,4-二甲氧基苯基)乙烯基]-1,3,5-三

等。 three

Compounds can be listed: 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-tri

wait.

Photopolymerization initiator can use commercially available photopolymerization initiator, for example: Irgacure907, Irgacure184, Irgacure651, Irgacure819, Irgacure250, Irgacure369 etc. Manufactured by Seiko Chemical Co., Ltd.); KayacureBP100 (manufactured by Nippon Kayaku Co., Ltd.); KayacureUVI-6992 (manufactured by Dow Corporation); AdekaOptomerSP-152, AdekaOptomerSP-170 (the above are all made by ADEKA Co., Ltd.); TAZ- A. TAZ-PP (all of the above are manufactured by Siberhegner Corporation of Japan); TAZ-104 (manufactured by Sanwa Chemical Corporation); EsacureOne, EsacureKIP150 (all of the above are manufactured by IGM Resins Corporation), etc.

The content of the polymerization initiator is preferably from 0.1% by mass to 30% by mass, further preferably from 0.5% by mass to 10% by mass, based on 100% by mass of the total amount of compound (1) and compound (2). Within the above range, compound (1) and compound (2) can be polymerized without disturbing the alignment of compound (1) and compound (2).

other additives

或紅螢烯。 The composition of the present invention may also contain a photosensitizer. Photosensitizers include, for example: xanthone compounds such as xanthone and thioxanthone (for example, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, etc.); anthracene or alkyl ethers, etc. Anthracene compounds having substituents (for example, dibutoxyanthracene, etc.); phenothione

or rubrene.

By using a photosensitizer, the polymerization of the compound (1) or the compound (2) can be sensitized, or the durability, especially the heat resistance, of the polarizing film obtained by the polymerization can be improved. Also, the content of the photosensitizer is preferably 0.1 to 30% by mass, more preferably 0.5 to 10% by mass relative to 100% by mass of the total amount of compound (1) and compound (2). As long as it is within the above range, polymerization can be performed without disturbing the alignment of compound (1) and compound (2).

The composition of the present invention may contain a polymerization inhibitor. Examples of polymerization inhibitors include: hydroquinone or hydroquinone compounds having substituents such as alkyl ethers; catechol compounds having substituents such as butyl catechol and alkyl ethers; pyrogallol compounds, 2,2,6 , Radical scavengers such as 6-tetramethyl-1-piperidinyloxy; thiophenol compounds, β-naphthylamine compounds, β-naphthol compounds, etc.

By using a polymerization inhibitor, the polymerization of compound (1) or compound (2) can be controlled, and the stability of the composition of the present invention can be improved. For another example, the content of the polymerization inhibitor is preferably 0.1 to 30 mass %, more preferably 0.5 to 10 mass %, based on 100 mass % of the total amount of compound (1) and compound (2). As long as it is within the above range, polymerization can be performed without disturbing the alignment of compound (1) and compound (2).

The composition of the present invention may contain a leveler. Examples of leveling agents include additives for radiation-curable paints (manufactured by BYK-Chemie Japan: BYK-352, BYK-353, BYK-361N), paint additives (manufactured by Dow Corning Toray Co., Ltd.: SH28PA, DC11PA, ST80PA) paint additives ( Shin-Etsu Chemical Co., Ltd.: KP321, KP323, X22-161A, KF6001) or fluorine-containing additives (DIC Co., Ltd.: F-445, F-470, F-477, F-479), etc.

By using a leveling agent, the surface of the polarizing film can be smoothed. In addition, in the preparation process of the polarizing film, the fluidity of the composition of the present invention can be controlled, or the crosslinking density of the polarizing film obtained by polymerizing the compound (1) or compound (2) can be adjusted. The content of the leveler is preferably from 0.01 to 30% by mass, more preferably from 0.05 to 10% by mass, relative to 100% by mass of the total amount of compound (1) and compound (2). Within the above range, polymerization can be performed without disturbing the alignment of the composition.

The composition of the present invention usually contains a solvent. The solvent is preferably an organic solvent that dissolves the components contained in the composition of the present invention and is inert to the polymerization reaction. Specifically, the solvent can include, for example: alcohol solvents such as methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, methyl cellosolve, butyl cellosolve, or propylene glycol monomethyl ether; such as ethyl acetate, butyl acetate, etc. , ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate or ethyl lactate and other ester solvents; acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl Ketone solvents such as amyl ketone or methyl isobutyl ketone; non-chlorinated aliphatic hydrocarbon solvents such as pentane, hexane or heptane; non-chlorinated aromatic solvents such as toluene, xylene or phenol; acetonitrile Nitrile solvents such as tetrahydrofuran or dimethoxyethane; ether solvents such as tetrahydrofuran or dimethoxyethane; chlorinated aliphatic hydrocarbon solvents such as chloroform or chlorobenzene, etc. Among them, the preferred ones are ketone solvents. These solvents may be used alone or in combination of two or more.

The usage amount of the solvent is preferably 50 to 98 mass % of the weight of the composition of the present invention. In other words, the solid content in the composition of the present invention is preferably 2 to 50% by mass. When the solid content is 2% by mass or more, the film thickness does not become too thin, and dichroism required for a polarizing film can be obtained. Moreover, when it is 50 mass % or less, since the viscosity of a composition is low, the film thickness of a coating film tends not to become uneven easily.

The viscosity of the composition of the present invention is preferably 0.1 to 10 mPa‧s, more preferably 0.1 to 7 mPa‧s. If the viscosity is within the above range, the thickness of the polarizing film tends not to become uneven easily.

polarizing film

The polarizing film of the present invention is obtained by polymerizing the compound (1) and compound (2) contained in the composition of the present invention. The polarizing film is a film that decomposes the unpolarized incident light into two orthogonal polarized components, makes one of the polarized components pass through, and absorbs the other polarized component. The axial direction of the transmitted polarized light component is called the transmission axis, and the axial direction of the absorbed polarized light component is called the absorption axis.

The polarizing film obtained by polymerizing compound (1) and compound (2) contained in the composition of the present invention is preferably a polymer in which compound (1) and compound (2) are fixed in an aligned state. In terms of easiness of producing such a polymer, it is preferable to polymerize compound (1) and compound (2) in the composition at a temperature at which the composition is aligned in a liquid crystal phase.

Hereinafter, the manufacturing method of the polarizing film of this invention is demonstrated.

The composition of the present invention is applied to a support substrate, dried, and the compound (1) and compound (2) contained in the composition of the present invention are polymerized on the support substrate, thus the present invention can be obtained. The polarizing film. In this way, the production cost can be reduced, and the polarizing film can be produced continuously or in roll form.

A non-polymerized composition film can be obtained by applying the composition of the present invention on a support substrate or a support substrate on which an alignment film or the like is formed, and drying. When the unpolymerized composition film exhibits a liquid crystal phase such as nematic or smectic, the obtained polarizing film exhibits dichroism. A more preferable liquid crystal phase is, for example, a smectic liquid crystal phase, and an especially preferable one is, for example, a smectic liquid crystal B phase.

