TW202113030A - Luminescent compound or salt thereof, and polarizing luminescent element, polarizing luminescent plate, and display comprising the same - Google Patents

Abstract

Provided is a luminescent compound or salt thereof represented by the following formula (1).

Description

Luminescent compound or its salt, and polarized light emitting element, polarized light emitting plate and display device containing the compound

The present invention relates to a novel luminescent compound or a salt thereof, and a polarizing light emitting element, a polarizing light emitting panel, and a display device (display) containing the compound.

A polarizing plate with light penetration and/or shielding functions is used as a basic component of a display device such as a liquid crystal display (LCD) together with a liquid crystal with a light switch function. The application field of this LCD has expanded from small machines such as computers and watches to notebook computers, word processors, liquid crystal projectors, liquid crystal TVs, car navigation and indoor and outdoor measuring machines. In addition, it can also be applied to lenses with polarizing function, such as sunglasses to improve visibility, or polarized glasses corresponding to 3D TVs in recent years. As mentioned above, polarizers are used in a wide range of applications, and their use environments have also expanded to range from low temperature to high temperature, low humidity to high humidity, low light intensity to high light intensity, etc. Therefore, polarizing plates with high polarization performance and high durability are required.

Generally speaking, the polarizing film constituting the polarizing plate is made by stretching and aligning a film of polyvinyl alcohol or its derivatives containing iodine or dichroic dye, or by dehydrochloric acid of polyvinyl chloride film or by polyvinyl alcohol The dehydration of the membrane produces polyenes and aligns them to manufacture. Since the polarizing plate composed of such a conventional polarizing film contains a dichroic pigment that absorbs in the visible light region, the transmittance is reduced. For example, the transmittance of a commercially available general polarizer is 35 to 45%.

In contrast to the problem of the conventional polarizing plate in which the transmittance in the visible light region is reduced, as a technique that maintains a certain degree of transmittance in the visible light region and imparts a polarizing function, Patent Document 1 describes the technique of a polarizing plate for ultraviolet rays. However, this technique uses a yellow pigment that absorbs in the visible light region, so the transmittance is insufficient, and a deep yellow coloration is confirmed.

If a polarizing plate with a low transmittance in the visible light region is used in a display, etc., the overall transmittance of the display will be reduced. Therefore, a method of obtaining polarized light without using the conventional polarizing plate is studied. As such a method, Patent Documents 2 to 4 describe a polarized light emitting element.

However, the polarized light-emitting devices described in Patent Documents 2 to 4 contain special metals, such as rare and expensive metals such as lanthanides or europium, which are expensive and difficult to manufacture, which is not conducive to mass production. In addition, among these polarized light-emitting elements, since the polarized light emission is weak, it is difficult to use in a display, and it is impossible to obtain linearly polarized light emission. Therefore, it is required to develop novel polarized light-emitting panels that exhibit polarized light emission, high transparency in the visible light region, and can be used in liquid crystal displays that require durability under severe environments, and materials for forming the polarized light-emitting panels.

[Prior Technical Literature]

[Patent Literature]

Patent Document 1: WO2005/015275

Patent Document 2: Japanese Patent Application Laid-Open No. 2008-224854

Patent Document 3: JP 2013-121921 A

Patent Document 4: WO2011/111607

The purpose of this case is to provide a novel luminescent compound, and a polarized light-emitting element, a polarized light-emitting panel and a display device containing the compound.

In order to achieve this objective, the inventors devoted themselves to research and found that a polarized light emitting element and a polarized light emitting plate containing a compound or its salt with a specific structure have a high dichroic ratio in the ultraviolet region and show high penetration in the visible region. Transmittance, and shows excellent durability in harsh environments. In addition, the compound or its salt having such a specific structure exhibits the effect of emitting polarized light in the visible light region by irradiating light from the ultraviolet region to the near-ultraviolet visible light region, for example, light of 300 to 430 nm, thereby completing the present invention.

That is, the present invention is related to the following, but is not limited to this.

[Invention 1]

A light-emitting compound or a salt thereof, wherein the light-emitting compound is represented by the following formula (1).

(In formula (1), (i) X and Y each independently include at least a group selected from the group consisting of a group represented by the above formula (2), a heterocyclic group containing a nitrogen atom or a sulfur atom, and a nitro group, However, it is excluded that both X and Y are nitro groups; or (ii) at least one of X and Y (when both are independent) is a nitro group, an amine group that may have a substituent, and C1 that may have a substituent Up to 4 alkyl groups, C1 to 4 alkoxy groups which may have substituents, aromatic groups which may have substituents, heterocyclic groups which may have substituents containing oxygen atoms, nitrogen atoms or sulfur atoms, or the formula ( 2) The group shown, wherein, when X or Y is not the group selected above, the X or Y is selected from any substituents,

M each independently represents a hydrogen atom, a metal ion, or an ammonium ion, each m independently represents an integer from 0 to 2, and s is 0 or 1,

In the formula (2), ※ represents the bonding position of X and/or Y in the formula (1), and Z is composed of a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a stilbene group which may have a substituent , Selected from the group consisting of a benzyl group which may have a substituent and a heterocyclic group which may have a substituent, and t represents an integer of 0 or 1).

[Invention 2]

The luminescent compound or its salt according to Invention 1, wherein X and Y in the above formula (1), and the above formula (2) when at least one of X and Y is represented by the above formula (2) At least one of Z is selected from the group consisting of substituents represented by the following formulas (3) to (7).

(In the above formulas (3) and (4), A is each independently composed of a hydrogen atom, a halogen group, a nitro group, a hydroxyl group, a C1 to 4 alkyl group, a C1 to 4 alkoxy group, and a C1 having a sulfonic acid group Alkyl group to 4, C1 to 4 alkyl group having a hydroxyl group, C1 to 4 alkyl group having a carboxyl group, C1 to 4 alkoxy group having a sulfonic acid group, C1 to 4 alkoxy group having a hydroxyl group, Choose from the group consisting of C1 to 4 alkoxy groups having a carboxyl group, q ¹ represents an integer from 0 to 4, M in the above formulas (3) to (7) is as defined in the above formula (1), n ¹ And n ² each independently represent an integer from 0 to 3, and * in the above formulas (3) to (7) respectively represent the bonding position of X or Y in the above formula (1), or the Z of the above formula (2) Bond position).

[Invention 3]

The luminescent compound or its salt according to Invention 1 or 2, wherein X and Y in the above formula (1) are each independently selected from the group consisting of substituents represented by formulas (2) to (7) When selecting formula (2), Z is selected from the group consisting of the substituents shown in formulas (3) to (7).

[Invention 4]

The luminescent compound or its salt according to Invention 1 or 2, wherein X and Y in the above formula (1) are selected from the group of substituents represented by formulas (2) to (7), and In formula (2), Z is selected from the group consisting of substituents shown in formulas (3) to (7).

[Invention 5]

The luminescent compound or the salt thereof according to any one of Inventions 1 to 4, wherein each m in the above formula (1) is 0.

[Invention 6]

The luminescent compound or the salt thereof according to any one of Inventions 1 to 5, wherein s is zero.

[Invention 7]

The luminescent compound or salt thereof according to any one of Inventions 1 to 5, wherein s is 1.

[Invention 8]

The luminescent compound or salt thereof according to Invention 7, wherein the above formula (1) is represented by the following formula (1').

(In the above formula (1'), X and Y are as defined in the above formula (1)).

[Invention 9]

A polarized light-emitting element, which has a polarized light-emitting function, and contains the light-emitting compound according to any one of Inventions 1 to 8 or a salt thereof.

[Invention 10]

The polarized light emitting element according to Invention 9, which further contains one or more organic dyes or fluorescent dyes other than the above-mentioned luminescent compound or a salt thereof.

[Invention 11]

The polarized light emitting device according to Invention 9 or 10, which further contains a substrate.

[Invention 12]

The polarized light emitting element according to Invention 11, wherein the substrate is a film containing a polyvinyl alcohol resin or a derivative thereof.

[Invention 13]

A polarized light-emitting plate is provided with a transparent protective film on at least one side of the polarized light-emitting element according to any one of Inventions 9 to 12.

[Invention 14]

A display device is provided with the polarized light emitting element according to any one of Inventions 9 to 12 or the polarized light emitting plate according to Invention 13.

The luminescent compound or its salt with a specific structure of the present invention absorbs light from ultraviolet light to visible light region, such as light from ultraviolet light region to near ultraviolet visible light region, specifically light from 300 to 430 nm, and uses its energy in visible light The area shows the effect of polarized light. In addition, the polarizing element and the polarizing plate produced by using the luminescent compound or its salt are novel polarizing light-emitting elements and polarizing light-emitting plates that exhibit polarized light emission. In one aspect, the luminescent compound or salt thereof of the present invention, and the polarized light emitting element and polarized light emitting plate containing the compound exhibit high polarization at the absorption wavelength. Therefore, by using the compound represented by the formula (1) or its salt, even if rare and expensive lanthanide metal etc. are not used, it can have a high degree of polarization in the absorption wavelength, and can provide a display of polarized light emission. Novel polarized light-emitting elements and polarized light-emitting panels. In one aspect, the polarized light-emitting element and the polarized light-emitting plate of the present invention exhibit high transmittance in the visible light region. In one aspect, the polarized light emitting element and the polarized light emitting plate of the present invention exhibit excellent durability against heat, humidity, and the like. Therefore, the polarized light-emitting element and polarized light-emitting plate can be applied to display devices such as liquid crystal displays that require high penetration in the visible light region and high durability under severe environments.

