Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
  • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
  • C07D277/84—Naphthothiazoles
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
  • C07C309/01—Sulfonic acids
  • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
  • C07C309/45—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
  • C07C309/51—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton at least one of the nitrogen atoms being part of any of the groups, X being a hetero atom, Y being any atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
  • C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
  • C07D249/18—Benzotriazoles
  • C07D249/20—Benzotriazoles with aryl radicals directly attached in position 2
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
  • C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
  • C07D249/22—Naphthotriazoles
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
  • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
  • C07D277/62—Benzothiazoles
  • C07D277/64—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2
  • C07D277/66—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2 with aromatic rings or ring systems directly attached in position 2
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
  • C09K11/06—Luminescent materials, e.g. electroluminescent or chemiluminescent containing organic luminescent materials
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
  • G02B1/14—Protective coatings, e.g. hard coatings
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/30—Polarising elements
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
  • C09K2211/10—Non-macromolecular compounds
  • C09K2211/1003—Carbocyclic compounds
  • C09K2211/1007—Non-condensed systems
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  • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
  • C09K2211/10—Non-macromolecular compounds
  • C09K2211/1003—Carbocyclic compounds
  • C09K2211/1011—Condensed systems
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  • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
  • C09K2211/10—Non-macromolecular compounds
  • C09K2211/1003—Carbocyclic compounds
  • C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
  • C09K2211/10—Non-macromolecular compounds
  • C09K2211/1018—Heterocyclic compounds
  • C09K2211/1025—Heterocyclic compounds characterised by ligands
  • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
  • C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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  • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
  • C09K2211/10—Non-macromolecular compounds
  • C09K2211/1018—Heterocyclic compounds
  • C09K2211/1025—Heterocyclic compounds characterised by ligands
  • C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms

Definitions

• the present invention relates to a novel luminescent compound or a salt thereof, a polarized light emitting device containing the same, a polarized light emitting plate, and a display device (display).
• a polarizing plate having a light transmitting and / or shielding function is a basic component of a display device such as a liquid crystal display (LCD) together with a liquid crystal having a light switching function.
• LCD liquid crystal display
• the fields of application of this LCD are expanding from small devices such as calculators and watches in the early days to notebook computers, word processors, liquid crystal projectors, liquid crystal televisions, car navigation systems, indoor and outdoor measuring devices, and the like. It can also be applied to lenses having a polarizing function, and for example, it has been applied to sunglasses with improved visibility and polarized glasses compatible with 3D televisions in recent years.
• the applications of the polarizing plate are wide-ranging, and the usage environment is wide, such as low temperature to high temperature, low humidity to high humidity, low light amount to high light amount, etc., so that it has high polarization performance and high durability.
• a polarizing plate is required.
• the polarizing film constituting the polarizing plate is produced by stretching and orienting a film of polyvinyl alcohol or a derivative thereof containing iodine or a dichroic dye, or dehydroxic acid or polyvinyl alcohol of a polyvinyl chloride film. It is produced by producing and orienting polyene by dehydrating the system film.
• a polarizing plate composed of such a conventional polarizing film contains a dichroic dye having absorption in the visible region, so that the transmittance is lowered.
• the transmittance of a general polarizing plate on the market is 35 to 45%.
• Patent Document 1 describes a technique for a polarizing plate for ultraviolet rays as a technique for providing a polarizing function while maintaining a certain degree of transmittance in the visible region, in response to the problem of a conventional polarizing plate in which the transmittance in the visible region is lowered. Has been done. However, this technique also uses a yellow pigment that absorbs in the visible region, so that the transmittance is not sufficient and a strong yellow coloring is confirmed.
• the polarized light emitting elements described in Patent Documents 2 to 4 are expensive because they contain special metals such as lanthanoids and europium, which have high rare values, and are extremely difficult to manufacture for mass production. Not suitable. Further, these polarized light emitting elements are difficult to use in a display because the light emission of polarized light is weak, and the emitted light which is linearly polarized light cannot be obtained. Therefore, we will develop a new polarized light emitting plate and materials for it that show polarized light emitting action, are highly transparent in the visible light range, and can be applied to liquid crystal displays that are required to be durable in harsh environments. Is desired.
• An object of the present application is to provide a novel luminescent compound, a polarized light emitting device containing the luminescent compound, a polarized light emitting plate, and a display device.
• a polarized light emitting element and a polarized light emitting plate containing a compound having a specific structure or a salt thereof have a high two-color ratio in the ultraviolet region. It has been found that it exhibits high transmittance in the visible light region and also exhibits excellent durability in a harsh environment. Further, a compound having such a specific structure or a salt thereof exhibits an action of emitting polarized light in the visible light region by irradiation with light in the ultraviolet to near-ultraviolet visible region, for example, light of 300 to 430 nm.
• the present invention has been completed.
• (In formula (1), at least one of X and Y (independently in both cases) is a nitro group, an amino group which may have a substituent, an amide group which may have a substituent, and the like. It may have an alkyl group of C1 to 4 which may have a substituent, an alkoxy group of C1 to 4 which may have a substituent, an aromatic group which may have a substituent, and a substituent.
• X or Y is selected from any substituent and M is each independently a hydrogen atom, metal ion, or Represents an ammonium ion, where m independently represents an integer of 0 to 2 and s is 0 or 1).
• M is each independently a hydrogen atom, metal ion, or Represents an ammonium ion, where m independently represents an integer of 0 to 2 and s is 0 or 1).
• X and Y in the above formula (1) is selected from the group consisting of substituents represented by the following formulas (2) to (8) (independently in both cases).
• Luminescent compound or salt thereof (In the above formula (2), R consists of a group consisting of a hydrogen atom, an alkyl group of C1 to 4, an alkyl group of C1 to 4 having a sulfo group, or a substituent represented by the formulas (3) to (7). Representing a substituent to be selected, in the above formulas (3) and (4), A is independently a hydrogen atom, a halogen group, a nitro group, a hydroxy group, an alkyl group of C1 to 4, and an alkoxy group of C1 to 4.
• C1-4 alkyl groups with sulfo groups C1-4 alkyl groups with hydroxy groups, C1-4 alkyl groups with carboxy groups, C1-4 alkoxy groups with sulfo groups, C1 with hydroxy groups Selected from the group consisting of an alkoxy group of up to 4 and an alkoxy group of C1 to 4 having a carboxy group, q 1 represents an integer of 0 to 4, and M in the above formulas (3) to (7) is the above formula.
• (1) are as defined in the above formula (3) and (4) n 1, the formula (5) ⁇ (7) n 2 in in each independently represent an integer of 0 to 3 , T in the above formula (8) is 0 or 1, Z is an amino group which may have a substituent, a phenyl group which may have a substituent, and a naphthyl group which may have a substituent.
• X and Y in the above formula (1) are independently a nitro group, an amino group which may have a substituent, an alkyl group which may have a substituent, and an alkoxy group which may have a substituent.
• the invention which is an aromatic group which may have a substituent, a heterocyclic group which may have a substituent, or a group selected from the group of substituents represented by the formulas (2) to (8).
• X and Y in the above formula (1) are independently selected from the group consisting of substituents represented by the formulas (2) to (8), and at least one of X and Y is of the formula (8).
• Z in the formula (8) is selected from the group consisting of substituents represented by the formulas (2) to (7) (* in each formula represents the bond position in Z in the formula (8)).
