JP7139404B2 - light absorption anisotropic plate - Google Patents

Description

TECHNICAL FIELD The present invention relates to a light absorption anisotropic plate and a method for manufacturing the light absorption anisotropic plate.

A liquid crystal composition containing a dichroic dye and a liquid crystalline compound is coated on a substrate as a light absorption anisotropic film for providing a peep prevention function to displays of mobile phones, bank ATMs, etc., and the liquid crystal A light absorption anisotropic film produced by aligning a compound and a dichroic dye perpendicularly to the film plane is known (Patent Document 1).

JP 2016-27387 A

On the other hand, there is a demand for an anisotropic light absorption film in which a liquid crystal compound and a dichroic dye are aligned perpendicular to the plane of the film, so that the film is less likely to be damaged when a force is applied. .

SUMMARY OF THE INVENTION It is an object of the present invention to provide a light absorption anisotropic plate including a vertically aligned light absorption anisotropic film that is less likely to be damaged when a force is applied.

The inventors of the present invention have completed the present invention as a result of intensive studies to solve the above problems. That is, the present invention includes the following aspects.
[1] A light absorption anisotropic plate comprising a film substrate and a light absorption anisotropic film,
The light absorption anisotropic film is a cured film of a liquid crystal composition containing a polymerizable liquid crystal compound, a reactive group-containing non-liquid crystal compound and a dichroic dye, and the polymerizable liquid crystal compound and the dichroic dye are the A light-absorbing anisotropic plate, which is a cured film that is oriented in a direction perpendicular to the plane of the light-absorbing anisotropic film.
[2] The light absorption anisotropic plate of [1] above, wherein the reactive group-containing non-liquid crystal compound has at least one reactive group selected from an acryloyloxy group and a methacryloyloxy group.
[3] Light absorption anisotropy according to [1] or [2], wherein the reactive group-containing non-liquid crystal compound is at least one selected from monofunctional (meth)acrylates and polyfunctional (meth)acrylates. board.
[4] The light absorption anisotropic plate according to any one of [1] to [3], wherein the reactive group-containing non-liquid crystal compound has 2 to 12 reactive groups in the molecule.
[5] The light absorption anisotropy according to any one of [1] to [4] above, wherein the reactive group possessed by the non-liquid crystal compound containing a reactive group and the polymerizable group possessed by the polymerizable liquid crystal compound are the same. board.
[6] Any one of the above [1] to [5], wherein the content of the reactive group-containing non-liquid crystal compound is 0.2 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the polymerizable liquid crystal compound. A light-absorbing anisotropic plate as described.
[7] The light absorption anisotropic plate according to any one of [1] to [6], wherein the polymerizable liquid crystal compound exhibits a smectic liquid crystal phase.
[8] The light absorption anisotropic plate according to any one of [1] to [7], wherein the dichroic dye is an azo dye.
[9] The light absorption anisotropic plate according to any one of [1] to [8], wherein the light absorption anisotropic film has a thickness of less than 2 μm.
[10] The light absorption anisotropic plate according to any one of [1] to [9], wherein the light absorption anisotropic film exhibits a Bragg peak in X-ray diffraction measurement.
[11] A resin film in which the film substrate is composed of at least one selected from the group consisting of polyimide-based resins, cellulose ester-based resins, cyclic olefin-based resins, polyester-based resins, and poly(meth)acrylic acid-based resins. The light absorption anisotropic plate according to any one of [1] to [10] above, wherein:
[12] The light-absorbing anisotropic plate according to any one of [1] to [11], wherein the film base and the light-absorbing anisotropic film are adjacent to each other.
[13] A method for producing a light-absorbing anisotropic plate including a film substrate and a light-absorbing anisotropic film,
forming a coating film of a liquid crystal composition containing a polymerizable liquid crystal compound, a reactive group-containing non-liquid crystal compound and a dichroic dye on a film substrate;
A step of drying the obtained coating film to obtain a dry coating film, and
A manufacturing method comprising a step of curing the dried coating film in a state in which the polymerizable liquid crystal compound and the dichroic dye are oriented in a direction perpendicular to the plane of the coating film.
[14] The light absorption anisotropic plate is elongated,
A long film substrate wound into a roll is unwound, and a coating film of a liquid crystal composition containing a polymerizable liquid crystal compound, a reactive group-containing non-liquid crystal compound, and a dichroic dye is formed on the film substrate. forming a
A step of continuously drying the obtained coating film to obtain a dry coating film, and
The step of aligning the polymerizable liquid crystal compound and the dichroic dye in the coating film in a direction perpendicular to the plane of the coating film and continuously irradiating the active energy ray to cure the [13]. The manufacturing method described in .
[15] A display material comprising the light-absorbing anisotropic plate according to any one of [1] to [12].
[16] A display device comprising the light-absorbing anisotropic plate according to any one of [1] to [12].

According to the present invention, it is possible to provide a light absorption anisotropic plate that includes a vertically aligned light absorption anisotropic film that is less likely to be damaged when a force is applied.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail. It should be noted that the scope of the present invention is not limited to the embodiments described here, and various modifications can be made without departing from the gist of the present invention.

The light absorption anisotropic plate of the present invention includes a film substrate and a light absorption anisotropic film.
<Light absorption anisotropic film>
In the present invention, the light absorption anisotropic film is a cured film of a liquid crystal composition containing a polymerizable liquid crystal compound, a reactive group-containing non-liquid crystal compound and a dichroic dye, and the polymerizable liquid crystal compound and the dichroic dye is a cured film cured in a state of being oriented in a direction perpendicular to the plane of the light absorption anisotropic film.

In the present invention, the polymerizable liquid crystal compound contained in the liquid crystal composition for forming the light absorption anisotropic film (hereinafter also referred to as the “light absorption anisotropic film forming composition”) has at least one polymerizable group. and has liquid crystallinity. Here, the polymerizable group means a group involved in a polymerization reaction, and is preferably a photopolymerizable group. A photopolymerizable group is a group that can participate in a polymerization reaction by an active radical generated from a polymerization initiator, an acid, or the like. Examples of the polymerizable group possessed by the polymerizable liquid crystal compound include a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, an acryloyloxy group, a methacryloyloxy group, an oxiranyl group, an oxetanyl group, and the like. is mentioned. Among them, a radically polymerizable group is preferred, an acryloyloxy group, a methacryloyloxy group, a vinyloxy group, an oxiranyl group and an oxetanyl group are more preferred, and an acryloyloxy group is even more preferred.

In the present invention, the polymerizable liquid crystal compound is preferably a liquid crystal compound exhibiting a smectic liquid crystal phase. By using a polymerizable liquid crystal compound exhibiting a smectic liquid crystal phase, it is possible to form a light absorption anisotropic film with a high degree of alignment order and an excellent polarizing function in oblique directions. From the viewpoint of realizing a higher degree of alignment order, the liquid crystal state exhibited by the polymerizable liquid crystal compound (A) is more preferably a high-order smectic phase (high-order smectic liquid crystal state). Here, the higher order smectic phase includes smectic B phase, smectic D phase, smectic E phase, smectic F phase, smectic G phase, smectic H phase, smectic I phase, smectic J phase, smectic K phase and smectic L phase. Among these, smectic B phase, smectic F phase and smectic I phase are more preferable. Thermotropic liquid crystals or lyotropic liquid crystals may be used as liquid crystals, but thermotropic liquid crystals are preferred because they allow precise film thickness control. Moreover, the polymerizable liquid crystal compound (A) may be a monomer, but may be an oligomer or polymer in which a polymerizable group is polymerized.

The polymerizable liquid crystal compound is not particularly limited as long as it is a liquid crystal compound having at least one polymerizable group, and known polymerizable liquid crystal compounds can be used, but compounds exhibiting smectic liquid crystallinity are preferred. Examples of such a polymerizable liquid crystal compound include compounds represented by the following formula (A) (hereinafter also referred to as "polymerizable liquid crystal compound (A)").
U ¹ -V ¹ -W ¹ -(X ¹ -Y ¹ ) _n -X ² -W ² -V ² -U ² (A)
[in formula (A),
X ¹ and X ² each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group, wherein the divalent aromatic group or divalent alicyclic hydrocarbon A hydrogen atom contained in the group may be substituted with a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group. A carbon atom constituting the divalent aromatic group or divalent alicyclic hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, or a nitrogen atom. However, at least one of X ¹ and X ² is an optionally substituted 1,4-phenylene group or an optionally substituted cyclohexane-1,4-diyl group.
Y ¹ is a single bond or a divalent linking group.
n is 1 to 3, and when n is 2 or more, multiple X ^1s may be the same or different. X ² may be the same as or different from any or all of the plurality of X ¹ 's. Moreover, when n is 2 or more, the plurality of Y ¹ may be the same or different. From the viewpoint of liquid crystallinity, n is preferably 2 or more.
U1 represents ^a hydrogen atom or a polymerizable group.
^U2 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 optionally substituted alkanediyl group having 1 to 20 carbon atoms, and —CH ₂ — constituting the alkanediyl group is —O—, -CO-, -S- or NH- may be substituted. ]

In the polymerizable liquid crystal compound (A), X ¹ and X ² are each independently preferably a 1,4-phenylene group optionally having a substituent, or a 1,4-phenylene group optionally having a substituent, or cyclohexane-1,4-diyl group, and at least one of X ¹ and X ² is a 1,4-phenylene group optionally having a substituent, or a 1,4-phenylene group optionally having a substituent cyclohexane-1,4-diyl group, preferably trans-cyclohexane-1,4-diyl group. Optionally substituted 1,4-phenylene group or optionally substituted cyclohexane-1,4-diyl group may have a methyl group, ethyl and alkyl groups having 1 to 4 carbon atoms such as butyl group, cyano group and halogen atoms such as chlorine atom and fluorine atom. It is preferably unsubstituted.

Further, the polymerizable liquid crystal compound (A) is represented by formula (A1) in formula (A):
-(X ¹ -Y ¹ ) _n -X ² - (A1)
[In the formula, X ¹ , Y ¹ , X ² and n each have the same meaning as above. ]
[hereinafter, also referred to as partial structure (A1)] has an asymmetric structure, because smectic liquid crystallinity is readily exhibited.
As the polymerizable liquid crystal compound (A) in which the partial structure (A1) is an asymmetric structure, for example, there is a polymerizable liquid crystal compound (A) in which n is 1 and one X ¹ and X ² are different structures. mentioned. Also, a compound in which n is 2, two Y ^1s have the same structure, two X ^1s have the same structure, and one X ² has a different structure from these two X ^1s Polymerizable liquid crystal compound (A), X ¹ bonded to W ¹ of two X ¹ has a different structure from the other X ¹ and X ² , and the other X ¹ and X ² have the same structure A polymerizable liquid crystal compound (A) is also included. Furthermore, a compound in which n is 3, three Y ^1s have the same structure as each other, and any one of the three X ^1s and one X ² has a different structure from all the other three. liquid crystal compound (A).

