KR20200138199A - Composition and polarizing film - Google Patents

Abstract

[식 중, m 은, 정수를 나타낸다. A¹ ∼ A³ 은, 2 가의 방향족기를 나타낸다. L¹ ∼ L² 는, 단결합이나 에스테르기 등을 나타낸다. R^c ∼ R^d 는, 수소 원자 또는 알킬기를 나타낸다. Z¹ 은, 중합성기를 나타낸다. Z² 는, 수소 원자 또는 중합성기를 나타낸다. Q¹ ∼ Q² 는, 알킬렌기 등의 기를 나타낸다. T¹ 은, 단결합 또는 에스테르기 등을 나타낸다. R^f 및 R^g 는, 수소 원자 또는 알킬기를 나타낸다.]A composition containing a polymerizable liquid crystal compound showing a smectic phase and a liquid crystal compound represented by formula (2).

[In formula, m represents an integer. A ¹ to A ³ represent a divalent aromatic group. L ¹ ~ L ² represents a single bond or the like ester group. R ^c to R ^d represent a hydrogen atom or an alkyl group. Z ¹ represents a polymerizable group. Z ² represents a hydrogen atom or a polymerizable group. Q ¹ to Q ² represent groups such as an alkylene group. T ¹ represents a single bond or an ester group. R ^f and R ^g represent a hydrogen atom or an alkyl group.]

Description

Composition and polarizing film

The present invention relates to a composition or the like used to manufacture a polarizing film.

Optical films, such as a polarizing plate and a retardation plate, are used for the flat panel display device (FPD). As such a polarizing plate, an iodine PVA polarizing plate comprising a protective film and a polarizing layer in which a dichroic dye such as iodine is oriented and adsorbed on a polyvinyl alcohol-based resin film is widely used. In recent years, a thin polarizing plate is required, and the following Patent Document 1 discloses a thin polarizing plate comprising a polymerizable liquid crystal having a smectic phase and a dichroic dye. Further, in Patent Document 2 below, a composition capable of producing a polarizing film excellent in stability over time is described. In addition, in the following Patent Document 3, a composition for producing a polarizing film having a high dichroic ratio is described.

Japanese Patent No. 4719156 Japanese Unexamined Patent Publication No. 2011-246696 Japanese Unexamined Patent Publication No. 2013-101328

The polarizing film produced by the composition of Patent Document 2 had a problem of low dichroism. Moreover, although the polarizing film manufactured by the composition of patent document 3 has high dichroism, there existed the subject that durability is not sufficient.

The present invention is to provide a composition capable of producing a polarizing film having high dichroic properties and excellent durability.

That is, the present invention is a polymerizable liquid crystal compound showing a smectic phase, and

Equation (2):

[In formula (2), m represents the integer of 0-3.

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

L ¹ and L ² are each independently 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 represents a CO-, or -N = N-.

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

Z ¹ represents a polymerizable group.

Z ² represents a hydrogen atom or a polymerizable group.

Q ¹ and Q ² are each independently a linear or branched alkylene group having 1 to 20 carbon atoms which may have a substituent, an alkenylene group having 1 to 20 carbon atoms which may have a substituent, or 1 carbon number which may have a substituent The alkynylene group of -20 is represented, and -CH ₂ -contained in these alkylene groups, alkenylene groups, or alkynylene groups may be substituted with -O-, -S-, or -NR ^e- .

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

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

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

R ^f and R ^g each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, but the alkyl group represented by R ^g may form a ring with Q ¹ or Q ² .

However, A ¹ -(L ¹ -A ² ) _m -L ² -A ³ represents at least one -A ^X1 -N=NA ^X2- (A ^X1 and A ^X2 each represent a divalent aromatic group.) Structure, and when T ² is -NR ^g -, Z ² represents a hydrogen atom.]

It provides a composition containing a liquid crystal compound represented by.

The present invention also provides the following aspects. :

The polymerizable liquid crystal compound showing the smectic phase is formula (1):

[In equation (1),

X ¹ and X ² each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group, wherein the hydrogen atom contained in the divalent aromatic group or the divalent alicyclic hydrocarbon group is a halogen atom or a C 1 to C 1 It may be substituted with a 4 alkyl group, a C1-C4 fluoroalkyl group, a C1-C4 alkoxy group, a cyano group, or a nitro group, and the carbon atom constituting the divalent aromatic group or the divalent alicyclic hydrocarbon group is an oxygen atom. , A sulfur atom or a nitrogen atom may be substituted. However, at least one of X ¹ and X ² is a 1,4-phenylene group which may have a substituent or a cyclohexane-1,4-diyl group which may have a substituent.

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

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

V ¹ and V ² each independently represent an alkanediyl group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ -constituting the alkanediyl group is -O-, -CO-, -S -Or it may be substituted with NH-.]

Represented by, the composition of the above.

Wherein U ¹ is the polymerizable group as the polymerizable group that the polymerizable group weeks the number of atoms of the main chain of atoms, or V ² chains and the number of atoms of the main chain or Z ² is a polymerizable group in Q ¹ of V ¹ connected to a The above composition, wherein the difference in the number of atoms of the main chain of Q ² connected with is 3 or less.

The above composition wherein U ¹ and Z ¹ , and U ² and Z ² are all the same polymerizable group, and the polymerizable group is an acryloyl group or a methacryloyl group.

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

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

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

A polarizing film obtained by polymerizing a compound represented by formula (1) and a compound represented by formula (2) in the above composition in a molecularly oriented state, wherein a Bragg peak is obtained in X-ray diffraction measurement.

Having the above polarizing film and a 1/4 wave plate, the angle formed by the absorption axis of the polarizing film and the slow axis of the 1/4 wave plate is 45 ± 10°, and the 1/4 wave plate satisfies the following formula (I) Circular polarizer.

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

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

Having the above-described polarizing film and a 1/4 wavelength plate, the angle formed by the absorption axis of the polarizing film and the slow axis of the 1/4 wavelength plate is 45 ± 10°, and the 1/4 wavelength plate is the following formula (I), Circular polarizing plate which satisfies both formula (II) and formula (III).

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

Re (450)/Re (550) ≤ 1.0 ... (II)

1.00 ≤ Re (650)/Re (550)… (III)

(In the formula, Re (450) is the in-plane retardation value for light having a wavelength of 450 nm, Re (550) is the in-plane retardation value for light having a wavelength of 550 nm, and Re (650) is the in-plane retardation value for light having a wavelength of 650 nm. Represents the in-plane retardation value.)

An organic EL display device comprising the circular polarizing plate.

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

1 is a schematic diagram showing a laminate 1 including a polarizing film 4 made of the composition of the present invention.
2 is a schematic diagram showing a liquid crystal display device 10 which is one of the display devices of the present invention.
3 is a schematic diagram showing a liquid crystal display device 24 which is one of the display devices of the present invention.
4 is a schematic diagram showing an EL display device 30 which is one of the display devices of the present invention.
5 is a schematic diagram showing an EL display device 44 which is one of the display devices of the present invention.
6 is a schematic diagram showing a projection type liquid crystal display device as one of the display devices of the present invention.

The composition of the present invention is a polymerizable liquid crystal compound showing a smectic phase, and

Equation (2):

[In formula (2), m represents the integer of 0-3.

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

L ¹ and L ² are each independently 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 represents a CO-, or -N = N-.

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

Z ¹ represents a polymerizable group.

Z ² represents a hydrogen atom or a polymerizable group.

Q ¹ and Q ² are each independently a linear or branched alkylene group having 1 to 20 carbon atoms which may have a substituent, an alkenylene group having 1 to 20 carbon atoms which may have a substituent, or 1 carbon number which may have a substituent The alkynylene group of -20 is represented, and -CH ₂ -contained in these alkylene groups, alkenylene groups, or alkynylene groups may be substituted with -O-, -S-, or -NR ^e- .

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

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

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

R ^f and R ^g each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, but the alkyl group represented by R ^g may form a ring with Q ¹ or Q ² .

However, A ¹ -(L ¹ -A ² ) _m -L ² -A ³ represents at least one -A ^X1 -N=NA ^X2- (A ^X1 and A ^X2 each represent a divalent aromatic group.) Structure, and when T ² is -NR ^g -, Z ² represents a hydrogen atom.]

It provides a composition containing a liquid crystal compound represented by. This composition contains a solvent as needed.

In the present invention, the polymerizable liquid crystal compound showing the smectic phase may be a polymerizable liquid crystal compound, but preferably, the formula (1):

[In equation (1),

X ¹ and X ² each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group, wherein the hydrogen atom contained in the divalent aromatic group or the divalent alicyclic hydrocarbon group is a halogen atom or a C 1 to C 1 It may be substituted with a 4 alkyl group, a C1-C4 fluoroalkyl group, a C1-C4 alkoxy group, a cyano group, or a nitro group, and the carbon atom constituting the divalent aromatic group or the divalent alicyclic hydrocarbon group is an oxygen atom. , A sulfur atom or a nitrogen atom may be substituted. However, at least one of X ¹ and X ² is a 1,4-phenylene group which may have a substituent or a cyclohexane-1,4-diyl group which may have a substituent.

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

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

V ¹ and V ² each independently represent an alkanediyl group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ -constituting the alkanediyl group is -O-, -CO-, -S -Or it may be substituted with NH-.]

It is a compound represented by.

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, it may be referred to as "compound (1)").