• Either one of X and Y in the above formula (1) is an amino group which may have a nitro group or a substituent, and the other is composed of a substituent represented by the formulas (2) to (8).
• Z in the formula (8) is selected from the group consisting of the substituents represented by the formulas (2) to (7).
• Either one of X and Y in the above formula (1) is an amino group which may have a nitro group or a substituent, and either one of X and Y is a substituent represented by the formula (8).
• the luminescent compound or salt thereof according to Invention 1 or 2, wherein both X and Y in the above formula (1) are amino groups which may have a nitro group or a substituent.
• [Invention 11] A polarized light emitting device containing the luminescent compound according to any one of Inventions 1 to 10 or a salt thereof, which has a polarized light emitting function.
• the polarized light emitting element according to the invention 11 further comprising one or more kinds of organic dyes or fluorescent dyes other than the above luminescent compound or a salt thereof.
• the polarized light emitting device according to Invention 13 wherein the base material is a film containing a polyvinyl alcohol resin or a derivative thereof.
• invention 15 A polarized light emitting plate provided with a transparent protective film on at least one surface of the polarized light emitting device according to any one of the inventions 11 to 14.
• invention 16 A display device including the polarized light emitting device according to any one of Inventions 11 to 14 or the polarized light emitting plate according to Invention 15.
• the luminescent compound having a specific structure according to the present invention or a salt thereof absorbs light in the ultraviolet to visible region, for example, light in the ultraviolet to near ultraviolet visible region, specifically, light having a diameter of 300 to 430 nm, and its energy. Shows a polarized light emitting effect in the visible light region.
• the polarizing element and the polarizing plate produced by using the luminescent compound or a salt thereof are a novel polarized light emitting element and a polarized light emitting plate exhibiting a polarized light emitting action.
• the luminescent compound or salt thereof according to the present invention and the polarized light emitting element and the polarized light emitting plate containing the same show a high degree of polarization at the absorption wavelength. Therefore, by using the compound represented by the formula (1) or a salt thereof, it has a high degree of polarization at the absorption wavelength and exhibits a polarized light emitting effect without using a lanthanoid metal having a high rare value.
• a novel polarized light emitting element and a polarized light emitting plate can be provided.
• the polarized light emitting device and the polarized light emitting plate according to the present invention exhibit high transmittance in the visible region.
• the polarized light emitting device and the polarized light emitting plate according to the present invention exhibit excellent durability against heat, humidity and the like. Therefore, the polarized light emitting element and the polarized light emitting plate can be applied to a display device such as a liquid crystal display which is required to have high transparency in the visible light region and high durability in a harsh environment.
• substituted includes a hydrogen atom for convenience.
• the phrase “may have a substituent” means that a case without a substituent is also included.
• a "phenyl group which may have a substituent” includes a simple phenyl group which is not substituted and a phenyl group which has a substituent.
• Luminescent compound The luminescent compound or a salt thereof according to the present invention is represented by the above formula (1).
• “luminescent compound or salt thereof” may be simply abbreviated as “luminescent compound”.
• At least one of X and Y (independently in both cases) is a nitro group, an amino group which may have a substituent, an amide group which may have a substituent, and a substitution.
• Selected from the group consisting of heterocyclic groups which may have substituents if X or Y is not the above-selected group, then X or Y is selected from any substituent and M is each independently. It represents a hydrogen atom, a metal ion, or an ammonium ion, where m independently represents an integer of 0 to 2 and s is 0 or 1.
• amino group which may have a substituent in the definition of X and Y includes, for example, an amino group; a methylamino group, an ethylamino group, an n-butylamino group, a phenylamino group, a naphthylamino group and the like.
• amide group which may have a substituent examples include a methylamide group, an ethylamide group, a phenylamide group and the like.
• Substituents represented by the formulas (2) and (8) described later are also included in the "amide group which may have a substituent", which is one of the preferable embodiments.
• alkyl group of C1-4 examples include methyl group, ethyl group, n-propyl group and iso-. Examples thereof include a propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group and a cyclobutyl group.
• alkoxy group of C1-4 examples include a methoxy group, an ethoxy group, an n-propoxy group, and iso-. Examples thereof include a propoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, a cyclobutoxy group and the like.
• heterocyclic group of the above “heterocyclic group which may have a substituent” in the definition of X and Y, for example, at least one of an oxygen atom, a nitrogen atom, and a sulfur atom is contained as a ring component.
• substituents for example, at least one of an oxygen atom, a nitrogen atom, and a sulfur atom is contained as a ring component.
• they include not only a monocyclic heterocycle but also a polycyclic heterocycle in which the monocyclic heterocycle further contains an aromatic ring such as a benzene ring or a naphthalene ring.
• heterocyclic group containing at least one oxygen atom, nitrogen atom, and sulfur atom as a ring component examples include a pyrrole group, a benzopyrrole group, a thiophene group, a benzothiophene group, a thiazole group, and a benzothiazole group. , Naftiazole group, triazole group, benzotriazole group, naphthotriazole group, thiadiazole group, benzothiazyl group, pyridine group, furan group, benzofuran group and the like.
• alkyl group of C1 to 4 which may have a substituent "alkoxy group of C1 to 4 which may have a substituent", "aromatic group which may have a substituent", " The substituent in the "heterocyclic group which may have a substituent” is not particularly limited, and examples thereof include a nitro group, a hydroxy group, a cyano group, a phosphate group, a sulfo group, a carboxy group, and an amino group. Be done.
• the "amino group which may have a substituent” and the "amide group which may have a substituent” may further have a substituent as exemplified herein.
• M independently represents a hydrogen atom, a metal ion, or an ammonium ion.
• the metal ion 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 for example, narrow ammonium ion (NH 4 +), methylammonium ion, dimethylammonium ion, triethylammonium ion, tetraethylammonium ion, tetra -n- propyl ammonium ion, tetra -n- butyl ammonium ion, mono- Examples thereof include ethanolammonium ion, diethanolammonium ion, triethanolammonium ion, monoisopropanolammonium ion, diisopropanolammonium ion, triisopropanolammonium ion, and triethanolammonium ion.
• narrow ammonium ion NH 4 +
• methylammonium ion dimethylammonium ion
• triethylammonium ion tetraethylammonium ion
• M is a hydrogen atom
• sulfonic acid -SO 3 H
• sodium sulfonate -SO 3 Na
• ammonium ion Represents ammonium sulfonate (-SO 3 NH 4 ), respectively.
• particularly preferable ones include lithium ion, ammonium ion, and sodium ion.
• R is selected from the group consisting of a hydrogen atom, an alkyl group of C1 to 4, an alkyl group of C1 to 4 having a sulfo group, or a substituent represented by the formulas (3) to (7).
• A independently represents a hydrogen atom, a halogen group, a nitro group, a hydroxy group, an alkyl group of C1 to 4, an alkoxy group of C1 to 4, respectively.
• C1-4 alkyl groups with sulfo groups C1-4 alkyl groups with sulfo groups, C1-4 alkyl groups with hydroxy groups, C1-4 alkyl groups with carboxy groups, C1-4 alkoxy groups with sulfo groups, C1-4 with hydroxy groups
• q 1 represents an integer of 0 to 4
• M in the above formulas (3) to (7) is , are as defined by the above formula (1)
• n 2 in the above formula (5) to (7) are each independently from 0 to 3
• t in the above formula (8) is 0 or 1
• Z may have a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a substituent.