In this specification and the scope of the patent application, the "substituent" conveniently includes a hydrogen atom. "May have a substituent" means that it does not have a substituent. For example, "phenyl which may have substituents" includes unsubstituted simple phenyl groups and substituted phenyl groups.

[Luminescent Compound]

The luminescent compound of the present invention or its salt is represented by the above formula (1). In this specification, the "luminescent compound or its salt" may be simply referred to as the "luminescent compound".

In the formula (1), (i) X and Y each independently include at least a group selected from the group consisting of the group represented by the above formula (2), a heterocyclic group containing a nitrogen atom or a sulfur atom, and a nitro group, However, it is excluded that both X and Y are nitro groups; or (ii) at least one of X and Y (when both are independent) is a nitro group, an amine group that may have a substituent, and C1 that may have a substituent Alkyl groups up to 4 (1 to 4 carbon atoms), C1 to 4 alkoxy groups that may have substituents, aromatic groups that may have substituents, oxygen atoms, nitrogen atoms, or sulfur atoms that may have substituents The heterocyclic group or the group represented by formula (2), wherein X or Y is not the above-selected group, the X or Y is selected from any substituents,

M each independently represents a hydrogen atom, a metal ion, or an ammonium ion, each independently represents an integer from 0 to 2, and s is 0 or 1.

In the formula (2), ※ represents the bonding position of X and/or Y in the formula (1), and Z is composed of a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a stilbene group which may have a substituent , Selected from the group consisting of a benzyl group which may have a substituent and a heterocyclic group which may have a substituent, and t represents an integer of 0 or 1.

In the definition of X and Y, the above-mentioned "amino group which may have a substituent" includes, for example, an amino group; methylamino group, ethylamino group, n-butylamino group, anilino group, naphthylamino group, acetylamino group (also That is, monosubstituted amino groups such as acetylamino groups; di-substituted amino groups such as dimethylamino groups, diethylamino groups, di-n-butylamino groups, diphenylamino groups, ethylmethylamino groups, and ethylanilino groups. In addition, the above-mentioned formula (2) described later is also included in the amine group which may have a substituent.

In the definition of X and Y, the "C1-4 alkyl group" of the above-mentioned "C1-4 alkyl group which may have substituents" includes, for example, methyl, ethyl, n-propyl, isopropyl, and n-butyl. , Second butyl, tertiary butyl, cyclobutyl, etc.

In the definition of X and Y, the "C1 to 4 alkoxy group" of the above "C1 to 4 alkoxy group which may have substituents" can be exemplified by methoxy, ethoxy, n-propoxy, isopropyl Oxy, n-butoxy, second butoxy, tertiary butoxy, cyclobutoxy, etc.

In the definitions of X and Y, the "aromatic group" of the "aromatic group which may have a substituent" includes, for example, a phenyl group, a naphthyl group, and an onion group.

The "heterocyclic group containing a nitrogen atom or a sulfur atom" in the definitions of X and Y means a heterocyclic ring having at least one of a nitrogen atom and a sulfur atom as a ring constituent. The above-mentioned "substitutable oxygen-containing atom, nitrogen The "heterocyclic group containing an oxygen atom, a nitrogen atom, or a sulfur atom" of the "heterocyclic group of an atom or a sulfur atom" means a heterocyclic ring having at least one of an oxygen atom, a nitrogen atom, and a sulfur atom as a ring constituent. These are not only monocyclic heterocycles, but also include polycyclic heterocycles in which the monocyclic heterocycle further contains aromatic rings such as a benzene ring or a naphthalene ring. The "heterocyclic group containing oxygen atom, nitrogen atom or sulfur atom" includes, for example, pyrrolyl, benzopyrrolyl, thienyl, benzothienyl, thiazolyl, benzothiazolyl, naphththiazolyl, triazole Group, benzotriazolyl, naphthotriazolyl, thiadiazolyl, benzothiadiazolyl, pyridyl, etc.

The above-mentioned "amino group which may have substituents", "C1 to 4 alkyl groups which may have substituents", "C1 to 4 alkoxy groups which may have substituents", and "aromatic groups which may have substituents" The substituent in the "oxygen atom, nitrogen atom or sulfur atom-containing heterocyclic group which may have a substituent" is not particularly limited, and examples thereof include a hydroxyl group, a cyano group, a phosphoric acid group, a sulfonic acid group, a carboxyl group, and an amino group. The "amino group which may have a substituent" may further have a substituent as exemplified here.

M in the above formula (1) each independently represents a hydrogen atom, a metal ion, or an ammonium ion. Examples of metal ions include alkali metal ions such as lithium ion, sodium ion, and potassium ion, and alkaline earth metal ions such as calcium ion and magnesium ion. Ammonium ions include, for example, narrowly defined ammonium ions (NH ₄ ⁺ ), methyl ammonium ions, dimethyl ammonium ions, triethyl ammonium ions, tetraethyl ammonium ions, tetra-n-propyl ammonium ions, and tetra-n-butyl ammonium ions. Ion, monoethanolammonium ion, diethanolammonium ion, triethanolammonium ion, monoisopropoxide ammonium ion, diisopropoxide ammonium ion, triisopropoxide ammonium ion, triethanolammonium ion, etc. More specifically, for example, when M is a hydrogen atom, it represents sulfonic acid (-SO ₃ H), when M is a sodium ion, it represents sodium sulfonate (-SO ₃ Na), and when M is an ammonium ion, it represents ammonium sulfonate (-SO ₃ NH ₄ ). Preferred ones of these include lithium ion, ammonium ion, and sodium ion.

In the above formula (2), ※ represents the bonding position of X and/or Y in the formula (1), and Z is composed of a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a stilbene which may have a substituent A group, a benzyl group which may have a substituent, and a heterocyclic group which may have a substituent are selected from the group. t represents an integer of 0 or 1.

The above-mentioned "heterocyclic group which may have a substituent" in the definition of Z is, for example, the same as the "heterocyclic group which may have a substituent containing an oxygen atom, a nitrogen atom or a sulfur atom" in the definition of X and Y in the above formula (1). "The same may be the same, and furthermore, furanyl, benzofuranyl, etc. containing an oxygen atom as a ring component may be used.

In the definition of Z, the preferable substituents of the above-mentioned "phenyl which may have substituents" include, for example, C1 to 4 alkoxy groups, nitro groups, sulfonic acid groups, and those represented by formulas (3) to (7) Substituents, preferred substituents of the above-mentioned "substitutable naphthyl group" in the definition of Z include, for example, a hydroxyl group, a sulfonic acid group, a nitro group, a C1 to 4 alkoxy group having a sulfonic acid group, and Z The preferable substituents of the above-mentioned "stilbene group which may have substituents" in the definition include, for example, sulfonic acid groups, nitro groups, amine groups which may have substituents, and the substitutions shown in formulas (3) to (7) In the definition of Z, the preferable substituent of the above-mentioned "benzyl group which may have a substituent" includes, for example, a sulfonic acid group and a nitro group. In the definition of Z, the above-mentioned "heterocyclic ring which may have a substituent" The preferred substituents of the "group" include, for example, a sulfonic acid group, a halogen group, a hydroxyl group, a C1 to 4 alkyl group, a C1 to 4 alkoxy group, a C1 to 4 alkyl group having a sulfonic acid group, and a hydroxyl group. C1 to 4 alkyl groups, C1 to 4 alkyl groups having carboxyl groups, C1 to 4 alkoxy groups having sulfonic acid groups, C1 to 4 alkoxy groups having hydroxy groups, C1 to 4 alkoxy groups having carboxyl groups Base and so on.

The above-mentioned "halo" in the definition of Z includes, for example, a fluoro group, a chloro group, a bromo group, and an iodo group.

The above-mentioned "C1 to 4 alkyl group" in the definition of Z includes, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, tertiary butyl, cyclobutyl and the like.

The above-mentioned "C1 to 4 alkoxy group" in the definition of Z includes, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, second butoxy, tertiary butoxy Oxy, cyclobutoxy, etc.

In the definition of Z, the above-mentioned "C1-4 alkyl with sulfonic acid group", "C1-4 alkyl with hydroxyl group" and "C1-4 alkyl with carboxyl group" can be exemplified in the above-mentioned "C1 Any position of the "alkyl up to 4" has a sulfonic acid group, a hydroxyl group, or a carboxyl group as a substituent.

In the definition of Z, the above-mentioned "C1 to 4 alkoxy group having a sulfonic acid group", "C1 to 4 alkoxy group having a hydroxyl group" and "C1 to 4 alkoxy group having a carboxyl group" can be exemplified in Those having a sulfonic acid group, a hydroxyl group, or a carboxyl group as a substituent at any position of the aforementioned "C1 to 4 alkoxy group".

Preferably, at least one of X and Y in the above formula (1) and Z in the above formula (2) when at least one of X and Y is represented by the above formula (2) is derived from the above formula ( 3) Choose from the group consisting of the substituents shown in (7).