Y ¹ is -CH ₂ CH ₂ -, -CH ₂ O-, -CH ₂ CH ₂ O-, -COO-, -OCOO-, a single bond, -N=N-, -CR ^a =CR ^b -, -C≡C-, -CR ^a =N- or -CO-NR ^a - are preferred. R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Y ¹ is -CH ₂ CH ₂ -, -CH ₂ O-, -COO-, -OCOO-, a single bond, -N=N-, -CR ^a =CR ^b -, -C≡C- or -CR more preferably ^a = N-, more preferably -CH ₂ CH ₂ -, -COO-, -CH ₂ O- or a single bond, and when multiple Y ¹ are present, bond with X ² It is more preferable that Y ¹ that binds to X 2 is —CH ₂ CH ₂ — or —CH ₂ O—, and Y ¹ that does not bond to X ² is —CH ₂ CH ₂ —, —COO— or a single bond. When X ¹ and X ² all have the same structure, it is preferred that there are two or more Y ¹ with different binding modes. When ^a plurality of Y1's with different bonding methods exist, the structure is asymmetrical, and smectic liquid crystallinity tends to occur.

^U2 is a polymerizable group. U ¹ is a hydrogen atom or a polymerizable group, preferably a polymerizable group. Both U ¹ and U ² are preferably polymerizable groups, more preferably photopolymerizable groups, and even more preferably photoradically polymerizable groups. Examples of the polymerizable group include the same groups as those previously exemplified as the polymerizable group possessed by the polymerizable liquid crystal compound. The polymerizable group represented by U ¹ and the polymerizable group represented by U ² may be different from each other, but are preferably groups of the same type, and at least one of U ¹ and U ² is (meta) It is preferably an acryloyloxy group, more preferably a (meth)acryloyloxy group, and still more preferably an acryloyloxy group. The polymerizable group may be in a polymerized state or in an unpolymerized state, preferably in an unpolymerized state.

The alkanediyl groups represented by V ¹ and V ² include methylene, ethylene, propane-1,3-diyl, butane-1,3-diyl, butane-1,4-diyl, pentane- 1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, decane-1,10-diyl group, tetradecane-1,14-diyl and icosane-1,20-diyl groups. V ¹ and V ² are preferably alkanediyl groups having 2 to 12 carbon atoms, more preferably alkanediyl groups having 6 to 12 carbon atoms.

Examples of the substituent optionally possessed by the alkanediyl group include a cyano group and a halogen atom such as a chlorine atom and a fluorine atom. A chain alkanediyl group is more preferred.

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

As the structure of the polymerizable liquid crystal compound that tends to exhibit smectic liquid crystallinity, it preferably has an asymmetric molecular structure in the molecular structure, and specifically has the following partial structures (Aa) to (Ai). However, polymerizable liquid crystal compounds exhibiting smectic liquid crystallinity are more preferable. It is more preferable to have a partial structure of (Aa), (Ab) or (Ac) from the viewpoint of easily exhibiting high-order smectic liquid crystallinity. In (Aa) to (Ai) below, * represents a bond (single bond).

Examples of the polymerizable liquid crystal compound (A) include compounds represented by the following formulas (A-1) to (A-25). When the polymerizable liquid crystal compound (A) has a cyclohexane-1,4-diyl group, the cyclohexane-1,4-diyl group is preferably a trans form.

Among these, formula (A-2), formula (A-3), formula (A-4), formula (A-6), formula (A-7), formula (A-8), formula (A- 13), and at least one selected from the group consisting of compounds represented by formulas (A-14) and (A-15). As the polymerizable liquid crystal compound (A), one type may be used alone, or two or more types may be used in combination.

The polymerizable liquid crystal compound (A) is described, for example, in Lub et al., Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996), or a known method described in Japanese Patent No. 4,719,156.

In the present invention, the light absorption anisotropic film is preferably formed by containing the polymerizable liquid crystal compound (A), and the composition for forming the light absorption anisotropic film may contain the polymerizable liquid crystal compound (A). preferable. When the composition for forming a light-absorbing anisotropic film contains two or more kinds of polymerizable liquid crystal compounds, the polymerizable liquid crystal compound ( The proportion of A) is preferably 51% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more. When the proportion of the polymerizable liquid crystal compound (A) is within the above range, it becomes easier to obtain a light absorption anisotropic film with a high degree of alignment order.

When the composition for forming a light-absorbing anisotropic film contains two or more polymerizable liquid crystal compounds, at least one of them may be the polymerizable liquid crystal compound (A), all of which are polymerizable liquid crystal compounds ( A) may be. By combining a plurality of polymerizable liquid crystal compounds, it may be possible to temporarily maintain liquid crystallinity even at temperatures below the liquid crystal-crystal phase transition temperature.

The content of the polymerizable liquid crystal compound in the composition for forming a light absorption anisotropic film is preferably 40 to 99.9% by mass, more preferably 60 to 99% by mass, based on the solid content of the liquid crystal composition. and more preferably 70 to 99% by mass. When the content of the polymerizable liquid crystal compound is within the above range, the orientation of the polymerizable liquid crystal compound tends to be high. In the present specification, the solid content of the composition for forming a light-absorbing anisotropic film means the total amount of components excluding volatile substances such as solvents from the composition. Hereinafter, the solid content of other compositions, etc., similarly means the total amount of components of the target composition, etc., excluding volatile substances such as solvents.

In the present invention, the reactive group-containing non-liquid crystal compound has a reactive group (functional group) capable of reacting with the polymerizable group of the polymerizable liquid crystal compound, and even with temperature changes, liquid crystal It means a compound that has no state. By forming the anisotropic light absorption film from a liquid crystal composition containing a reactive group-containing non-liquid crystal compound, the film strength of the anisotropic light absorption film is improved and high flexibility is obtained. In particular, according to the studies of the inventors of the present invention, in the cured liquid crystal film in which the polymerizable liquid crystal compound is oriented in the direction perpendicular to the film plane, the liquid crystal compound is arranged in layers in the direction perpendicular to the film plane. It has been clarified that such delamination can be suppressed by blending a reactive group-containing non-liquid crystal compound, which tends to cause delamination between the layers. Furthermore, in the case of a cured film of a liquid crystal phase exhibiting (higher-order) smectic liquid crystals, delamination tends to occur more easily as the liquid crystal compound aligns in the vertical direction with a higher degree of alignment order. In addition to the effect of improving film strength and flexibility by blending, the effect of suppressing delamination can be obtained more remarkably.

The reactive group-containing non-liquid crystal compound (i) itself has no coloring (absorption of visible light), (ii) has compatibility to the extent that it can be uniformly mixed with the polymerizable liquid crystal compound, and (iii) Those that do not inhibit the formation of the liquid crystal state exhibited by the polymerizable liquid crystal compound are preferred.

The reactive group possessed by the reactive group-containing non-liquid crystal compound includes, for example, a reactive group capable of crosslinking or polymerizing between the polymerizable liquid crystal compound and/or between the reactive group-containing non-liquid crystal compounds by a radical reaction. Specifically, vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloyloxy group, methacryloyloxy group, oxiranyl group, oxetanyl group, thiol group, isocyanate group, etc. mentioned. The reactive group is preferably a polymerizable group, more preferably a radically polymerizable group. Among them, an acryloyloxy group, a methacryloyloxy group, a vinyloxy group, an oxiranyl group and an oxetanyl group are more preferable, and an acryloyloxy group and a methacryloyloxy group are more preferable.

In the present invention, the reactive group-containing non-liquid crystal compound preferably has at least one reactive group (polymerizable group) selected from an acryloyloxy group and a methacryloyloxy group. By containing a reactive group-containing non-liquid crystal compound having at least one reactive group selected from an acryloyloxy group and a methacryloyloxy group, the film strength of the obtained liquid crystal cured film is easily improved, and vertically aligned liquid crystal curing It becomes easier to suppress delamination in the film.

Examples of reactive group-containing non-liquid crystal compounds include monofunctional (meth)acrylates and polyfunctional (meth)acrylates. Monofunctional means having one reactive group, and polyfunctional means having multiple reactive groups. In the present invention, the reactive group-containing non-liquid crystal compound constituting the light absorption anisotropic film is preferably at least one selected from monofunctional (meth)acrylates and polyfunctional (meth)acrylates. It is more preferably at least one selected from acrylates and polyfunctional acrylates, and the polyfunctional acrylate is the polyfunctional acrylate in that the polymerization reaction between the polymerizable liquid crystal compound and the reactive group-containing non-liquid crystal compound tends to proceed continuously. More preferred. As the reactive group-containing non-liquid crystal compound, one type may be used alone, or two or more types may be used in combination. In this specification, (meth)acrylate means acrylate or methacrylate, and the same applies to (meth)acryloyloxy and the like. Moreover, since such monofunctional (meth)acrylates and polyfunctional (meth)acrylates are non-liquid crystalline, those having no mesogenic structure are preferred. Furthermore, in the coating film of the composition for forming a light-absorbing anisotropic film, a urethane structure, an amino structure, an epoxy structure, It may contain ethylene glycol structures and polyester structures.

A monofunctional (meth)acrylate has one (meth)acryloyloxy group [that is, an acryloyloxy group (CH ₂ =CHCOO-) or a methacryloyloxy group (CH ₂ =C(CH ₃ )COO-)] in the molecule. It is a unique compound.

Monofunctional (meth)acrylates having one (meth)acryloyloxy group include alkyl (meth)acrylates having 4 to 16 carbon atoms, β-carboxyalkyl (meth)acrylates having 2 to 14 carbon atoms, and 2 to 1 carbon atoms. 14 alkylated phenyl (meth)acrylates, methoxypolyethyleneglycol (meth)acrylates, phenoxypolyethyleneglycol (meth)acrylates and isobornyl (meth)acrylates.

A polyfunctional (meth)acrylate is a compound having two or more (meth)acryloyloxy groups in the molecule. In the present invention, the polyfunctional (meth)acrylate used as the reactive group-containing non-liquid crystal compound preferably has 2 to 8 (meth)acryloyloxy groups in the molecule.

Bifunctional (meth)acrylates having two (meth)acryloyloxy groups include 1,3-butanediol di(meth)acrylate; 1,3-butanediol (meth)acrylate; 1,6-hexanediol di( meth)acrylate; ethylene glycol di(meth)acrylate; diethylene glycol di(meth)acrylate; neopentyl glycol di(meth)acrylate; triethylene glycol di(meth)acrylate; tetraethylene glycol di(meth)acrylate; polyethylene glycol diacrylate bis(acryloyloxyethyl) ether of bisphenol A; ethoxylated bisphenol A di(meth)acrylate; propoxylated neopentyl glycol di(meth)acrylate; ethoxylated neopentyl glycol di(meth)acrylate and 3-methylpentanediol A di(meth)acrylate etc. are illustrated.