• alkyl group of C1 to 4" in the definition of R examples include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group and cyclobutyl. Group etc. can be mentioned.
• alkyl group of C1 to C4 having a sulfo group examples include a sulfomethyl group, a sulfoethyl group, a sulfo-n-propyl group, a sulfo-n-butyl group, a sulfo-sec-butyl group and the like. Can be mentioned.
• halogen group in the definition of A include a fluorine group, a chlorine group, a bromine group, an iodine group and the like.
• alkyl groups of C1 to 4" in the definition of A are as defined in R.
• alkoxy group of C1 to 4" in the definition of A examples include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group and cyclo. Examples thereof include a butoxy group.
• alkyl group of C1-4 having a sulfo group in the definition of A is as defined in R.
• alkyl group of C1-4 having a hydroxy group in the definition of A includes, for example, a hydroxymethyl group, a hydroxyethyl group, a hydroxy-n-propyl group, a hydroxy-iso-propyl group, and a hydroxy-n-butyl group. , Hydroxy-sec-butyl group, hydroxy-tert-butyl group, hydroxycyclobutyl group and the like.
• alkyl group of C1-4 having a carboxy group in the definition of A includes, for example, a carboxymethyl group, a carboxyethyl group, a carboxy-n-propyl group, a carboxy-iso-propyl group, and a carboxy-n-butyl group. , Carboxy-sec-butyl group, carboxy-tert-butyl group, carboxycyclobutyl group and the like.
• alkoxy group of C1-4 having a sulfo group in the definition of A includes, for example, a sulfomethoxy group, a sulfoethoxy group, a sulfo-n-propoxy group, a sulfo-iso-propoxy group, and a sulfo-n-butoxy group. , Sulfo-sec-butoxy group, sulfo-tert-butoxy group, sulfocyclobutoxy group and the like.
• alkoxy group of C1 to 4 having a hydroxy group examples include a hydroxymethoxy group, a hydroxyethoxy group, a hydroxy-n-propoxy group, a hydroxy-iso-propoxy group, and a hydroxy-n-butoxy group. , Hydroxy-sec-butoxy group, hydroxy-tert-butoxy group, hydroxycyclobutoxy group and the like.
• alkoxy group of C1-4 having a carboxy group in the definition of A includes, for example, a carboxymethoxy group, a carboxyethoxy group, a carboxy-n-propoxy group, a carboxy-iso-propoxy group, and a carboxy-n-butoxy group. , Carboxy-sec-butoxy group, carboxy-tert-butoxy group, carboxycyclobutoxy group and the like.
• heterocyclic group of the above "heterocyclic group which may have a substituent" in the definition of Z is as defined in X and Y.
• X and Y in the above formula (1) may independently have a nitro group, an amino group which may have a substituent, an amide group which may have a substituent, and C1 to 4 which may have a substituent.
• any one of X and Y in the above formula (1) is an amino group which may have a nitro group or a substituent, and is already One is a substituent selected from the group consisting of substituents represented by the formulas (2) to (8), and when the substituent represented by the formula (8) is selected, Z is the formula (Z). It is also preferable that the substituent is selected from the group consisting of the substituents represented by 2) to (7); either one of X and Y in the above formula (1) has a nitro group or a substituent.
• the amino group may be an amino group, the other of which is a substituent represented by the formula (8), and Z in the formula (8) is an amino group which may have a nitro group or a substituent. It is also preferable that both X and Y are amino groups which may have a nitro group or a substituent; both X and Y in the above formula (1) are formulas (2) to (8).
• the group consisting of the substituents represented by the formula (8) is selected and the substituent represented by the formula (8) is selected, the group consisting of the substituents represented by the formulas (2) to (7) in Z. It is also preferable to be selected from.
• each m is 0.
• s is 0.
• a method for synthesizing the compound represented by the formula (1) will be described below.
• each of X, Y, M, and m is as defined in the above formula (1).
• s is 1.
• a method for synthesizing the compound represented by the formula (1) will be described below.
• each X, Y, M, and m are as defined in the above formula (1), respectively.
• the compound represented by the above formula (1) or a salt thereof is useful as a compound capable of emitting polarized light.
• the compound represented by the formula (1) or a salt thereof may be combined with one or more organic dyes or fluorescent dyes other than the luminescent compound or the salt thereof, if necessary, and a substrate, for example, polyvinyl alcohol or a derivative thereof.
• a polarized light emitting element can be manufactured by a method of containing and orienting a polymer film such as the above by a known method.
• the obtained polarized light emitting element is provided with a transparent protective film to form a polarized light emitting plate, and the polarized light emitting plate is further provided with a hard coat layer (protective layer) or an AR (antireflection) layer, a support, or the like, if necessary. It is applied to LCD projectors, calculators, watches, laptop computers, word processors, LCD TVs, car navigation systems, security displays, anti-counterfeiting, and indoor and outdoor measuring instruments, indicators, lenses, glasses, etc.
• organic dyes or fluorescent dyes other than the luminescent compound or a salt thereof according to the present invention may be abbreviated as "other organic dyes”.
• a polarized light emitting device containing a luminescent compound represented by the above formula (1) or a salt thereof is also included in the present invention.
• the polarized light emitting element is preferably a polarized light emitting element containing a luminescent compound represented by the above formula (1) or a salt thereof and a substrate on which the polarized compound or a salt thereof is adsorbed and oriented.
• the polarized light emitting device may contain one kind alone or a plurality of kinds of a luminescent compound represented by the above formula (1) or a salt thereof.
• the base material is preferably a film obtained by forming a film of a luminescent compound represented by the formula (1) or a hydrophilic polymer capable of adsorbing a salt thereof.
• the hydrophilic polymer is not particularly limited, and examples thereof include polyvinyl alcohol-based resins, amylose-based resins, starch-based resins, cellulosic resins, and polyacrylate-based resins. Among such resins, a polyvinyl alcohol-based resin or a derivative thereof is preferable from the viewpoint of adsorptivity, processability, orientation, etc. of the luminescent compound represented by the formula (1) or a salt thereof.
• the polyvinyl alcohol-based resin derivative any one generally known in this art can be used.
• unsaturated carboxylic acids such as crotonic acid, acrylic acid, methacrylic acid, maleic acid, vinyl sulfonic acid, acrylic sulfonic acid, methacrylic sulfonic acid, p-styrene sulfonic acid, 2-acrylamide-2-
• unsaturated carboxylic acids such as crotonic acid, acrylic acid, methacrylic acid, maleic acid, vinyl sulfonic acid, acrylic sulfonic acid, methacrylic sulfonic acid, p-styrene sulfonic acid, 2-acrylamide-2-
• unsaturated carboxylic acids such as crotonic acid, acrylic acid, methacrylic acid, maleic acid, vinyl sulfonic acid, acrylic sulfonic acid, methacrylic sulfonic acid, p-styrene sulfonic acid, 2-acrylamide-2-
• unsaturated sulfonic acids such as methylpropane sulfonic acid and
• the shape of the base material is not particularly limited, and the base material can be produced in any shape such as a film shape, a sheet shape, a flat plate shape, a curved plate shape, and a hemispherical shape.
• the thickness of the base material is usually 10 to 100 ⁇ m, preferably 20 to 80 ⁇ m.
• the content of the luminescent compound represented by the above formula (1) in the polarized light emitting element is not particularly limited, and the combined amount can be designed based on an arbitrary transmittance, and the transmission required for the polarized light emitting element. Depending on the rate, the blending amount (combined amount) may be arbitrarily set.