The method for applying the composition of the present invention to a support substrate includes extrusion coating, direct gravure coating, reverse gravure coating, CAP coating, and die coating. Moreover, the method etc. which apply using the coating machine, such as a dip coater, a bar coater, and a spin coater, are mentioned, for example.

Examples of the supporting substrate include glass, plastic sheets, plastic films, and translucent films. In addition, examples of the above-mentioned light-transmitting film include polyolefin films such as polyethylene, polypropylene, and norbornene-based polymers; polyvinyl alcohol films, polyethylene terephthalate films, polymethacrylate films, etc. film, polyacrylate film, cellulose ester film, polyethylene naphthalate film, polycarbonate film, polysulfide film, polyethersulfide film, polyetherketone film, polyphenylene sulfide film, and polyphenylene ether film etc. By using the support substrate, the polarizing film can be easily handled without causing breakage or the like when the polarizing film is manufactured, transported or stored.

Among the polarizing films of the present invention, it is preferable to coat the composition of the present invention on the alignment film after forming the alignment film on the supporting substrate. It is preferable that the alignment film has solvent resistance that does not dissolve due to coating of the composition of the present invention. In addition, those having heat resistance during the heat treatment for removing the solvent or aligning the liquid crystal compound are preferable. In addition, an alignment film that does not cause peeling or the like due to friction due to rubbing or the like is preferable. Such an alignment film is preferably composed of an alignment polymer or a composition containing an alignment polymer.

The aforementioned alignment polymers include, for example, polyamide or gelatin having an amide bond in the molecule, polyamide acid having an amide bond in the molecule, and polyamide acid, polyvinyl alcohol, and alkyl Polymers such as modified polyvinyl alcohol, polyacrylamide, polyoxazole, polyvinylamine, polystyrene, polyvinylpyrrolidone, polyacrylate compounds, and polyacrylate compounds. 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 such as dehydration or deamination polymerization, radical polymerization, anionic polymerization or cationic polymerization, coordination polymerization, ring-opening polymerization and the like.

The alignment polymer can be dissolved in a solvent and coated. The solvent is not particularly limited, but specifically, water; alcohol solvents such as methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, methyl cellosolve, butyl cellosolve, or propylene glycol methyl ether; ethyl acetate, Ester solvents such as butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate or ethyl lactate; acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone Ketone solvents such as , methyl amyl ketone or methyl isobutyl ketone; non-chlorinated aliphatic hydrocarbon solvents such as pentane, hexane or heptane; non-chlorinated aromatic hydrocarbon solvents such as toluene or xylene; acetonitrile Nitrile solvents such as tetrahydrofuran or dimethoxyethane; ether solvents such as tetrahydrofuran or dimethoxyethane; chlorinated aliphatic hydrocarbon solvents such as chloroform or chlorobenzene, etc. These organic solvents may be used alone or in combination of two or more.

In order to form an alignment film, a commercially available alignment film material may be used as it is. Examples of commercially available alignment film materials include SunEver (registered trademark, manufactured by Nissan Chemical Co., Ltd.) and Optomer (registered trademark, manufactured by JSR Corporation). When such an alignment film is used, since unevenness is reduced, a polarizing film having further improved environmental resistance or mechanical resistance can be provided.

The method of forming an alignment film on a support substrate, for example, a commercially available alignment film material or a compound used as an alignment film material can be prepared into a solution and coated on a support substrate, and then an alignment is formed on the support substrate by performing annealing. membrane.

The thickness of the alignment film thus obtained is, for example, 10 nm to 10000 nm, preferably 10 nm to 1000 nm. Within the above range, the compound (1) or compound (2) can be aligned at a desired angle on the alignment film.

In the alignment film, compound (1) or compound (2) can be aligned in a desired direction by brushing or by irradiating polarized UV light as needed. That is, the direction of the absorption axis of the manufactured polarizing film can be adjusted to a desired direction.

As a method of brushing the alignment film, for example, a brush cloth may be wound and a rotating brush roller may be brought into contact with the alignment film placed on a stage for transportation. When brushing or polarized UV irradiation is performed, masking may be performed to form a plurality of regions (patterns) having different slow axis directions in the obtained polarizing film.

As a method of drying the solvent, for example, methods of natural drying, ventilation drying and reduced-pressure drying are mentioned. When heating and drying the unpolymerized film, the specific drying temperature is preferably from 0 to 250°C, more preferably from 50 to 220°C, and more preferably from 80 to 170°C. In addition, the drying time is preferably from 10 seconds to 60 minutes, more preferably from 30 seconds to 30 minutes. As long as the drying temperature and drying time are within the above-mentioned ranges, a supporting base material that does not necessarily have sufficient heat resistance can be used as the above-mentioned supporting base material.

The drying of the solvent may be performed simultaneously with the polymerization, but it is preferable to dry most of the solvent before the polymerization from the viewpoint of film-forming properties.

Compound (1) and compound (2) contained in the above-mentioned unpolymerized composition film are polymerized and hardened. The compound (1) and the compound (2) become a polymer while maintaining alignment to obtain an alignment-fixed polymer. Thereby, since the polymer obtained becomes hard to be affected by thermal alignment, the polarizing film excellent in durability (especially heat resistance) can be obtained.

The method for polymerizing the compound (1) and the compound (2) contained in the unpolymerized composition film may be selected according to the types of polymerizable groups contained in the compound (1) and the compound (2). If the polymerizable group is photopolymerizable, the unpolymerized composition film can be polymerized by photopolymerization; if the polymerizable group is thermally polymerizable, thermal polymerization can be selected. In the polarizing film of the present invention, it is preferable to polymerize the unpolymerized composition film by photopolymerization. With the photopolymerization method, since an unpolymerized film can be polymerized at low temperature, it is possible to use a supporting base material having low heat resistance. Furthermore, it is also easy to manufacture industrially. The photopolymerization method is performed by irradiating the unpolymerized composition film with visible light, ultraviolet light or laser light. From the viewpoint of ease of handling, it is preferable to use ultraviolet light. Light irradiation is preferably carried out at the alignment temperature of the liquid crystal phase of compound (1) and compound (2), more preferably at the alignment temperature of the smectic phase, particularly preferably at the alignment temperature of the smectic B phase temperature. At this time, the polarizing film may be patterned by methods such as masking.

An alignment film may be further laminated and polymerized on the upper surface of the unpolymerized composition film.

The method can be for example: coating an alignment film on two supporting substrates respectively, presenting the two coated surfaces facing each other to form a cell, and then filling the composition of the present invention into the cell, Then, compound (1) and compound (2) contained in the composition of the present invention are polymerized.

After polymerization, the laminate of the alignment film and the polarizing film of the present invention can be obtained by peeling off the supporting substrate, or a single layer of the polarizing film of the present invention can be obtained by peeling off the alignment film. The film thickness of the polarizing film of the present invention is preferably 0.5 to 20 μm.