In the above formula (3) and formula (4), A is each independently composed of a hydrogen atom, a halogen group, a nitro group, a hydroxyl group, a C1 to 4 alkyl group, a C1 to 4 alkoxy group, and a C1 having a sulfonic acid group Alkyl group to 4, C1 to 4 alkyl group having a hydroxyl group, C1 to 4 alkyl group having a carboxyl group, C1 to 4 alkoxy group having a sulfonic acid group, C1 to 4 alkoxy group having a hydroxyl group, And selected from the group consisting of C1 to 4 alkoxy groups having a carboxyl group, q ¹ represents an integer of 0 to 4, and M in the above formulas (3) to (7) is as defined in the above formula (1), n ¹ and n ² each independently represent an integer from 0 to 3, and * in the above formulas (3) to (7) respectively represents the bonding position of X or Y in the above formula (1), or Z in the above formula (2) The position of the bond.

The above-mentioned "C1 to 4 alkyl group" in the definition of A includes, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, tertiary butyl, cyclobutyl and the like.

In the definition of A, the above-mentioned "C1 to 4 alkyl group with sulfonic acid group" includes, for example, sulfomethyl, sulfoethyl, sulfo-n-propyl, sulfo-n-butyl, and sulfo-second-butyl Wait.

Examples of the "halo" in the definition of A include fluoro, chloro, bromo, and iodo.

The above-mentioned "C1 to 4 alkoxy group" in the definition of A includes, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, second butoxy, tertiary butoxy Oxy, cyclobutoxy, etc.

In the definition of A, the above-mentioned "C1 to 4 alkyl group having a hydroxyl group" includes, for example, hydroxymethyl, hydroxyethyl, hydroxyn-propyl, hydroxyisopropyl, hydroxyn-butyl, hydroxy-second-butyl, and hydroxy Tertiary butyl, hydroxycyclobutyl, etc.

In the definition of A, the above-mentioned "C1 to 4 alkyl group having a carboxyl group" includes, for example, carboxymethyl, carboxyethyl, carboxy n-propyl, carboxy isopropyl, carboxy n-butyl, carboxy second butyl, carboxyl Tertiary butyl, carboxycyclobutyl, etc.

In the definition of A, the above-mentioned "C1 to 4 alkoxy group having a sulfonic acid group" includes, for example, sulfonic acid methoxy group, sulfonic acid group ethoxy group, sulfonic acid group n-propoxy group, and sulfonic acid group isopropyl group. Oxy group, sulfonic acid group n-butoxy group, sulfonic acid group second butoxy group, sulfonic acid group tertiary butoxy group, sulfonic acid group cyclobutoxy group and the like.

The above-mentioned "C1 to 4 alkoxy group with hydroxyl group" in the definition of A includes, for example, hydroxymethoxy, hydroxyethoxy, hydroxyn-propoxy, hydroxyisopropoxy, hydroxyn-butoxy, and hydroxy The second butoxy group, hydroxy-tertiary butoxy group, hydroxycyclobutoxy group and the like.

In the definition of A, the above-mentioned "C1 to 4 alkoxy group having a carboxyl group" includes, for example, carboxymethoxy, carboxyethoxy, carboxy n-propoxy, carboxy isopropoxy, carboxy n-butoxy, carboxyl The second butoxy group, the carboxyl third butoxy group, the carboxycyclobutoxy group and the like.

Preferably, at least one of X and Y in the above formula (1) is selected from the group of substituents shown in formulas (2) to (7). When formula (2) is selected, Z is determined by the formula Choose from the group consisting of the substituents shown in (3) to (7). More preferably, X and Y in the above formula (1) are each independently from formula (2) to (7) When selecting formula (2), Z is selected from the group of substituents shown in formulas (3) to (7). More preferably, X and Y in the above formula (1) are all selected from the group of substituents shown in formulas (2) to (7). When formula (2) is selected, Z is determined by formula (3). ) To (7) selected from the group formed by the substituents.

In one aspect of the present invention, each m is 0.

In one aspect of the present invention, s is zero.

In one aspect of the present invention, s is 1. In this aspect, the above formula (1) is preferably represented by the above formula (1'). In the formula (1'), X and Y are as defined in the above formula (1), respectively.

Next, the method for synthesizing the compound represented by formula (1) in which s is 0 will be explained.

For example, the compound represented by formula (9) and the compound represented by formula (10) are heated in water, and sodium hydroxide is added and dissolved. 1 equivalent of terephthalic acid chloride represented by formula (8), which is commercially available, is added and reacted, thereby obtaining the target product.

In the above formulas (8) to (10), each of X, Y, M, and m is as defined in the above formula (1).

Next, specific examples of the light-emitting compound represented by the above formula (1) or a salt thereof in which s is 0 are given below. In addition, the sulfonic acid group in the formula is expressed in the form of free acid.

Next, the method for synthesizing the compound represented by formula (1) in which s is 1 will be explained.

For example, each 1 equivalent of the compound represented by the following formula (8-A) and the compound represented by the formula (8-B) is heated in water, sodium hydroxide is added and dissolved. 1 equivalent of terephthalic acid chloride represented by formula (8), which is commercially available, is added and reacted, thereby obtaining the target product.

In formulas (8), (8-A) and (8-B), X, Y, M, and m are as defined in formula (1), respectively.

Next, specific examples of the light-emitting compound represented by the above formula (1) or a salt thereof in which s is 1 are given below. In addition, the sulfonic acid group in the formula is expressed in the form of free acid.

The compound represented by the above formula (1) or its salt can be used as a compound capable of polarizing light. Combine one or more kinds of organic dyes or fluorescent dyes other than the compound represented by the formula (1) or its salt, and optionally the aforementioned luminescent compound or its salt, and are contained in a substrate by a known method, such as polyvinyl alcohol or Its derivatives and other polymer films are aligned, thereby making it possible to manufacture polarized light-emitting devices. The polarized light-emitting element obtained is attached with a transparent protective film and used as a polarized light-emitting plate. The polarized light-emitting plate is further provided with a hard coat (protective layer) or AR (anti-reflection) layer and support, etc., as needed, and is applied to liquid crystal projection Computers, computers, clocks, notebooks, word processors, LCD TVs, car navigation, security displays, anti-counterfeiting, and indoor and outdoor measuring instruments or displays, lenses, glasses, etc. In addition, in this specification, the organic dyes or fluorescent dyes other than the light-emitting compound or its salt of the present invention may be simply referred to as "other organic dyes".

[Polarized light emitting element]

The present invention also includes a polarized light emitting device containing the luminescent compound represented by the above formula (1) or a salt thereof.

The polarized light-emitting element preferably contains the light-emitting compound represented by the above formula (1) or its salt, and a substrate for adsorbing and aligning the polarizing compound or its salt. The polarized light emitting element may contain one or more kinds of the luminescent compound represented by the above formula (1) or its salt.

The substrate is preferably a film obtained by forming a film of a hydrophilic polymer capable of adsorbing the luminescent compound represented by the above formula (1) or a salt thereof. The hydrophilic polymer is not particularly limited, and examples thereof include polyvinyl alcohol-based resins, amylose-based resins, starch-based resins, cellulose-based resins, and polyacrylate-based resins. Among such resins, polyvinyl alcohol-based resins or derivatives thereof are preferred from the viewpoints of the adsorptivity, processability, and alignment properties of the light-emitting compound represented by the above formula (1) or its salt. As the polyvinyl alcohol-based resin derivative, any one generally known in the technical field can be used. Although not particularly limited, examples include unsaturated carboxylic acids such as crotonic acid, acrylic acid, methacrylic acid, and maleic acid, vinyl sulfonic acid, propylene sulfonic acid, methacrylic acid, p-styrene sulfonic acid, and 2-propylene Unsaturated sulfonic acid such as amide-2-methylpropane sulfonic acid, (meth)acryloxyethyl sulfonic acid, or modified polyvinyl alcohol resin by copolymerizing olefins such as ethylene or propylene with vinyl alcohol Wait. The shape of the substrate is not particularly limited, and the substrate can be produced in any shape such as a film, a sheet, a flat plate, a curved plate, and a hemispherical shape. In addition, the thickness of the substrate is usually 10 to 100 μm, preferably 20 to 80 μm.

The content of the luminescent compound represented by formula (1) in the polarized light-emitting element is not particularly limited, and the content can be set according to any transmittance, and the blending amount (content) can be set arbitrarily according to the required transmittance of the polarized light-emitting element . The polarization performance of the polarized light-emitting device is not only changed by the blending ratio of the luminescent compound represented by formula (1) contained in the polarized light-emitting device, but also due to the swelling degree, elongation ratio, and dyeing time of the substrate that adsorbs the luminescent compound. , Dyeing temperature, pH during dyeing, the influence of salt and other factors change. Therefore, the blending ratio of the luminescent compound represented by formula (1) contained in the polarized light-emitting element can be determined according to the swelling degree of the substrate, the dyeing temperature, the dyeing time, the pH at the time of dyeing, the type of salt, the salt concentration, the extension ratio, etc. . The above-mentioned blending ratio can be adjusted appropriately.

The above-mentioned polarized light emitting element may further contain one or more other organic dyes as needed within a range that does not hinder the polarization performance or for the purpose of color adjustment. Other organic dyes used in combination are not particularly limited, but they are preferably dyes with high dichroism, and are preferably in the absorption band region of the luminescent compound represented by formula (1), such as polarized light from the ultraviolet region to the near-ultraviolet visible region. Dyes with less performance impact. Other organic dyes used in combination include, for example, CI Direct Yellow 12, CI Direct Yellow 28, CI Direct Yellow 44, CI Direct Orange 26, CI Direct Orange 39, CI Direct Orange 71, CI Direct Orange 107, CI Direct Red 2, CI Direct Red 31, CI Direct Red 79, CI Direct Red 81, CI Direct Red 247, CI Direct Blue 69, CI Direct Blue 78, CI Direct Green 80, and CI Direct Green 59. These other organic dyes may be in the form of free acid, alkali metal salt (such as Na salt, K salt, and Li salt), ammonium salt, or amine salt.