[In equation (1),

X ¹ and X ² each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group, wherein the hydrogen atom contained in the divalent aromatic group or the divalent alicyclic hydrocarbon group is a halogen atom or a C 1 to C 1 It may be substituted with a 4 alkyl group, a C1-C4 fluoroalkyl group, a C1-C4 alkoxy group, a cyano group, or a nitro group, and the carbon atom constituting the divalent aromatic group or the divalent alicyclic hydrocarbon group is an oxygen atom. Alternatively, it may be substituted with a sulfur atom or a nitrogen atom. However, at least one of X ¹ and X ² is a 1,4-phenylene group which may have a substituent or a cyclohexane-1,4-diyl group which may have a substituent.

n is 1-3, and when n is 2 or more, X ¹ and X ² may be different, respectively. From the viewpoint of liquid crystallinity, n is preferably 2 or more.

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

V ¹ and V ² each independently represent an alkanediyl group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ -constituting the alkanediyl group is -O-, -CO-, -S -Or it may be substituted with NH-.]

Compound (1) is usually, W ¹ -(X ¹ -Y ¹ ) _n -X ² -W ³ , -A ^X1 -N=NA ^X2- (A ^X1 and A ^X2 each represent a divalent aromatic group It does not have a structure representing .).

In compound (1), X ¹ and X ² are each independently, preferably, a 1,4-phenylene group which may have a substituent or a cyclohexane-1,4-diyl group which may have a substituent At least one of, X ¹ , X ² is a 1,4-phenylene group which may have a substituent or a cyclohexane-1,4-diyl group which may have a substituent, and trans-cyclohexane-1,4-di It is preferable to be in a diary. As a substituent optionally having a 1,4-phenylene group which may have a substituent or a cyclohexane-1,4-diyl group which may have a substituent, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group and a butyl group, And halogen atoms such as furnace and chlorine atom and fluorine atom. It is preferably unsubstituted. In formula (1), when n is 2 or more and Y ¹ is the same structure, it is preferable that at least one of X ¹ and X ² is a different structure. When n is 2 or more and at least one of X ¹ and X ² is a different structure, there is a tendency that smectic liquid crystal properties are easily expressed.

Y ¹ is each independently a single bond or a divalent linking group. The divalent linking group is -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 -is preferred. R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. It is more preferable that Y ¹ is -CH ₂ CH ₂ -, -COO-, or a single bond, and it is more preferable that Y ¹ is -CH ₂ CH ₂ -or CH ₂ O-. In formula (1), when n is 2 or more and both of X ¹ and X ² have the same structure, it is preferable that Y ¹ is a different bonding method. When n is 2 or more and Y ¹ is a mutually different bonding method, smectic liquid crystal properties tend to be easily expressed.

U ² is a polymerizable group. U ¹ is a hydrogen atom or a polymerizable group, preferably a polymerizable group. It is preferable that both U ¹ and U ² are polymerizable groups, and it is preferable that both are radical polymerizable groups. Examples of the polymerizable group include vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloyloxy group, methacryloyloxy group, oxiranyl group, oxetanyl group, and the like. . Among them, an acryloyloxy group, a methacryloyloxy group, a vinyloxy group, an oxiranyl group, and an oxetanyl group are preferable, and an acryloyloxy group is more preferable. The polymerizable group represented by U ¹ and the polymerizable group represented by U ² may be different from each other, but a group of the same type is preferable. Further, the polymerizable group may be in a polymerized state or in a non-polymerized state, but is preferably in a non-polymerized 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-, and more preferably a single bond or -O-.

V ¹ and V ² each independently represent an alkanediyl group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ -constituting the alkanediyl group is -O-, -CO-, -S- Alternatively, it may be substituted with NH-. Examples of the alkanediyl group include methylene group, ethylene group, propane-1,3-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, and hexane- 1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, decane-1,10-diyl group, tetradecane-1,14-diyl group, and icosan-1,20 -The diary, etc. are mentioned. V ¹ and V ² are preferably an alkanediyl group having 2 to 12 carbon atoms, and more preferably an alkanediyl group having 6 to 12 carbon atoms.

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

As compound (1), the compound represented by formula (1-1)-formula (1-25) is mentioned, for example. When compound (1) has a cyclohexane-1,4-diyl group, the cyclohexane-1,4-diyl group is preferably a trans chain.

Among these, formula (1-2), formula (1-3), formula (1-4), formula (1-5), formula (1-6), formula (1-7), formula (1-8 ), at least one member selected from the group consisting of compounds represented by formula (1-13), formula (1-14), formula (1-15), formula (1-16) and formula (1-17) is preferred. . As the compound (1), one type may be used alone, or two or more types may be used in combination.

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

The content of the compound (1) is preferably 70 to 99.99% by mass, and more preferably 90 to 99.9% by mass, based on the solid content of the composition. When it is within the said range, there exists a tendency for the orientation of compound (1) to become high. Here, the solid content means the total amount of the components excluding the solvent from the composition.

Compound represented by formula (2)

The composition of the present invention contains a liquid crystal compound represented by formula (2) (hereinafter, it may be referred to as "compound (2)"). The compound (2) is preferably a liquid crystal compound exhibiting dichroism in the visible region. The dichroism refers to a property in which the absorbance in the direction of the major axis of the molecule and the absorbance in the minor axis direction are different.

Equation (2):

[In formula (2), m represents the integer of 0-3.

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

L ¹ and L ² are each independently 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 represents a CO-, or -N = N-.

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

Z ¹ represents a polymerizable group.

Z ² represents a hydrogen atom or a polymerizable group.

Q ¹ and Q ² are each independently a linear or branched alkylene group having 1 to 20 carbon atoms which may have a substituent, an alkenylene group having 1 to 20 carbon atoms which may have a substituent, or 1 carbon number which may have a substituent The alkynylene group of -20 is represented, and -CH ₂ -contained in these alkylene groups, alkenylene groups, or alkynylene groups may be substituted with -O-, -S-, or -NR ^e- .

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

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

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

R ^f and R ^g each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, but the alkyl group represented by R ^g may form a ring with Q ¹ or Q ² .

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

m represents the integer of 0-3. Preferably, m is 1-3.

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

As a divalent aromatic group, a 1,4-phenylene group, a naphthalene-1,4-diyl group, and the divalent heterocyclic group which may have a substituent are mentioned, for example. Examples of the divalent heterocyclic group include groups in which two hydrogen atoms have been removed from quinoline, thiazole, benzothiazole, thienothiazole, imidazole, benzoimidazole, oxazole and benzoxazole. When A ² is a divalent heterocyclic group, a structure in which the molecular bonding angle is substantially 180° is preferable, and specifically, a thienothiazole structure in which two five-membered rings are condensed is more preferable.

Examples of the substituent which the divalent aromatic group may have include an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group and a butyl group; Alkoxy groups having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, and a butoxy group; C1-C4 fluorinated alkyl groups, such as a trifluoromethyl group; Cyano group; Nitro group; Halogen atoms such as chlorine atom and fluorine atom; Substituted or unsubstituted amino groups such as amino groups, diethylamino groups and pyrrolidino groups (Substituted amino groups are amino groups having 1 or 2 alkyl groups having 1 to 6 carbon atoms, or a cyclic type having an alkanediyl group having 2 to 8 carbon atoms It means an amino group, and the unsubstituted amino group is -NH ₂ ). Moreover, as a C1-C6 alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, etc. are mentioned. Examples of the alkanediyl group having 2 to 8 carbon atoms include ethane-1,2-diyl group, propane-1,3-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, and pentane-1 ,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, etc. are mentioned.

As the divalent aromatic group which may have a substituent, specifically, a 1,4-phenylene group in which unsubstituted or hydrogen is substituted with a methyl group or a methoxy group, or the aforementioned divalent heterocyclic group is preferable.

L ¹ and L ² are each independently 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 represents a CO-, or -N = N-. R ^c and R ^d each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Like the above, the alkyl group having 1 to 4 carbon atoms includes a methyl group, an ethyl group, a propyl group, and a butyl group. L ¹ and L ² are preferably -COO-, -CH=CH-, -C≡C-, -CONH-, or -N=N-, and among them, -COO-, -OCO-, or It is particularly preferred that -N=N-.

Z ¹ is a polymerizable group, and Z ² is a hydrogen atom or a polymerizable group. Herein, the polymerizable group means a group that can participate in the polymerization reaction by an active radical generated from a polymerization initiator, an acid, etc., and the photopolymerizable group means an active radical generated from the photo polymerization initiator, a group that can participate in the polymerization by an acid, etc. Say. When both Z ¹ and Z ² are polymerizable groups, Z ¹ and Z ² are preferably the same type of polymerizable group, more preferably the same polymerizable group. The polymerizable group may be in a polymerized state or may be in an unpolymerized state, but is preferably in an unpolymerized state.

Examples of the polymerizable group include vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloyloxy group, methacryloyloxy group, oxiranyl group, oxetanyl group, and the like. . Among them, an acryloyloxy group, a methacryloyloxy group, a vinyloxy group, an oxiranyl group, and an oxetanyl group are preferable, and an acryloyloxy group is more preferable.

Q ¹ and Q ² are each independently a linear or branched alkylene group having 1 to 20 carbon atoms which may have a substituent, an alkenylene group having 1 to 20 carbon atoms which may have a substituent, or 1 carbon number which may have a substituent The alkynylene group of -20 is represented, and -CH ₂ -contained in these alkylene groups, alkenylene groups, or alkynylene groups may be substituted with -O-, -S-, or -NR ^e- .