The polarizing film of the present invention can be applied to various display devices. In addition, the polarizing film of the present invention is a thin film compared to a polarizing film obtained by adding iodine and a dichroic dye to polyvinyl alcohol (PVA) and then stretching.

circular polarizer

The above-mentioned polarizing film can be combined with a quarter-wavelength plate to obtain a circular polarizing plate with a polarizing film and a quarter-wavelength plate. At this moment, the angle formed by the absorption axis of the polarizing film and the slow axis of the quarter-wave plate is 45 ± 10°, and the quarter-wave plate satisfies the following formula (I):

100nm<Re(550)<160nm...(I)

(In the formula, Re(550) represents the in-plane retardation value with respect to light having a wavelength of 550 nm.)

The circular polarizing plate can also be a circular polarizing plate satisfying all formulas (I), formula (II) and formula (III) in addition to the quarter-wavelength plate:

100nm<Re(550)<160nm...(I)

Re(450)/Re(550)≦1.0...(II)

1.00≦Re(650)/Re(550)…(III)

(In the formula, Re(450) represents the in-plane retardation value for light with a wavelength of 450nm, Re(550) represents the in-plane retardation value for light with a wavelength of 550nm, and Re(650) represents the in-plane retardation value for light with a wavelength of 650nm In-plane phase difference value of light.)

Fig. 1 is a view showing a laminate 1 including a polarizing film 4 according to an embodiment of the present invention.

The laminate 1 is a laminate in which an alignment film 3 is laminated on a support base 2 and a polarizing film 4 of the present invention is laminated on the alignment film 3 . The polarizing film 4 is made of polymers after compound (1) and compound (2) are aligned.

The display device of the present invention includes a polarizing film 4 and a light emitting source. Examples of such display devices include: electroluminescence (EL; electroluminescence) display devices, field emission (fieldemission) display devices (FED), surface conduction electron emission display devices (SED; Surface-conduction Electron-emitter Display), liquid crystal display devices (transmission Transmissive liquid crystal display devices, semi-transmissive liquid crystal display devices, reflective liquid crystal display devices, direct-view liquid crystal display devices, projection liquid crystal display devices) and electronic paper, etc. In addition, for example, a 3D display device, a stereoscopic display device such as a hologram, and the like may be cited.

FIG. 2 shows a schematic diagram of a liquid crystal display device 10, which is one of the display devices of the present invention. The liquid crystal layer 17 is sandwiched between the two substrates 14a and 14b. By using the polarizing film of the present invention in a liquid crystal display device, the liquid crystal display device can be thinned.

Liquid crystals used in the liquid crystal layer 17 include: nematic liquid crystals, cholesteric liquid crystals, smectic liquid crystals, discotic liquid crystals, thermotropic liquid crystals, lyotropic liquid crystals, lyotropic liquid crystals, low-molecular liquid crystals, polymer liquid crystals, iron Electric liquid crystal, antiferroelectric liquid crystal, main chain type liquid crystal, side chain type polymer liquid crystal, polymer dispersed liquid crystal (PDLC), buckling type liquid crystal, etc. The liquid crystal mode used in the liquid crystal display device of the present invention includes, for example: TN (twisted nematic) mode, STN (super twisted nematic) mode, IPS (in-plane switching) mode, FFS (fringe field switching) mode, MVA Multi-domain Vertical Alignment (PV) mode, Patterned Vertical Alignment (PVA) mode, Advanced Super View (ASV) mode, Axisymmetric Aligned Microcell (ASM) mode, Optically Compensated Birefringence (OCB) mode, ECB( Electrically controlled birefringence) mode, FLC (ferroelectric liquid crystal) mode, AFLC (antiferroelectric liquid crystal) mode, PDLC (polymer dispersed liquid crystal) mode, guest-host mode, etc.

A color filter 15 is disposed on one side of one substrate 14a. The color filter 15 is disposed at a position facing the pixel electrode 22 across the liquid crystal layer 17, and the black matrix 20 is disposed at a position facing a boundary between the pixel electrodes. These are covered with transparent electrodes 16 . In some cases, an overcoat may be provided between the color filter 15 and the transparent electrode 16 .

Thin film transistors 21 and pixel electrodes 22 are regularly arranged on one side of the other substrate 14b. The pixel electrode 22 is arranged at a position facing the color filter 15 with the liquid crystal layer 17 interposed therebetween. The interlayer insulating film 18 is arranged between the thin film transistor 21 and the pixel electrode 22 .

The substrate 14b on which the thin film transistor 21 is formed is a glass substrate so as to be able to withstand the high temperature when the thin film transistor 21 is manufactured. In addition, when forming the thin film transistor 21 at a low temperature, a glass substrate can also be used.

The thin film transistor 21 can include high temperature polysilicon transistors formed on quartz substrates, low temperature polysilicon transistors formed on glass substrates, and amorphous silicon transistors formed on glass substrates or plastic substrates. In order to reduce the thickness of the liquid crystal display device, a driver IC may be formed on a glass substrate.

The liquid crystal layer 17 is arranged between the transparent electrode 16 and the pixel electrode 22 . A spacer 23 is formed in the liquid crystal layer 17 in order to maintain a certain gap between the two substrates that sandwich the liquid crystal layer 17 . Alignment films for aligning liquid crystal compounds contained in the liquid crystal layer 17 in desired directions may be formed on surfaces in contact with the liquid crystal layer 17, respectively.

Each member is laminated in the order of substrate 14a, black matrix 20, color filter 15, transparent electrode 16, liquid crystal layer 17, interlayer insulating film 18, thin film transistor 21, pixel electrode 22, and substrate 14b.

Films having various optical functions are laminated on the outer sides of the substrates 14 a and 14 b sandwiching the liquid crystal layer 17 . On the outside of the substrate 14a, a retardation film 13a (for example, a quarter-wavelength plate) and a polarizing film 12a of the present invention (for example, a linear polarizing film) are stacked in this order, and a retardation film is arranged on the outside of the substrate 14b 13b (for example, a quarter-wavelength plate) and the polarizing film 12b of the present invention (for example, a linear polarizing film) are laminated in this order. An antireflection film 11 for preventing reflection of external light is laminated on the outer side of the polarizing film 12a.

A backlight unit 19 as a light emitting source is formed outside the polarizing film 12b of the present invention. The backlight unit 19 includes: a light source, a light guide, a reflector, a diffusion sheet, and a viewing angle adjustment sheet. Various light sources such as electroluminescence (EL), cold cathode tubes, hot cathode tubes, LEDs, laser light sources, mercury lamps, etc. can be used. The polarizing film of the present invention can be selected according to the characteristics of the light source. In order to make the display device thinner, a backlight, which is a light emitting source, may be provided on the sides or on the upper and lower surfaces.

When the liquid crystal display device 10 is a transmissive liquid crystal display device, the white light emitted by the light source enters the light guide body, is turned by the reflection plate, and is diffused by the diffusion sheet. After the diffused light is adjusted to have a desired directivity by adjusting the viewing angle adjustment sheet, it enters the polarizing film 12 b of the present invention from the backlight unit 19 .