• the polarization performance of the polarized light emitting element includes not only the blending ratio of the luminescent compound represented by the formula (1) contained in the polarized light emitting element, but also the degree of swelling, the draw ratio, and the dyeing time of the base material that adsorbs the luminescent compound. It changes depending on various factors such as the staining temperature, the pH at the time of staining, and the influence of salt.
• the blending ratio of the luminescent compound represented by the formula (1) contained in the polarized light emitting element includes the degree of swelling of the base material, the dyeing temperature, the dyeing time, the pH at the time of dyeing, the type of salt, and the concentration of salt. , It can be determined according to the draw ratio and the like. Such adjustment of the blending ratio can be appropriately performed.
• the polarized light emitting element may further contain one or more other organic dyes as necessary within a range that does not impair the polarization performance or for the purpose of color adjustment.
• the other organic dye used in combination is not particularly limited, but a dye having high dichroism is preferable, and the absorption band of the luminescent compound represented by the formula (1), for example, in the ultraviolet region to the near-ultraviolet visible region. A dye that has little effect on the polarization performance is preferable.
• Other organic dyes used in combination include, for example, C.I. I. Direct. Yellow12, C.I. I. Direct. Yellow28, C.I. I. Direct. Yellow44, C.I. I. Direct. Orange 26, C.I. I. Direct. Orange39, C.I. I.
• These other organic dyes may be in the form of free acids, alkali metal salts (eg Na salt, K salt, and Li salt), ammonium salts, or salts of amines.
• the types of other organic dyes to be blended can be selected according to the purpose such as adjusting the color of the polarized light emitting element to be manufactured.
• the content thereof is not particularly limited, but generally, when the mass of the luminescent compound represented by the above formula (1) is 1, the total mass of the other organic dyes used in combination is It is preferably in the range of 0.01 to 10.
• the manufacturing method is not limited to the following manufacturing methods, but for example, a step of preparing a base material, a swelling step of immersing the base material in a swelling liquid and stretching the base material by swelling, and swelling.
• a base material for containing the luminescent compound represented by the above formula (1) is prepared.
• the base material for example, a commercially available film containing a polyvinyl alcohol-based resin or a derivative thereof may be used, or a base material may be produced by forming a film of the polyvinyl alcohol-based resin.
• the film-forming method of the polyvinyl alcohol-based resin is not particularly limited, and for example, a method of melt-extruding a hydrous polyvinyl alcohol, a casting film-forming method, a wet film-forming method, and a gel film-forming method (the polyvinyl alcohol aqueous solution is once cooled).
• a known film-forming method can be adopted, such as a method of extracting and removing the solvent after gelation), a cast film-forming method (flowing a polyvinyl alcohol aqueous solution on a substrate and drying), and a method using a combination thereof.
• the degree of polymerization of polyvinyl alcohol those of 1000 to 10000 can be used, and the degree of polymerization is preferably 1500 to 6000, more preferably 2000 to 6000.
• the swelling treatment is preferably performed by immersing the base material in a swelling solution at 20 to 50 ° C. for 30 seconds to 10 minutes, and the swelling solution is preferably water.
• the draw ratio of the base material with the swelling liquid is preferably adjusted to 1.00 to 1.50 times, more preferably 1.10 to 1.35 times.
• the substrate obtained by performing the swelling treatment as described above is adsorbed and impregnated with at least one luminescent compound represented by the formula (1) or a salt thereof.
• the dyeing step is not particularly limited as long as it is a method of adsorbing and impregnating the base material with the luminescent compound represented by the formula (1) or a salt thereof, but for example, the base material is represented by the formula (1). It is preferable to immerse it in a dyeing solution containing the luminescent compound represented or a salt thereof, and it can also be adsorbed by applying the dyeing solution to the substrate.
• the concentration of the luminescent compound represented by the formula (1) or a salt thereof in the dyeing solution is particularly limited as long as the luminescent compound represented by the formula (1) or a salt thereof is sufficiently adsorbed in the substrate. However, for example, it is preferably 0.0001 to 3% by mass, more preferably 0.001 to 1% by mass in the dyeing solution.
• the temperature of the dyeing solution in the dyeing step is preferably 5 to 80 ° C, more preferably 20 to 50 ° C, and particularly preferably 40 to 50 ° C.
• the time for immersing the substrate in the dyeing solution can be appropriately adjusted, and is preferably adjusted between 30 seconds and 20 minutes, more preferably between 1 and 10 minutes.
• the luminescent compound represented by the above formula (1) may be used alone or in combination of two or more. Since the luminescent compound represented by the above formula (1) has a different luminescent color due to the difference in structure, two or more kinds of luminescent compounds represented by the above formula (1) are used as a base material. Alternatively, the luminescent color produced by containing the luminescent compound represented by the above formula (1) or a salt thereof and one or more other luminescent compounds may be appropriately adjusted to a desired color. it can. Further, if necessary, the dyeing solution may further contain one kind or two or more kinds of the above-mentioned other organic dyes. In the description in the manufacture of the polarized light emitting device and the polarized light emitting plate in the present specification, the luminescent compound represented by the formula (1) and other organic dyes may be generally referred to as "polarized dye".
• the dyeing solution may further contain a dyeing aid, if necessary, in addition to the polarizing dye.
• the dyeing aid include sodium carbonate, sodium hydrogencarbonate, sodium chloride, sodium sulfate (Glauber's salt), anhydrous sodium sulfate, sodium tripolyphosphate and the like, and sodium sulfate is preferable.
• the content of the dyeing aid can be arbitrarily adjusted depending on the time of immersion and the temperature of the dyeing solution based on the dyeability of the polarizing dye used, but it should be 0.1 to 10% by mass in the dyeing solution. Is preferable, and 0.1 to 2% by mass is more preferable.
• a pre-cleaning step can be optionally performed in order to remove the dyeing solution adhering to the surface of the base material in the dyeing step.
• a pre-cleaning step it is possible to prevent the luminescent compound represented by the formula (1) remaining on the surface of the base material or a salt thereof from being transferred into the treatment liquid in the next step.
• water is generally used as the cleaning liquid.
• cleaning method it is preferable to immerse the dyed base material in the cleaning liquid, and on the other hand, cleaning can also be performed by applying the cleaning liquid to the base material.
• the washing time is not particularly limited, but is preferably 1 to 300 seconds, and more preferably 1 to 60 seconds.
• the temperature of the cleaning liquid in the pre-cleaning step needs to be a temperature at which the material constituting the base material does not dissolve, and the cleaning treatment is generally performed at 5 to 40 ° C. Even if there is no pre-cleaning step, the pre-cleaning step can be omitted because it does not have a particularly large effect on the performance of the polarized light emitting element.
• the substrate can contain a cross-linking agent.
• a cross-linking agent As a method of incorporating a cross-linking agent into the base material, it is preferable to immerse the base material in a treatment solution containing the cross-linking agent, while the treatment solution may be applied or coated on the base material.
• the cross-linking agent in the treatment solution it is preferable to use a solution containing boric acid.
• the solvent in the treatment solution is not particularly limited, but water is preferable.
• the concentration of the cross-linking 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.
• the treatment time of this cross-linking step is preferably 30 seconds to 10 minutes, more preferably 1 to 6 minutes.