As a C1-C20 alkylene group, a C1-C20 polymethylene group, that is, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a de Silene group, undecylene group, dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, heptadecylene group, octadecylene group, nonadecylene group, eicosylene group And propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group, tridecylene group, tetradecylene group, and butyl Particularly preferred are a ene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, and a tridecylene group.

Examples of the alkenylene group having 1 to 20 carbon atoms include ethenylene group, propenylene group, butenylene group, pentenylene group, hexenylene group, heptenylene group, octenylene group, nonenylene group, decenylene group, undecenylene group, Dodecenylene group, tridecenylene group, tetradecenylene group, pentadecenylene group, hexadecenylene group, heptadecenylene group, octadecenylene group, nonadecenylene group and eicosenylene group, and propenylene group , Butenylene group, pentenylene group, hexenylene group, heptenylene group, octenylene group, nonenylene group, decenylene group, undecenylene group, dodecenylene group, tridecenylene group, tetradecenylene group, Particularly preferred is a butenylene group, a pentenylene group, a hexenylene group, a heptenylene group, an octenylene group, a nonenylene group, a decenylene group, an undecenylene group, a dodecenylene group, and a tridecenylene group.

Examples of the alkynylene group having 1 to 20 carbon atoms include ethynylene group, propynylene group, butynylene group, pentynylene group, hexynylene group, heptynylene group, octynylene group, nonynylene group, decynylene group, undecynylene group , Dodecinylene group, tridecinylene group, tetradecinylene group, pentadecinylene group, hexadecinylene group, heptadecinylene group, octadecinylene group, nonadecinylene group, and eicocinylene group, and propy Nylene group, butynylene group, pentynylene group, hexynylene group, heptynylene group, octynylene group, nonynylene group, decynylene group, undecinylene group, dodecinylene group, tridecinylene group, tetradecinylene group Preferred, butynylene group, pentynylene group, hexynylene group, heptynylene group, octynylene group, nonynylene group, decynylene group, undecynylene group, dodecynylene group, and tridecynylene group are particularly preferred.

Examples of the substituent that the alkylene group, alkenylene group, or alkynylene group may have include a cyano group; And halogeno groups such as a fluoro group, a chloro group, and a bromo group.

The alkylene group, alkenylene group, or alkynylene group is preferably an unsubstituted alkylene group, alkenylene group or alkynylene group, and more preferably an unsubstituted linear alkylene group, alkenylene group or alkynylene group. .

R ^e represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. As a C1-C4 alkyl group, a methyl group, an ethyl group, a butyl group, etc. are mentioned.

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

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

When T ¹ and T ² are each of the terminal groups Z ¹ and Z ² as a polymerizable group, a functional group bonded parallel to the major axis direction of the compound is preferable. In such a case, it is preferably a single bond, -O-, and -COO-.

R ^f and R ^g each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, but the alkyl group represented by R ^g may form a ring with Q ¹ or Q ² .

In formula (2), A ¹ -(L ¹ -A ² ) _m -L ² -A ³ is at least one -A ^X1 -N=NA ^X2- (A ^X1 and A ^X2 are each a divalent aromatic group In the case where the structure shown is included and T ² is -NR ^g- , Z ² represents a hydrogen atom. Examples of the divalent aromatic group represented by A ^X1 and A ^X2 include the same groups as the divalent aromatic group represented by A ¹ and A ² described above.

Examples of the compound (2) include compounds represented by formulas (2-1) to (2-115). Compound (2) is preferably -A ^X1 -N=NA ^X2 -N=NA ^X3- (A ^X1 and A ^X2 are each the same as the above definition. A ^X3 represents a divalent aromatic group.) It is preferable to include a structure representing Moreover, as the divalent aromatic group represented by A ^X3 , the same group as A ^X1 and A ^{X2 is} mentioned. As A ^X1 , A ^X2 and A ^X3 , a divalent C6-C12 aromatic hydrocarbon group or a divalent C6-C12 aromatic heterocyclic group which has a sulfur atom or a nitrogen atom is preferable. More preferably, at least one of A ^X1 , A ^X2 and A ^X3 is a divalent C6-C12 aromatic hydrocarbon group such as a phenylene group and a naphthylene group.

Compound (2) is a known organic synthesis reaction described in Methoden der Organischen Chemie, Organic Reactions, Organic Syntheses, Comprehensive Organic Synthesis, new experimental chemistry courses, etc. (condensation reaction, esterification reaction, Williamson reaction, Ullmann reaction, Wittich Reaction, Cipro base formation reaction, benzylation reaction, Sonogashira reaction, Suzuki-Miyaura reaction, Negishi reaction, Kumada reaction, Hiyama reaction, Buchwald-Hartwig reaction, Friedelcraft reaction, Heck reaction, Aldol reaction, etc.) , According to the structure, it can be produced by appropriately combining.

In the present invention, it is preferable that the compound (1) and the compound (2) satisfy the following requirements. That is, the U ¹ is as a polymerization number of atoms of the main chain of the atoms, or V ² the main chain of the V ¹ is connected to the group and the number of atoms of the main chain or Z ² is a polymerization of the Q ¹ group as a polymerizable group that It is preferable that the difference in the number of atoms of the main chain of Q ² connected to the polymerizable group is 3 or less. U ¹ -V ¹ -, U ² -V ² -, Z ¹ -Q ¹ -and Z ² -Q ² -are all acryloylalkyl or methacryloylalkyl, and the difference in the number of carbon atoms of the alkyl group is preferably 3 or less. Do.

The content of the compound (2) is preferably 0.01 to 30% by mass, more preferably 0.1 to 10% by mass, based on the solid content of the composition. Within the above range, since the compound (1) and the compound (2) can be polymerized without disturbing the orientation of the compound (1), the dichroic ratio of the polarizing film tends to increase. Compound (2) may be used independently and may use multiple types together.

The dichroic ratio refers to the absorption intensity ratio of two linearly polarized lights vibrating perpendicularly to each other of light incident on the polarizing film. It is defined as the ratio (AV/AH) of the absorbance (AV) (measured by vertical incidence) along the extinction axis to the absorbance (AH) along the transmission axis. The transmission axis (polarization axis) refers to the polarization direction of a component that passes through the polarizing film among incident light to the polarizing film, and the extinction axis (absorption axis) refers to the polarization direction of the component absorbed by the polarizing film among incident light to the polarizing film. Say.

Usually, the liquid crystal compound having a polymerizable group tends to distort the orientation when polymerized after being aligned, but since the compound (2) itself exhibits liquid crystal properties, the compound (1) and the compound (2) Even when mixed, the obtained composition tends to stably exhibit a liquid crystal phase. Moreover, since compound (1) and compound (2) can be polymerized without disturbing these orientations, the obtained polarizing film tends to have a high dichroic ratio.

Polymerization initiator

It is preferable that the composition of this invention is a composition further containing a polymerization initiator. The polymerization initiator is a compound that initiates polymerization of the compounds (1) and (2), and is preferably a photopolymerization initiator that generates an acid or radical by irradiation with light, and a photopolymerization initiator that generates radicals by irradiation with light Is more preferable.

As a photoinitiator, a benzoin compound, a benzophenone compound, an acetophenone compound, an acylphosphine oxide compound, a triazine compound, an iodonium salt, a sulfonium salt, etc. are mentioned.

As a benzoin compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned.

Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra (tert-butylper Oxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, and the like.

As an acetophenone compound, diethoxyacetophenone, 2-methyl-2-morpholino-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-dimethoxyethan-1-one, 2- Hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-[4 Oligomers of -(1-methylvinyl)phenyl]propan-1-one, and the like.

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

As a triazine compound, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-( 4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2, 4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6- [2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl) Ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine And the like.

As photopolymerization initiators, Irgacure 907, Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369 (above, all manufactured by Chiba Japan Co., Ltd.) , Sakeall BZ, Sakeall Z, Sakeall BEE (above, all manufactured by Seiko Chemical Co., Ltd.), Kayacure BP100 (manufactured by Nippon Explosives Co., Ltd.), Kayacure UVI-6992 (manufactured by Dow Corporation), Adeka Optomer SP-152 or Adeka Optomer SP-170 (above, all manufactured by ADEKA Co., Ltd.), TAZ-A, TAZ-PP (above, manufactured by Nippon Sibel Hegner), TAZ-104 (Sanwa Chemical Co., Ltd.), Esacure One, Esacure KIP 150 (above, all manufactured by IGM Resins), and other commercially available photopolymerization initiators can also be used.

The content of the polymerization initiator is preferably 0.1 to 30 parts by mass, and more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the total amount of the compound (1) and the compound (2). If it is within the above range, the compounds (1) and (2) can be polymerized without disturbing the orientation of the compounds (1) and (2).

Other additives

The composition of the present invention may contain a photosensitizer. As a photosensitizer, for example, xanthone compounds such as xanthone or thioxanthone (e.g., 2,4-diethyl thioxanthone, 2-isopropyl thioxanthone, etc.), anthracene or alkyl ether An anthracene compound having a substituent (eg, dibutoxyanthracene, etc.), phenothiazine, or rubrene.