Among the non-polarized incident light, only a certain linearly polarized light will pass through the polarizing film 12b of the present invention. The linearly polarized light is transformed into circularly polarized light by the retardation film 13b (for example, a quarter-wavelength plate), and sequentially penetrates the substrate 14b, the pixel electrode 22, and the like to reach the liquid crystal layer 17.

The alignment state of the liquid crystal molecules in the liquid crystal layer 17 is controlled by the potential difference between the pixel electrode 22 and the opposite transparent electrode 16 (counter electrode). When the circularly polarized light incident to the liquid crystal layer 17 penetrates the liquid crystal layer 17 and the transparent electrode 16 as it is, penetrates the color filter 15 and the retardation film 13a, and penetrates the polarizing film 12a of the present invention, the pixel is color-filtered. The color determined by the detector is displayed as the brightest color.

In addition, when the polarization state of the light passing through the liquid crystal layer 17 changes, and the light passing through the color filter 15 is almost completely absorbed by the retardation film 13a and the polarizing film 12a of the present invention, the pixel displays black. When the liquid crystal molecules of the liquid crystal layer 17 are in an alignment state between these two states, light is partially transmitted and partially absorbed, so that the pixel displays an intermediate color.

When the liquid crystal display device 10 is a transflective liquid crystal display device, the pixel electrode 22 has a transmissive portion formed of a transparent material and a reflective portion formed of a light-reflecting material. In the transmissive portion, an image is displayed in the same manner as in the aforementioned transmissive liquid crystal display device. On the other hand, in the reflective part, external light is incident to the liquid crystal display device from the direction of the antireflection film 11, and the circularly polarized light after penetrating the polarizing film 12a and the retardation film 13a penetrates the liquid crystal layer 17 and passes through the pixel electrode. 22 reflections for display.

FIG. 3 shows a schematic diagram of a liquid crystal display device 24, one of the display devices of the present invention. In the liquid crystal display device 24, each member is successively respectively antireflection film 11, retardation film 13a, substrate 14a, polarizing film 12a of the present invention, color filter 15 and black matrix 20, transparent electrode 16, liquid crystal layer 17, interlayer The insulating film 18, the thin film transistor 21 and the pixel electrode 22, the polarizing film 12b of the present invention, the substrate 14b, the phase difference film 13b and the backlight unit 19 are sequentially laminated.

In the liquid crystal display device 24 , the polarizing films 12 a and 12 b of the present invention are disposed between the substrates 14 a and 14 b and the liquid crystal layer 17 , respectively.

Fig. 4 shows a schematic diagram of an EL display device 30, which is one of the display devices of the present invention. In the EL display device 30 of the present invention, a light-emitting layer 36 and a cathode electrode 37 as a light-emitting source are laminated on a substrate 33 on which a pixel electrode 35 is formed. The light-emitting layer 36 emits light by applying a positive voltage to the pixel electrode 35 and a negative voltage to the cathode electrode 37 and applying a direct current between the pixel electrode 35 and the cathode electrode 37 .

To manufacture the EL display device 30, first, the thin film transistor 40 is formed on the substrate 33 in a desired shape. Next, an interlayer insulating film 34 is formed, and then a pixel electrode 35 is formed and patterned by a sputtering method. Thereafter, the light emitting layer 36 is laminated.

Examples of the substrate 33 include a sapphire substrate, a quartz substrate, a soda substrate, a ceramic substrate such as alumina, a metal substrate such as copper, and a plastic substrate. A thermally conductive film may also be formed on the substrate. Examples of the thermally conductive film include diamond thin films (DLC, etc.). When a material that reflects light is used as the pixel electrode 35 , light is emitted in a direction opposite to that of the substrate 33 . Therefore, not only transparent materials but also opaque materials such as stainless steel can be used. The substrate may be a single material, or may be a laminated substrate in which a plurality of substrates are bonded with an adhesive. These substrates may be in the form of plates or films.

Examples of the thin film transistor 40 include the same transistors as those of the thin film transistor 21 described above.

Ridges 41 are formed on the interlayer insulating film 34 . The convex lines 41 are arranged on the peripheral portion of the pixel electrode 35 (between adjacent pixels). The material of the protruding lines 41 includes, for example, acrylic resin, polyamide resin, and the like. The thickness of the convex line 41 is preferably not less than 1.0 μm and not more than 3.5 μm, and more preferably not less than 1.5 μm and not more than 2.5 μm.

Next, description will be given regarding the EL element constituted by the pixel electrode 35 which is a transparent electrode, the light emitting layer 36 , and the cathode electrode 37 . In the case of an organic electroluminescent display device, the light emitting layer 36 is laminated with at least one hole transport layer, for example, an electron injection transport layer, a light emitting layer, a hole transport layer, a hole injection layer, etc. in order to become a light emitting layer. source.

Examples of the pixel electrode 35 include ITO (tin-doped indium oxide), IZO (zinc-doped indium oxide), ZnO, SnO ₂ , In ₂ O ₃ , and the like, and are particularly preferably ITO and IZO. The thickness of the pixel electrode 35 may be more than a certain thickness enough to smoothly inject holes, and is preferably about 10 to 500 nm.

The pixel electrode 35 can also be formed by vapor deposition or the like, but is preferably formed by sputtering. The gas used for sputtering is not particularly limited, and examples thereof include inert gases such as Ar, He, Ne, Kr, and Xe, or mixed gases thereof.

The constituent material of cathode electrode 37 can enumerate for example: the metal element monomer such as K, Li, Na, Mg, La, Ce, Ca, Sr, Ba, Al, Ag, In, Sn, Zn, Zr, or in order to improve stability It is preferred to use alloy systems containing these two or three components. Alloy system, preferably for example: Ag‧Mg (Ag: 1 to 20 at%), Al‧Li (Li: 0.3 to 14 at%), In‧Mg (Mg: 50 to 80 at%), Al‧Ca (Ca : 5 to 20at%), etc.

The cathode electrode 37 can be formed by vapor deposition, sputtering, etc., preferably by vapor deposition. The thickness of the cathode electrode 37 is more than 0.1 nm, preferably 1 to 500 nm.

The function of the hole injection layer is to easily inject holes from the pixel electrode 35 , and the hole transport layer has the function of transporting holes and blocking electrons.

The thickness of the light emitting layer, the combined thickness of the hole injection layer and the hole transport layer, and the thickness of the electron injection transport layer are not particularly limited and may vary depending on the formation method, but are preferably 5 to 100 nm. Various organic compounds can be used for the hole injection layer and the hole transport layer. Regarding the formation of the hole injection transport layer, the light emitting layer, and the electron injection transport layer, it is preferable to use a vacuum evaporation method so that a uniform thin film can be formed.

For the light-emitting layer 36, for example, those using light emission (fluorescence) from singlet excitons, those using light emission (phosphorescence) from triplet excitons, those containing light emission (fluorescence) from singlet excitons, and those using light emission from triplet Exciton luminescence (phosphorescence), those formed by organic substances, those formed by inorganic substances, those formed by organic substances and inorganic substances, high molecular weight materials, low molecular weight materials, and those containing high molecular weight materials and low molecular weight materials such substances. However, the present invention is not limited thereto, and an EL display device having various materials can be used as the EL element.