(Meth) As a polyfunctional (meth) acrylate having 3 to 6 acryloyloxy groups,
trimethylolpropane tri(meth)acrylate; pentaerythritol tri(meth)acrylate; tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate; ethoxylated trimethylolpropane tri(meth)acrylate; propoxylated trimethylolpropane tri( meth)acrylate; pentaerythritol tetra(meth)acrylate; dipentaerythritol penta(meth)acrylate; dipentaerythritol hexa(meth)acrylate; tripentaerythritol tetra(meth)acrylate; Erythritol hexa(meth)acrylate; Tripentaerythritol hepta(meth)acrylate; Tripentaerythritol octa(meth)acrylate;
reaction product of pentaerythritol tri(meth)acrylate and acid anhydride; reaction product of dipentaerythritol penta(meth)acrylate and acid anhydride; reaction product of tripentaerythritol hepta(meth)acrylate and acid anhydride;
Caprolactone-modified trimethylolpropane tri(meth)acrylate; Caprolactone-modified pentaerythritol tri(meth)acrylate; Caprolactone-modified tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate; Caprolactone-modified pentaerythritol tetra(meth)acrylate; Caprolactone-modified Dipentaerythritol penta (meth) acrylate; caprolactone-modified dipentaerythritol hexa (meth) acrylate; caprolactone-modified tripentaerythritol tetra (meth) acrylate; caprolactone-modified tripentaerythritol penta (meth) acrylate; ) acrylate; caprolactone-modified tripentaerythritol hepta (meth) acrylate; caprolactone-modified tripentaerythritol octa (meth) acrylate; reaction product of caprolactone-modified pentaerythritol tri (meth) acrylate and acid anhydride; caprolactone-modified dipentaerythritol penta ( A reaction product of meth)acrylate and an acid anhydride, a reaction product of caprolactone-modified tripentaerythritol hepta(meth)acrylate and an acid anhydride, and the like. Note that caprolactone modification means that a ring-opened product or a ring-opened polymer of caprolactone is introduced between the alcohol-derived site and the (meth)acryloyloxy group of the (meth)acrylate compound.

Polyfunctional (meth)acrylates having 7 or more (meth)acryloyloxy groups include tripentaerythritol hepta (meth) acrylate; tripentaerythritol octa (meth) acrylate; tripentaerythritol hepta (meth) acrylate and an acid anhydride caprolactone-modified tripentaerythritol hepta(meth)acrylate; caprolactone-modified tripentaerythritol octa(meth)acrylate; caprolactone-modified tripentaerythritol hepta(meth)acrylate and acid anhydride.

A commercially available polyfunctional (meth)acrylate can also be used as the reactive group-containing non-liquid crystal compound. Such commercial products include, for example, A-DOD-N, A-HD-N, A-NOD-N, APG-100, APG-200, APG-400, A-GLY-9E, A-GLY- 20E, A-TMM-3, A-TMPT, AD-TMP, ATM-35E, A-TMMT, A-9550, A-DPH, HD-N, NOD-N, NPG, TMPT (Shin Nakamura Chemical Co., Ltd. company), ARONIX M-220, ARONIX M-325, ARONIX M-240, ARONIX M-270, ARONIX M-309, ARONIX M-310, ARONIX M-321, ARONIX M-350, ARONIX M-360, ARONIX M-305, ARONIX M-306, ARONIX M-450, ARONIX M-451, ARONIX M-408, ARONIX M-400, ARONIX M-402, ARONIX M-403, ARONIX M-404, ARONIX M-405, ARONIX M-406 (manufactured by Toagosei Co., Ltd.), EBECRYL11, EBECRYL145, EBECRYL150, EBECRYL40, EBECRYL140, EBECRYL180, DPGDA, HDDA, TPGDA, HPNDA, PETIA, PETRA, TMPTA, TMPEOTA, DPHA, EBECRYL series (above, Daicel Cytech Co., Ltd.) and the like.

Preferred polyfunctional (meth)acrylates include compounds represented by formulas (B-1) to (B-14) below.

The reactive group-containing non-liquid crystal compound preferably has 2 to 12 reactive groups in the molecule, and more preferably has 2 to 12 polymerizable groups in the molecule. Polyfunctional (meth)acrylates having 2 or more and 12 or less polymerizable groups are more preferable. From the viewpoint of more easily improving the film strength, the reactive group (number of polymerizable groups) possessed by the reactive group-containing non-liquid crystal compound is preferably 3 or more, more preferably 4 or more, and still more preferably 5 in one molecule. at least one. In addition, a light absorption anisotropic film that achieves a good balance between moderate film strength and high alignment order in the resulting liquid crystal cured film, has excellent flexibility, suppresses delamination, and has a high polarizing function in oblique directions. , the number of polymerizable groups possessed by the reactive group-containing non-liquid crystal compound is preferably 10 or less, more preferably 9 or less, and still more preferably 8 or less per molecule.

In the present invention, it is preferable that the reactive group (polymerizable group) of the reactive group-containing non-liquid crystal compound and the polymerizable group of the polymerizable liquid crystal compound are the same. Incidentally, when at least one compound selected from the polymerizable liquid crystal compound and the reactive group-containing non-liquid crystal compound has a plurality of types of reactive groups, at least one polymerizable group possessed by the polymerizable liquid crystal compound and a reactive group It is preferable that at least one reactive group possessed by the contained non-liquid crystal compound is the same. For example, when the reactive group-containing non-liquid crystal compound is a monofunctional (meth)acrylate, the polymerizable liquid crystal compound also preferably has a (meth)acryloyloxy group. When the reactive group-containing non-liquid crystal compound is a polyfunctional (meth)acrylate, the polymerizable liquid crystal compound also preferably has a (meth)acryloyloxy group.

The content of the reactive group-containing non-liquid crystal compound in the light absorption anisotropic film is preferably 0.2 parts by mass or more and 15 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound constituting the light absorption anisotropic film. It is below. When the content of the reactive group-containing non-liquid crystal compound is within the above range, the reactive group-containing non-liquid crystal compound is unlikely to disturb the orientation of the polymerizable liquid crystal compound and the dichroic dye, and the film has a high polarizing function. Easy to improve strength. From the viewpoint of making it easier to obtain a light-absorbing anisotropic film with excellent polarizing function while exhibiting high film strength and flexibility and having an excellent balance between moderate film strength and the alignment order of the polymerizable liquid crystal compound, a reactive group is added. The content of the contained non-liquid crystal compound is more preferably 0.5 parts by mass or more, still more preferably 1 part by mass or more, and particularly preferably 1.2 parts by mass or more with respect to 100 parts by mass of the polymerizable liquid crystal compound, Also, it is more preferably 12 parts by mass or less, still more preferably 10 parts by mass or less, particularly preferably 9 parts by mass or less, and most preferably 8 parts by mass or less.

A dichroic dye means a dye having a property that the absorbance in the long axis direction and the absorbance in the short axis direction of the molecule are different. The dichroic dye that can be used in the present invention is not particularly limited as long as it has the above properties, and may be a dye or a pigment. Also, two or more dyes or pigments may be used in combination, or a dye and a pigment may be used in combination. Moreover, the dichroic dye may have polymerizability or may have liquid crystallinity.

As the dichroic dye, those having a maximum absorption wavelength (λ _MAX ) in the wavelength range of 300 to 700 nm in the light absorption anisotropic film are preferred.

Examples of such dichroic dyes include acridine dyes, oxazine dyes, cyanine dyes, naphthalene dyes, azo dyes and anthraquinone dyes. Among them, azo dyes are preferred. The azo dyes include monoazo dyes, bisazo dyes, trisazo dyes, tetrakisazo dyes and stilbene azo dyes, preferably bisazo dyes and trisazo dyes.

Examples of azo dyes include compounds represented by formula (I) (hereinafter also referred to as "compound (I)").
K ¹ (-N=N-K ² ) _p -N=N-K ³ (I)
[In formula (I), K ¹ and K ³ are, independently of each other, a phenyl group optionally having substituent(s), a naphthyl group optionally having substituent(s), It represents a phenyl benzoic acid ester group or a monovalent heterocyclic group which may have a substituent. K ² is a p-phenylene group optionally having substituents, a naphthalene-1,4-diyl group optionally having substituents, 4,4′- optionally having substituents represents a stilbenylene group or an optionally substituted divalent heterocyclic group; p represents an integer from 0 to 4; When p is an integer of ² or more, multiple K2 may be the same or different. -N=N-bonds may be replaced with -C=C-, -COO-, -NHCO- and -N=CH-bonds within the range of absorption in the visible region. ]

Examples of monovalent heterocyclic groups include groups obtained by removing one hydrogen atom from heterocyclic compounds such as quinoline, thiazole, benzothiazole, thienothiazole, imidazole, benzimidazole, oxazole, and benzoxazole. The divalent heterocyclic group includes a group obtained by removing two hydrogen atoms from the above heterocyclic compound.

Phenyl group, naphthyl group, phenyl benzoic acid ester group and monovalent heterocyclic group for K ¹ and K ³ , and p-phenylene group, naphthalene-1,4-diyl group and 4,4'-stilbenylene group for K ² And the substituent optionally possessed by the divalent heterocyclic group include an alkyl group having 1 to 20 carbon atoms, an alkyl group having a polymerizable group and having 1 to 20 carbon atoms, an alkenyl group having 1 to 4 carbon atoms; a methoxy group; , ethoxy group, alkoxy group having 1 to 20 carbon atoms such as butoxy group; alkoxy group having 1 to 20 carbon atoms having a polymerizable group; fluorinated alkyl group having 1 to 4 carbon atoms such as trifluoromethyl group; cyano group a nitro group; a halogen atom; an amino group, a diethylamino group, a substituted or unsubstituted amino group such as a pyrrolidino group (a substituted amino group is an amino group having one or two alkyl groups having 1 to 6 carbon atoms, a polymerizable means an amino group having one or two alkyl groups of 1 to 6 carbon atoms having a An unsubstituted amino group is —NH _2. ) and the like. In addition, a (meth)acryloyl group, a (meth)acryloyloxy group, etc. are mentioned as said polymerizable group.