By using a photosensitizer, the polymerization of the compound (1) or the compound (2) can be highly sensitized, or the durability of a polarizing film obtained by polymerization, particularly, heat resistance can be improved. Moreover, as content of a photosensitizer, 0.1-30 mass parts is preferable with respect to 100 mass parts of the total amount of compound (1) and compound (2), and 0.5-10 mass parts is more preferable. Within the above range, polymerization can be performed without disturbing the orientation of the compound (1) and the compound (2).

The composition of the present invention may contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone compounds having substituents such as hydroquinone or alkyl ether, catechol compounds having substituents such as alkyl ethers such as butylcatechol, pyrogallol compounds, 2,2,6,6-tetra Radical supplements such as methyl-1-piperidinyloxy radical, thiophenol compounds, β-naphthylamine compounds, β-naphthol compounds, and the like.

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. Further, the content of the polymerization inhibitor is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the total amount of the compound (1) and the compound (2). Within the above range, polymerization can be performed without disturbing the orientation of the compound (1) and the compound (2).

The composition of the present invention may contain a leveling agent. As a leveling agent, for example, additives for radiation curing paints (manufactured by Big Chemie Japan: BYK-352, BYK-353, BYK-361N), paint additives (manufactured by Toray Dow Corning Co., Ltd.: SH28PA, DC11PA, ST80PA), Paint additives (manufactured by Shin-Etsu Chemical Co., Ltd.: KP321, KP323, X22-161A, KF6001) or fluorine-based additives (manufactured by DIC Corporation: F-445, F-470, F-477, F-479), etc. I can.

By using a leveling agent, the surface of a polarizing film can be made smooth. In addition, in the manufacturing 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 the compound (2) can be adjusted. The content of the leveling agent is preferably 0.01 to 30 parts by mass, more preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the total amount of the compound (1) and the compound (2). If it is within the above range, polymerization can be performed without disturbing the orientation of the composition.

The composition of the present invention usually contains a solvent. As the solvent, an organic solvent inert to the polymerization reaction by dissolving the component contained in the composition of the present invention is more preferable. Specifically, the solvent is an alcohol solvent such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl cellosolve, butyl cellosolve or propylene glycol monomethyl ether; Ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, or ethyl lactate; Ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone, or methyl isobutyl ketone; Non-chlorine-based aliphatic hydrocarbon solvents such as pentane, hexane or heptane; Non-chlorine aromatic solvents, such as toluene, xylene, or phenol; Nitrile solvents such as acetonitrile; Ether solvents such as tetrahydrofuran or dimethoxyethane; Chlorine-based aliphatic hydrocarbon solvents such as chloroform or chlorobenzene; And the like. Among them, ketone solvents are preferred. These solvents may be used individually or may be used in combination of a plurality.

The amount of the solvent used is preferably 50 to 98% by 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 the polarizing film is obtained. Moreover, if it is 50 mass% or less, since the viscosity of a composition is low, there exists a tendency for the film|membrane thickness of a coating film to be less likely to be uneven.

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. When the viscosity is within the above range, there is a tendency that unevenness is less likely to occur in the film thickness of the polarizing film.

Polarizing film

The polarizing film of the present invention is obtained by polymerizing compound (1) and compound (2) contained in the composition of the present invention. The polarizing film is a film that decomposes incident light that is not polarized into two orthogonal polarization components, transmits one polarization component, and absorbs the other polarization component. The axial direction of the transmitted polarization component is called the transmission axis, and the axial direction of the absorbing polarization component is called the absorption axis.

It is preferable that the polarizing film obtained by polymerizing the compound (1) and compound (2) contained in the composition of the present invention is a polymer fixed in a state in which the compound (1) and the compound (2) are oriented. From the viewpoint of easy production of such a polymer, it is preferable to polymerize the compound (1) and the compound (2) in the composition at a temperature at which the composition aligns in a liquid crystal phase.

The manufacturing method of the polarizing film of this invention is demonstrated below.

The polarizing film of the present invention can be obtained on the supporting substrate by applying the composition of the present invention to a supporting substrate, drying, and polymerizing the compound (1) and compound (2) contained in the composition of the present invention. Therefore, the production cost can be reduced, furthermore, continuous production of the polarizing film becomes possible, and the production of the polarizing film on a roll is possible.

An unpolymerized composition film can be obtained by applying and drying the composition of the present invention on a support substrate or a support substrate on which an alignment film or the like is formed. When the unpolymerized composition film shows a liquid crystal phase such as a nematic phase or a smectic phase, the obtained polarizing film exhibits dichroism. As a more preferable liquid crystal phase, a Smectic phase is mentioned, Especially preferably, a Smectic B phase is mentioned.

As a method of applying the composition of the present invention to the supporting substrate, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a CAP coating method, or a die coating method may be mentioned. Further, a method of applying using a coater such as a dip coater, a bar coater, or a spin coater may be mentioned.

Examples of the supporting substrate include glass, plastic sheet, plastic film, and translucent film. In addition, as the translucent film, a polyolefin film such as polyethylene, polypropylene, norbornene-based polymer, a polyvinyl alcohol film, a polyethylene terephthalate film, a polymethacrylic acid ester film, a polyacrylic acid ester film, a cellulose ester film, a polyethylene naphthalate Films, polycarbonate films, polysulfone films, polyether sulfone films, polyether ketone films, polyphenylene sulfide films, and polyphenylene oxide films. When a supporting substrate is used, there is no tear or the like when producing, transporting, or storing a polarizing film, so that it can be handled easily.

In the polarizing film of the present invention, preferably, after forming the alignment film on the supporting substrate, it is preferable to apply the composition of the present invention on the alignment film. It is preferable that the alignment film has a solvent resistance that is not dissolved by application of the composition of the present invention or the like. Moreover, it is preferable to have heat resistance in heat treatment for removal of a solvent and orientation of a liquid crystal compound. Further, it is preferable that it is an alignment film that does not cause peeling or the like due to friction due to rubbing. As such an alignment film, it is preferable that it consists of an alignment polymer or a composition containing an alignment polymer.

Examples of the orientation polymer include polyamide or gelatin having an amide bond in the molecule, polyimide having an imide bond in the molecule, and a hydrolyzate thereof such as polyamic acid, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, polyoxa Polymers, such as a sol, polyethyleneimine, polystyrene, polyvinylpyrrolidone, a polyacrylic acid ester compound, and a polyacrylic acid ester compound, are mentioned. These polymers may be used alone, or two or more of them may be mixed or copolymerized. These polymers can be easily obtained by polycondensation by dehydration or deamination, chain polymerization such as radical polymerization, anionic polymerization, and cationic polymerization, coordination polymerization or ring-opening polymerization.

Orienting polymer is dissolved in a solvent and can be applied. The solvent is not particularly limited, but specifically, water; Alcohol solvents such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl cellosolve, butyl cellosolve, or propylene glycol monomethyl ether; Ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, or ethyl lactate; Ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone, or methyl isobutyl ketone; Non-chlorine-based aliphatic hydrocarbon solvents such as pentane, hexane or heptane; Non-chlorine-based aromatic hydrocarbon solvents such as toluene or xylene, and nitrile solvents such as acetonitrile; Ether solvents such as tetrahydrofuran or dimethoxyethane; Chlorine-based aliphatic hydrocarbon solvents such as chloroform or chlorobenzene; And the like. These organic solvents may be used alone or in combination of a plurality of them.

In order to form an alignment film, a commercially available alignment film material may be used as it is. As a commercially available alignment film material, Sunever (registered trademark, manufactured by Nissan Chemical Industries, Ltd.) or Optimer (registered trademark, manufactured by JSR Corporation), etc. are mentioned. When such an alignment film is used, since unevenness is reduced, a polarizing film having more improved environmental resistance and mechanical resistance can be provided.

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

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

The alignment film can align the compound (1) or the compound (2) in a desired direction by performing rubbing or polarized UV irradiation as necessary. That is, the direction of the absorption axis of the manufactured polarizing film can be adjusted to a desired direction.

As a method of rubbing the alignment layer, for example, a rubbing cloth is wound and a rotating rubbing roll is loaded on a stage and brought into contact with the alignment layer. When performing rubbing or polarized UV irradiation, when masking is performed, a plurality of regions (patterns) having different slow axis directions may be formed in the obtained polarizing film.

Examples of the drying method of the solvent include methods such as natural drying, air drying, and vacuum drying. When heating and drying an unpolymerized film, as a specific drying temperature, 0-250 degreeC is preferable, 50-220 degreeC is more preferable, 80-170 degreeC is still more preferable. Moreover, as a drying time, it is preferable that it is for 10 seconds-60 minutes, and it is more preferable that it is 30 seconds-30 minutes. When the drying temperature and drying time are within the above ranges, as the supporting substrate, a supporting substrate whose heat resistance is not necessarily sufficient can be used.

Although drying of the solvent may be carried out while advancing polymerization, drying most of the solvent before polymerization is preferable from the viewpoint of film-forming properties.

Compound (1) and compound (2) contained in the unpolymerized composition film are polymerized and cured. Compound (1) and compound (2) become a polymer while maintaining the orientation, and a polymer with a fixed orientation is obtained. Thereby, the obtained polymer is less affected by heat orientation, and it becomes possible to obtain a polarizing film excellent in durability (especially heat resistance).