When the above-mentioned other organic dyes are used in combination as needed, the types of other organic dyes to be blended separately can be selected for the purpose of color adjustment of the polarized light-emitting element for manufacturing purposes. In addition, the content is not particularly limited. Generally, when the mass of the luminescent compound represented by the above formula (1) is 1, the total mass of other organic dyes used in combination is preferably in the range of 0.01-10.

<Manufacturing Method of Polarized Light Emitting Device>

Next, the manufacturing method of the polarized light emitting device of the present invention will be described. The manufacturing method is not limited to the following manufacturing methods. For example, it may include the following steps: a step of preparing a substrate; a swelling step of immersing the substrate in a swelling liquid and extending the substrate by swelling; impregnating the swollen substrate In a dyeing solution containing at least one luminescent compound represented by formula (1) above, and the dyeing step of making the substrate adsorb the luminescent compound represented by formula (1); the luminescent compound represented by formula (1) will be adsorbed The substrate is immersed in a solution containing a crosslinking agent such as boric acid to crosslink the luminescent compound represented by formula (1) in the substrate; the luminescent compound represented by formula (1) is crosslinked The material is uniaxially stretched in a fixed direction, and the luminescent compound represented by formula (1) is arranged in a fixed direction; the washing step of washing the stretched substrate with a washing liquid; and making the washed substrate The drying step of drying.

(Prepare the base material)

Prepare a substrate for containing the luminescent compound represented by the above formula (1). As the substrate, for example, a commercially available film containing a polyvinyl alcohol-based resin or a derivative thereof can be used, and the substrate can be produced by forming a polyvinyl alcohol-based resin into a film. The film forming method of polyvinyl alcohol resin is not particularly limited. For example, a method of melt-extruding water-containing polyvinyl alcohol, a casting film method, a wet film method, and a gel film method (polyvinyl alcohol After the aqueous solution is temporarily cooled and gelled, the solvent is extracted and removed), the casting film forming method (the polyvinyl alcohol aqueous solution is flowed on the substrate and dried), and the method of combining these known film forming methods. The degree of polymerization of polyvinyl alcohol can be from 1,000 to 10,000, and the degree of polymerization is preferably from 1,500 to 6,000, more preferably from 2,000 to 6,000.

(Swelling step)

Next, swelling treatment is performed on the above-mentioned base material. The swelling treatment is preferably performed by impregnating the substrate with a swelling liquid at 20 to 50° C. for 30 seconds to 10 minutes, and the swelling liquid is preferably water. The stretching ratio of the swelling liquid and the substrate is preferably adjusted to 1.00 to 1.50 times, more preferably to 1.10 to 1.35 times.

(Dyeing step)

Then, the substrate obtained by the swelling treatment as described above is adsorbed and impregnated with at least one type of luminescent compound represented by formula (1) or its salt. The dyeing step is not particularly limited as long as it is a method of adsorbing and impregnating the substrate with the luminescent compound represented by formula (1) or its salt. For example, it is preferable to immerse the substrate in the substrate containing the luminescent compound represented by formula (1) or The dyeing solution of the salt can also be adsorbed by coating the dyeing solution on the substrate. In the dyeing solution, the concentration of the luminescent compound represented by formula (1) or its salt is not particularly limited as long as it can sufficiently adsorb the luminescent compound represented by formula (1) or its salt in the substrate. For example, the concentration of the luminescent compound represented by formula (1) or its salt is not particularly limited. It is preferably 0.0001 to 3% by mass, more preferably 0.001 to 1% by mass.

The temperature of the dyeing solution in the dyeing step is preferably 5 to 80°C, more preferably 20 to 50°C, particularly preferably 40 to 50°C. In addition, the time for the substrate to be immersed in the dyeing solution can be adjusted appropriately, preferably between 30 seconds and 20 minutes, and more preferably between 1 and 10 minutes.

As the compound contained in the above-mentioned dyeing solution, the luminescent compound represented by the above-mentioned formula (1) may be used alone or in combination of two or more kinds. In this way, the light-emitting compound represented by the above formula (1) will have different luminous colors due to structural differences, so by making the substrate contain two or more types of the light-emitting compound represented by the above formula (1) or a salt thereof, or the above formula (1) The luminescent compound or its salt, and one or more other luminescent compounds, so that the luminescent color produced can be appropriately adjusted to the desired color. In addition, the dyeing solution may further contain one or more of the above-mentioned other organic dyes as needed. In the description of the production of a polarizing light-emitting element and a polarizing light-emitting plate in this specification, the luminescent compound represented by formula (1) and other organic dyes may be collectively referred to as "polarizing dye".

The said dyeing solution system may further contain a dyeing auxiliary agent as needed in addition to the said polarizing dye. Examples of the dyeing auxiliary agent include sodium carbonate, sodium bicarbonate, sodium chloride, sodium sulfate (glauber's salt), anhydrous sodium sulfate, and sodium tripolyphosphate, and sodium sulfate is preferred. The content of the dyeing auxiliary agent can be arbitrarily adjusted according to the dyeability of the polarizing pigment used, by the above-mentioned immersion time and the temperature of the dyeing solution, but it is preferably 0.1 to 10% by mass in the dyeing solution, more preferably 0.1 to 2% by mass %.

After the dyeing step, in order to remove the dyeing solution adhering to the surface of the substrate in the dyeing step, a preliminary washing step can be optionally performed. By performing the preliminary washing step, it is possible to prevent the luminescent compound represented by formula (1) or its salt remaining on the surface of the substrate from being transferred to the treatment solution in the following step. In the preliminary washing step, the washing liquid generally uses water. The cleaning method is preferably to immerse the dyed substrate in the cleaning solution. On the other hand, it can also be cleaned by applying the cleaning solution to the substrate. The washing time is not particularly limited, but is preferably 1 to 300 seconds, more preferably 1 to 60 seconds. In the preliminary cleaning step, the temperature of the cleaning solution needs to be a temperature that does not dissolve the material constituting the substrate, and the cleaning treatment is generally performed at 5 to 40°C. Moreover, even if there is no preliminary cleaning step, the performance of the polarized light emitting device will not be greatly affected, so the preliminary cleaning step can be omitted.

(Crosslinking step)

After the dyeing step or the preliminary washing step, a crosslinking agent may be included in the substrate. The method of containing a crosslinking agent in the substrate is preferably to immerse the substrate in a treatment solution containing the crosslinking agent. On the other hand, the treatment solution may be applied or applied to the substrate. The crosslinking agent in the treatment solution is preferably a solution containing boric acid. The solvent in the treatment solution is not particularly limited, but water is preferred. The concentration of the crosslinking agent such as boric acid in the treatment solution is preferably 0.1 to 15% by mass, more preferably 0.1 to 10% by mass. The temperature of the treatment solution is preferably 30 to 80°C, more preferably 40 to 75°C. In addition, the processing time of the cross-linking step is preferably 30 seconds to 10 minutes, more preferably 1 to 6 minutes. Preparation of the polarized light emitting element of the present invention The manufacturing method has this cross-linking step, whereby the obtained polarized light-emitting element can emit light with high brightness and high degree of polarization. This is an excellent effect that is completely unpredictable due to the function of boric acid used for the purpose of improving moisture resistance or light penetration in the prior art. In the crosslinking step, if necessary, an aqueous solution containing a cationic polymer compound may be further used for fixing treatment together. The polarizing pigment can be immobilized by fixing treatment. In this case, the cationic polymer compound can use, for example, cation-releasing compounds, dicyanide compounds, polyamine compounds, polycationic compounds, dimethyldiallylammonium chloride/dioxide ion copolymers, and Allylamine salt polymer, dimethyldiallylammonium chloride polymer, allylamine salt polymer, dialkylaminoethyl acrylate quaternary salt polymer. Examples of the dicyanide compound include a dicyandiamide/formalin polycondensate. Examples of the polyamine compound include dicyandiamine/diethylenetriamine polycondensate. Examples of the polycationic compound include an epichlorohydrin/dimethylamine addition polymer.

(Extension step)

The extension step may be performed after or at the same time as the crosslinking step. The stretching step is performed by uniaxially stretching the substrate in a fixed direction. The extension method may be either a wet extension method or a dry extension method. The stretching ratio is preferably 3 times or more, more preferably 5 to 9 times.

In the dry stretching method, when the stretching heating medium is an air medium, it is preferable to perform the stretching of the substrate at a temperature of the air medium from room temperature to 180°C. In addition, the humidity is preferably in an environment of 20 to 95% RH. The heating method of the base material may include, for example, an inter-roll zone extension method, a roll heating extension method, a hot press extension method, and an infrared heating extension method, but it is not limited to these extension methods. The dry extension step can be implemented with one-stage extension, or with two-stage or more multi-stage extension.

In the wet stretching method, it is preferable to stretch the substrate in water, a water-soluble organic solvent, or a mixed solution thereof. It is more preferable to immerse the substrate in a solution containing at least one crosslinking agent while immersing Extend while processing. As the cross-linking agent, for example, the boric acid in the above-mentioned cross-linking agent step can be used, and it is preferable to perform an extension treatment in the treatment solution used in the cross-linking step. The extension temperature is preferably 40 to 70°C, more preferably 45 to 60°C. The extension time is usually 30 seconds to 20 minutes, preferably 2 to 7 minutes. The wet stretching step can be implemented with one-stage stretching, or with more than two stages of multi-stage stretching. In addition, the extension treatment may be optionally performed before the dyeing step. In this case, the alignment of the luminescent compound represented by formula (1) or its salt may be performed together at the time of dyeing.