［式（Ｉ－１）～（Ｉ－８）中、
Ｂ^１～Ｂ^３０は、互いに独立して、水素原子、炭素数１～６のアルキル基、炭素数１～６のアルケニル基、炭素数１～４のアルコキシ基、シアノ基、ニトロ基、置換または無置換のアミノ基（置換アミノ基および無置換アミノ基の定義は前記のとおり）、塩素原子またはトリフルオロメチル基を表わす。
ｎ１～ｎ４は、互いに独立に０～３の整数を表わす。
ｎ１が２以上である場合、複数のＢ^２は互いに同一でも異なっていてもよく、
ｎ２が２以上である場合、複数のＢ^６は互いに同一でも異なっていてもよく、
ｎ３が２以上である場合、複数のＢ^９は互いに同一でも異なっていてもよく、
ｎ４が２以上である場合、複数のＢ^１４は互いに同一でも異なっていてもよい。］ Among compounds (I), compounds represented by any one of the following formulas (I-1) to (I-8) are preferred.

[In the formulas (I-1) to (I-8),
B ¹ to B ³⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, a nitro group, substituted or represents an unsubstituted amino group (the definitions of substituted amino group and unsubstituted amino group are as described above), chlorine atom or trifluoromethyl group;
n1 to n4 each independently represents an integer of 0 to 3;
When n1 is ² or more, the plurality of B2 may be the same or different,
When n2 is 2 or more, the plurality of ^B6 may be the same or different,
When n3 is ² or more, multiple B9 may be the same or different,
When n4 is 2 or more, the plurality of ^B14 may be the same or different. ]

［式（Ｉ－９）中、
Ｒ^１～Ｒ^８は、互いに独立して、水素原子、－Ｒ^ｘ、－ＮＨ_２、－ＮＨＲ^ｘ、－ＮＲ^ｘ _２、－ＳＲ^ｘまたはハロゲン原子を表わす。
Ｒ^ｘは、炭素数１～４のアルキル基または炭素数６～１２のアリール基を表わす。］ As the anthraquinone dye, a compound represented by formula (I-9) is preferable.

[In the formula (I-9),
R ¹ to R ⁸ independently represent a hydrogen atom, —R ^x , —NH ₂ , —NHR ^x , —NR ^x ₂ , —SR ^x or a halogen atom.
R ^x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms. ]

［式（Ｉ－１０）中、
Ｒ^９～Ｒ^１５は、互いに独立して、水素原子、－Ｒ^ｘ、－ＮＨ_２、－ＮＨＲ^ｘ、－ＮＲ^ｘ _２、－ＳＲ^ｘまたはハロゲン原子を表わす。
Ｒ^ｘは、炭素数１～４のアルキル基または炭素数６～１２のアリール基を表わす。］ As the oxazone dye, a compound represented by formula (I-10) is preferable.

[In the formula (I-10),
R ⁹ to R ¹⁵ each independently represent a hydrogen atom, —R ^x , —NH ₂ , —NHR ^x , —NR ^x ₂ , —SR ^x or a halogen atom.
R ^x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms. ]

［式（Ｉ－１１）中、
Ｒ^１６～Ｒ^２３は、互いに独立して、水素原子、－Ｒ^ｘ、－ＮＨ_２、－ＮＨＲ^ｘ、－ＮＲ^ｘ _２、－ＳＲ^ｘまたはハロゲン原子を表わす。
Ｒ^ｘは、炭素数１～４のアルキル基または炭素数６～１２のアリール基を表わす。］
式（Ｉ－９）、式（Ｉ－１０）および式（Ｉ－１１）において、Ｒ^ｘの炭素数１～６のアルキル基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基およびヘキシル基等が挙げられ、炭素数６～１２のアリール基としては、フェニル基、トルイル基、キシリル基およびナフチル基等が挙げられる。 As the acridine dye, a compound represented by formula (I-11) is preferable.

[In the formula (I-11),
R ¹⁶ to R ²³ each independently represent a hydrogen atom, —R ^x , —NH ₂ , —NHR ^x , —NR ^x ₂ , —SR ^x or a halogen atom.
R ^x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms. ]
In formula (I-9), formula (I-10) and formula (I-11), the alkyl group having 1 to 6 carbon atoms for R ^x includes a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl group. and hexyl group, and the aryl group having 6 to 12 carbon atoms includes phenyl group, toluyl group, xylyl group, naphthyl group and the like.

［式（Ｉ－１２）中、
Ｄ^１およびＤ^２は、互いに独立に、式（Ｉ－１２ａ）～式（Ｉ－１２ｄ）のいずれかで表される基を表わす。

ｎ５は１～３の整数を表わす。］

［式（Ｉ－１３）中、
Ｄ^３およびＤ^４は、互いに独立に、式（Ｉ－１３ａ）～式（１－１３ｈ）のいずれかで表される基を表わす。

ｎ６は１～３の整数を表わす。］ As the cyanine dye, a compound represented by formula (I-12) and a compound represented by formula (I-13) are preferable.

[In the formula (I-12),
D ¹ and D ² each independently represent a group represented by any one of formulas (I-12a) to (I-12d).

n5 represents an integer of 1-3. ]

[In the formula (I-13),
D ³ and D ⁴ each independently represent a group represented by any one of formulas (I-13a) to (1-13h).

n6 represents an integer of 1-3. ]

Dichroic dyes may be used alone or in combination. Since azo dyes have high linearity, they are suitable for producing light absorption anisotropic films with excellent polarization performance. From the viewpoint of polarizing performance, it is preferable to include an azo dye in which any one of K ¹ to K ³ in formula (I) is thienothiazole or benzothiazole. When polarization properties are required over the entire visible light range, preferably two or more dichroic dyes, more preferably three or more dichroic dyes are combined to facilitate control of the polarization performance.

When a plurality of types of dichroic dyes are combined, it is preferable to include at least one dye having a maximum absorption wavelength in the range of 500 nm to 600 nm in the light absorption anisotropic film. When combining two types of dichroic dyes, it is preferable to further include those having a maximum absorption wavelength in the range of 350 nm to 499 nm, or 601 nm to 750 nm. When combining three types of dichroic dyes, 350 nm to It is preferable to contain dichroic dyes having maximum absorption wavelengths in the ranges of 499 nm, 500 nm to 600 nm, and 601 nm to 750 nm, respectively. By combining the dichroic dyes in this way, the polarizing function in the oblique direction can be more easily improved, and the light absorption anisotropic plate can be suitable for use as, for example, an optical film for preventing prying eyes.

The weight average molecular weight of the dichroic dye is usually 300-2000, preferably 400-1000.

In one embodiment of the present invention, the dichroic dye constituting the light absorption anisotropic film is preferably hydrophobic. When the dichroic dye is hydrophobic, the compatibility between the dichroic dye and the polymerizable liquid crystal compound is improved, the dichroic dye and the polymerizable liquid crystal compound form a uniform phase state, and the orientation order is high. It becomes easy to obtain a light absorption anisotropic film. In the present invention, the hydrophobic dichroic dye means a dye having a solubility of 1 g or less in 100 g of water at 25°C.

The content of the dichroic dye in the composition for forming a light absorption anisotropic film can be appropriately determined according to the type of the dichroic dye used. 0.1 to 50 parts by mass, more preferably 0.1 to 30 parts by mass, still more preferably 0.1 to 10 parts by mass, and particularly preferably 0.1 to 5 parts by mass. When the content of the dichroic dye is within the above range, the alignment of the polymerizable liquid crystal compound is less likely to be disturbed, and a light absorption anisotropic film with high alignment order can be obtained. When two or more dichroic dyes are included, the total amount of all dichroic dyes is preferably within the above range.

The composition for forming a light-absorbing anisotropic film may contain a polymerization initiator. A polymerization initiator is a compound capable of initiating a polymerization reaction, such as a polymerizable liquid crystal compound or a reactive group-containing non-liquid crystal compound. As the polymerization initiator, a photopolymerization initiator that generates active radicals or acids by the action of light is preferable in that the polymerization reaction can be initiated under lower temperature conditions, and a photopolymerization initiator that generates radicals by the action of light is more preferred. preferable. The polymerization initiators may be used alone or in combination of two or more.

As the photopolymerization initiator, known photopolymerization initiators can be used. For example, photopolymerization initiators that generate active radicals include self-cleavage photopolymerization initiators and hydrogen abstraction photopolymerization initiators. There is
Self-cleavage photopolymerization initiators include self-cleavage benzoin compounds, acetophenone compounds, hydroxyacetophenone compounds, α-aminoacetophenone compounds, oxime ester compounds, acylphosphine oxide compounds, and azo compounds. Available. In addition, as a hydrogen abstraction type photopolymerization initiator, hydrogen abstraction type benzophenone compounds, benzoin ether compounds, benzyl ketal compounds, dibenzosuberone compounds, anthraquinone compounds, xanthone compounds, thioxanthone compounds, and halogenoacetophenone compounds. compounds, dialkoxyacetophenone-based compounds, halogenobisimidazole-based compounds, halogenotriazine-based compounds, triazine-based compounds, and the like can be used.

As photopolymerization initiators that generate acid, iodonium salts, sulfonium salts, and the like can be used.

Among them, the reaction at low temperature is preferable from the viewpoint of preventing dissolution of the dye, and the self-cleavage type photopolymerization initiator is preferable from the viewpoint of reaction efficiency at low temperature. Compounds and oxime ester compounds are preferred.

Specific examples of photopolymerization initiators include the following.
Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether;
2-hydroxy-2-methyl-1-phenylpropan-1-one, 1,2-diphenyl-2,2-dimethoxyethan-1-one, 2-hydroxy-2-methyl-1-[4-(2- Hydroxyacetophenones such as hydroxyethoxy)phenyl]propan-1-one, oligomers of 1-hydroxycyclohexylphenyl ketone and 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one system compound;
α-Aminoacetophenones such as 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one and 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butan-1-one system compound;
1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3 -Oxime ester compounds such as yl]-, 1-(O-acetyloxime);
Acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide;
benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenylsulfide, 3,3′,4,4′-tetra(tert-butylperoxycarbonyl)benzophenone and 2,4, Benzophenone compounds such as 6-trimethylbenzophenone;
Dialkoxyacetophenone compounds such as diethoxyacetophenone;
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- Triazines, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine and 2,4-bis(trichloromethyl)-6- triazine compounds such as [2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine;
The photopolymerization initiator may be appropriately selected from the above photopolymerization initiators, for example, in relation to the polymerizable liquid crystal compound and the reactive group-containing non-liquid crystal compound forming the light absorption anisotropic film.