The method of polymerizing the compound (1) and compound (2) contained in the unpolymerized composition film may be selected according to the kind of the polymerizable group contained in the compound (1) and compound (2). If the polymerizable group is photopolymerizable, the unpolymerized composition film can be polymerized by the photopolymerization method, and if the polymerizable group is thermally polymerizable, the unpolymerized composition film can be polymerized by the thermal polymerization method. In the polarizing film of the present invention, it is preferable to polymerize an unpolymerized composition film by a photopolymerization method. According to the photopolymerization method, since the unpolymerized film can be polymerized at a low temperature, a supporting substrate having low heat resistance can also be used. It is also industrially easy to manufacture. The photopolymerization method is performed by irradiating the unpolymerized composition film with visible light, ultraviolet light, or laser light. In terms of ease of handling, ultraviolet light is preferred. The light irradiation is preferably carried out at a temperature at which compounds (1) and (2) are oriented in a liquid crystal phase, more preferably carried out at a temperature at which they oriented in a smectic phase, and they are oriented in a smectic B phase. It is particularly preferred to carry out at temperature. At this time, the polarizing film may be patterned by masking or the like.

An alignment film may be further laminated on the upper surface of the unpolymerized composition film to perform polymerization.

After applying an alignment film to each of the two supporting substrates, making the coated surfaces face each other, forming a cell, and filling the cell with the composition of the present invention, the compound (1) and the compound ( The method of polymerizing 2) is also mentioned.

After polymerization, by peeling the supporting substrate, a laminate of the alignment film and the polarizing film of the present invention may be obtained, or the alignment film may be peeled to obtain the polarizing film of the present invention in a single layer. It is preferable that the film thickness of the polarizing film of this invention is 0.5-20 micrometers.

The polarizing film of the present invention can be used for various display devices. Moreover, the polarizing film of this invention is a thin film compared with the polarizing film obtained by adding iodine or a dichroic dye to polyvinyl alcohol (PVA) and extending|stretching.

Circular polarizer

When the polarizing film is combined with a 1/4 wave plate, a circular polarizing plate including a polarizing film and a 1/4 wave plate can be obtained. At that time, the angle between the absorption axis of the polarizing film and the slow axis of the 1/4 wave plate is 45 ± 10°, and the 1/4 wave plate satisfies the following formula (I):

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

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

The circular polarizing plate may further be a circular polarizing plate in which the 1/4 wave plate satisfies all of the formulas (I), (II) and (III):

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

Re (450)/Re (550) ≤ 1.0 ... (II)

1.00 ≤ Re (650)/Re (550)… (III)

(In the formula, Re (450) is the in-plane retardation value for light having a wavelength of 450 nm, Re (550) is the in-plane retardation value for light having a wavelength of 550 nm, and Re (650) is the in-plane retardation value for light having a wavelength of 650 nm. Represents the in-plane retardation value.)

1 is a diagram showing a laminate 1 including a polarizing film 4 which is an example of the present invention.

The laminate (1) is a laminate in which an alignment film (3) is laminated on a support substrate (2), and a polarizing film (4) of the present invention is laminated on the alignment film (3). The polarizing film 4 is composed of a polymer in which compound (1) and compound (2) are oriented.

The display device of the present invention includes a polarizing film 4 and a light emitting source. Such display devices include EL (electroluminescence) display devices, field emission (field emission) display devices (FED), surface-conduction electron emission displays (SED), and liquid crystal displays. A device (transmissive liquid crystal display device, transflective liquid crystal display device, reflective liquid crystal display device, direct-view liquid crystal display device, projection liquid crystal display device), and electronic paper are mentioned. Moreover, a 3D display device, a three-dimensional display device, such as a hologram, etc. are mentioned.

2 is a schematic diagram showing a liquid crystal display device 10 which is one of the display devices of the present invention. The liquid crystal layer 17 is placed between the two substrates 14a and 14b. By using the polarizing film of the present invention for a liquid crystal display device, it becomes possible to reduce the thickness of the liquid crystal display device.

Examples of the liquid crystal used in the liquid crystal layer 17 include nematic liquid crystal, cholesteric liquid crystal, smectic liquid crystal, discotic liquid crystal, thermotropic liquid crystal, lyotropic liquid crystal, lyotropic liquid crystal, low molecular liquid crystal, polymer liquid crystal, ferroelectric liquid crystal, Antiferroelectric liquid crystal, main chain liquid crystal, side chain polymer liquid crystal, plasma address liquid crystal (PDLC), banana liquid crystal, and the like. In addition, the liquid crystal modes used in the liquid crystal display of the present invention include TN (Twisted Nematic) mode, STN (Super Twisted Nematic) mode, IPS (In-Plane-Switching) mode, FFS (Fringe Field Switching) mode, MVA ( Multi-domain Vertical Alignment) mode, PVA (Patterned Vertical Alignment) mode, ASV (Advanced Super View) mode, ASM (Axially Symmetric aligned Micro-cell) mode, OCB (Optical Compensated Birefringence) mode, ECB (Electrically Controlled Birefringence) mode , FLC (Ferroelectric Liquid Crystal) mode, AFLC (AntiFerroelectric Liquid Crystal) mode, PDLC (Polymer Dispersed Liquid Crystal) mode, and a guest host mode.

A color filter 15 is disposed on one side of one substrate 14a. The color filter 15 is disposed at a position opposite to the pixel electrode 22 with the liquid crystal layer 17 therebetween, and the black matrix 20 is disposed at a position opposite to the boundary between the pixel electrodes. The transparent electrode 16 covers them. In some cases, an overcoat layer is provided between the color filter 15 and the transparent electrode 16.

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

As the substrate 14b for forming the thin film transistor 21, a glass substrate is used so that it can withstand the high temperature when manufacturing the thin film transistor 21. Further, when forming the thin film transistor 21 at a low temperature, a plastic substrate may be used.

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

A liquid crystal layer 17 is disposed between the transparent electrode 16 and the pixel electrode 22. The liquid crystal layer 17 is provided with a spacer 23 in order to hold the gap constant by sandwiching two substrates or the like.

On the surface in contact with the liquid crystal layer 17, an alignment film for aligning the liquid crystal compound contained in the liquid crystal layer 17 in a desired direction may be formed, respectively.

Each member includes a substrate 14a, a black matrix 20 and a color filter 15, a transparent electrode 16, a liquid crystal layer 17, an interlayer insulating film 18, a thin film transistor 21, and a pixel electrode 22. And the substrates 14b are sequentially stacked.

Films having various optical functions are laminated on the outside of the substrate 14a and the substrate 14b with such a liquid crystal layer 17 interposed therebetween. On the outside of the substrate 14a, a retardation film 13a (for example, a 1/4 wavelength plate) and a polarizing film 12a of the present invention (for example, a linear polarizing film) are sequentially stacked, and the substrate 14b ) Outside, a retardation film 13b (for example, a 1/4 wavelength plate) and a polarizing film 12b (for example, a linear polarizing film) of the present invention are laminated in this order. On the outside of the polarizing film 12a, an antireflection film 11 for preventing reflection of external light is laminated.

A backlight unit 19 serving 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 reflecting plate, a diffusion sheet, and a viewing angle adjustment sheet. As the light source, various light sources, such as an electroluminescence (EL), a cold cathode tube, a hot cathode tube, an LED, a laser light source, and a mercury lamp, can be used. The polarizing film of the present invention may 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 disposed on the side surface or the upper and lower surfaces.

When the liquid crystal display device 10 is a transmissive liquid crystal display device, white light emitted from the light source enters the light guide, the path is changed by the reflector, and diffuses into the diffusion sheet. The diffused light enters the polarizing film 12b of the present invention from the backlight unit 19 after being adjusted to have a desired directivity by the viewing angle adjustment sheet.

Of the incident light that is non-polarized light, only one linearly polarized light passes through the polarizing film 12b of the present invention. This linearly polarized light becomes circularly polarized by the retardation film 13b (for example, a 1/4 wavelength plate), and sequentially transmits the substrate 14b, the pixel electrode 22, and the like to reach the liquid crystal layer 17.

The alignment state of liquid crystal molecules of the liquid crystal layer 17 is controlled by the potential difference between the pixel electrode 22 and the opposite transparent electrode (counter electrode) 16. The circularly polarized light incident on the liquid crystal layer 17 is transmitted through the liquid crystal layer 17 and the transparent electrode 16 as it is, and the color filter 15 and the retardation film 13a are transmitted through the polarizing film of the present invention. When passing through (12a), this pixel displays the color determined by the color filter brightest.

In addition, when the polarization state of light passing through the liquid crystal layer 17 changes and the retardation film 13a and the polarizing film 12a of the present invention almost completely absorb the light that has passed through the color filter 15, this pixel Indicates black. When the liquid crystal molecules of the liquid crystal layer 17 are in the intermediate alignment state of these two states, since light is partially transmitted and partially absorbed, this 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 material that reflects light, and the transmissive portion is the same as the transmissive liquid crystal display device described above. So that the image is displayed. On the other hand, in the reflection part, external light enters the liquid crystal display device in the direction of the antireflection film 11, and circularly polarized light transmitted through the polarizing film 12a and the retardation film 13a passes through the liquid crystal layer 17, and the pixel electrode It is reflected by (22) and used for display.