(Washing step)

After the stretching step is performed, the precipitation of the crosslinking agent or the adhesion of foreign matter will occur on the surface of the substrate, so a cleaning step of cleaning the surface of the substrate can be performed. The washing time is preferably 1 second to 5 minutes. The cleaning method is preferably to immerse the substrate in a cleaning solution, but on the other hand, it may be cleaned by coating or coating the substrate with the cleaning solution. The washing liquid is preferably water. The washing treatment can be carried out in one stage, or in multiple stages with more than two stages. The temperature of the cleaning solution in the cleaning step is not particularly limited, and is usually 5 to 50°C, preferably 10 to 40°C, and may also be room temperature.

In addition to the above-mentioned water, the solvent of the solution or treatment liquid used in each of the above-mentioned steps may also include, for example, alcohols, amines, and the like. Alcohols include, for example, dimethyl sulfoxide, N-methylpyrrolidone, methanol, ethanol, propanol, isopropanol, glycerin, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethyl Glycol, and trimethylolpropane, etc. Examples of amines include ethylenediamine and diethylenetriamine. The solvent of the solution or treatment liquid is not limited to these, but water is most preferable. In addition, the solvents of these solutions or treatment liquids may be used singly, or a mixture of two or more kinds may be used.

(Drying step)

After the washing step, it is preferable to perform a drying step of the substrate. Drying treatment can be carried out by natural drying, but in order to improve drying efficiency, it can be removed by roller compression, air knife or suction roller, etc. Surface moisture, etc., and air drying is also possible. The temperature of the drying treatment is preferably 20 to 100°C, more preferably 60 to 100°C. The drying time is preferably 30 seconds to 20 minutes, more preferably 5 to 10 minutes.

Taking the above description as an example, the polarized light emitting device of the present invention can be manufactured. In addition, the light-emitting compound represented by formula (1) in the present invention can be aligned by a method of mixing with liquid crystal and aligning on a substrate, or by a method of sharing and coating on a substrate, by This can produce polarized light-emitting elements with various colors or neutral gray.

[Polarized light-emitting board]

The present invention also includes a polarized light-emitting panel provided with the above-mentioned polarized light-emitting element.

The polarized light-emitting plate of the present invention preferably has a transparent protective film on at least one surface of the above-mentioned polarized light-emitting element. The transparent protective film is used to improve the water resistance or handling properties of the polarized light emitting element. Therefore, such a transparent protective film is preferably one that does not have any influence on the polarization effect displayed by the polarized light emitting device of the present invention.

The above-mentioned transparent protective film is preferably a transparent protective film excellent in optical transparency and mechanical strength. In addition, the transparent protective film is preferably a film with a layer shape that can maintain the shape of the polarized light emitting element. In addition to transparency and mechanical strength, it is preferably a plastic film that is excellent in thermal stability and moisture shielding properties. The material for forming such a transparent protective film can include, for example, cellulose acetate film, acrylic film, fluorine film such as tetrafluoroethylene/hexafluoropropylene copolymer, or polyester resin, polyolefin resin or polyamide For the film or the like composed of a resin, it is preferable to use a triacetate cellulose (TAC) film or a cycloolefin-based film. The thickness of the transparent protective film is preferably in the range of 1 to 200 μm, more preferably in the range of 10 to 150 μm, particularly preferably in the range of 40 to 100 μm. Manufacturing method of polarized light emitting plate of the present invention It is not particularly limited, and for example, a polarizing light emitting plate can be produced by overlaying a transparent protective film on a polarizing light emitting element and laminating it with a known recipe.

The above-mentioned polarized light emitting plate may further include an adhesive layer for bonding the transparent protective film to the polarized light emitting element between the transparent protective film and the polarized light emitting element. The adhesive constituting the adhesive layer is not particularly limited, and examples thereof include: polyvinyl alcohol-based adhesives, urethane emulsion-based adhesives, acrylic-based adhesives, polyester isocyanate-based adhesives, etc., preferably polyvinyl alcohol-based adhesives, urethane emulsion-based adhesives, and polyester isocyanate-based adhesives Vinyl alcohol adhesive. After bonding the transparent protective film and the polarized light-emitting element with the adhesive, they are dried or heat-treated at an appropriate temperature to produce a polarized light-emitting plate.

In addition, the above-mentioned polarizing light-emitting plate may appropriately include various known functional layers such as an anti-reflection layer, an anti-glare layer, and a reinforced transparent protective film on the exposed surface of the transparent protective film. When making layers with such various functions, it is preferable to coat the exposed surface of the transparent protective film with materials with various functions. On the other hand, the layer or film with such functions can be interposed with an adhesive or The adhesive is attached to the exposed surface of the transparent protective film.

Examples of the reinforced transparent protective film include hard coats such as acrylic, urethane, and polysiloxane. In addition, in order to further increase the monomer transmittance, an anti-reflection layer can be provided on the exposed surface of the transparent protective film. The anti-reflective layer can be formed, for example, by evaporating or sputtering a substance such as silicon dioxide and titanium oxide on the transparent protective film, or thinly coating a fluorine-based substance on the transparent protective film.

The above-mentioned polarized light-emitting plate may be further provided with transparent supports such as glass, crystal, sapphire, etc., if necessary. In order to bond the polarizing light-emitting plate, the support body preferably has a flat surface, and from the viewpoint of optical use, a transparent support body is preferable. Transparent supports are divided into inorganic supports and organic supports. For example, supports made of inorganic materials include: soda glass, borosilicate Supports made of acid glass, crystal, sapphire, spinel and other materials. Examples of organic supports include acrylic, polycarbonate, polyethylene terephthalate, polyethylene naphthalate, Support composed of cyclic olefin polymer, etc. The thickness and size of the transparent support are not particularly limited, and can be appropriately determined. In addition, in a polarized light emitting panel with such a transparent support, in order to further increase the transmittance of the monomer, it is preferable to provide an anti-reflection layer on one or both surfaces of the support surface or the polarized light emitting panel. In order to bond the polarized light-emitting plate to the flat part of the support, a transparent adhesive (adhesive) can be coated on the flat part of the support, and then the polarized light-emitting plate of the present invention can be pasted on the coated surface. The adhesive or adhesive used is not particularly limited, and commercially available products can be used, and acrylic adhesives or adhesives are preferred.

In addition, the above-mentioned polarized light emitting plate can be used as a circularly polarized light emitting plate or an elliptical polarized light emitting plate to which a phase difference plate is pasted. At this time, when a support or the like is further provided on the polarized light emitting plate, the support may be a phase difference plate. The retardation plate generally includes, for example, a retardation value of 1/4λ or a retardation value of 1/2λ with respect to the absorption wavelength or emission wavelength of light, but it is not limited to this. By having a retardation value of 1/4λ, it functions as a circularly polarized plate or a circularly polarized light-emitting plate with respect to the wavelength, and can be used for conversion of polarized light in the direction of 90° by using 1/2λ. As mentioned above, the polarized light-emitting panel can be further provided with various functional layers, supports, etc., so that the polarized light-emitting panel can be used for liquid crystal projectors, computers, clocks, notebook computers, word processors, LCD TVs, car navigation and indoors. Outdoor measuring instruments or monitors and other lenses, or glasses and other products.

The polarized light-emitting element and polarized light-emitting panel of the present invention can display high polarization in the light from ultraviolet light region to near ultraviolet visible light region, for example, in the region of 300 to 430 nm, and exhibit polarized light emission and high transmittance in the visible light region. In addition, the polarized light-emitting element and polarized light-emitting plate of the present invention show excellent durability against heat, humidity, light, etc., so even in severe conditions It can maintain its performance under the environment, and has high durability compared with the previous iodine-based polarizers. Therefore, the polarized light-emitting element and polarized light-emitting panel of the present invention can be applied to liquid crystal displays that require high transparency in the visible light region and high durability in harsh environments, such as TVs, portable terminals, tablet terminals, smart phones, and automotive applications. Various display devices such as monitors, digital signage used outdoors or indoors, and smart windows.

[Display device]

The present invention also includes a display device (display) provided with the above-mentioned polarized light-emitting element or polarized light-emitting plate.