• the obtained polarized light emitting element can emit light having high brightness and high degree of polarization. This is an excellent action that cannot be expected from the function of boric acid, which has been used in the prior art for the purpose of improving water resistance or light transmission.
• a fixing treatment may be further performed with an aqueous solution containing a cationic polymer compound.
• examples of the cationic polymer compound include a cation-releasing compound, a dicyan compound, a polyamine compound, a polycation compound, a dimethyldiallylammonium chloride / dioxide ion copolymer, a diallylamine salt polymer, and a dimethyldialylammonium chloride.
• Polymers, polymers of allylamine salts, dialkylaminoethyl acrylate quaternary salt polymers can be used.
• examples of the cyanogen compound include a cyanamide / formalin polymerization condensate.
• examples of polyamine compounds include dicyandiamide / diethylenetriamine polycondensate products.
• examples of the polycationic compound include epichlorohydrin and dimethylamine addition polymers.
• the stretching step is carried out.
• the stretching step is performed by uniaxially stretching the base material in a certain direction.
• the stretching method may be either a wet stretching method or a dry stretching method.
• the draw ratio is preferably 3 times or more, more preferably 5 to 9 times.
• the stretching heating medium is an air medium
• the humidity is preferably in an atmosphere of 20 to 95% RH.
• the method for heating the base material include, but are not limited to, an inter-roll zone stretching method, a roll heating stretching method, a hot pressure stretching method, and an infrared heating stretching method.
• the dry stretching step may be carried out by one-step stretching or by two or more steps of multi-step stretching.
• the stretching treatment is performed while immersing the base material in a solution containing at least one cross-linking agent.
• the cross-linking agent for example, boric acid in the above-mentioned cross-linking agent step can be used, and preferably, the stretching treatment can be performed in the treatment solution used in the cross-linking step.
• the stretching temperature is preferably 40 to 70 ° C, more preferably 45 to 60 ° C.
• the stretching time is usually 30 seconds to 20 minutes, preferably 2 to 7 minutes.
• the wet stretching step may be carried out by one-step stretching or by two or more steps of multi-step stretching.
• the stretching treatment may be optionally performed before the dyeing step, and in this case, the orientation of the luminescent compound represented by the formula (1) or a salt thereof is also performed at the time of dyeing. Can be done.
• the cross-linking agent may precipitate or foreign matter may adhere to the surface of the base material, so that the cleaning step of cleaning the surface of the base material can be performed.
• the washing time is preferably 1 second to 5 minutes.
• a cleaning method it is preferable to immerse the base material in the cleaning liquid, and on the other hand, the base material can be cleaned by applying or applying the cleaning liquid to the base material. Water is preferable as the cleaning liquid.
• the cleaning treatment may be carried out in one step or in two or more steps.
• the temperature of the washing solution in the washing step is not particularly limited, but is usually 5 to 50 ° C., preferably 10 to 40 ° C., and may be room temperature.
• Examples of the solvent of the solution or treatment liquid used in each of the above-mentioned steps include alcohols, amines and the like in addition to the above-mentioned water.
• Examples of alcohols include dimethyl sulfoxide, N-methylpyrrolidone, methanol, ethanol, propanol, isopropyl alcohol, glycerin, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and trimethyl propane. ..
• Examples of amines include ethylenediamine and diethylenetriamine.
• the solvent of the solution or the treatment liquid is not limited to these, but is most preferably water. Further, the solvent of these solutions or the treatment liquid may be used alone or as a mixture of two or more kinds.
• drying process After the cleaning step, it is preferable to carry out a drying step of the base material.
• the drying treatment can be carried out by natural drying, in order to further improve the drying efficiency, it can be carried out by compression with a roll, removal of moisture on the surface with an air knife or a water absorption roll, etc. It is also possible to do it.
• 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.
• the polarized light emitting device can be manufactured.
• the luminescent compound represented by the formula (1) in the present invention can be mixed with a liquid crystal and oriented on a base material, or can be oriented by a coating method shared on the base material to obtain various colors or.
• a polarized light emitting element having a neutral gray can be manufactured.
• a polarized light emitting plate provided with the above polarized light emitting element is also included in the present invention.
• the polarized light emitting plate according to the present invention preferably has a transparent protective film on at least one surface of the above polarized light emitting element.
• the transparent protective film is used to improve the water resistance and handleability of the polarizing light emitting element. Therefore, it is preferable that such a transparent protective film does not affect the polarization action exhibited by the polarized light emitting device according to the present invention.
• the transparent protective film is preferably a transparent protective film having excellent optical transparency and mechanical strength. Further, the transparent protective film is preferably a film having a layer shape capable of maintaining the shape of the polarizing light emitting element, and is a plastic film having excellent thermal stability, moisture shielding property, etc. in addition to transparency and mechanical strength. It is preferable to have.
• the material for forming such a transparent protective film include a cellulose acetate film, an acrylic film, a fluorine film such as an ethylene tetrafluoride / propylene hexafluoride copolymer, a polyester resin, and a polyolefin.
• Examples thereof include a film made of a resin or a polyamide-based resin, and a triacetyl cellulose (TAC) film or a cycloolefin-based film is preferably used.
• the thickness of the transparent protective film is preferably in the range of 1 to 200 ⁇ m, more preferably in the range of 10 to 150 ⁇ m, and particularly preferably in the range of 40 to 100 ⁇ m.
• the method for producing the polarized light emitting plate according to the present invention is not particularly limited, but for example, the polarized light emitting plate is produced by superimposing a transparent protective film on the polarized light emitting element and laminating with a known formulation. be able to.
• the polarized light emitting plate may further include an adhesive layer for adhering 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 adhesives, polyester-isocyanate-based adhesives, and the like, preferably polyvinyl. Alcohol-based adhesives are used.
• a polarized light emitting plate can be produced by adhering the transparent protective film and the polarized light emitting element with an adhesive and then drying or heat-treating at an appropriate temperature.
• the polarized light emitting plate may appropriately have various known functional layers such as an antireflection layer, an antiglare layer, and a further transparent protective film on the exposed surface of the transparent protective film.
• an antireflection layer such as an antireflection layer
• an antiglare layer such as an antiglare layer
• a further transparent protective film on the exposed surface of the transparent protective film.
• the further transparent protective film examples include a hard coat layer such as an acrylic type, a urethane type, and a polysiloxane type.
• a hard coat layer such as an acrylic type, a urethane type, and a polysiloxane type.
• an antireflection layer can be provided on the exposed surface of the transparent protective film.
• the antireflection layer can be formed, for example, by depositing or sputtering a substance such as silicon dioxide or titanium oxide on the transparent protective film, or by applying a thin layer of a fluorine-based substance on the transparent protective film. ..
• the polarized light emitting plate may be further provided with a transparent support such as glass, crystal, or sapphire, if necessary.
• a transparent support such as glass, crystal, or sapphire
• Such a support preferably has a flat surface portion for attaching the polarizing light emitting plate, and is preferably a transparent support from the viewpoint of optical application.
• the transparent support is divided into an inorganic support and an organic support.
• examples of the support made of an inorganic material include a support made of a material such as soda glass, borosilicate glass, crystal, sapphire, and spinel.
• the organic support include a support composed of acrylic, polycarbonate, polyethylene terephthalate, polyethylene naphthalate, cycloolefin polymer and the like.
• the thickness and size of the transparent support are not particularly limited and can be appropriately determined. Further, it is preferable that the polarized light emitting plate having such a transparent support is provided with an antireflection layer on one or both surfaces of the support surface or the polarized light emitting plate surface in order to further improve the single transmittance.