3 is a schematic diagram showing a liquid crystal display device 24 which is one of the display devices of the present invention. In the liquid crystal display device 24, each member is an antireflection film 11, a retardation film 13a, a substrate 14a, a polarizing film 12a of the present invention, a color filter 15, and a black matrix 20, Transparent electrode 16, liquid crystal layer 17, interlayer insulating film 18, thin film transistor 21 and pixel electrode 22, polarizing film 12b, substrate 14b, retardation film 13b of the present invention, The backlight units 19 are sequentially stacked.

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

4 is a schematic diagram showing 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 as a light emitting source and a cathode electrode 37 are laminated on a substrate 33 on which the pixel electrode 35 is formed. 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, the light emitting layer 36 emits light.

In order to manufacture the EL display device 30, first, the thin film transistor 40 is formed on the substrate 33 in a desired shape. Then, the interlayer insulating film 34 is formed, and then the pixel electrode 35 is formed by a sputtering method and patterned. After that, the light emitting layer 36 is laminated.

Examples of the substrate 33 include a sapphire glass substrate, a quartz glass substrate, a soda glass substrate, a ceramic substrate such as alumina, a metal substrate such as copper, and a plastic substrate. A thermally conductive film may be formed on the substrate. As a thermally conductive film, a diamond thin film (DLC, etc.) is mentioned. When a material that reflects light is used as the pixel electrode 35, light is emitted in a direction opposite to the substrate 33. Therefore, not only transparent materials but also non-transparent materials such as stainless steel can be used. The substrate may be a single material or a laminated substrate obtained by bonding a plurality of substrates together with an adhesive. These substrates may be in a plate shape or a film shape.

As the thin film transistor 40, the same ones as those of the thin film transistor 21 described above can be mentioned.

On the interlayer insulating film 34, a rib 41 is formed. The ribs 41 are disposed in the periphery (between adjacent pixels) of the pixel electrode 35. As a material of the rib 41, an acrylic resin, a polyimide resin, etc. are mentioned. The thickness of the rib 41 is preferably 1.0 µm or more and 3.5 µm or less, and more preferably 1.5 µm or more and 2.5 µm or less.

Next, an EL element comprising the pixel electrode 35 as a transparent electrode, the light emitting layer 36, and the cathode electrode 37 will be described. In the case of an organic EL display device, the light emitting layer 36 is stacked with at least one hole transport layer, respectively, and, for example, an electron injection transport layer, a light emitting layer, a hole transport layer, and a hole injection layer are sequentially stacked to become a light emitting 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, particularly preferably ITO and IZO. The thickness of the pixel electrode 35 may have a thickness of a certain or more capable of sufficiently performing hole injection, and is preferably about 10 to 500 nm.

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

As a constituent material of the cathode electrode 37, for example, a single metal element 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 preferable to use a two-component and three-component alloy system containing them. As an alloy system, 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: 5-20 at%), etc. are preferable. The cathode electrode 37 is formed by vapor deposition, sputtering, or the like, preferably by a vapor deposition method. The thickness of the cathode electrode 37 is preferably 0.1 nm or more, preferably 1 to 500 nm.

The hole injection layer has a function of facilitating injection of holes from the pixel electrode 35, and the hole transport layer has a function of transporting holes and a function of interfering with 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 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. In forming the hole injection transport layer, the light emitting layer, and the electron injection transport layer, since a homogeneous thin film can be formed, it is preferable to use a vacuum evaporation method.

As the light emitting layer 36, light emission from singlet excitons (fluorescence) is used, light emission from triplet excitons (phosphorescence) is used, light emission from singlet excitons (fluorescence) is used, and light emission from triplet excitons is used. Including those using light emission (phosphorescence), those formed by organic substances, those formed by inorganic substances, those formed by organic substances and those formed by inorganic substances, polymer materials, low molecular materials, polymer materials and low molecules It is possible to use those containing materials of. However, the present invention is not limited to this, and an EL display device using various types of EL elements can be used.

A drying agent 38 is disposed in the space between the cathode electrode 37 and the sealing lid 39. Moisture is absorbed by the desiccant 38 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 exit surface of the EL display device 30 is not limited to a linear polarizing film, and may be an elliptically polarizing film. Moreover, the polarizing film 31 of this invention may be the said laminated body (1), and a plurality of polarizing films 4 and retardation films of this invention may be bonded together.

5 is a schematic diagram showing 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 an array substrate (cathode electrode 37, light emitting layer 36, pixel electrode 35, interlayer insulating film 34, and The substrate 33 can also be formed on the polarizing film 31 side of the present invention.

As the thin film encapsulation film 42, it is preferable to use a film in which DLC (diamond-like carbon) is vapor-deposited because moisture-proof property is high. The DLC-deposited film may be formed by direct vapor deposition on the surface of the cathode electrode 37. Further, a thin resin film and a metal thin film may be laminated in multiple layers to form the thin film sealing film 42.

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

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

The light beam emitted from the light source (eg, a high-pressure mercury lamp) 111 as a light emitting source is first, the first lens array 112, the second lens array 113, the polarization conversion element 114, the superimposed lens 115 By passing through, uniformity and polarization of the luminance in the cross section of the semi-beam is performed.

Specifically, the light beam emitted from the light source 111 is divided into a plurality of microscopic light beams by the first lens array 112 in which microscopic lenses 112a are formed in a matrix. The second lens array 113 and the superimposed lens 115 are provided so that each of the divided light beams irradiates the whole of the three liquid crystal panels 140R, 140G, and 140B to be illuminated, so that each liquid crystal panel The incidence-side surface has an almost uniform roughness as a whole.

The polarization conversion element 114 has a function of separating incident light into its polarization components, and is disposed between the second lens array 113 and the superimposed lens 115. Thereby, random polarization from the light source is converted into polarized light having a specific polarization direction in advance, reducing the amount of light loss in the incident-side polarizing film described later, and improving the brightness of the screen.

The light whose luminance is equalized and divided into polarization components is sequentially by dichroic mirrors 121, 123, 132 for separating into three primary colors of RGB via a reflection mirror 122, and a red channel (R in FIG. 6, It is separated into a solid arrow), a green channel (G in Fig. 6, a dashed-dotted arrow), and a blue channel (B in Fig. 6, a broken line arrow), and is incident on 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 disposed on the incidence side and the polarizing film 143 of the present invention is disposed on the emission side.

Two polarizing films disposed on the incidence side and the emission side with the liquid crystal panel interposed between the respective RGB optical paths will be described. The polarizing film 142 and the polarizing film 143 of the present invention arranged in each optical path are arranged so that their absorption axes are orthogonal, and each liquid crystal panel 140R, 140G, 140B arranged in each optical path is The polarization state controlled for each pixel is converted into an amount of light.

The polarizing film of the present invention is useful as a polarizing film excellent in durability in any of the blue channel, green channel, and red channel.

An optical image produced by transmitting incident light at a transmittance different for each pixel according to the image data of the liquid crystal panels 140R, 140G, 140B is synthesized by the cross dichroic prism 150, and is synthesized by the projection lens 170. , Is enlarged and projected on the screen 180.

The polarizing film of the present invention can be used also as a polarizing film of electronic paper, and their thickness can be made thin. As electronic papers, those displayed by molecules such as optical anisotropy and orientation of dye molecules, those displayed by particles such as electrophoresis, particle movement, particle rotation, and phase change, and those displayed by moving one end of a film, It refers to things that are displayed by the color/phase change of molecules, those that are displayed by the absorption of light by molecules, and those that are displayed by self-luminescence by bonding of electrons and holes. For example, as an electronic paper, the display method is not particularly limited, and microcapsule type electrophoresis, horizontal movement type electrophoresis, vertical movement type electrophoresis, spherical twist ball, magnetic twist ball, circumferential twist ball method, charged toner, electronic powder Fluid, magnetophoretic type, magnetic thermal type, electrowetting, light scattering (transparent/cloudy change), cholesteric liquid crystal/photoconductive layer, cholesteric liquid crystal, bistable nematic liquid crystal, ferroelectric liquid crystal, dichroic dye/liquid crystal Disperse type, movable film, discoloration by leuco dye, photochromic, electrochromic, electrodeposition, flexible organic EL, and the like can be used.

Electronic paper may be used not only for personal use of texts and images, but also for advertisement display (signage). According to the polarizing film of this invention, the thickness of an electronic paper can be made thin.

In the three-dimensional display device, a polarizing film having a plurality of regions having different directions of the slow axis is used (for example, Japanese Unexamined Patent Publication No. 2002-185983). In the polarizing film of the present invention, a plurality of regions having different slow axis directions can be easily formed on the polarizing film by masking a part of the alignment film and performing rubbing or polarized UV irradiation. It is also useful as a polarizing film.

Example

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

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

Synthesis Example 1

Compound (1-6) is described in Lub et al. Recl. Trav. Chim. It was synthesized by the method described in Pays-Bas, 115, 321-328 (1996).