Moreover, you may use a commercially available photoinitiator. Commercially available polymerization initiators include Irgacure® 907, 184, 651, 819, 250 and 369, 379, 127, 754, OXE01, OXE02, OXE03 (manufactured by BASF); Omnirad BCIM, Esacure 1001M , Esacure KIP160 (manufactured by IDM Resins B.V.); Seikuol® BZ, Z, and BEE (manufactured by Seiko Chemical Co., Ltd.); kayacure® BP100, and UVI-6992 (Dow Chemical Co., Ltd.); Adeka Optomer SP-152, N-1717, N-1919, SP-170, Adeka Arkles NCI-831, Adeka Arkles NCI-930 (manufactured by ADEKA Co., Ltd.); TAZ-A, and and TAZ-104 (manufactured by Sanwa Chemical Co., Ltd.) and the like.

The content of the polymerization initiator is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and still more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. Parts by weight, particularly preferably 0.5 to 8 parts by weight. When the content of the polymerization initiator is within the above range, the polymerization reaction can be carried out without significantly disturbing the alignment of the polymerizable liquid crystal compound.

The light absorption anisotropic film may contain a leveling agent. The leveling agent has the function of adjusting the fluidity of the composition for forming a light-absorbing anisotropic film and making the coating film obtained by applying the composition more flat. agents. The leveling agent is preferably at least one selected from the group consisting of a leveling agent containing a polyacrylate compound as a main component and a leveling agent containing a fluorine atom-containing compound as a main component. A leveling agent can be used individually or in combination of 2 or more types.

Examples of leveling agents mainly composed of polyacrylate compounds include BYK-350, BYK-352, BYK-353, BYK-354, BYK-355, BYK-358N, BYK-361N, BYK-380 and BYK-381. and BYK-392 (BYK Chemie).

Examples of the leveling agent containing a fluorine atom-containing compound as a main component include Megafac (registered trademark) R-08, R-30, R-90, F-410, F-411, F-443, F-445, F-470, F-471, F-477, F-479, F-482 and F-483 (DIC Corporation); Surflon® S-381, S-382, S-383, S-393 , SC-101, SC-105, KH-40 and SA-100 (AGC Seimi Chemical Co., Ltd.); E1830, E5844 (Daikin Fine Chemicals Laboratory); F-top EF352 (Mitsubishi Materials Electronics Chemical Co., Ltd.) can be mentioned.

When the light absorption anisotropic film contains a leveling agent, the content thereof is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, with respect to 100 parts by mass of the polymerizable liquid crystal compound. . When the content of the leveling agent is within the above range, the polymerizable liquid crystal compound is easily oriented, unevenness is less likely to occur, and a smoother light absorption anisotropic film tends to be obtained.

The light absorption anisotropic film may contain additives other than the leveling agent. Other additives include, for example, photosensitizers, antioxidants, release agents, stabilizers, colorants such as bluing agents, flame retardants, and lubricants. When other additives are contained, the content of the other additives is preferably more than 0% and 20% by mass or less with respect to the solid content of the composition for forming a light-absorbing anisotropic film. More preferably, it exceeds 0% and is 10% by mass or less.

The composition for forming a light absorption anisotropic film can be produced by a conventionally known method for preparing a liquid crystal composition, and usually comprises a polymerizable liquid crystal compound, a reactive group-containing non-liquid crystal compound and a dichroic dye, and It can be prepared by mixing and stirring the polymerization initiator, the above additives, etc., if necessary. In addition, since liquid crystal compounds exhibiting smectic liquid crystallinity generally have high viscosity, from the viewpoint of improving the coatability of the liquid crystal composition and facilitating the formation of a light absorption anisotropic film, a solvent is added to the liquid crystal composition. Viscosity adjustments may be made.

The solvent may be appropriately selected according to the solubility of the polymerizable liquid crystalline compound, reactive group-containing non-liquid crystal compound, dichroic dye, etc., which can completely dissolve the above components and is incompatible with the polymerization reaction. Active solvents are preferred.

Solvents include alcohol solvents such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether and propylene glycol monomethyl ether; ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone or ester solvents such as propylene glycol methyl ether acetate and ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane and heptane; and aromatic hydrocarbon solvents such as xylene, nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran and dimethoxyethane; chlorine-containing solvents such as chloroform and chlorobenzene; These solvents may be used alone or in combination of two or more.

The content of the solvent is preferably 100 to 1,900 parts by mass, more preferably 150 to 1,000 parts by mass, and even more preferably 180 to 800 parts by mass.

In the present invention, the light absorption anisotropic film is a film cured in a state in which the polymerizable liquid crystal compound and the dichroic dye are oriented in the direction perpendicular to the plane of the film. When an arbitrary direction is the x-axis, a direction orthogonal to the x-axis in the film plane is the y-axis, and a film thickness direction orthogonal to the x-axis and the y-axis is the z-axis, the following formula (1) is satisfied.
Az>(Ax+Ay)/2 (1)
[Ax, Ay and Az are absorbances at the absorption maximum wavelength of the dichroic dye in the light absorption anisotropic film,
Ax represents the absorbance of linearly polarized light oscillating in the x-axis direction,
Ay represents the absorbance of linearly polarized light oscillating in the y-axis direction,
Az represents the absorbance of linearly polarized light oscillating in the z-axis direction. ]

Ax can be measured by entering linearly polarized light vibrating in the x-axis direction from the z-axis direction toward the film surface. Ay can be measured by entering linearly polarized light vibrating in the y-axis direction from the z-axis direction toward the film surface. Az is, for example, from the xy plane direction toward the film side surface, that is, when the light absorption anisotropic film is assumed to be the xy plane, it is perpendicular to the side surface (thickness direction) and in the z axis direction. Oscillating linearly polarized light can be incident and measured.

The absorbance in the z-direction in Equation (1) may be difficult to measure because the light is incident from the side surface of the film. Therefore, assuming that the angle formed by the vibration plane of the linearly polarized light, which is the measurement light, and the xy plane of the film is 90°, the xy plane of the film is oriented 30° in the direction of incidence of the linearly polarized light with respect to this vibration plane. The absorbance in the Az direction can be estimated by measuring with an inclination of .degree. and 60.degree.

Specifically, it can be estimated by the following methods.
Ax (z=30) and Ax (z=60) were obtained by entering the same linearly polarized light as the linearly polarized light for measuring Ax while rotating the film by 30° and 60° with the y-axis as the axis of rotation. Similarly, with the film rotated 30° and 60° with the x-axis as the rotation axis, Ay (z = 30) and Ay (z=60) is measured.
At this time, if Ax (z = 30) < Ax (z = 60) and Ay (z = 30) = Ay (z = 60), then Ax (z = 30) < Ax (z = 60) < Ax ( If z=90)=Az and Ay(z=30)<Ay(z=60) and Ax(z=30)=Ax(z=60) then Ay(z=30)<Ay( Since z=60)<Ay(z=90)=Az, it can be said that the formula (1) is necessarily satisfied.

In particular, when there is no absorption anisotropy in the xy plane, ie when Ax and Ay are equal, Ax (z = 30) = Ay (z = 30) and Ax (z = 60) = Ay (z = 60), Ax(z=30) and Ay(z=30) can be A(z=30), and Ax(z=60) and Ay(z=60) can be A(z= 60). That is, if A(z=30)<A(z=60), the relationship A(z=30)<A(z=60)<A(z=90)=Az is satisfied. Furthermore, if A(z=30)>(Ax+Ay)/2, it can be said that Az necessarily satisfies the formula (1).

Further, in the present invention, the light absorption anisotropic film preferably satisfies the following formulas (2) and (3) in addition to the above formula (1).
Ax(z=60)/Ax>5 (2)
Ay (z=60)/Ay>5 (3)
[Ax, Ay and Az have the same meanings as above. Ax (z = 60) and Ay (z = 60) are both the absorbance at the absorption maximum wavelength of the dichroic dye in the light absorption anisotropic film,
Ax (z = 60) represents the absorbance of linearly polarized light vibrating in the x-axis direction when the film is rotated 60° around the y-axis,
Ay (z=60) represents the absorbance of linearly polarized light vibrating in the y-axis direction when the film is rotated 60° around the x-axis. ]

Ax (z=60) can be measured by injecting the same linearly polarized light as that for measuring Ax with the film rotated by 60° around the y-axis. Here, the film is rotated by rotating the film in the state of measuring Ax by 60° in the incident direction of the linearly polarized light with the y-axis as the rotation axis. Ay (z=60) can be measured by injecting the same linearly polarized light as that for measuring Ay with the film rotated 60° around the x-axis. Here, the film is rotated by rotating the film in the state where Ay was measured by 60° in the incident direction of the linearly polarized light with the x-axis as the rotation axis.

Ax (z=60)/Ax and Ay (z=60)/Ay mean that the larger the value, the better the light absorption anisotropy. These numerical values may be, for example, 50 or less, or 30 or less.
Furthermore, in the present invention, the light absorption anisotropic film more preferably satisfies the following formulas (4) and (5).
Ax(z=60)/Ax>10 (4)
Ay (z=60)/Ay>10 (5)
By using a compound that forms a smectic liquid crystal phase, particularly a high-order smectic liquid crystal phase, as the polymerizable liquid crystal compound, light absorption that also satisfies the above formulas (2) and (3) or formulas (4) and (5) An anisotropic film is easily obtained.

If the light absorption anisotropic film satisfies the formulas (1), (2) and (3), it can be said to have excellent absorption anisotropy, that is, to have excellent polarization performance. Due to this excellent property, it is possible to effectively transmit light from the front direction and to effectively absorb light from oblique directions.

The thickness of the light absorption anisotropic film is preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.1 μm or more, preferably less than 2 μm, more preferably 1.5 μm or less, and even more preferably. is 1 μm or less. When the thickness of the light absorption anisotropic film is at least the above lower limit, the light absorption from the oblique direction is improved, and the polarization characteristics in the oblique direction are likely to be improved. In addition, the orientation of the dichroic dye is hardly disturbed, high transmittance in the front direction can be secured, and thinning can be expected when incorporated into a display device or the like. The thickness of the light-absorbing anisotropic film can be measured by a laser microscope, a film thickness meter, or the like, and the thickness of each layer such as the film substrate constituting the light-absorbing anisotropic plate is measured in the same way.

In the present invention, the light absorption anisotropic film is preferably a cured liquid crystal film with a high degree of orientational order. A cured liquid crystal film with a high degree of orientational order provides a Bragg peak derived from a higher-order structure such as a hexatic phase or a crystal phase in X-ray diffraction measurement. A Bragg peak means a peak derived from a periodic plane structure of molecular orientation. Therefore, the light absorption anisotropic film constituting the light absorption anisotropic plate of the present invention preferably exhibits a Bragg peak in X-ray diffraction measurement. That is, in the light absorption anisotropic film constituting the light absorption anisotropic plate of the present invention, the polymerizable liquid crystal compound or its polymer is oriented so that the film exhibits a Bragg peak in X-ray diffraction measurement. preferably. In the present invention, a light absorption anisotropic film having a plane period interval of molecular orientation of 3.0 to 6.0 Å is preferred. A high degree of orientational order exhibiting a Bragg peak can be realized by controlling the type of polymerizable liquid crystal compound used, the type and amount of dichroic dye, the type and amount of polymerization initiator, and the like.