The above-mentioned display device can display polarized light emission by irradiating light from the ultraviolet region to the visible light region, for example, the light from the ultraviolet region to the near-ultraviolet visible light region, specifically 300 to 430 nm. display. The display device of the present invention has a high transmittance in the visible light region, so there is no reduction in the transmittance in the visible light region of the conventional polarizing plate. Even if there is a decrease in the transmittance, compared to the transmittance of the conventional polarizing plate, it is The reduction in penetration is significantly reduced. For example, iodine-based polarizers that belong to the conventional polarizers, or dye-based polarizers that use other dyes, should make the degree of polarization almost 100%, and the visibility in the visible light region should be corrected to about 35 to 45%. The reason is that the conventional polarizing plate has both a vertical axis and a horizontal axis as the absorption axis of light. However, in order to obtain a degree of polarization of almost 100%, it is necessary to absorb the incident light on either the vertical axis or the horizontal axis. Light is absorbed in one axis and polarized by penetrating light in the other axis. At this time, the light of one axis is absorbed but not penetrated, so the transmittance will inevitably become less than 50%. In addition, in the past, a polarizing plate was prepared by aligning dichroic dyes in a stretched film, but the dichroic dyes are not necessarily 100% aligned, and they also have a slight absorption component with respect to the transmission axis of light. Therefore, if the transmittance is not reduced to about 45% or less by the reflection of the material surface, the polarization degree of almost 100% cannot be achieved, that is, if the transmittance is not reduced, High degree of polarization cannot be achieved. In this regard, the polarized light emitting element and polarized light emitting plate of the present invention have an axis that absorbs light from the ultraviolet region to the near ultraviolet visible light region, for example, an axis that absorbs light at 300 to 430 nm (its polarization function), that is, for the ultraviolet region to near ultraviolet visible light Regional light, for example, 300 to 430 nm has the effect of absorbing light and exhibiting polarized light emission in the visible light region. On the other hand, it hardly absorbs light in the visible light region, so the transmittance of the visible light region is very high. In addition, the visible light region exhibits a polarized light emission effect, so compared to the use of the conventional polarizing plate, the light loss is less, that is, the reduction in the transmittance of the conventional polarizing plate is extremely small. Therefore, a display device using the polarized light-emitting element and polarized light-emitting plate of the present invention, such as a liquid crystal display, can obtain high brightness compared to a liquid crystal display equipped with a conventional polarizing plate. In addition, the display device using the polarized light emitting element and the polarized light emitting plate of the present invention has high transparency, so although it is a liquid crystal display, it can be an almost transparent display. In addition, when displaying characters and images, it is designed to allow polarized light to pass through. Therefore, although it is a transparent liquid crystal display, a display that can be displayed is available, that is, a display that can display characters and the like on a transparent display is available. Therefore, the display device of the present invention can obtain a transparent liquid crystal display without light loss, especially a see-through display.

In addition, the above-mentioned display device can be polarized with respect to light in the ultraviolet region to the near ultraviolet visible region, which is invisible or difficult to see by the human eye, for example, with respect to the light of 300 to 430 nm, so it can be applied to display by ultraviolet light. LCD Monitor. For example, the images displayed in the ultraviolet region to the near ultraviolet and visible light region can be confirmed by a computer, etc., by which a simple and safe liquid crystal display can be produced, which only irradiates light from the ultraviolet region to the near ultraviolet and visible light region, such as 300 to It can be seen at 430nm light.

In addition, the above-mentioned display device irradiates light from the ultraviolet region to the near-ultraviolet visible light region, such as light from 300 to 430 nm, thereby displaying the polarized light emission effect, which can be manufactured and utilized. The light-emitting liquid crystal display is not a general liquid crystal display that uses visible light. It can realize a liquid crystal display that uses light from the ultraviolet region to the near-ultraviolet visible light region. That is, a light-emitting liquid crystal display can be produced, which can display text, images, etc. to be displayed in a dark space without visible light, as long as it can irradiate light from the ultraviolet region to the near-ultraviolet visible light region.

In addition, the bands of light in the visible light region and the ultraviolet light region are different, so a display with two different displays can be made at the same time, which is the liquid crystal display part in the visible light region that can be displayed by light in the visible light region, and by The liquid crystal display part of the light displayed by polarized luminescence caused by ultraviolet light. So far, there are displays that can perform two different displays, but there is no display that can perform different displays with the same liquid crystal panel using different light sources in the ultraviolet light region and the visible light region. From this point of view, the display device of the present invention can produce novel displays by using the above-mentioned polarized light-emitting element or polarized light-emitting plate.

The present invention also includes a liquid crystal display equipped with the above-mentioned polarized light-emitting element, polarized light-emitting panel or display device. The liquid crystal cell used in the liquid crystal display is not limited to, for example, TN liquid crystal cell, STN liquid crystal cell, VA liquid crystal cell, IPS liquid crystal cell, etc., and can be used in various liquid crystal display modes. The liquid crystal display has high durability, so it can provide liquid crystal display for car or outdoor display.

The present invention also includes a neutral gray polarized light-emitting panel for vehicle or outdoor display equipped with the above-mentioned polarized light-emitting element, polarized light-emitting panel or display device. The neutral gray polarized light-emitting panel for vehicle or outdoor display has excellent polarized light-emitting performance, and it will not cause discoloration or degradation of polarization performance even in the high temperature and high humidity conditions in the vehicle or outdoor. In addition, neutral gray means that in the transmittance of the polarized light emitting plate at the orthogonal position of the visible light region, the transmittance of each wavelength is significantly reduced, or has a solid Those who set the penetration rate. Specifically, the orthogonal transmittance is 0.3% or less, more preferably 0.1% or less, still more preferably 0.03% or less, particularly preferably 0.01% or less. The fixed transmittance means the average transmittance with respect to each wavelength Its penetration rate difference is within 1%.

[Example]

Hereinafter, the present invention will be described in further detail with examples, but the present invention is not limited to these exemplified ones. In addition, the "%" and "parts" described below are quality standards unless otherwise specified. In addition, in each structural formula of the compound used in each example and comparative example, acidic functional groups such as sulfonic acid groups are described in the form of free acids.

[Example 1]

(Synthesis example)

84 parts of the compound represented by formula (25) was added to 600 parts of water and heated to 60° C., while adjusting the pH to 6 to 7, 25% sodium hydroxide was added to dissolve the aforementioned compound. Add 20.2 parts of terephthalate chloride in small portions for about 1 hour. After all the addition, it was stirred at 60°C for 1 hour and reacted. After the reaction, the mixture was allowed to cool to room temperature and filtered, and the obtained solid was dried at 70°C, thereby obtaining 67.4 parts of the compound represented by formula (15).

(Production of polarized light-emitting elements and polarized light-emitting panels)

A 75 μm-thick polyvinyl alcohol film (VF-PS#7500 manufactured by Kuraray) was immersed in water at 40°C for 3 minutes to swell the film. The film obtained by swelling was immersed in a 45°C aqueous solution containing 0.2 parts by mass of the compound represented by formula (15) obtained in Synthesis Example 1, 1.0 part by mass of Glauber's salt, and 1000 parts by mass of water for 4 minutes, so that the compound represented by formula (15) contained In the film. The film containing the compound represented by the formula (15) was stretched 5 times in 5 minutes in a 3% concentration boric acid aqueous solution at 50°C. The stretched film was washed with water at room temperature for 20 seconds under tension and dried at 70°C to obtain a polarized light emitting device. On both sides of the obtained polarized light emitting element, a 60μm thick cellulose triacetate film (ZRD-60 manufactured by FUJIFILM), which was surface saponified with 1.5N sodium hydroxide, was used with 4% by mass polyvinyl alcohol (JAPAN). The NH-26 (manufactured by VAN & POVAL) aqueous solution was laminated as an adhesive to obtain a polarizing light-emitting plate, which was used as a measurement sample of Example 1.

In addition, even if a cellulose triacetate film (ZRD-60 manufactured by FUJIFILM) that does not contain an ultraviolet absorber is attached to the polarized light-emitting element, it will not have any influence on the optical characteristics of the polarized light-emitting element. In the following examples and comparative examples, a cellulose triacetate film that does not contain an ultraviolet absorber is also attached to the polarized light emitting element, and similarly, it will not have any influence on the optical properties.

[Example 2]

60 parts of the compound represented by formula (26) was added to 600 parts of water and heated to 60° C., while adjusting the pH to 6 to 7, 25% sodium hydroxide was added to dissolve the aforementioned compound. Add 20 parts of terephthalate chloride in small portions for about 1 hour. After all the addition, it was stirred at 60°C for 1 hour and reacted. After the completion of the reaction, it was allowed to cool to room temperature and filtered, and the obtained solid was dried at 70°C, thereby obtaining 51.5 parts of the compound represented by formula (14). In the production of the polarized light-emitting element and the polarized light-emitting plate of Example 1, the measurement sample of Example 2 was obtained in the same manner except that the compound represented by formula (14) was used instead of the compound represented by formula (15).

[Example 3]

21.8 parts of the compound represented by formula (27) and 10.8 parts of the compound represented by formula (28) were added to 400 parts of water, and while adjusting the pH to 6 to 7, 25% sodium hydroxide was added to dissolve the aforementioned compound, and benzene chloroformate was added. 15.6 parts of the ester was stirred at 50 to 70°C for 6 hours and ureidolated. It was salted out with sodium chloride, filtered, and dried at 70°C to obtain 24.6 parts of the ureido compound represented by the formula (29). 24.6 parts of the compound represented by the obtained formula (29) was added to 500 parts of water and heated to 60° C., while adjusting the pH to 6 to 7, 25% sodium hydroxide was added to dissolve the aforementioned compound. 7.0 parts of terephthalic acid chloride was added in small portions for about 1 hour. After all the addition, it was stirred at 60°C for 1 hour and reacted. After the reaction, the mixture was cooled to room temperature and filtered, and the obtained solid was dried at 70° C., thereby obtaining 5.7 parts of a mixture of the compound represented by formula (16) and the compound represented by formula (30). In the production of the polarized light-emitting element and polarized light-emitting plate of Example 1, except that a mixture of the compound represented by formula (16) and the compound represented by formula (30) was used to replace the compound represented by formula (15), they were obtained in the same manner The measurement sample of Example 3.