Compound (1-6):

Synthesis Example 2

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

Compound (1-8):

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

Synthesis Example 3

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

(Step 1)

16.8 parts of sodium hydrogen sulfite and 30.0 parts of water were mixed, the temperature was raised to 70°C, and 10.5 parts of a 37% formalin aqueous solution was added dropwise thereto over 1 hour. Then, it cooled to 40 degreeC, and 10 parts of aniline was dripped over 1 hour, and it stirred for 3 hours, maintaining 40 degreeC. After that, the resultant was cooled to room temperature, and the precipitated crystals were 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, cooled to 0 to 5°C, and 8.5 parts of a 30% nitrous acid aqueous solution was added dropwise thereto over 30 minutes. Then, stirring was performed for 30 minutes while maintaining 0-5 degreeC, 0.3 part of amide sulfuric acid was added further, and the diazo liquid of 4-butylaniline was prepared. On the other hand, 7.7 parts of N-sulfomethylaniline sodium salt, 11.0 parts of sodium acetate, and 100 parts of water were mixed, cooled to 0 to 5°C, and the total amount of the diazo solution of 4-butylaniline just prepared was added dropwise over 1 hour. After completion of the dropwise addition, the temperature was raised to room temperature, and the precipitated solid was separated by filtration to obtain a compound represented by the formula (2-1-b) (hereinafter, the compound is referred to as "compound (2-1-b)"). The total amount of compound (2-1-b) was used in Step 3 without drying.

(Step 3)

The total amount of the compound (2-1-b) obtained in step 2, 61.8 parts of water and 16.7 parts of a 20% caustic soda aqueous 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 for liquid separation, and the obtained oil layer was dried over magnesium sulfate, the solvent was distilled off, and the compound represented by the formula (2-1-c) (hereinafter, the compound is referred to as "Compound (2 -1-c)".) 7.6 parts were obtained.

(Step 4)

5.0 parts of compound (2-1-c), 4.1 parts of 35% hydrochloric acid, and 100 parts of water were mixed, cooled to 0 to 5°C, and 5.0 parts of 30% nitrous acid aqueous solution was added dropwise thereto over 30 minutes. Then, it stirred for 30 minutes, maintaining 0-5 degreeC, and 0.2 part of amide sulfuric acid was added further, and the diazo liquid of compound (2-1-c) was prepared. On the other hand, 2.0 parts of phenol, 6.5 parts of sodium acetate, 20 parts of water, and 40 parts of methanol were mixed, cooled to 0 to 5°C, and the total amount of the diazo liquid of the just-prepared compound (2-1-c) was added dropwise over 1 hour. I did. After completion of the dropwise addition, the temperature was raised to room temperature, and the precipitated solid was separated by filtration, washed with methanol, and then dried, a compound represented by formula (2-1-d) (hereinafter, the compound was referred to as "compound (2-1-d). ".) 6.1 copies were obtained.

(Step 5)

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 were mixed, heated to 100° C., and stirred for 5 hours. After that, it was cooled to room temperature, poured into 100 g of ice water, and the precipitated solid was separated by filtration, washed with water and then dried, and the compound represented by formula (2-1-e) (hereinafter, the compound was referred to as "Compound (2-1 -e)".) 2.4 copies were obtained.

(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, cooled to 0-10° C., and 6.2 parts of acrylic acid chloride were added dropwise thereto over 1 hour. I did. After that, the temperature was raised to room temperature, 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 purified by column chromatography to obtain 2.0 parts of compound (2-1).

Synthesis Example 4

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

(Step 1)

A compound represented by formula (2-2-a) synthesized according to the method described in Japanese Patent Application Laid-Open No. 2017-082217 (hereinafter, the compound is referred to as "compound (2-2-a)") 5.0 parts, ethanol 75 parts and 11.6 parts of 10% caustic soda aqueous solution were mixed, it heated up to 80 degreeC, and stirred for 2 hours. After that, the mixture was cooled to room temperature, and the precipitated solid was separated by filtration, washed with methanol and then dried, and the compound represented by the formula (2-2-b) (hereinafter, the compound was referred to as "compound (2-2-b)" It is called.) 4.5 copies were obtained.

(Step 2)

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 are mixed, cooled to 0 to 5°C, and di 6.8 parts of isopropylcarbodiimide was added dropwise over 30 minutes. Thereafter, the temperature was raised to room temperature, stirred overnight, and after completion of the reaction, the mixture was mixed with 100 parts of water to separate liquid. After drying the obtained oil layer with magnesium sulfate, the solvent was distilled off and purified by column chromatography, the compound represented by the formula (2-2-c) (hereinafter, the compound is referred to as "compound (2-2-c)" It is called.) 1.2 copies were obtained.

(Step 3)

1.0 part of compound (2-2-c), 0.3 parts of dimethylaniline, 0.02 parts of dibutylhydroxytoluene, and 10 parts of dimethylacetamide were mixed, cooled to 0-10°C, and 0.2 parts of acrylic acid chloride was added dropwise thereto over 15 minutes. I did. Then, the temperature was raised to room temperature, stirred overnight, and after completion of the reaction, 50 parts of water and 50 parts of chloroform were added and the mixture was separated. After drying the obtained oil layer with magnesium sulfate, the solvent was distilled off and purified by column chromatography to obtain 0.7 parts of compound (2-2).

Synthesis Example 5

Compound (2-3), compound (2-4), compound (2-5) and compound (2-113) are described in the method described in Synthesis Example 3 or Synthesis Example 4, and Japanese Laid-Open Patent Publication No. 2011-246696. It was synthesized with reference to a known method.

Compound (2-3):

Compound (2-4):

Compound (2-5):

Compound (2-113):

[Measurement of phase transition temperature]

The phase transition temperature of compound (1-6) was confirmed by obtaining the phase transition temperature of the film made of compound (1-6). The operation is as follows.

On the glass substrate on which the alignment film was formed, a film made of compound (1-6) was formed, and the phase transition temperature was confirmed by texture observation with a polarizing microscope (BX-51, manufactured by Olympus) while heating. Compound (1-6) was heated to 120°C, and then, at the time of lowering the temperature, the phase transition was performed at 112°C to the nematic phase, at 110°C to the Smectic A phase, and at 94°C to the Smectic B phase.

It carried out similarly to the phase transition temperature measurement of compound (1-6), and confirmed the phase transition temperature of compound (1-8). Compound (1-8) was heated to 140°C, and then at the time of lowering, the phase transitioned from 131°C to the nematic phase, 80°C to the Smectic A phase, and then to the Smectic B phase at 68°C.

Example 1

[Preparation of the composition]

Composition (A) was obtained by mixing the following components and stirring at 80 degreeC for 1 hour.

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 Chiba Specialty Chemicals): 6 parts

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

Solvent; Xylene: about 450 copies

[Preparation and evaluation of polarizing film]

1. Formation of alignment layer

A glass substrate was used as the transparent substrate.

On the glass substrate, a 2% by mass aqueous solution (composition for orientation layer formation) of polyvinyl alcohol (polyvinyl alcohol 1000 complete saponification type, manufactured by Wako Pure Chemical Industries, Ltd.) was applied by spin coating, and after drying, a thickness of 100 A film of nm was formed. Subsequently, an alignment layer was formed by performing a rubbing treatment on the surface of the obtained film. The rubbing treatment was performed using a semi-automatic rubbing device (brand name: LQ-008 type, manufactured by Joyo Engineering Co., Ltd.), and using a cloth (brand name: YA-20-RW, manufactured by Yoshikawa Chemical Industries, Ltd.), with a press fit of 0.15 mm and rotation speed of 500. It implemented under the conditions of rpm and 16.7 mm/s. By such rubbing treatment, the laminate (1) in which the alignment layer was formed on a glass substrate was obtained.

2. Formation of polarizing film

On the alignment layer of the laminate (1), the composition (A) was applied by a spin coating method, heated and dried on a hot plate at 120° C. for 3 minutes, then quickly cooled to room temperature, and then onto the alignment layer. A dry film was formed. In such a dry film, the liquid crystal state of the contained polymerizable liquid crystal composition (polymerizable liquid crystal compound) was Smectic B phase. Next, using a UV irradiation device (SPOT CURE SP-7; manufactured by Ushio Electric Co., Ltd.), by irradiating the dried film with ultraviolet rays at an exposure amount of 2400 mJ/cm 2 (365 nm basis), the polymerizable liquid crystal contained in the dried film The compound was polymerized while maintaining the liquid crystal state of the polymerizable liquid crystal composition, and a polarizing film was formed from the dried film. The thickness of the polarizing film at this time was measured with a laser microscope (OLS3000 manufactured by Olympus Corporation), and it was 1.7 µm.

3. X-ray diffraction measurement

About the polarizing layer of the obtained laminated body 2, X-ray diffraction measurement was performed using the X-ray diffraction apparatus X'Pert PRO MPD (manufactured by Spectres Co., Ltd.). Using Cu as a target, X-rays generated under conditions of X-ray tube current of 40 ㎃ and X-ray tube voltage of 45 kV are fixed in the rubbing direction through 1/2° of the divergence slit (the rubbing direction of the alignment layer under the polarizing layer is determined in advance. .), and scanning in 2θ = 0.01671° steps in a scanning range of 2θ = 4.0 to 40.0°. As a result, the peak half width (FWHM) = about 0.312° sharp diffraction peak at 2θ = 20.08° Was obtained. Moreover, the same result was obtained even in the incident from the rubbing vertical direction. The ordered period (d) obtained from the peak position was about 4.42 Å, and it was found that a structure reflecting the high-order smectic phase was formed.