<Film substrate>
The light absorption anisotropic film is formed by a method such as applying a composition for forming a light absorption anisotropic film containing a polymerizable liquid crystal compound, a reactive group-containing non-liquid crystal compound, and a dichroic dye onto a film substrate. can do.
As the substrate film, conventionally known resin film substrates in the field of optical films can be used. If the material is transferred and not peeled off, it is preferably a transparent resin film substrate. The transparent resin film substrate means a film substrate having translucency that can transmit light, particularly visible light, and translucency means visibility correction transmittance for light rays over a wavelength range of 380 nm to 780 nm. is 80% or more.

Examples of the resin constituting the film substrate include polyolefin resins such as polyethylene and polypropylene; cyclic olefin resins such as norbornene polymers; polyester resins such as polyethylene terephthalate and polyethylene naphthalate; poly(meth)acrylic acid-based resins such as methyl (meth)acrylate; cellulose ester-based resins such as triacetyl cellulose, diacetyl cellulose and cellulose acetate propionate; vinyl alcohol-based resins such as polyvinyl alcohol and polyvinyl acetate; polystyrene resins; polyarylate resins; polysulfone resins; polyethersulfone resins; polyamide resins; polyimide resins; etc. can be mentioned. Among them, at least one selected from the group consisting of polyimide-based resins, cellulose ester-based resins, cyclic olefin-based resins, polyester-based resins and poly(meth)acrylic acid-based resins is preferable from the viewpoint of versatility, heat resistance, and the like. , cellulose ester-based resins and cyclic olefin-based resins are more preferred. These may be used alone or in combination of two or more. Such a resin can be formed into a resin film substrate by known means such as a solvent casting method and a melt extrusion method.

Commercially available products may be used as the film base material or the resin constituting the film base material. Commercially available cellulose ester resin film substrates include Fujitac Film (manufactured by Fuji Photo Film Co., Ltd.); KC8UX2M, KC8UY and KC4UY (manufactured by Konica Minolta Opto Co., Ltd.). Commercially available cyclic olefin resins include Topas (registered trademark) (manufactured by Ticona (Germany)), Arton (registered trademark) (manufactured by JSR Corporation), ZEONOR (registered trademark), ZEONEX (registered trademark) (manufactured by Nippon Zeon Co., Ltd.) and APEL (registered trademark) (manufactured by Mitsui Chemicals, Inc.). Such a cyclic olefin resin can be formed into a film substrate by known means such as a solvent casting method and a melt extrusion method. Examples of commercially available cyclic olefin resin substrates include Escina (registered trademark), SCA40 (registered trademark) (manufactured by Sekisui Chemical Co., Ltd.), Zeonor Film (registered trademark) (manufactured by Optes Co., Ltd.) and Arton Film (registered trademark). trademark) (manufactured by JSR Corporation).

The film substrate may be surface-treated. Examples of surface treatment methods include a method of treating the surface of the film substrate with corona or plasma under an atmosphere of vacuum to atmospheric pressure, a method of laser-treating the surface of the film substrate, and a method of treating the surface of the film substrate with ozone. a method of saponifying the surface of the film base, a method of flame-treating the surface of the film base, a method of applying a coupling agent to the surface of the film base, and a primer treatment of the surface of the film base. and a graft polymerization method in which a reactive monomer or a reactive polymer is adhered to the surface of a film substrate and then irradiated with radiation, plasma or ultraviolet rays for reaction. Among them, a method of subjecting the surface of the film substrate to corona or plasma treatment under an atmosphere of vacuum to atmospheric pressure is preferred.

As a method of surface-treating a film substrate with corona or plasma, the film substrate is placed between opposing electrodes under a pressure near atmospheric pressure, and corona or plasma is generated to surface-treat the film substrate. a method in which a gas is caused to flow between opposing electrodes, the gas is turned into plasma between the electrodes, and the plasmatized gas is sprayed onto the film substrate; A method of surface-treating the material, and the like.

Among them, a method in which a film substrate is placed between opposing electrodes under a pressure near atmospheric pressure and corona or plasma is generated to surface-treat the film substrate, or gas is flowed between the opposing electrodes, A method of plasmatizing gas between electrodes and spraying the plasmatized gas onto the film substrate is preferred. Such corona or plasma surface treatment is usually carried out by commercially available surface treatment equipment.

The film substrate may have a protective film on the surface opposite to the surface on which the composition for forming a light-absorbing anisotropic film is applied. Examples of protective films include films of polyethylene, polyethylene terephthalate, polycarbonate, polyolefin, and the like, and films further having an adhesive layer thereon. Among them, polyethylene terephthalate is preferable because of its small thermal deformation during drying. By having the protective film on the surface opposite to the surface on which the composition for forming a light-absorbing anisotropic film is applied, it is possible to suppress shaking of the film and slight vibration of the coated surface during transportation of the film substrate. , can improve the uniformity of the coating film.

The thickness of the film substrate is preferably thin from the viewpoint of practical handling, but is preferably thick from the viewpoint of strength and workability. In one aspect of the present invention, the thickness of the film substrate is preferably 5 μm to 300 μm, more preferably 20 μm to 200 μm.

<Method for producing a light-absorbing anisotropic plate>
In the present invention, the light absorption anisotropic film is obtained by orienting the absorption axis of the dichroic dye in a direction orthogonal to the film surface. The direction of the absorption axis of the dichroic dye in such a host-guest type light absorption anisotropic film is usually controlled by the orientation direction of the polymerizable liquid crystal compound. Ordinarily, the absorption axis of the dichroic dye can be oriented in the direction orthogonal to the film surface by aligning the molecular long axis of the polymerizable liquid crystal compound in the direction orthogonal to the film surface. The alignment direction of the polymerizable liquid crystal compound depends on the properties of the substrate or the alignment film on which the liquid crystal composition containing the polymerizable liquid crystal compound, the reactive group-containing non-liquid crystal compound, and the dichroic dye is applied, and the polymerizability. It can be controlled by the properties of the liquid crystal compound.

In the present invention, the light absorption anisotropic plate is, for example,
A liquid crystal composition (composition for forming a light absorption anisotropic film) containing a polymerizable liquid crystal compound, a reactive group-containing non-liquid crystal compound and a dichroic dye is applied onto a film substrate with or without an alignment film. a step of forming a coating film;
A step of drying the obtained coating film to obtain a dry coating film, and
It can be produced by a method including a step of curing in a state in which the polymerizable liquid crystal compound and the dichroic dye in the coating film are oriented in the direction perpendicular to the plane of the coating film.

In the present invention, the light absorption anisotropic film may be formed on the alignment film. The alignment film has an alignment regulating force that aligns the polymerizable liquid crystal compound in a desired direction. Anisotropic films are easily obtained. The alignment film has solvent resistance so that it does not dissolve when the composition for forming a light-absorbing anisotropic film is applied, etc., and has heat resistance in heat treatment for removing the solvent and for aligning the polymerizable liquid crystal compound. things are preferred. Examples of such an alignment film include an alignment film containing an alignment polymer, a photo-alignment film, and the like. Alignment films may be used. In one embodiment of the present invention, the film substrate and the light absorption anisotropic film are laminated adjacent to each other.

Examples of methods for applying the composition for forming a light-absorbing anisotropic film onto a film substrate include spin coating, extrusion, gravure coating, die coating, bar coating, and applicator methods. Known methods such as a coating method and a printing method such as a flexographic method can be used.

When the composition for forming a light-absorbing anisotropic film contains a solvent, the solvent is usually removed from the applied composition. Methods for removing the solvent include a natural drying method, a ventilation drying method, a heat drying method, a reduced pressure drying method, and the like. The dried coating film is preferably dried so that the residual solvent in the light-absorbing anisotropic film is 1% by weight or less with respect to the total weight of the light-absorbing anisotropic film. The amount of residual solvent is measured by peeling the anisotropic light absorption film from the film substrate, weighing the obtained anisotropic light absorption film, and immersing the obtained anisotropic light absorption film in a solvent such as tetrahydrofuran that dissolves the anisotropic light absorption film. After irradiating ultrasonic waves for 10 minutes to extract the dissolved components, the solution can be analyzed by gas chromatography for quantification. Conditions such as drying temperature and drying time can be appropriately determined depending on the composition of the composition for forming a light-absorbing anisotropic film, the material of the film substrate, and the like.

The polymerizable liquid crystal compound in the coating film is usually heated to a temperature higher than the temperature at which it transitions to a liquid crystal state or a solution state, and then cooled to a temperature for liquid crystal alignment to align with the dichroic dye and form a liquid crystal phase.

The temperature at which the polymerizable liquid crystal compound in the coating film is oriented may be obtained in advance by observing the texture using a composition containing the polymerizable liquid crystal compound. Alternatively, solvent removal and liquid crystal orientation may be performed at the same time. The temperature at this time is preferably in the range of 50 to 200.degree. C., more preferably in the range of 80 to 130.degree.

By polymerizing and curing the polymerizable liquid crystal compound while maintaining the liquid crystal state of the polymerizable liquid crystal compound, a light absorption anisotropic film is formed as a cured film of the liquid crystal composition. A photopolymerization method is preferable as the polymerization method. In the photopolymerization, the light irradiated to the dry coating film includes types such as polymerizable liquid crystal compounds and reactive group-containing non-liquid crystal compounds contained in the dry coating film (especially polymerizable liquid crystal compounds / reactive group-containing non-liquid crystal It is appropriately selected according to the type of polymerizable group possessed by the compound), the type and amount of the polymerization initiator, and the like. A liquid crystal cured film containing a polymerizable liquid crystal compound polymerized while maintaining the liquid crystal phase of the smectic phase is a conventional host-guest type liquid crystal cured film, that is, a polymerizable liquid crystal compound or the like is added while maintaining the liquid crystal phase of the nematic phase. The polarizing performance is higher than that of a liquid crystal cured film obtained by polymerization, and the polarizing performance and film strength are superior to those coated with only a dichroic dye or a lyotropic liquid crystal.

Examples of light sources for active energy rays include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, halogen lamps, carbon arc lamps, tungsten lamps, gallium lamps, excimer lasers, and a wavelength range of 380. LED light sources, chemical lamps, black light lamps, microwave-excited mercury lamps, metal halide lamps, etc., that emit light of up to 440 nm can be used. Preferably, a light source having a light emission distribution at a wavelength of 400 nm or less, such as a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a chemical lamp, a black light lamp, a microwave-excited mercury lamp, a metal halide lamp, and the like. Ultraviolet rays parallel to the line direction are more preferable.