The desiccant 38 is arranged in the space between the cathode electrode 37 and the sealing cover 39 . The desiccant 38 absorbs moisture to prevent deterioration of the light emitting layer 36 .

The polarizing film 31 of the present invention formed on the light incident surface or the light exiting surface of the EL display device 30 is not limited to a linear polarizing film, and may also be an elliptical polarizing film. In addition, the polarizing film 31 of the present invention may be the above-mentioned laminate 1, or may be a laminate of a plurality of polarizing films 4 and/or retardation films of the present invention.

Fig. 5 shows a schematic diagram of an EL display device 44, which is one of the display devices of the present invention. The EL display device 44 of the present invention has a sealing structure using a thin film sealing film 42, and the array substrate (cathode electrode 37, light-emitting layer 36, pixel electrode 35, interlayer insulating film 34 and substrate 33) can also be arranged on the polarized light of the present invention. side of the membrane 31.

The thin film sealing film 42 has high moisture resistance, and it is preferable to use a film formed by vapor deposition of DLC (diamond-like carbon). The DLC-deposited film may be directly deposited and formed on the surface of the cathode electrode 37 . In addition, the thin film sealing film 42 may also be formed by laminating a plurality of resin thin films and metal thin films.

Fig. 6 is a schematic diagram showing a projection type liquid crystal display device which is one of the display devices of the present invention.

For example, the polarizing film 142 and the polarizing film 143 of the present invention are used in a projection type liquid crystal display device (projector).

A light beam emitted from a light source 111 (for example, a high-pressure mercury lamp) as a light emission source first passes through the first lens array 112, the second lens array 113, the polarization conversion element 114, the overlapping lens 115, etc., thereby reflecting the light beam. The brightness of the cross-section is uniform and polarized.

Specifically, the light beam emitted from the light source 111 is divided into a large number of small light beams by the first lens array 112 in which the small lens 112a is formed in a matrix. The second lens array 113 and the overlapping lens 115 are arranged so that each of the divided light beams is irradiated to the whole of the three liquid crystal panels 140R, 140G, and 140B belonging to the irradiation target, so that the entire surface of each liquid crystal panel on the incident side has an almost uniform of illumination.

The polarization conversion element 114 has a function of separating the incident light into its polarization components, and is provided between the second lens array 113 and the overlapping lens 115 . In this way, the random polarized light from the light source is converted into polarized light with a specific polarized direction in advance, reducing the loss of light quantity at the polarizing film on the incident side described later, and improving the brightness of the screen.

After the light system with uniform brightness and separated polarized components passes through the reflector 122, it is sequentially separated into red light beams by the dichroic filters 121, 123, and 132 used to separate the three primary colors of RGB (R in Figure 6, the solid arrow) , green light beams (G in FIG. 6 , dotted line arrows) and blue light beams (B in FIG. 6 , dotted line arrows), and then enter the liquid crystal panels 140R, 140G and 140B respectively.

In the liquid crystal panels 140R, 140G, and 140B, the polarizing film 142 of the present invention is arranged on the incident side thereof, and the polarizing film 143 of the present invention is arranged on the outgoing side thereof.

The following describes two polarizing films disposed on the incident side and the outgoing side with the liquid crystal panel interposed therebetween in the optical paths of the respective RGB. The polarizing film 142 and the polarizing film 143 of the present invention arranged in each optical path are arranged in such a way that their absorption axes are perpendicular to each other, and each liquid crystal panel 140R, 140G, and 140B arranged in each optical path will transmit the image signal The polarization state controlled by each pixel is converted into light quantity.

The polarizing film of the present invention is suitably used as a polarizing film having excellent durability in any optical path among blue channel, green channel, and red channel.

According to the image data of the liquid crystal panels 140R, 140G, and 140B, the optical images generated by passing the incident light with different transmittances according to the pixels are synthesized by a cross dichroic prism 150 , And enlarged by the projection lens 170 and projected onto the screen 180 .

The polarizing film of the present invention can also be used as a polarizing film for electronic paper, and its thickness can be reduced. Electronic paper refers to: electronic paper displayed by molecules such as optical anisotropy and dye molecule alignment; electronic paper displayed by particles such as electrophoresis, particle migration, particle rotation, phase transition, etc.; Electronic paper displayed by moving one end; electronic paper displayed by color/phase transition of molecules; electronic paper displayed by light absorption of molecules; and electronic paper displayed by combined electron and hole autoluminescence Paper. The display method of electronic paper is not particularly limited, and for example, microcapsule electrophoresis, horizontal movement electrophoresis, vertical movement electrophoresis, spherical torsion ball, magnetic force torsion ball, cylindrical torsion ball method, charged toner, electronic powder fluid, magnetic Migration type, magnetron constant temperature type, electrowetting type, light scattering type (transparent/turbidity change), cholesteric liquid crystal/photoconductive layer, cholesteric liquid crystal, bistable nematic liquid crystal, ferroelectric liquid crystal, dichroism Dye‧LCD dispersion type, movable film, leuco dye coloring and decolorization, photochromic, electrochromic, electrodeposition, flexible organic EL, etc.

Electronic paper can be utilized not only for personal use of text and images but also for advertisement display (signage) and the like. Using the polarizing film of the present invention can reduce the thickness of electronic paper.

A polarizing film having a plurality of regions with different slow-axis directions is used in a stereoscopic display device (see, for example, Japanese Patent Application Laid-Open No. 2002-185983). By masking a part of the alignment film and performing brushing or polarized UV irradiation, the polarizing film of the present invention can easily form multiple regions with different slow axis directions on the polarizing film, so it can also be effectively used as a stereoscopic display device polarizing film.

(Example)

Hereinafter, the present invention will be described in more detail by examples. Unless otherwise specified, "%" and "parts" in the examples mean mass % and mass parts.

[Synthesis example of compound represented by formula (1)]

Synthesis Example 1

Compound (1-6) was synthesized using the method described in the literature: Lub et al., Recl. Trav. Chim. Pays-Bas, Vol. 115, pages 321 to 328 (1996).

Synthesis example 2

Compound (1-8) was synthesized using the same method as described in Synthesis Example 1.

[Synthesis example of compound represented by formula (2)]

Synthesis example 3

The compound represented by formula (2-1) (hereinafter, this compound is referred to as "compound (2-1)") was synthesized according to the following scheme.

(step 1)

After mixing 16.8 parts of sodium bisulfite and 30.0 parts of water, the temperature was raised to 70° C., and 10.5 parts of 37% formalin aqueous solution was added dropwise thereto over 1 hour. Then, it was cooled to 40° C., and 10 parts of aniline was added dropwise over 1 hour, and the mixture was continuously kept at 40° C. and stirred for 3 hours. After cooling to room temperature, the precipitated crystal was separated by filtration and dried to obtain 18.6 parts of N-sulfomethylaniline sodium salt.