[Example 4]

21.8 parts of the compound represented by formula (28) was added to 400 parts of water, and sodium hydroxide was added to dissolve it, and 20.2 parts of terephthalic acid chloride was added in small portions for about 1 hour. After all the addition, it was stirred at 60°C for 1 hour and reacted. After the reaction is over, add 80.0 parts of 4-nitro-4'-aminostilbene-2,2'-disulfonic acid, and dissolve it while adding sodium hydroxide. Add 31.2 parts of phenyl chloroformate in a small amount for about 1 hour. Join in installments. After all the addition, it was stirred at 60°C for 1 hour and reacted. After the reaction, the mixture was cooled to room temperature and filtered, and the obtained solid was dried at 70° C., thereby obtaining 12.4 parts of a mixture of the compound represented by formula (18) and the compound represented by formula (31). In the production of the polarized light-emitting element and polarized light-emitting plate of Example 1, except that a mixture of the compound represented by formula (18) and the compound represented by formula (31) was used to replace the compound represented by formula (15), they were obtained in the same manner The measurement sample of Example 4.

[Example 5]

Add 40.0 parts of 4-nitro-4'-aminostilbene-2,2'-disulfonic acid and 10.8 parts of the compound represented by formula (28) into 400 parts of water, and dissolve it while adding sodium hydroxide. 20.2 parts of terephthalic acid chloride was added in small portions for about 1 hour. After all the addition, it was stirred at 60°C for 1 hour and reacted. After the reaction, 40.0 parts of 4-nitro-4'-aminostilbene-2,2'-disulfonic acid were added, and sodium hydroxide was added to dissolve them, and 15.6 parts of phenyl chloroformate was added in a small amount for about 1 hour. Join in installments. After all the addition, it was stirred at 60°C for 1 hour and reacted. After the completion of the reaction, it was allowed to cool to room temperature and filtered, and the solid obtained was dried at 70°C, thereby obtaining the compound represented by formula (22) and the compound represented by formula (32). 8.9 parts of a mixture of compounds. In the production of the polarized light-emitting element and polarized light-emitting plate of Example 1, except that a mixture of the compound represented by formula (22) and the compound represented by formula (32) was used to replace the compound represented by formula (15), they were obtained in the same manner The measurement sample of Example 5.

[Example s1]

120.4 parts of the compound represented by the formula (s28) was added to 500 parts of water and heated to 60° C., while adjusting the pH to 6 to 7, 25% sodium hydroxide was added to dissolve the aforementioned compound. Add 20.2 parts of terephthalate chloride in small portions for about 1 hour. After all the addition, it was stirred at 60°C for 1 hour and reacted. After the completion of the reaction, it was allowed to cool to room temperature and filtered, and the obtained solid was dried at 70°C, thereby obtaining 93.4 parts of the compound represented by formula (s29). In the production of the polarized light-emitting element and the polarized light-emitting plate of Example 1, the measurement sample of Example s1 was obtained in the same manner except that the compound represented by formula (s29) was used instead of the compound represented by formula (15).

[Example s2]

114 parts of the compound represented by formula (s30) was added to 500 parts of water and heated to 60° C., while adjusting the pH to 6 to 7, 25% sodium hydroxide was added to dissolve the aforementioned compound. Will be right 20.2 parts of phthalic acid chloride was added in small portions for about 1 hour. After all the addition, it was stirred at 60°C for 1 hour and reacted. After completion of the reaction, it was allowed to cool to room temperature and filtered, and the obtained solid was dried at 70°C, thereby obtaining 103 parts of the compound represented by formula (s14). In the production of the polarized light-emitting element and polarized light-emitting plate of Example 1, the measurement sample of Example s2 was obtained in the same manner except that the compound represented by formula (s14) was used instead of the compound represented by formula (15).

[Example s3]

Add 40 parts of 4-nitro-4'-aminostilbene-2,2'-disulfonic acid and 60.2 parts of the compound represented by formula (s28) into 500 parts of water and heat to 60°C, while changing the pH to 6 to 7 Adjust the method while adding 25% sodium hydroxide to dissolve the aforementioned compounds. Add 20.2 parts of terephthalate chloride in small portions for about 1 hour. After all the addition, it was stirred at 60°C for 1 hour and reacted. After the completion of the reaction, it was allowed to cool to room temperature and filtered, and the obtained solid was dried at 70°C, thereby obtaining 84.1 parts of the compound represented by formula (s31). In the production of the polarized light-emitting element and the polarized light-emitting plate of Example 1, the measurement sample of Example s3 was obtained in the same manner except that the compound represented by formula (s31) was used instead of the compound represented by formula (15).

[Example s4]

21.8 parts by weight of the compound represented by formula (s32) and 37 parts by weight of 4,4'-diaminostilbene-2,2'-disulfonic acid were added to 500 parts of water and heated to 60°C, while the pH became 6 to 7 Adjust the method while adding 25% sodium hydroxide to dissolve the aforementioned compounds. Add 20.2 parts of terephthalate chloride in small portions for about 1 hour. After all the addition, it was stirred at 60°C for 1 hour and reacted. After the reaction, the mixture was allowed to cool to room temperature and filtered, and the obtained solid was dried at 70°C, thereby obtaining 24.5 parts of a mixture of compounds represented by formula (s15) and formula (s33). In the production of the polarized light-emitting element and polarized light-emitting plate of Example 1, except that a mixture of compounds represented by formula (s15) and formula (s33) was used instead of the compound represented by formula (15), Example s4 was obtained in the same manner The measurement sample.

[Example s5]

Add 40 parts of 4-nitro-4'-aminostilbene-2,2'-disulfonic acid to 500 parts of water and heat to 60°C, adjust the pH to 6 to 7 while adding 25% sodium hydroxide to make The aforementioned compound dissolves. 15.6 parts of phenyl chloroformate and 37 parts of 4,4'-diaminostilbene-2,2'-disulfonic acid were added in small portions for about 1 hour. After all was added, it was stirred at 60°C for 1 hour. To the resulting solution, 10.1 parts of terephthalate chloride was added in small portions for about 1 hour, and after all was added, the mixture was stirred at 60°C for 1 hour and reacted. After the completion of the reaction, it was allowed to cool to room temperature and filtered, and the obtained solid was dried at 70°C, thereby obtaining 22.3 parts of the compound represented by formula (s19). In the production of the polarized light-emitting element and the polarized light-emitting plate of Example 1, the measurement sample of Example s5 was obtained in the same manner except that the compound represented by formula (s19) was used instead of the compound represented by formula (15).

[Comparative Example 1]

In the production of the polarized light-emitting element and polarized light-emitting plate of Example 1, except that the compound represented by formula (c1) described in JP 4-226162 A was used instead of the compound represented by formula (15), they were obtained in the same manner The measurement sample of Comparative Example 1.

[Comparative Example 2]

In the production of the polarized light-emitting element and polarized light-emitting plate of Example 1, the measurement of Comparative Example 2 was obtained in the same manner except that CI Direct Yellow 4 of the compound represented by formula (c2) was used instead of the compound represented by formula (15) Sample.

[Comparative Example 3]

In the production of the polarized light emitting element and the polarized light emitting plate of Example 1, except that the compound represented by formula (c3) was used instead of the compound represented by formula (15), the measurement sample of Comparative Example 3 was obtained in the same manner.

[Evaluation]

The measurement samples obtained in Examples 1 to 5 and s1 to s5 and Comparative Examples 1 to 3 were used and evaluated in the following manner.

(a) Measurement of monomer penetration rate Ts, parallel position penetration rate Tp, and orthogonal position penetration rate Tc

Measure the monomer transmittance Ts (%), parallel transmittance Tp (%), and orthogonal transmittance Tc (%) of each measurement sample using a spectrophotometer ("U-4100" manufactured by Hitachi, Ltd.) ). Here, the monomer transmittance Ts (%) is the transmittance of each wavelength when measuring one measurement sample. Parallel transmittance Tp (%) is the spectral transmittance of each wavelength measured by superimposing two measurement samples so that their absorption axis directions are parallel. Orthogonal transmittance Tc (%) is the spectral transmittance measured by superimposing two measurement samples so that their absorption axes are orthogonal to each other. The measurement of each transmittance is performed at a wavelength of 220 to 780 nm.

(b) Calculation of polarization degree ρ

Substituting the parallel transmittance Tp and the orthogonal transmittance Tc with the following formula (I), the polarization degree ρ (%) of each measurement sample was obtained.

ρ ={(Tp-Tc)/(Tp+Tc)} ^1/2 ×100 (I)

(c) Calculation of monomer penetration rate Ys after visibility correction

The visibility-corrected monomer transmittance Ys (%) of each measurement sample is calculated in the wavelength region of 400 to 700 nm in the visible light region with a specific wavelength interval dλ (here, 5 nm). The transmittance Ts is the transmittance obtained by correcting the visibility according to JIS Z 8722:2009. Specifically, the monomer penetration rate Ts is substituted into formula (II) and the visibility correction monomer penetration rate Ys is calculated. In addition, in the following formula (II), Pλ represents the spectral distribution of the standard light (C light source), and yλ represents the 2-degree visual field color matching function.