The irradiation energy of the active energy ray is preferably set so that the irradiation intensity in the wavelength region effective for activation of the polymerization initiator is 10 to 5000 mJ/cm ² , more preferably 100 to 2000 mJ/cm ² . .

The light-absorbing anisotropic plate of the present invention may be in the form of a long film, and can be continuously produced by the Roll to Roll method. As such a manufacturing method,
A long film substrate wound into a roll is unwound, and a polymerizable liquid crystal compound, a reactive group-containing non-liquid crystal compound, and a dichroic compound are applied onto the film substrate with or without an alignment film. a step of forming a coating film of a liquid crystal composition containing a sex dye;
A step of continuously drying the obtained coating film to obtain a dry coating film, and
A method including a step of aligning the polymerizable liquid crystal compound and the dichroic dye in the coating film in a direction perpendicular to the coating film plane and curing by continuous irradiation with active energy rays. .

As a method for unwinding a long film base wound in a roll, an appropriate rotating means is installed on the core on which the film base is wound, and the film base is wound by the rotating means. A method in which the roll is rotated, a method in which an appropriate auxiliary roll is installed in the direction in which the film base is conveyed from the film base roll, and the film base is unwound by rotating means of the auxiliary roll, etc. and it is preferable to unwind the film substrate while applying an appropriate tension to the film substrate.

The size of the elongated film substrate may be appropriately determined, and the longitudinal length of the film substrate is, for example, 10 to 3000 m, preferably 100 to 2000 m. The length of the film substrate in the transverse direction is, for example, 0.1 to 5 m, preferably 0.2 to 2 m.

The film substrate unwound from the film substrate roll is coated with the light-absorbing anisotropic film-forming composition on its surface while passing through a suitable coating device. A gravure coating method, a die coating method, and a flexographic method are preferable as a coating device for continuously coating the composition for forming a light-absorbing anisotropic film.

The film substrate that has passed through the coating device is conveyed to a drying oven and dried in the drying oven, thereby continuously forming a dry coating film of the composition for forming a light-absorbing anisotropic film on the surface of the film substrate. . As the drying furnace, for example, a hot air drying furnace combining a ventilation drying method and a heat drying method is used.

By passing through a drying oven, the solvent is removed from the composition for forming a light-absorbing anisotropic film, and the polymerizable liquid crystal compound contained in the composition is oriented by thermal energy. The drying oven may consist of a plurality of zones with mutually different set temperatures, or may be a series installation of a plurality of drying ovens with mutually different set temperatures.

Next, the coating film is transported to an active energy ray irradiation device while the polymerizable liquid crystal compound in the coating film is oriented. In the active energy ray irradiation apparatus, the polymerizable liquid crystal compound is polymerized in an oriented state by irradiating the active energy ray, and a light absorption anisotropic film is continuously obtained.

A light-absorbing anisotropic plate wound into a roll can be obtained by winding the continuously produced light-absorbing anisotropic plate around the second winding core. In addition, when winding, you may perform co-winding using a suitable spacer.

The light-absorbing anisotropic plate of the present invention has an excellent balance between the appropriate film strength and the alignment order of the polymerizable liquid crystal compound, and exhibits high film strength and flexibility while exhibiting a polarizing function in oblique directions. It can be suitably used as a constituent material for devices, organic electroluminescence (EL) display devices, and the like. Accordingly, the present invention also covers display materials comprising the light-absorbing anisotropic plate of the present invention, and display devices comprising the light-absorbing anisotropic plate of the present invention.

The light-absorbing anisotropic plate of the present invention can be used, for example, as a film for preventing prying eyes or as a material for improving the appearance of displays. In addition, the light-absorbing anisotropic plate of the present invention has excellent polarizing performance and flexibility, and is therefore suitable as a material for flexible displays.

When incorporated into a display device as a display material, specifically, for example, a viscous adhesive is added to the viewing side of a circularly polarizing plate including a polarizing film or a retardation film having a polarizing function having an absorption axis in a direction parallel to the film surface. They can be laminated via an adhesive layer.

The display device includes a device having a display element and including a light-emitting element or a light-emitting device as a light source, such as a liquid crystal display device, an organic electroluminescence (EL) display device, an inorganic electroluminescence (EL) display device, and a touch panel display device. , electron emission display (for example, field emission display (FED), surface field emission display (SED)), electronic paper (display using electronic ink or electrophoretic element, plasma display, projection display (for example, grating light valve (GLV) displays, displays with digital micromirror devices (DMD)) and piezoelectric ceramic displays.

Each material and member constituting the display device, such as a polarizing film and a retardation film having a polarizing function having an absorption axis in a direction parallel to the film surface, is appropriately selected from known materials and members used in the display device and used. be able to.

The present invention will be described in more detail below with reference to examples and comparative examples. "%" and "parts" in Examples and Comparative Examples are "% by mass" and "parts by mass" unless otherwise specified.

1. Example 1
(1) Preparation of Composition for Forming Light-Absorbing Anisotropic Film A composition for forming a light-absorbing anisotropic film was obtained by mixing the following components and stirring at 80° C. for 1 hour. As the dichroic dye, an azo dye described in Examples of JP-A-2013-101328 was used.

・式（Ａ－７）で表される重合性液晶化合物 ２５部

・下記に示す二色性色素（１） １部

・重合開始剤：２－ジメチルアミノ－２－ベンジル－１－（４－モルホリノフェニル）ブタン－１－オン（イルガキュア３６９；チバスペシャルティケミカルズ社製） ６部
・反応性基含有非液晶化合物（１）：ジペンタエリスリトールヘキサアクリレート（６官能） １．５部
・溶剤：o－キシレン ６５０部 · 75 parts of the polymerizable liquid crystal compound represented by the formula (A-6)

· 25 parts of a polymerizable liquid crystal compound represented by the formula (A-7)

・ 1 part of dichroic dye (1) shown below

・Polymerization initiator: 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butan-1-one (Irgacure 369; manufactured by Ciba Specialty Chemicals) 6 parts ・Reactive group-containing non-liquid crystal compound (1) : Dipentaerythritol hexaacrylate (hexafunctional) 1.5 parts Solvent: o-xylene 650 parts

(2) Preparation of light absorption anisotropic film A triacetyl cellulose film (KC4UY-TAC manufactured by Konica Minolta Co., Ltd., thickness 40 μm) was cut into a square as a film substrate, and a corona treatment apparatus (AGF-B10; manufactured by Kasuga Denki Co., Ltd.) was used. ) was used to perform corona treatment once under the conditions of an output of 0.3 kW and a treatment speed of 3 m/min. After applying the light-absorbing anisotropic film-forming composition to the corona-treated surface of the film substrate using a bar coater, the composition was dried in a drying oven set at 100° C. for 1 minute.

Then, using a high-pressure mercury lamp (Unicure VB-15201BY-A, manufactured by Ushio Inc.), ultraviolet light is irradiated (under a nitrogen atmosphere, wavelength: 365 nm, integrated light amount at wavelength 365 nm: 1000 mJ/cm ² ), A light absorption anisotropic plate (1) comprising a film substrate and a light absorption anisotropic film, in which a polymerizable liquid crystal compound and a dichroic dye form a light absorption anisotropic film vertically aligned with respect to the plane of the coating film. got At this time, when the thickness of the light absorption anisotropic film was measured by an ellipsometer, it was 0.4 μm.

(3) Characteristic Evaluation [Evaluation of Film Strength]
An adhesive was laminated on the light absorption anisotropic film side of the obtained light absorption anisotropic plate (1), and a triacetyl cellulose film was laminated to the adhesive layer. The interface between the anisotropic light absorption film and the pressure-sensitive adhesive layer was used as a starting point for the laminate comprising the film substrate, the anisotropic light absorption film, the adhesive layer, and the triacetyl cellulose film obtained by the lamination. After that, the light-absorbing anisotropic plate (1) was peeled off at a peeling speed of 100 mm/min. Table 2 shows the results.
<Evaluation Criteria>
A: The light absorption anisotropic plate was peeled off at the interface with the adhesive (no material breakage)
B: Less than 1/3 of the peeled surface of the light-absorbing anisotropic plate was damaged C: More than 1/3 of the peeled surface of the light-absorbing anisotropic plate was damaged D: The entire surface of the light-absorbing anisotropic plate was torn down by

[Flexibility evaluation]
Flexibility of the obtained light-absorbing anisotropic plate (1) was evaluated using the general test method for paints-flexibility (cylindrical mandrel method) described in JIS-K-5600-5-1. , went as follows.
A light-absorbing anisotropic plate (1) was cut into a 25 mm x 200 mm square, and a cylindrical mandrel bending resistance tester type II (manufactured by TP Giken Co., Ltd.) was used to test the material at a temperature of 25 ° C. and a relative humidity of 55% RH. Under the conditions, a bending test was performed by winding the film around a mandrel rod having a diameter of 6 mm (bending radius R=3 mm) with the light-absorbing anisotropic film facing outward. After bending 10,000 times, after bending 50,000 times, and after bending 100,000 times, the light-absorbing anisotropic plate was visually confirmed under a darkroom environment with transmitted light. Table 2 shows the results.
<Evaluation Criteria>
A: No change before and after the test B: Peeling confirmed after flexing 100,000 times C: Peeling confirmed after flexing 50,000 times D: Peeling confirmed after flexing 10,000 times E: Destruction of base material confirmed after bending 1 time

[Front/oblique angle absorbance ratio]
The light absorption anisotropic plate (1) was measured for absorbance as follows.
Using a spectrophotometer (UV-3150 manufactured by Shimadzu Corporation) with a folder with a prism polarizer set, the double-beam method is used to perform three-dimensional analysis at wavelengths exhibiting maximum absorption in the wavelength range of 380 to 680 nm in steps of 2 nm. Absorbance was measured. The three-dimensional absorbance here means that an arbitrary direction in the film plane of the light absorption anisotropic film is the x-axis, the direction orthogonal to the x-axis in the film plane is the y-axis, and the film thickness direction is the z-axis. is the absorbance (Ax, Ay, Az) in each direction for linearly polarized light. Specifically, the measurement was performed by rotating the sample with respect to the linearly polarized light that is the measurement light.
Also, the absorbance in the z-direction is difficult to measure because light is incident from the side of the sample by definition. Therefore, the absorbance in the Az direction was estimated by tilting the xy plane of the sample by 60° with respect to the plane of vibration of the linearly polarized light that is the measurement light.
Specifically, with the sample rotated 30° and 60° so as to include the y-axis, Ax (z = 60) was measured by entering the same linearly polarized light as when Ax was measured, and similarly 2, Ay (z=60) was measured by irradiating the same linearly polarized light as that used for measuring Ay with the sample rotated by 60° so as to include the x-axis.
When there is no absorption anisotropy in the xy plane, that is, when Ax and Ay are equal, Ax (z = 60) = Ay (z = 60), so Ax (z = 60) and Ay (z=60) was defined as A (z=60). The value of Ax (z=60)/Ax was taken as the front/oblique angle absorbance ratio.