(step 2)

5.0 parts of 4-butylaniline, 7.0 parts of 35% hydrochloric acid and 20.0 parts of water were mixed and cooled to 0 to 5°C, and 8.5 parts of 30% aqueous nitrous acid solution was added dropwise thereto over 30 minutes. Thereafter, the mixture was continuously stirred at a temperature of 0 to 5° C. for 30 minutes, and then 0.3 part of sulfamic acid was added to prepare a diazonium solution of 4-butylaniline. In addition, 7.7 parts of N-sulfomethylaniline sodium salt, 11.0 parts of sodium acetate and 100 parts of water were mixed and cooled to 0 to 5°C. After that, all the 4-butyl aniline prepared just now was added dropwise over a period of 1 hour. Diazo solution of aniline. After the dropwise addition is completed, the temperature is raised to normal temperature, and the precipitated solid is filtered and separated to obtain a compound represented by formula (2-1-b) (hereinafter, the compound is referred to as "compound (2-1-b) b)"). The obtained compound (2-1-b) was used in Step 3 in its entirety without drying.

(step 3)

The whole amount of compound (2-1-b) obtained in Step 2, 61.8 parts of water and 16.7 parts of 20% aqueous sodium hydroxide solution were mixed, the temperature was raised to 90° C., and the mixture was stirred for 2 hours. After cooling to room temperature, 100 parts of ethyl acetate were mixed and separated, and the resulting oil layer was dried with magnesium sulfate, and then the solvent was distilled off to obtain a compound represented by formula (2-1-c) (hereinafter, the compound is referred to as referred to as "compound (2-1-c)").

(step 4)

5.0 parts of compound (2-1-c), 4.1 parts of 35% hydrochloric acid and 100 parts of water were mixed and cooled to 0 to 5°C, and 5.0 parts of 30% aqueous nitric acid solution was added dropwise thereto over 30 minutes. Thereafter, the mixture was continuously stirred at a temperature of 0 to 5° C. for 30 minutes, and 0.2 part of sulfamic acid was further added to prepare a diazonium solution of compound (2-1-c). In addition, 2.0 parts of phenol, 6.5 parts of sodium acetate, 20 parts of water and 40 parts of methanol were mixed and cooled to 0 to 5 °C, and all of them were dropped into the weight of the compound (2-1-c) just prepared over a period of 1 hour. nitrogen solution. After the dropwise addition was completed, the temperature was raised to normal temperature, the solid was filtered and separated, washed with methanol and dried to obtain 6.1 parts of the compound represented by the formula (2-1-d) (hereinafter, the compound is referred to as "compound (2 -1-d)").

(step 5)

After mixing 2.0 parts of compound (2-1-d), 2.8 parts of 11-bromoundecanol, 2.3 parts of potassium carbonate and 20 parts of dimethylacetamide, the mixture was heated up to 100° C. and stirred for 5 hours. Thereafter, it was cooled to normal temperature, poured into 100 g of ice water and filtered to separate the separated solid, washed with water and dried to obtain 2.4 parts of the compound represented by formula (2-1-e) (hereinafter, the compound is referred to as "Compound (2-1-e)").

(step 6)

2.3 parts of compound (2-1-e), 0.8 parts of dimethylaniline, 0.05 parts of dibutylhydroxytoluene, and 25 parts of dimethylacetamide were mixed and cooled to 0 to 10° C., and placed therein for 1 hour Add 6.2 parts of acryloyl chloride dropwise at the right time. Thereafter, the temperature was raised to normal temperature and stirred overnight, and after completion of the reaction, 50 parts of water was added to precipitate a solid. The precipitated solid was separated by filtration, washed with methanol, dried, and then purified by column chromatography to obtain 2.0 parts of compound (2-1). ¹ H-NMR (CDCl ₃ ) δ: 0.90-0.96 (t, 3H), 1.25-1.51 (m, 16H), 1.60-1.69 (m, 4H), 1.78-1.86 (m, 2H), 2.66-2.72 ( t, 2H), 4.01-4.07(t, 2H), 4.11-4.17(t, 2H), 5.77-5.82(d, 1H), 6.05-6.14(dd, 1H), 6.35-6.40(d, 1H), 6.97-7.01(d, 2H), 7.30-7.33(d, 2H)7.84-8.05(m, 8H)

Synthesis Example 4

The compound represented by formula (2-2) (hereinafter, this compound is referred to as "compound (2-2)") was synthesized according to the following scheme.

(step 1)

The compound represented by formula (2-2-a) was synthesized according to the method described in Japanese Patent Laid-Open No. 2017-082217 (hereinafter, this compound is referred to as "compound (2-2-a)") 5.0 parts, and mixed with 75 parts of ethanol and 11.6 parts of 10% aqueous sodium hydroxide solution, the temperature was raised to 80° C., and the mixture was stirred for 2 hours. Then, cool to room temperature and filter the separated solid, dry after washing with methanol, and finally obtain 4.5 parts of compounds represented by formula (2-2-b) (hereinafter, this compound is referred to as "compound (2- 2-b)").

(step 2)

Mix 2.0 parts of compound (2-2-b), 1.9 parts of 1,10-decanediol, 0.13 parts of 4-(N,N-dimethyl)aminopyridine, and 150 parts of chloroform, then cool to 0 to 5 °C, and 6.8 parts of diisopropylcarbodiimide was added dropwise thereto over a period of 30 minutes. Thereafter, the temperature was raised to normal temperature and stirred overnight, and after completion of the reaction, this was mixed with 100 parts of water and liquid-separated. Next, the obtained oil layer was dried with magnesium sulfate, and after the solvent was distilled off, it was purified by column chromatography to obtain 1.2 parts of the compound represented by the formula (2-2-c) (hereinafter, the compound is referred to as " Compound (2-2-c)").

(step 3)

Mix 1.0 parts of compound (2-2-c), 0.3 parts of dimethylaniline, 0.02 parts of dibutylhydrophenyltoluene and 10 parts of dimethylacetamide and cool to 0 to 10° C. Add 0.2 parts of acryloyl chloride dropwise in minutes. Thereafter, the temperature was raised to normal temperature and stirred overnight, and after completion of the reaction, 50 parts of water and 50 parts of chloroform were added and liquid-separated. Next, the obtained oil layer was dried over magnesium sulfate, and the solvent was distilled off, followed by purification by column chromatography to obtain 0.7 parts of compound (2-2). ¹ H-NMR (CDCl ₃ ) δ: 1.25-1.51 (m, 12H), 1.60-1.69 (m, 2H), 1.73-1.81 (m, 2H), 3.09 (s, 6H), 4.10-4.16 (t, 2H), 4.31-4.37(t, 2H), 5.78-5.80(d, 1H), 6.07-6.14(dd, 1H), 6.35-6.40(d, 1H), 6.74-6.77(d, 2H), 7.78-7.99 (m, 6H) 8.03-8.07 (d, 2H), 8.14-8.18 (d, 2H)

Synthesis Example 5

Compound (2-3), Compound (2-4), Compound (2-5) and Compound (2-113) are based on the method described in Synthesis Example 3 or Synthesis Example 4 above, and refer to Japanese Patent Laid-Open It is prepared by a known method described in Publication No. 2011-246696 or the like.