(d) Measurement of luminous polarized light

The light source uses an ultraviolet LED 375nm handheld black light ("PW-UV943H-04" made by Nichia Chemical Industry Co., Ltd.), and an ultraviolet penetration and visible light cutoff filter ("IUV-340" made by Gosu Seiko Glass Co., Ltd.) is installed in Light source and cut off visible light. Set the measurement samples obtained in each of the Examples and Comparative Examples, and use a spectroradiometer ("USR-40" manufactured by USHIO Electric Co., Ltd.) to measure the polarization of the measurement sample's luminescence. At this time, it will have a polarization function in the visible light region and the ultraviolet light region. A polarizing plate ("SKN-18043P" manufactured by Polatechno Co., Ltd., thickness 180 μm, Ys of 43%) was installed on the light receiving part of the spectroradiometer, and the amount of polarized light emission of the measurement samples obtained in each of the Examples and Comparative Examples was measured. That is, the light from the light source is arranged in such a way that the light from the light source passes through the ultraviolet penetrating and visible light cut-off filter, the measurement sample, the polarizing plate that has polarized light in the visible light region and the ultraviolet light region, and is incident on the spectroradiometer. And determine. At this time, the absorption axis that maximizes the ultraviolet absorption of the measurement sample and the polarizing plate with polarization in the visible light region and the ultraviolet light region ("SKN-18043P" manufactured by Polatechno) The absorption axis direction becomes parallel to overlap, and the spectral luminescence amount of each wavelength measured by this is Lw (weak luminescence axis), so that the absorption axis of the maximum ultraviolet absorption of the measurement sample is aligned with The absorption axis directions of polarizers (“SKN-18043P” manufactured by Polatechno Co., Ltd.) that have polarized light in the visible light region and the ultraviolet light region overlap so that the absorption axis directions are orthogonal, and the spectral luminous intensity of each wavelength measured by this is Ls (strong luminous axis) , And determine Lw and Ls. It is confirmed that when the absorption axis of the measurement sample and the general polarizer are parallel or orthogonal, the light energy emitted in the visible light region can be used to evaluate the polarized light emission in the visible light region from 400 to 700 nm.

(e) Light resistance test

SX-75 manufactured by Suga Tester Co., Ltd. was used to irradiate light for 500 hours at an illuminance of 60 W, an ambient temperature of 50° C., and a relative humidity of 30% RH to conduct a light resistance test. Confirm the change of Ls and Lw of each wavelength at this time.

Table 1 shows the wavelength showing the maximum polarization degree, the monomer transmittance Ts (%), and the parallel position in the wavelength showing the maximum polarization degree of each measurement sample obtained in Examples 1 to 5 and s1 to s5 and Comparative Examples 1 to 3 Transmittance Tp (%), orthogonal position transmittance Tc (%), and polarization degree ρ (%), visibility correction monomer transmittance Ys (%), visibility correction polarization degree ρy (%).

The following Table 2 shows the Ls and Lw of each wavelength of each measurement sample obtained in Examples 1 to 5 and s1 to s5 and Comparative Examples 1 to 3.

The following Table 3 shows the Ls and Lw of each wavelength after the light resistance test of each measurement sample obtained in Examples 1 to 5 and s1 to s5 and Comparative Example 1.

As shown in Table 1, it can be seen that the measurement samples of Examples 1 to 5 and s1 to s5 and Comparative Example 1 have absorption in the ultraviolet region to the near-ultraviolet visible region, and function as a polarized light emitting plate in this band. On the other hand, the transmittance (visibility correction transmittance Ys) in the visible light region is about 90%, which shows that it has a polarizing function from the ultraviolet light region to the near-ultraviolet visible light region, and the visible transparency is high. In contrast, in Comparative Examples 2 and 3, the wavelength showing the maximum polarization degree is 400 nm or more, the visibility correction transmittance Ys decreases, and the visible transmittance decreases.

In addition, as shown in Table 2, in Examples 1 to 5 and s1 to s5 and Comparative Example 1, Lw and Ls were detected. Therefore, it can be seen that the samples are polarized by irradiating ultraviolet rays. On the other hand, compared to Comparative Example 1, in Examples 1 to 5 and s1 to s5, the maximum luminous brightness is higher, or higher polarized light is emitted in a wide band from 400 to 700 nm.

In addition, as shown in Table 3, compared to Comparative Example 1, Examples 1 to 5 and s1 to s5 have high light resistance. Therefore, the measurement samples of Examples 1 to 5 and s1 to s5 not only function as a polarized light emitting element that can emit polarized light in the visible light region by ultraviolet irradiation, but also have high light resistance.

(f) Durability test

The polarized light-emitting panels obtained in Examples 1 to 5 and s1 to s5 were placed in an environment of 105°C for 1000 hours, and placed in an environment of 60°C and a relative humidity of 90% for 1000 hours, and the durability test was carried out. At this time, no observation The degree of polarization decreases and the luminescence of polarized light changes. From this point of view, the polarized light-emitting elements and polarized light-emitting panels of Examples 1 to 5 and s1 to s5 have high durability even in severe environments.

[Industrial availability]

When the luminescent compound of the present invention is contained in a substrate and used, it is possible to obtain a polarized light-emitting element and a polarized light-emitting plate that have a high degree of polarization at an absorption wavelength and exhibit a polarized light emission effect. In addition, such a polarized light-emitting element and a polarized light-emitting plate have excellent durability and high transmittance in the visible light region. Therefore, the display device equipped with the polarized light-emitting element or polarized light-emitting plate of the present invention has high transparency in the visible light region and can display images with polarized light for a long time. Therefore, it can be applied to TVs, computers, flat-panel terminals, and even transparent displays (see-through displays). ) And other wide-ranging uses. In addition, the polarized light-emitting element and polarized light-emitting plate containing the luminescent compound of the present invention can emit light from the ultraviolet region to the near-ultraviolet visible region, such as light from 300 to 430 nm, so it can be applied to displays or displays that require high security. medium.

Claims (14)

A luminescent compound or a salt thereof, wherein the luminescent compound is represented by the following formula (1),

In formula (1), (i) X and Y each independently include at least a group selected from the group consisting of a group represented by the above formula (2), a heterocyclic group containing a nitrogen atom or a sulfur atom, and a nitro group, but Excluding the case where both X and Y are nitro groups; or (ii) at least one of X and Y (when both are independent) is a nitro group, an amine group that may have a substituent, and C1 to 4 that may have a substituent The alkyl group, the C1 to 4 alkoxy group which may have a substituent, the aromatic group which may have a substituent, the heterocyclic group containing an oxygen atom, a nitrogen atom or a sulfur atom which may have a substituent, or the formula (2) In the group shown, when X or Y is not the group selected above, the X or Y is selected from any substituents, M each independently represents a hydrogen atom, a metal ion, or an ammonium ion, each m independently represents an integer from 0 to 2, and s is 0 or 1, In the formula (2), ※ represents the bonding position of X and/or Y in the formula (1), and Z is composed of a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a stilbene group which may have a substituent , Selected from the group consisting of a benzyl group which may have a substituent and a heterocyclic group which may have a substituent, and t represents an integer of 0 or 1. The luminescent compound or salt thereof according to claim 1, wherein X, Y in the above formula (1), and the above formula (2) when at least one of X and Y is represented by the above formula (2) At least one of Z in) is selected from the group consisting of substituents represented by the following formulas (3) to (7),

In the above formulas (3) and (4), A is each independently composed of a hydrogen atom, a halogen group, a nitro group, a hydroxyl group, a C1 to 4 alkyl group, a C1 to 4 alkoxy group, and a C1 to C1 to sulfonic acid group. 4 alkyl groups, C1 to 4 alkyl groups having hydroxyl groups, C1 to 4 alkyl groups having carboxyl groups, C1 to 4 alkoxy groups having sulfonic acid groups, C1 to 4 alkoxy groups having hydroxyl groups, The carboxyl group is selected from the group consisting of C1 to 4 alkoxy groups, q ¹ represents an integer from 0 to 4, M in the above formulas (3) to (7) is as defined in the above formula (1), n ¹ and n ² each independently represents an integer from 0 to 3, and * in the above formulas (3) to (7) respectively represents the bonding position of X or Y in the above formula (1), or the bond of Z in the above formula (2) Knot position. The luminescent compound or its salt according to claim 1 or 2, wherein X and Y in the above formula (1) are each independently grouped by substituents represented by formulas (2) to (7) When selecting formula (2), Z is selected from the group consisting of the substituents shown in formulas (3) to (7). The luminescent compound or its salt according to claim 1 or 2, wherein X and Y in the above formula (1) are all selected from the group of substituents represented by formulas (2) to (7), When formula (2) is selected, Z is selected from the group of substituents shown in formulas (3) to (7). The luminescent compound or salt thereof according to any one of claims 1 to 4, wherein each m in the above formula (1) is 0. The luminescent compound or salt thereof according to any one of claims 1 to 5, wherein s is zero. The luminescent compound or salt thereof according to any one of claims 1 to 5, wherein s is 1. The luminescent compound or salt thereof according to claim 7, wherein the above formula (1) is represented by the following formula (1'),

In the above formula (1'), X and Y are as defined in the above formula (1), respectively. A polarized light-emitting element, which has a polarized light-emitting function, and contains the light-emitting compound according to any one of claims 1 to 8 or a salt thereof. The polarized light-emitting element according to claim 9, which further contains one or more organic dyes or fluorescent dyes other than the above-mentioned luminescent compound or a salt thereof. The polarized light emitting device according to claim 9 or 10, which further contains a substrate. The polarized light-emitting element according to claim 11, wherein the substrate is a film containing a polyvinyl alcohol resin or a derivative thereof. A polarized light-emitting panel is provided with a transparent protective film on at least one side of the polarized light-emitting element according to any one of claims 9 to 12. A display device is provided with the polarized light-emitting element according to any one of claims 9 to 12 or the polarized light-emitting panel according to claim 13.