• a transparent adhesive (adhesive) agent may be applied to the flat surface portion of the support, and then the polarized light emitting plate according to the present invention may be attached to the coated surface. ..
• the adhesive or pressure-sensitive adhesive to be used is not particularly limited, and commercially available ones can be used, and an acrylic ester-based adhesive or pressure-sensitive adhesive is preferable.
• the polarized light emitting plate can also be used as a circularly polarized light emitting plate or an elliptically polarized light emitting plate to which a retardation plate is attached.
• the support may be a retardation plate.
• the retardation plate generally include, but are not limited to, those having a retardation value of 1 / 4 ⁇ with respect to the absorption wavelength or emission wavelength of light and those having a retardation value of 1 / 2 ⁇ . ..
• phase difference value of 1 / 4 ⁇ By having a phase difference value of 1 / 4 ⁇ , it functions as a circularly polarizing plate or a circularly polarized light emitting plate for that wavelength, and by using 1 / 2 ⁇ , it is possible to use such that polarized light can be converted in the direction of 90 °. It becomes.
• various functional layers, supports, etc. can be further provided on the polarized light emitting plate, and such polarized light emitting plates can be used, for example, in liquid crystal projectors, calculators, watches, notebook computers, word processors, liquid crystal televisions, and the like. It can be used for various products such as car navigation systems, indoor and outdoor measuring instruments and indicators, lenses, and glasses.
• the polarized light emitting element and the polarized light emitting plate according to the present invention show a high degree of polarization in light in the ultraviolet region to near-ultraviolet visible region, for example, in the region of 300 to 430 nm, and further, have a polarized light emitting action and high transmittance in the visible light region. Shows the rate. Further, since the polarized light emitting element and the polarized light emitting plate according to the present invention show excellent durability against heat, humidity, light and the like, their performance can be maintained even in a harsh environment, and the performance thereof has been conventionally maintained. It has higher durability than the iodine-based polarizing plate of.
• the polarized light emitting element and the polarized light emitting plate according to the present invention are liquid crystal displays, for example, televisions, wearable terminals, tablet terminals, smartphones, which are required to have high transparency in the visible light region and high durability in harsh environments. It can be applied to various display devices such as in-vehicle monitors, digital signage used outdoors or indoors, and smart windows.
• a display device including the polarized light emitting element or the polarized light emitting plate is also included in the present invention.
• the display device exhibits a polarized light emitting effect by irradiating light in the ultraviolet region to visible region, for example, light in the ultraviolet region to near ultraviolet visible region, specifically, light having a diameter of 300 to 430 nm, and utilizes this effect. Can be displayed by. Since the display device according to the present invention has a high transmittance in the visible light region, even if there is no decrease in the transmittance in the visible light region like a conventional polarizing plate, or even if there is a decrease in the transmittance. The decrease in transmittance is significantly smaller than that of the conventional polarizing plate.
• iodine-based polarizing plates which are conventional polarizing plates, and dye-based polarizing plates using other dyes require a luminosity factor correction of 35 to 45 in the visible light region in order to make the degree of polarization approximately 100%. It is about%.
• the conventional polarizing plate has both the vertical axis and the horizontal axis as the light absorption axis, but the incident light on either the vertical axis or the horizontal axis is obtained in order to obtain a degree of polarization of almost 100%. That is, polarization is generated by absorbing light on one axis and transmitting light on the other axis.
• a polarizing plate is produced by orienting a dichroic dye in a stretched film, but the dichroic dye is not necessarily 100% oriented, and the light transmission axis is used. On the other hand, it has some absorbing components. Therefore, a degree of polarization of almost 100% cannot be realized unless the transmittance is about 45% or less due to the surface reflection of the substance, that is, a high degree of polarization cannot be realized unless the transmittance is lowered.
• the polarized light emitting element and the polarized light emitting plate according to the present invention have an axis (its polarization function) for absorbing light in the ultraviolet region to near-ultraviolet visible region, for example, 300 to 430 nm, that is, the ultraviolet region to.
• Light in the near-ultraviolet visible region, for example, 300 to 430 nm has a light absorbing effect and exhibits a polarized light emitting effect that emits polarized light in the visible light region, but hardly absorbs light in the visible light region, so that it is visible light.
• the transparency in the area is very high.
• a display device using the polarized light emitting element and the polarized light emitting plate according to the present invention for example, a liquid crystal display, can obtain higher brightness than a liquid crystal display provided with a conventional polarizing plate. Further, since the display device using the polarized light emitting element and the polarized light emitting plate according to the present invention has high transparency, a substantially transparent display can be obtained even though it is a liquid crystal display.
• the display device can obtain a transparent liquid crystal display having no light loss, particularly a see-through display.
• the display device can polarize light in the ultraviolet to near-ultraviolet visible region, which is invisible or difficult to see by humans, for example, light of 300 to 430 nm, it can be displayed by ultraviolet light. It can be applied to liquid crystal displays. For example, by recognizing an image or the like displayed in the ultraviolet-near-ultraviolet-visible region by a computer or the like, it can be visually recognized only when light in the ultraviolet-near-ultraviolet-visible region, for example, light of 300 to 430 nm is irradiated. A simple and highly secure liquid crystal display can be produced.
• the display device since the display device exhibits a polarized light emitting action by irradiating light in the ultraviolet region to near-ultraviolet visible region, for example, light of 300 to 430 nm, a liquid crystal display utilizing the polarized light emission can be manufactured. It is also possible to realize a liquid crystal display that uses light in the ultraviolet to near-ultraviolet visible range instead of a normal liquid crystal display that uses visible light. That is, even in a dark space without visible light, it is possible to manufacture a light emitting liquid crystal display on which displayed characters, images, etc. are displayed as long as the space can be irradiated with light in the ultraviolet to near-ultraviolet visible region. It becomes.
• the visible light region has a liquid crystal display portion that can be displayed by the light in the visible light region and a liquid crystal display by the polarized light emitting action by the ultraviolet light. It is also possible to manufacture a display capable of two different displays in which the display portion coexists. There have been two displays capable of different displays, but there is no display capable of different displays in the ultraviolet light region and the visible light region by different light sources even though they are the same liquid crystal panel. .. From this, the display device according to the present invention can produce a new display by using the above-mentioned polarized light emitting element or polarized light emitting plate.
• the present invention also includes a liquid crystal display including the above-mentioned polarized light emitting element, polarized light emitting plate or display device.
• the liquid crystal cell used in the liquid crystal display is not limited to, for example, a TN liquid crystal cell, an STN liquid crystal cell, a VA liquid crystal cell, an IPS liquid crystal cell, and the like, and can be used in any liquid crystal display mode. Since the liquid crystal display has high durability, it is possible to provide a liquid crystal display for in-vehicle or outdoor display.
• the present invention also includes a neutral gray polarized light emitting plate for in-vehicle or outdoor display provided with the above-mentioned polarized light emitting element, polarized light emitting plate or display device.
• the neutral gray polarized light emitting plate for in-vehicle or outdoor display is excellent in polarized light emitting performance, and further has a feature that discoloration and deterioration of polarization performance do not occur even in a high temperature and high humidity state inside or outdoors.
• the neutral gray refers to a polarized light emitting plate having a significantly low transmittance or a constant transmittance at each wavelength in the transmittance at orthogonal positions in the visible region.