2. Examples 2-5
A light absorption anisotropic plate (2) was prepared in the same manner as in Example 1, except that the amount of the reactive group-containing non-liquid crystal compound in the composition for forming a light absorption anisotropic film was changed to the amount shown in Table 1. (5) were produced and the characteristics were evaluated in the same manner as in Example 1. Table 2 shows the results.

3. Example 6
Light absorption anisotropy in the same manner as in Example 2, except that the following dichroic dye (2) was used instead of the dichroic dye (1) in the composition for forming a light absorption anisotropic film. A plate (6) was produced and the characteristics were evaluated in the same manner as in Example 1. Table 2 shows the results.

4. Example 7
Light absorption anisotropy in the same manner as in Example 2, except that the following dichroic dye (3) was used instead of the dichroic dye (1) in the composition for forming a light absorption anisotropic film. A plate (7) was produced and the characteristics were evaluated in the same manner as in Example 1. Table 2 shows the results.

5. Example 8
In the same manner as in Example 2, except that 1 part by mass of each of the dichroic dyes (1), (2) and (3) was added as the dichroic dyes in the composition for forming a light absorption anisotropic film. A light-absorbing anisotropic plate (8) was produced, and the characteristics were evaluated in the same manner as in Example 1. Table 2 shows the results.

6. Examples 9-17
Example 2 except that the reactive group-containing non-liquid crystal compound (1) in the composition for forming a light absorption anisotropic film was changed to the reactive group-containing non-liquid crystal compounds (2) to (10) shown in Table 1. Light absorption anisotropic plates (9) to (17) were produced in the same manner as in Example 1, and the characteristics were evaluated in the same manner as in Example 1. Table 2 shows the results.
As the reactive group-containing non-liquid crystal compounds (2) to (10) shown in Table 1, the following compounds were used.

- Reactive group-containing non-liquid crystal compound (2): tricyclodecanedimethanol diacrylate (bifunctional)
- Reactive group-containing non-liquid crystal compound (3): ditrimethylolpropane tetraacrylate (tetrafunctional)
- Reactive group-containing non-liquid crystal compound (4): ethoxylated dipentaerythritol polyacrylate (hexafunctional)
- Reactive group-containing non-liquid crystal compound (5): tripentaerythritol octaacrylate (octafunctional)
- Reactive group-containing non-liquid crystal compound (6): trimethylolpropane trimethacrylate (trifunctional)
- Reactive group-containing non-liquid crystal compound (7): pentaerythritol tetrakis (3-mercaptopropionate) (tetrafunctional)
- Reactive group-containing non-liquid crystal compound (8): dipentaerythritol hexakis (3-mercaptopropionate) (hexafunctional)
- Reactive group-containing non-liquid crystal compound (9): 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (bifunctional)
- Reactive group-containing non-liquid crystal compound (10): 2-isocyanatoethyl acrylate (bifunctional)

7. Example 18
In the composition for forming a light absorption anisotropic film, 0.3 parts by mass of a polyacrylate compound (BYK-361N; manufactured by BYK-Chemie) is blended as a leveling agent, and the amount of the dichroic dye (1) is A light-absorbing anisotropic plate (18) was produced in the same manner as in Example 2, except that the amount of the solvent was changed to 250 parts by mass, and the characteristics were evaluated in the same manner as in Example 1. rice field. Table 2 shows the results.

8. Example 19
Light absorption anisotropy was determined in the same manner as in Example 2, except that a film obtained by forming a 40 μm thick cycloolefin polymer film with a 3 μm thick hard coat layer (a layer composed of an acrylic resin) was used as the film substrate. A plate (19) was produced and the characteristics were evaluated in the same manner as in Example 1. Table 2 shows the results.

9. Comparative example 1
In the same manner as in Example 18, except that a glass plate (thickness 0.7 mm) was used instead of the film substrate, and the reactive group-containing non-liquid crystal compound was not added to the composition for forming a light absorption anisotropic film. A light-absorbing anisotropic plate (20) was produced, and the characteristics were evaluated in the same manner as in Example 1. Table 2 shows the results.

10. Comparative example 2
A light absorption anisotropic plate (21) was prepared in the same manner as in Example 1, except that the reactive group-containing non-liquid crystal compound was not added to the composition for forming a light absorption anisotropic film. Characterization was performed in the same manner. Table 2 shows the results.

11. Comparative example 3
A light-absorbing anisotropic plate (22) was prepared in the same manner as in Example 19, except that the reactive group-containing non-liquid crystal compound was not added to the composition for forming a light-absorbing anisotropic film. Characterization was performed in the same manner. Table 2 shows the results.

Claims (12)

A light absorption anisotropic plate comprising a film substrate and a light absorption anisotropic film,
The light absorption anisotropic film is a cured film of a liquid crystal composition containing a polymerizable liquid crystal compound, a reactive group-containing non-liquid crystal compound and a dichroic dye, and the polymerizable liquid crystal compound and the dichroic dye are the A cured film cured in a state of being oriented in a direction perpendicular to the light absorption anisotropic film plane,
When an arbitrary direction in the plane of the light absorption anisotropic film is the x-axis, a direction perpendicular to the x-axis in the film plane is the y-axis, and a film thickness direction perpendicular to the x-axis and the y-axis is the z-axis, The light absorbance of the film satisfies the following formulas (4) and (5),
The polymerizable liquid crystal compound is a liquid crystal compound exhibiting a smectic liquid crystal phase,
The reactive group-containing non-liquid crystal compound contains a polyfunctional (meth)acrylate having 5 or 6 reactive groups in the molecule,
A light absorption anisotropic plate, wherein the content of the reactive group-containing non-liquid crystal compound is 0.5 parts by mass or more and 8 parts by mass or less per 100 parts by mass of the polymerizable liquid crystal compound.
Ax(z=60)/Ax>10 (4)
Ay (z=60)/Ay>10 (5)
[In formulas (4) and (5), Ax, Ay, Ax (z = 60) and Ay (z = 60) are all absorption maximum wavelengths of the dichroic dye in the light absorption anisotropic film is the absorbance at
Ax represents the absorbance of linearly polarized light oscillating in the x-axis direction,
Ay represents the absorbance of linearly polarized light oscillating in the y-axis direction,
Ax (z = 60) represents the absorbance of linearly polarized light vibrating in the x-axis direction when the film is rotated 60° around the y-axis,
Ay (z=60) represents the absorbance of linearly polarized light vibrating in the y-axis direction when the film is rotated 60° around the x-axis. ] 2. The light absorption anisotropic plate according to claim 1, wherein the reactive group-containing non-liquid crystal compound has at least one reactive group selected from an acryloyloxy group and a methacryloyloxy group. 3. The light absorption anisotropic plate according to claim 1, wherein the reactive group possessed by the reactive group-containing non-liquid crystal compound and the polymerizable group possessed by the polymerizable liquid crystal compound are the same. 4. The light absorption anisotropic plate according to claim 1, wherein the dichroic dye is an azo dye. 5. The light absorption anisotropic plate according to claim 1, wherein the light absorption anisotropic film has a thickness of less than 2 μm. 6. The light absorption anisotropic plate according to claim 1, wherein the light absorption anisotropic film exhibits a Bragg peak in X-ray diffraction measurement. The film substrate is a resin film composed of at least one selected from the group consisting of polyimide-based resins, cellulose ester-based resins, cyclic olefin-based resins, polyester-based resins, and poly(meth)acrylic acid-based resins. The light absorption anisotropic plate according to any one of claims 1 to 6. 8. The light absorption anisotropic plate according to claim 1, wherein the film base and the light absorption anisotropic film are adjacent to each other. A method for producing a light-absorbing anisotropic plate including a film substrate and a light-absorbing anisotropic film,
forming a coating film of a liquid crystal composition containing a polymerizable liquid crystal compound, a reactive group-containing non-liquid crystal compound and a dichroic dye on a film substrate;
A step of drying the obtained coating film to obtain a dry coating film, and
A step of curing the polymerizable liquid crystal compound and the dichroic dye in the coating film in a state of being oriented in a direction perpendicular to the plane of the coating film,
The polymerizable liquid crystal compound is a liquid crystal compound exhibiting a smectic liquid crystal phase,
The reactive group-containing non-liquid crystal compound contains a polyfunctional (meth)acrylate having 5 or 6 reactive groups in the molecule,
The content of the reactive group-containing non-liquid crystal compound is 0.5 parts by mass or more and 8 parts by mass or less with respect to 100 parts by mass of the polymerizable liquid crystal compound ,
When an arbitrary direction in the plane of the light absorption anisotropic film is the x-axis, a direction perpendicular to the x-axis in the film plane is the y-axis, and a film thickness direction perpendicular to the x-axis and the y-axis is the z-axis, A manufacturing method, wherein the light absorbance of the film satisfies the following formulas (4) and (5) .
Ax(z=60)/Ax>10 (4)
Ay (z=60)/Ay>10 (5)
[In formulas (4) and (5), Ax, Ay, Ax (z = 60) and Ay (z = 60) are all absorption maximum wavelengths of the dichroic dye in the light absorption anisotropic film is the absorbance at
Ax represents the absorbance of linearly polarized light oscillating in the x-axis direction,
Ay represents the absorbance of linearly polarized light oscillating in the y-axis direction,
Ax (z = 60) represents the absorbance of linearly polarized light vibrating in the x-axis direction when the film is rotated 60° around the y-axis,
Ay (z=60) represents the absorbance of linearly polarized light vibrating in the y-axis direction when the film is rotated 60° around the x-axis. ] The light absorption anisotropic plate is elongated,
A long film substrate wound into a roll is unwound, and a coating film of a liquid crystal composition containing a polymerizable liquid crystal compound, a reactive group-containing non-liquid crystal compound and a dichroic dye is formed on the film substrate. forming a
A step of continuously drying the obtained coating film to obtain a dry coating film, and
Claim 9, comprising a step of aligning the polymerizable liquid crystal compound and the dichroic dye in the dry coating film in a direction perpendicular to the plane of the coating film, and curing by continuously irradiating active energy rays. The manufacturing method described in . A display material comprising the light-absorbing anisotropic plate according to any one of claims 1 to 8. A display device comprising the light-absorbing anisotropic plate according to any one of claims 1 to 8.