[Measurement of Phase Transition Temperature]

The phase transition temperature of compound (1-6) was confirmed by measuring the phase transition temperature of a film formed from compound (1-6). Its operation is described below.

A film made of compound (1-6) was formed on a glass substrate on which an alignment film was formed, and while heating, it was observed by structural observation using a polarizing microscope (BX-51, manufactured by Olympus Corporation). Confirm the phase transition temperature. After raising the temperature to 120°C, compound (1-6) phase-transferred to nematic phase at 112°C, phase-transferred to smectic A phase at 110°C, and phase Transferred to smectic B phase.

The phase transition temperature of compound (1-8) was confirmed in the same manner as the measurement of the phase transition temperature of compound (1-6). After raising the temperature to 140°C, compound (1-8) phase shifted to nematic phase at 131°C, phase shifted to smectic A phase at 80°C, and phase transition at 68°C during the cooling process. Transferred to smectic B phase.

Example 1

[Preparation of composition]

The following components were mixed and stirred at 80° C. for 1 hour to obtain a composition (A).

Compound (1-6): 75 parts.

Compound (1-8): 25 parts.

Compound (2-1): 4.0 parts.

Polymerization initiator; 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butan-1-one (Irgacure 369, manufactured by Ciba Specialty Chemicals): 6 parts.

Leveling agent; polyacrylate compound (BYK-361N, manufactured by BYK-Chemie): 1.2 parts.

Solvent; xylene: about 450 parts.

[Manufacture and evaluation of polarizing film]

1. Form an alignment layer

A glass substrate is used as a transparent substrate.

On this glass substrate, a 2% by mass aqueous solution (composition for forming an alignment layer) of polyvinyl alcohol (polyvinyl alcohol 1000 complete saponification type, manufactured by Wako Pure Chemical Industries, Ltd.) was coated by spin coating, and A 100 nm thick film was formed after drying. Subsequently, brushing treatment was performed on the surface of the obtained film to form an alignment layer. The brushing process uses a semi-automatic brushing device (trade name: LQ-008, manufactured by Changyang Engineering Co., Ltd.) and a cloth (trade name: YA-20-RW, manufactured by Yoshikawa Chemical Co., Ltd.), with a driving force of 0.15 mm, rotating speed 500rpm, 16.7mm/s conditions. By this brushing treatment, a laminate 1 in which an alignment layer was formed on a glass substrate was obtained.

2. Form polarizing film

The above-mentioned composition (A) was coated on the alignment layer of the laminate 1 by spin coating, heated and dried on a hot plate at 120°C for 3 minutes, and then rapidly cooled to room temperature to form a dry film on the above-mentioned alignment layer. The polymerizable liquid crystal composition (polymerizable liquid crystal compound) contained in this dry film has a liquid crystal state of the smectic B phase. Then, using a UV irradiation device (SPOTCURESP-7, manufactured by Ushio Electric Co., Ltd.), the film was dried by irradiating ultraviolet light at an exposure amount of 2400 mJ/cm ² (365 nmru standard), so that the polymerizable liquid crystal contained in the dry film was obtained. The compound is polymerized while maintaining the liquid crystal state of the polymerizable liquid crystal composition, so that the dried film forms a polarizing film. The thickness of the polarizing film at this time was measured to be 1.7 μm by a laser microscope (OLS3000, manufactured by Olympus Co., Ltd.).

3. X-ray diffraction measurement

The polarizing layer of the obtained laminate 2 was subjected to X-ray diffraction measurement using an X-ray diffractometer X'Pert PRO MPD (manufactured by Spectris Co., Ltd.). Using Cu as the target and producing X-rays under the condition that the X-ray tube current is 40mA and the X-ray tube voltage is 45kV, it passes through the fixed divergence slit 1/2° from the brushing direction (the alignment under the polarizing layer is obtained in advance). The brushing direction of the layer) is incident, and within the scanning range 2θ=4.0 to 40.0°, the results of scanning measurement are carried out at 2θ=0.01671° steps, and the full amplitude at half maximum (FWHM) near 2θ=20.08° is obtained. = sharp diffraction peak at about 0.312°. In addition, the same results were obtained from the incidence of the vertical direction of the brush. The order period (d) determined from the peak position is about 4.42 Å, which shows that a structure reflecting a higher-order smectic phase is formed.

4. Manufacture of polarized film laminates

In addition, corona treatment was carried out on the surface of the polarizing film of the polarizer obtained as described above, and then on the surface after corona treatment, carboxyl-modified polyvinyl alcohol (KlarePoval KL318, Kuraray Co., Ltd.) 7 parts, and a water-soluble polyamide epoxy resin (Sumirez resin 650 (aqueous solution with a solid concentration of 30% by mass), manufactured by SumikaChemtex Co., Ltd.) as a thermal crosslinking agent 3.5 parts (Viscosity: 92cP) Coating was performed with a spin coater, and then the above-mentioned aqueous solution was dried at 80° C. for 5 minutes to form a protective layer, and a polarizer with a protective layer was produced. In addition, on the protective layer, a triacetyl cellulose film (KC4UY, manufactured by KonicaMinolta Co., Ltd.) was attached through an adhesive layer formed by a pressure-sensitive adhesive (manufactured by Lintec Co., Ltd., film thickness 25 μm), and thus obtained Polarizing film laminate.

5. Measuring dichroic ratio

In order to confirm the usefulness of this polarizing film, the measurement of the dichroic ratio was performed as follows.

When a spectrophotometer (UV-3150, manufactured by Shimadzu Corporation) is equipped with a folder with a polarizing film, the maximum absorption wavelength in the direction of the absorption axis is measured by the double-beam method Absorbance in the direction of the transmission axis (A ¹ ) and absorbance in the direction of the absorption axis (A ² ). In this folder, a mesh that reduces the amount of light by 50% is provided on the reference side. The ratio (A ² /A ¹ ) is calculated from the measured values of absorbance in the direction of the transmission axis (A ¹ ) and absorbance in the direction of the absorption axis (A ² ), and is defined as the dichromatic ratio, Display its results in a table. It is considered that the higher the dichroic ratio is, the more useful it is as a polarizing film. Table 1 shows the maximum absorption wavelength of the absorbance (A ² ) in the absorption axis direction, and the measurement results of the dichromatic ratio at this wavelength.

6. Evaluation of heat and humidity resistance

About the laminated body of Example 1, the heat-and-moisture resistance was evaluated by the following method. The results are shown in Table 1.

The laminate described in Example 1 was placed in an oven at 60°C and 90% RH, and after 500 hours, the absorbance (A ³ ) of the laminate in the direction of its absorption axis at the maximum absorption wavelength was measured again to calculate The change rate of absorbance in the direction of the absorption axis before and after the moisture resistance test. The heat and humidity resistance was calculated by the following formula.