• the transmittance at the orthogonal position is 0.3% or less, more preferably 0.1% or less, still more preferably 0.03% or less, particularly preferably 0.01% or less, and the transmittance is constant. Indicates that the difference in transmittance is within 1% with respect to the average transmittance of each wavelength.
• Example 1 (Synthesis example) 84 parts of the compound represented by the formula (25) was added to 1000 parts of water and heated to 60 ° C., and 25% caustic soda was added while adjusting the pH to 6 to 7 to dissolve the compound. 27.8 parts of 4,4'-biphenyldicarbonyl chloride was added little by little over about 1 hour. After all the additions were made, the mixture was stirred at 60 ° C. for 1 hour to react. After completion of the reaction, the mixture was allowed to cool to room temperature and filtered, and the obtained solid was dried at 70 ° C. to obtain 73.4 parts of the compound represented by the formula (16).
• a polyvinyl alcohol film having a thickness of 75 ⁇ m (VF-PS # 7500 manufactured by Kuraray Co., Ltd.) was immersed in water at 40 ° C. for 3 minutes to swell the film.
• the film obtained by swelling contains 0.2 parts by mass of the compound represented by the formula (16) obtained in Synthesis Example 1, 1.0 part by mass of sardine, and 1000 parts by mass of water at 45 ° C.
• the film was impregnated with the compound represented by the formula (16) by immersing it in an aqueous solution for 4 minutes.
• the film containing the compound represented by the formula (16) was stretched 5 times over 5 minutes in a 3% aqueous boric acid solution at 50 ° C.
• the film obtained by stretching was washed with water at room temperature for 20 seconds while maintaining a tense state, and dried at 70 ° C. to obtain a polarized light emitting device.
• a polarized 4% by mass polyvinyl alcohol (NH-26 manufactured by Japan Vam & Poval Co., Ltd.) aqueous solution was laminated as an adhesive to obtain a polarized light emitting plate, which was used as a measurement sample of Example 1. Even if a triacetyl cellulose film (ZRD-60 manufactured by FUJIFILM Corporation) containing no ultraviolet absorber was attached to the polarized light emitting element, it did not affect the optical characteristics of the polarized light emitting element in any way. In the following examples and comparative examples, a triacetyl cellulose film containing no ultraviolet absorber was attached to the polarized light emitting element, but similarly, it did not affect the optical characteristics at all.
• Example 2 61.6 parts of the compound represented by the formula (26) was added to 600 parts of water and heated to 60 ° C., and 25% caustic soda was added while adjusting the pH to 6 to 7 to dissolve the compound. 27.8 parts of 4,4'-biphenyldicarbonyl chloride was added little by little over about 1 hour. After all the additions were made, the mixture was stirred at 60 ° C. for 1 hour to react. After completion of the reaction, the mixture was allowed to cool to room temperature and filtered, and the obtained solid was dried at 70 ° C. to obtain 57.5 parts of the compound represented by the formula (15). In the production of the polarized light emitting device and the polarized light emitting plate of Example 1, the measurement of Example 2 was carried out in the same manner except that the compound represented by the formula (15) was used instead of the compound represented by the formula (16). A sample was obtained.
• Example 3 Add 21.8 parts of the compound represented by the formula (27) and 10.8 parts of the compound represented by the formula (28) to 400 parts of water, and add 25% caustic soda while adjusting the pH to 6 to 7. , The compound was dissolved, and 15.6 parts of phenyl chloroformate was stirred at 50 to 70 ° C. for 6 hours to form ureido. 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). Add 24.6 parts of the obtained ureido compound represented by the formula (29) and 27.8 parts of 4,4'-biphenyldicarbonyl chloride to 1000 parts of water and heat to 60 ° C.
• Example 3 In the production of the polarized light emitting device and the polarized light emitting plate of Example 1, the measurement of Example 3 was carried out in the same manner except that the compound represented by the formula (20) was used instead of the compound represented by the formula (16). A sample was obtained.
• Example 4 61.6 parts of the compound represented by the formula (30) was added to 600 parts of water and heated to 60 ° C., and 25% caustic soda was added while adjusting the pH to 6 to 7 to dissolve the compound. 27.8 parts of 4,4'-biphenyldicarbonyl chloride was added little by little over about 1 hour. After all the additions were made, the mixture was stirred at 60 ° C. for 1 hour and reacted. After completion of the reaction, the mixture was allowed to cool to room temperature and filtered, and the obtained solid was dried at 70 ° C. to obtain 57.5 parts of the compound represented by the formula (18). In the production of the polarized light emitting device and the polarized light emitting plate of Example 1, the measurement sample of Example 4 was obtained in the same manner except that the compound represented by the formula (18) was used instead of the compound represented by the formula (16). Got
• Example 35.2 parts of the compound represented by the formula (31) and 66.7 parts of 4-nitro-4'-aminostilbene-2,2'-disulfonic acid are added to 800 parts of water and heated to 60 ° C. to pH 6 to. 25% caustic soda was added while adjusting to 7 to dissolve the compound.
• 25.9 parts of phenyl chloroformate was added little by little over about 1 hour. After all the additions were made, the mixture was stirred at 60 ° C. for 1 hour and reacted. After completion of the reaction, the mixture was allowed to cool to room temperature and filtered, and the obtained solid was dried at 70 ° C. to obtain 66.5 parts of the compound represented by the formula (22).
• the measurement of Example 5 was carried out in the same manner except that the compound represented by the formula (22) was used instead of the compound represented by the formula (16). A sample was obtained.
• Example s1 Add 80 parts of 4-nitro-4'-aminostilbene-2,2'-disulfonic acid to 1000 parts of water, heat to 60 ° C., and add 25% caustic soda while adjusting the pH to 6-7. The compound was dissolved. 27.8 parts of 4,4'-biphenyldicarbonyl chloride was added little by little over about 1 hour. After all the additions were made, the mixture was stirred at 60 ° C. for 1 hour to react. After completion of the reaction, the mixture was allowed to cool to room temperature and filtered, and the obtained solid was dried at 70 ° C. to obtain 70 parts of the compound represented by the formula (s14).
• Example s1 In the production of the polarized light emitting device and the polarized light emitting plate of Example 1, the measurement of Example s1 is carried out in the same manner except that the compound represented by the formula (s14) is used instead of the compound represented by the formula (16). A sample was obtained.
• Example s2 136 parts of the compound represented by the formula (s28) was added to 1000 parts of water and heated to 60 ° C., and 25% caustic soda was added while adjusting the pH to 6 to 7 to dissolve the compound. 27.8 parts of 4,4'-biphenyldicarbonyl chloride was added little by little over about 1 hour. After all the additions were made, the mixture was stirred at 60 ° C. for 1 hour to react. After completion of the reaction, the mixture was allowed to cool to room temperature and filtered, and the obtained solid was dried at 70 ° C. to obtain 103 parts of the compound represented by the formula (s15).
• Example s2 In the production of the polarized light emitting device and the polarized light emitting plate of Example 1, the measurement of Example s2 is carried out in the same manner except that the compound represented by the formula (s15) is used instead of the compound represented by the formula (16). A sample was obtained.