4. Preparation of a polarizing film laminate

In addition, after corona treatment was performed on the surface of the polarizing film of the polarizer obtained as described above, on the surface subjected to corona treatment, 7 parts of carboxyl group-modified polyvinyl alcohol ["Kurarepoval KL318" manufactured by Kuraray Co., Ltd.) in 100 parts of water and , As a thermal crosslinking agent, an aqueous solution (viscosity: 92 cP) to which 3.5 parts of a water-soluble polyamide epoxy resin ["Sumirez Resin 650" obtained from Sumica Chemtex Co., Ltd. (aqueous solution having a solid content concentration of 30% by mass)) was added was added to a spin coater method. And then dried at 80° C. for 5 minutes to dry the aqueous solution to form a protective layer to prepare a polarizer with a protective layer. Further, on the protective layer, a triacetyl cellulose film (KC4UY, manufactured by Konica Minolta Co., Ltd.) was pasted through an adhesive layer formed of a pressure-sensitive adhesive (manufactured by Lintec Co., Ltd., a film thickness of 25 µm). In this way, a polarizing film laminate was obtained.

5. Measurement of dichroic ratio

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

Set the absorbance in the transmission axis direction (A ¹ ) and the absorbance in the absorption axis direction (A ² ) in the maximum absorption wavelength in the absorption axis direction, and a folder with a polarizing film attached to a spectrophotometer (UV-3150 manufactured by Shimadzu Corporation). Measurements were made by the double beam method using one apparatus. In the folder, a mesh for cutting the amount of light by 50% was provided on the reference side. The ratio (A ² /A ¹ ) was calculated from the measured values of the absorbance in the direction of the transmission axis (A ¹ ) and the absorbance in the direction of the absorption axis (A ² ), and it was set as the dichroic ratio. The results are shown in the table. It can be said that the higher the dichroic ratio, the more useful as a polarizing film.

Table 1 shows the maximum absorption wavelength of the absorbance (A ² ) in the direction of the absorption axis and the measurement results of the dichroic ratio at that wavelength.

6. Evaluation of moisture and heat resistance

About the layered product of Example 1, heat-and-moisture resistance was evaluated according to the following method. Table 1 shows the results.

The laminate described in Example 1 was put into an oven at 60° C. 90% RH, and after 500 hours had passed, the absorbance (A ³ ) in the absorption axis direction at the maximum absorption wavelength of the laminate was measured again before and after the moist heat resistance test. The amount of change in the absorbance in the direction of the absorption axis was calculated. Moisture and heat resistance was calculated by the following equation.

Moisture and heat resistance = absorbance in the absorption axis direction at the maximum absorption wavelength before test injection (A ² )/absorbance in the absorption axis direction at the maximum absorption wavelength after test injection (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, a polarizing film was prepared in the same manner as in Example 1, except that the kind of compound (2) was changed to that described in Table 1. The maximum absorption wavelength of the absorbance (A ² ) and the dichroic ratio at that wavelength were measured. In the comparative example, it is an example using a polymerizable diazo liquid crystal compound which does not belong to the compound (2), and a reference example is an example using a liquid crystal compound having dichroism which does not have a polymerizable group. Moreover, it carried out similarly to Example 1, and evaluated the heat-and-moisture resistance. The results are shown in Table 1. In addition, the compounds of the comparative examples and reference examples described 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.

1 laminate
2 supporting materials
3 alignment film
4 Polarizing film of the present invention
10 liquid crystal display
11 Anti-reflective film
12a, 12b polarizing film of the present invention
13a, 13b retardation film
14a, 14b substrate
15 color filters
16 transparent electrodes
17 liquid crystal layer
18 interlayer insulating film
19 backlight unit
20 black matrix
21 thin film transistor
22 pixel electrode
23 spacer
24 liquid crystal display
30 EL display device
31 Polarizing film of the present invention
32 retardation film
33 substrate
34 interlayer insulating film
35 pixel electrode
36 emitting layer
37 cathode electrode
38 Desiccant
39 bag cover
40 thin film transistor
41 rib
42 thin film encapsulant
44 EL display device
111 light source
112 first lens array
112a lens
113 Second Lens Array
114 polarization conversion element
115 superposition lens
121, 123, 132 dichroic mirrors
122 reflective mirror
140R, 140G, 140B liquid crystal panel
142, 143 Polarizing film of the present invention
150 cross dichroic prism
170 projection lens
180 screen

Claims (11)

A polymerizable liquid crystal compound showing a smectic phase, and
Equation (2):

[In formula (2), m represents the integer of 0-3.
A ¹ , A ^2, and A ³ each independently represent a divalent aromatic group which may have a substituent.
L ¹ and L ² are each independently 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 represents a CO-, or -N = N-.
R ^c and R ^d each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
Z ¹ represents a polymerizable group.
Z ² represents a hydrogen atom or a polymerizable group.
Q ¹ and Q ² are each independently a linear or branched alkylene group having 1 to 20 carbon atoms which may have a substituent, an alkenylene group having 1 to 20 carbon atoms which may have a substituent, or 1 carbon number which may have a substituent The alkynylene group of -20 is represented, and -CH ₂ -contained in these alkylene groups, alkenylene groups, or alkynylene groups may be substituted with -O-, -S-, or -NR ^e- .
R ^e represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
T ¹ represents a single bond, -O-, -S-, -CO-, -COO-, -OCO-, -OCOO-, or -CONR ^f -, or -NR ^f CO-,
T ² is a single bond, -O-, -S-, -CO-, -COO-, -OCO-, -OCOO-, -CONR ^f -, -NR ^f CO-, or when Z ² is a hydrogen atom Only -NR ^g -is represented.
R ^f and R ^g each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, but the alkyl group represented by R ^g may form a ring with Q ¹ or Q ² .
However, A ¹ -(L ¹ -A ² ) _m -L ² -A ³ represents at least one -A ^X1 -N=NA ^X2- (A ^X1 and A ^X2 each represent a divalent aromatic group.) Structure, and when T ² is -NR ^g -, Z ² represents a hydrogen atom.]
A composition containing a liquid crystal compound represented by. The method of claim 1,
The polymerizable liquid crystal compound showing a smectic phase is formula (1):

[In equation (1),
X ¹ and X ² each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group, wherein the hydrogen atom contained in the divalent aromatic group or the divalent alicyclic hydrocarbon group is a halogen atom or a C 1 to C 1 It may be substituted with a 4 alkyl group, a C1-C4 fluoroalkyl group, a C1-C4 alkoxy group, a cyano group, or a nitro group, and the carbon atom constituting the divalent aromatic group or the divalent alicyclic hydrocarbon group is an oxygen atom. , A sulfur atom or a nitrogen atom may be substituted. However, at least one of X ¹ and X ² is a 1,4-phenylene group which may have a substituent or a cyclohexane-1,4-diyl group which may have a substituent.
n is 1-3, and when n is 2 or more, X ¹ and X ² may be different, respectively.
Y ¹ is 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 are each independently a single bond or a divalent linking group.
V ¹ and V ² each independently represent an alkanediyl group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ -constituting the alkanediyl group is -O-, -CO-, -S -Or it may be substituted with NH-.]
Represented by, the composition. The method of claim 1 or 2
Wherein U ¹ is the polymerizable group as the polymerizable group that the polymerizable group weeks the number of atoms of the main chain of atoms, or V ² chains and the number of atoms of the main chain or Z ² is a polymerizable group in Q ¹ of V ¹ connected to a The composition, wherein the difference in the number of atoms of the main chain of Q ² connected with is 3 or less. The method according to any one of claims 1 to 3,
The U ¹ and Z ¹ , and U ² and Z ² are all the same polymerizable group, and the polymerizable group is an acryloyl group or a methacryloyl group. The method according to any one of claims 1 to 4,
The composition, wherein the liquid crystal compound of the formula (2) is a compound exhibiting dichroic light absorption in a visible light region. The method according to any one of claims 1 to 5,
The composition in which the liquid crystal compound (1) of the formula (1) is a thermotropic liquid crystal and a compound having a smectic liquid crystal phase. A polarizing film obtained by polymerizing a compound represented by formula (1) and a compound represented by formula (2) in the composition according to any one of claims 1 to 6 in a molecular orientation. A polarizing film obtained by polymerizing a compound represented by formula (1) and a compound represented by formula (2) in the composition according to any one of claims 1 to 6 in a molecularly oriented state, wherein the Bragg peak in X-ray diffraction measurement The polarizing film from which is obtained. Having the polarizing film according to claim 7 or 8 and a 1/4 wave plate, the angle formed by the absorption axis of the polarizing film and the slow axis of the 1/4 wave plate is 45 ± 10°, and the 1/4 wave plate is Circular polarizing plate satisfying the following formula (I).
100 nm <Re (550) <160 nm. (I)
(In the formula, Re (550) represents an in-plane retardation value for light having a wavelength of 550 nm.) Having the polarizing film according to claim 7 or 8 and a 1/4 wavelength plate, the angle formed by the absorption axis of the polarizing film and the slow axis of the 1/4 wave plate is 45 ± 10°, and a 1/4 wavelength A circular polarizing plate in which the plate satisfies all of the following formulas (I), (II) and (III).
100 nm <Re (550) <160 nm. (I)
Re (450)/Re (550) ≤ 1.0 ... (II)
1.00 ≤ Re (650)/Re (550)… (III)
(In the formula, Re (450) is the in-plane retardation value for light having a wavelength of 450 nm, Re (550) is the in-plane retardation value for light having a wavelength of 550 nm, and Re (650) is the in-plane retardation value for light having a wavelength of 650 nm. Represents the in-plane retardation value.) An organic EL display device comprising the circular polarizing plate according to claim 9 or 10.

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