Moisture and heat resistance = absorbance in the direction of the absorption axis at the maximum absorption wavelength before the test (A ² ) / absorbance in the direction of the absorption axis at the maximum absorption wavelength after the test (A ³ ) × 100

Examples 2 to 6, Comparative Examples 1 to 2 and Reference Example 1

In Examples 2 to 6, Comparative Examples 1 to 2, and Reference Example 1, except that the kind of compound (2) was changed to the kind described in Table 1, a polarizing film was prepared in the same manner as in Example 1, Measure the maximum absorption wavelength of the absorbance (A ² ) along the absorption axis, and the dichromatic ratio at this wavelength. The comparative example is an example using a polymerizable diazo liquid crystal compound not belonging to the compound (2), and the reference example is an example using a dichroic liquid crystal compound without a polymerizable group. In addition, the heat-and-moisture resistance was evaluated in the same manner as in Example 1, and the results are shown in Table 1. Also, the compounds of Comparative Examples and Reference Examples shown in Table 1 were synthesized in the same manner as in Synthesis Examples 1 to 5.

(industrial availability)

According to the composition of the present invention, a polarizing film having high dichroism and excellent durability (especially heat resistance) can be provided.

Claims (9)

A polarizing film obtained by polymerizing a compound represented by formula (1) and a compound represented by formula (2) in a molecular alignment state,

In formula (1), X ¹ and X ² each independently represent an unsubstituted divalent aromatic group or an unsubstituted divalent alicyclic hydrocarbon group, wherein the divalent aromatic group or The carbon atom of the divalent alicyclic hydrocarbon group may be substituted by an oxygen atom, a sulfur atom or a nitrogen atom, however, at least one of ^X1 and ^X2 is an unsubstituted 1,4-phenylene group or an unsubstituted Cyclohexane-1,4-diyl, n is 1 to 3, and when n is 2 or more, ^X1 and ^X2 can be different groups respectively, and ^Y1 is independently a single bond or a divalent Linking group, U ¹ represents a hydrogen atom or an acryloxyl group, U ² represents an acryloxyl group, W ¹ and W ² each independently represent a single bond or a divalent linking group, V ¹ and V ² each independently represent a The substituent is an alkanediyl group with 1 to 20 carbon atoms, and the -CH ₂ - constituting the alkanediyl group can be substituted by -O-, -CO-, -S- or NH-;

In formula (2), m represents an integer from 1 to 3, and A ¹ , A ² and A ³ each independently represent unsubstituted 1,4-phenylene or hydrogen in which is substituted by methyl or methoxy The 1,4-phenylene group, or an unsubstituted divalent aromatic group or a divalent aromatic group in which hydrogen is replaced by methyl or methoxy, L ¹ and L ² are each independently Indicates single bond, -CH ₂ -, -CH ₂ CH ₂ -, -O-, -CH ₂ O-, -OCH ₂ -, -CO-, -COO-, -OCO-, -OCOO-, -CR ^c =CR ^d -, -C≡C-, -CR ^c =N-, -CONR ^c -, -NR ^c CO-, or -N=N-, R ^c and R ^d each independently represent a hydrogen atom or carbon number 1 to 4 alkyl groups, ^Z1 represents an acryloxy group, ^Z2 represents a hydrogen atom or an acryloxy group, ^Q1 and ^Q2 each independently represent an unsubstituted straight chain or branched chain with 1 to 20 carbon atoms Alkylene, unsubstituted alkenylene with 1 to 20 carbons, or unsubstituted alkynylene with 1 to 20 carbons, wherein, among the alkylene, alkenylene or alkynylene The contained -CH ₂ - can be substituted by -O-, -S- or -NR ^e -, ^Re represents a hydrogen atom or an alkyl group with 1 to 4 carbons, T ¹ represents a single bond, -O-, -S- , -CO-, -COO-, -OCO-, -OCOO- or -CONR ^f -or -NR ^f CO-, T ² represents a single bond, -O-, -S-, -CO-, -COO-, -OCO-, -OCOO-, ^-CONRf- , ^-NRfCO- , or, when ^Z2 is only a hydrogen atom, represents ^-NRg- , ^Rf and ^Rg each independently represent a hydrogen atom or a carbon 1 to 4 alkyl groups, but the alkyl group represented by R ^g can form a ring with Q ¹ or Q ² , provided that A ¹ -(L ¹ -A ² ) _m -L ² -A ³ contains at least one group consisting of - A ^X1 -N=NA ^X2 - (where A ^X1 and A ^X2 each represent a divalent aromatic group), and when T ² is -NR ^g -, Z ² represents a hydrogen atom. The polarizing film as described in item 1 of the scope of the patent application, wherein, when the above-mentioned ^U1 is an acryloxy group, the number of atoms in the main chain of ^V1 or the number of atoms in the main chain of ^V2 connected to the acryloxy group is equal to the number of atoms in the main chain of V2 The difference between the number of main chain atoms of ^Q1 and the number of main chain atoms of ^Q2 connected to the acryloxy group when ^Z2 is an acryloxy group is 3 or less. The polarizing film as described in item 1 or 2 of the scope of the patent application, wherein the above-mentioned U ¹ and Z ¹ and U ² and Z ² are the same acryloxy group. The polarizing film as described in claim 1 or 2 of the patent claims, wherein the liquid crystal compound of the above formula (2) is a compound that exhibits dichroic light absorption in the visible light range. The polarizing film according to claim 1 or 2, wherein the liquid crystal compound (1) of the above formula (1) is a thermotropic liquid crystal and a compound having a smectic liquid crystal phase. The polarizing film as described in item 1 or 2 of the scope of application, which can obtain Bragg peaks in X-ray diffraction measurement. A circular polarizing plate, which has a polarizing film and a quarter-wavelength plate described in any one of items 1 to 6 of the patent scope, wherein the absorption axis of the above-mentioned polarizing film is the same as that of the quarter-wavelength plate The angle formed by the slow axis is 45±10°, and the quarter-wavelength plate satisfies the following formula (I), 100nm<Re(550)<160nm...(I) In the formula, Re(550) represents that for a wavelength of 550nm The in-plane phase difference value of light. A circular polarizing plate, which has a polarizing film and a quarter-wavelength plate described in any one of items 1 to 6 of the patent scope, wherein the absorption axis of the above-mentioned polarizing film is the same as that of the quarter-wavelength plate The angle formed by the slow axis is 45±10°. In addition, the quarter-wavelength plate satisfies all of the following formulas (I), formula (II) and formula (III), 100nm<Re(550)<160nm...(I ) Re(450)/Re(550)≦1.0…(II) 1.00≦Re(650)/Re(550)…(III) In the formula, Re(450) represents the in-plane retardation value for light with a wavelength of 450nm, Re(550) represents the in-plane retardation value for light with a wavelength of 550nm, Re(650) represents the value for light with a wavelength of 650nm The in-plane phase difference. An organic electroluminescent display device, which includes the circular polarizing plate described in item 7 or 8 of the scope of application.

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