• Example s3 Add 40 parts of 4-nitro-4'-aminostilbene-2,2'-disulfonic acid and 68.2 parts of the compound represented by the formula (s28) to 1000 parts of water and heat to 60 ° C., pH 6-7. 25% caustic soda was added to dissolve the compound. 40 parts of 4,4'-biphenyldicarbonyl chloride was added little by little over about 1 hour. After all were added manually, the mixture was stirred at 60 ° C. for 1 hour to react. After completion of the reaction, the mixture was allowed to cool to room temperature and filtered, and the obtained solid was dried at 70 ° C. to obtain 90.1 parts of the compound represented by the formula (s29).
• Example s3 In the production of the polarized light emitting device and the polarized light emitting plate of Example 1, the measurement of Example s3 was carried out in the same manner except that the compound represented by the formula (s29) was used instead of the compound represented by the formula (16). A sample was obtained.
• Example s4 Add 74.0 parts of 4,4'-diaminostilbene-2,2'-disulfonic acid to 1000 parts of water, heat to 60 ° C., and add 25% caustic soda while adjusting the pH to 6-7. The compound was dissolved. 27.8 parts of 4,4'-biphenyldicarbonyl chloride was added little by little over about 1 hour. After all the additions were made, the mixture was stirred at 60 ° C. for 1 hour and reacted. After completion of the reaction, the mixture was allowed to cool to room temperature and filtered, and the obtained solid was dried at 70 ° C. to obtain 66.2 parts of the compound represented by the formula (s12).
• Example s4 In the production of the polarized light emitting device and the polarized light emitting plate of Example 1, the measurement of Example s4 was carried out in the same manner except that the compound represented by the formula (s12) was used instead of the compound represented by the formula (16). A sample was obtained.
• Example s5 Add 94.6 parts of the compound represented by the formula (s12) obtained in Example 4 and 80 parts of 4-nitro-4'-aminostilbene-2,2'-disulfonic acid to 1000 parts of water up to 60 ° C. The compound was dissolved by heating and adding 25% caustic soda while adjusting the pH to 6-7. 31.2 parts of phenyl chloroformate was added little by little over about 1 hour. After all the additions were made, the mixture was stirred at 60 ° C. for 1 hour and reacted. After completion of the reaction, the mixture was allowed to cool to room temperature and filtered, and the obtained solid was dried at 70 ° C. to obtain 122.2 parts of the compound represented by the formula (s19).
• Example s5 In the production of the polarized light emitting device and the polarized light emitting plate of Example 1, the measurement of Example s5 was carried out in the same manner except that the compound represented by the formula (s19) was used instead of the compound represented by the formula (16). A sample was obtained.
• Comparative Example 1 In the production of the polarized light emitting device and the polarized light emitting plate of Example 1, the compound represented by the formula (c1) described in JP-A-4-226162 is used instead of the compound represented by the formula (16). The measurement sample of Comparative Example 1 was obtained in the same manner except that the sample was obtained.
• Comparative Example 2 In the production of the polarized light emitting device and the polarized light emitting plate of Example 1, the compound represented by the formula (c2) is replaced with the compound represented by the formula (16). I. A measurement sample of Comparative Example 2 was obtained in the same manner except that Direct Yellow 4 was used.
• Comparative Example 3 In the production of the polarized light emitting device and the polarized light emitting plate of Example 1, the measurement of Comparative Example 3 was carried out in the same manner except that the compound represented by the formula (c3) was used instead of the compound represented by the formula (16). A sample was obtained.
• Orthogonal transmittance Tc (%) is a spectral transmittance measured by superimposing two measurement samples so that their absorption axes are orthogonal to each other. Measurements of each transmittance were performed over wavelengths of 220 to 780 nm.
• the single transmittance Ys (%) corrected to the visual sensitivity of each measurement sample is a predetermined wavelength interval d ⁇ (in the wavelength region of 400 to 700 nm in the visible region).
• d ⁇ the transmittance obtained by correcting the single transmittance Ts obtained every 5 nm) to the visual sensitivity according to JIS Z 8722: 2009.
• the single transmittance Ts was substituted into the equation (II) to calculate the visual sensitivity correction single transmittance Ys.
• P ⁇ represents the spectral distribution of standard light (C light source)
• y ⁇ represents the two-degree visual field color matching function.
• a polarizing plate having a polarization function in the region and ultraviolet rays (“SKN-18043P” manufactured by Polar Techno Co., Ltd., thickness 180 ⁇ m, Ys is 43%) was installed in the light receiving part of the spectroirradiance meter, and obtained in each Example and Comparative Example.
• the amount of polarized light emitted from the measurement sample was measured. That is, the light from the light source passed through the ultraviolet transmission and visible light cut filter, the measurement sample, the polarizing plate having polarization in the visible region and the ultraviolet light in this order, and was arranged so as to be incident on the spectroirradiance meter for measurement.
• the absorption axis that maximizes the absorption of ultraviolet rays of the measurement sample and the polarizing plate having polarization in the visible region and ultraviolet rays (“SKN-18043P” manufactured by Polar Techno Co., Ltd.) are overlapped so as to be parallel to each other.
• Lw and Ls were measured with the spectral emission amount of each wavelength measured by superimposing them so that the absorption axis directions of) were orthogonal to each other as Ls (strong emission axis).
• Table 1 shows the wavelengths indicating the maximum polarization degree of each of the measurement samples obtained in Examples 1 to 5 and s1 to s5 and Comparative Examples 1 to 3, and the single transmittance Ts (%) at the wavelength indicating the maximum polarization degree, parallel.
• Position transmittance Tp (%), orthogonal position transmittance Tc (%), polarization degree ⁇ (%), single transmittance Ys (%) corrected for visual sensitivity, and polarization degree ⁇ y (%) corrected for visual sensitivity. ) Is shown.
• Table 2 shows 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.
• Table 3 below shows Ls and Lw of each wavelength after the light resistance test of each of the measurement samples obtained in Examples 1 to 5 and s1 to s5 and Comparative Example 1.
• the measurement samples of Examples 1 to 5 and s1 to s5 and Comparative Example 1 have absorption in the ultraviolet to near-ultraviolet visible region and function as a polarizing light emitting plate in that band.
• the transmittance in the visible region (luminosity correction transmittance Ys) was 90% or more, and it was found that the visible transparency was high while having a polarization function in the ultraviolet region to the near-ultraviolet visible region.
• Comparative Examples 2 and 3 since the wavelength showing the maximum degree of polarization was 400 nm or more and the luminosity factor correction transmittance Ys was decreased, the visible transmittance was decreased.
• Examples 1 and s1 to s3 had higher light resistance than Comparative Example 1. Therefore, the polarized light emitting element of the present invention and the polarized light emitting plate using the same function not only function as a polarized light emitting element that emits polarized light in the visible region by irradiation with ultraviolet rays, but also have high light resistance. It has been shown.
• the luminescent compound according to the present invention in a substrate, it is possible to obtain a polarized light emitting element and a polarized light emitting plate which not only have a high degree of polarization in the absorption wavelength but also exhibit a polarized light emitting action. Further, such a polarized light emitting element and a polarized light emitting plate have high transmittance in the visible light region while having excellent durability. Therefore, the display device provided with the polarized light emitting element or the polarized light emitting plate according to the present invention has high transparency in the visible light region and can display an image by polarized light emission for a long period of time. It can be applied to a wide range of applications such as displays (see-through displays).
• the polarized light emitting element and the polarized light emitting plate containing the luminescent compound according to the present invention can emit light from the ultraviolet region to the near ultraviolet visible region, for example, the light of 300 to 430 nm, a display requiring high security. It can also be applied to and media.

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