JP7327151B2 - Luminescent material, luminescent material composition, luminescence conversion member, backlight unit, and liquid crystal display device - Google Patents

Description

The present invention relates to a luminescent material containing perovskite-type semiconductor nanoparticles, and a luminescent material composition, a wavelength conversion member, and the like using the luminescent material. The perovskite-type semiconductor nanoparticles of the present invention have good luminescence properties, and can maintain these properties for a long period of time.

Compounds having a perovskite crystal structure are known to have many unique physical properties such as magnetism, piezoelectricity, dielectricity, electroluminescence and electrical conductivity. In particular, when a perovskite compound having a perovskite crystal structure composed of A, B, and X, wherein A is a monovalent cation, B is a divalent cation, and X is a monovalent anion, By changing the type and ratio of X, it is possible to obtain emission colors in almost the entire visible light range from blue to red (Non-Patent Documents 1 to 3).
Furthermore, the light emitted by the perovskite compound has a narrow full width at half maximum and high color purity, so it is suitable for light-emitting materials and wavelength conversion materials, and can be used as materials for various light-emitting devices (Patent Documents 1 and 2).
However, the perovskite compounds described in Patent Documents 1 and 2 are not sufficiently stable. In addition, complicated post-treatments and processes are required in order to enhance stability, and their use may be limited to specific applications.

Patent Document 3 discloses a technique for enhancing stability by dispersing a perovskite compound in a polymer. However, diversification alone cannot guarantee long-term stability. Moreover, in Patent Document 3, since a polymer having a mass 50 times that of the perovskite compound is used, the emission intensity per volume is low, and the polymer, which is an insulator, is excessive. It is unsuitable for display applications such as materials and electroluminescence.

Patent Document 4 discloses a technique for improving the stability by treating the surface of a perovskite compound with a special ligand. However, the perovskite compound obtained by such a method is not stable for a long period of time, although it can withstand the adjustment of the device. Moreover, in order to obtain the perovskite compound, a large number of processes such as precursor preparation, ligand surface treatment, and multi-step cleaning are required, which is not suitable for mass production processes. Furthermore, although this method is suitable for _CsPbBr3 compounds, it is difficult to apply to perovskite compounds of other compositions.

Patent Document 5 discloses a technique for enhancing the stability of perovskite compounds by using tri-n-octylphosphine as a ligand compound. However, it is described that depending on the type of perovskite compound, aggregation of particles or phase transition occurs over time, and long-term stability is a problem.

Patent Document 6 relates to an ink composition containing semiconductor nanoparticles containing a perovskite compound and a curable resin composition, and having high emission intensity and solvent resistance of the cured product. Specifically disclosed is an ultraviolet curable composition comprising a perovskite compound synthesized below and an acrylic monomer having no basic group.
However, the technical idea of Patent Document 6 is that resistance is imparted only after the composition is irradiated with ultraviolet rays to cure the coating material on the surface of the semiconductor nanoparticles, and the resistance of the semiconductor nanoparticles themselves is improved. long-term stability is insufficient.

Therefore, it is desired to increase the stability of the perovskite compound alone by a simple method without relying on post-treatments such as curing and sealing.

JP 2016-132638 A JP 2017-108129 A Japanese Patent Publication No. 2018-522959 Japanese Patent Publication No. 2018-530633 JP 2019-016772 A WO2019/022195

Nano Lett. 2015, 15, 3692-3696 J. Am. Chem. Soc. 2015, 137, 10276-10281 Chem. Commun. 2016, 52, 7265-7268

Therefore, the present invention provides a perovskite compound and a luminescent material composition which themselves have high stability and excellent luminescent properties without depending on post-treatments such as curing and sealing, and luminous conversion materials having excellent luminescent properties. An object of the present invention is to provide a member, a backlight unit, and a liquid crystal display device.

As a result of earnest studies to solve the above problems, the inventors have found that the above problems can be solved by the following embodiments, and have completed the present invention.

An embodiment of the present invention includes a core containing a semiconductor nanoparticle having a perovskite crystal structure, a ligand bound to the surface of the core, and a shell covering at least a portion of the core bound to the ligand. , wherein the ligand comprises an organic acid salt, and the shell comprises a basic group-containing compound.

Another embodiment of the present invention relates to the luminescent material, wherein the organic acid salt is a fatty acid salt having 1 to 30 carbon atoms.

Another embodiment of the present invention relates to the luminescent material, wherein the organic acid salt is a sodium salt.

Another embodiment of the present invention relates to the light-emitting material, wherein the basic group-containing compound is a polymer containing a repeating unit derived from a basic group-containing monomer.

Another embodiment of the present invention relates to the light-emitting material, wherein the basic group of the basic group-containing compound is a group represented by the following general formula (1).

General formula (1)

[In general formula (1), R ¹ to R ⁴ each independently represent an alkyl group having 1 to 10 carbon atoms. R ⁵ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an aryl group. n is an integer of 0-2. ]

Another embodiment of the present invention relates to the luminescent material, wherein the basic group-containing compound has an amine value of 1 to 400 mgKOH/g.

Another embodiment of the present invention relates to a luminescent material composition comprising the above luminescent material and a solvent.

Another embodiment of the present invention relates to a wavelength conversion member having a wavelength conversion layer formed from the luminescent material composition.

Another embodiment of the present invention relates to a backlight unit including the wavelength conversion member and a light source.

Another embodiment of the present invention relates to a liquid crystal display device including the above backlight unit and a liquid crystal cell.

According to the present invention, a perovskite compound and a luminescent material composition that themselves have high stability and excellent luminescence properties without depending on post-treatment such as curing or sealing, and a luminescence conversion member that has excellent luminescence properties, A backlight unit and a liquid crystal display device can be provided.

The luminescent material of the present invention includes a core containing semiconductor nanoparticles having a perovskite crystal structure, a ligand bound to the surface of the core, and a shell covering at least a portion of the core bound to the ligand, wherein the ligand is It contains an organic acid salt, and the shell contains a basic group-containing compound.
The present invention will be described in detail below.

<Semiconductor nanoparticles>
The semiconductor nanoparticles contained in the core of the luminescent material have a perovskite crystal structure composed of A (monovalent cation), B (divalent cation), and X (monovalent anion including halide anion). have.
Analysis of the perovskite crystal structure and the molar ratio of A and B (A/B) can be obtained based on X-ray photoelectric analysis (XPS). The X-ray photoelectric analysis is a suitable method from the viewpoint that each element to be analyzed can be analyzed simultaneously and the measurement accuracy is high. The perovskite crystal structure includes a 0- to 3-dimensional structure, and a 3-dimensional structure is particularly preferred.

[A (monovalent cation)]
A is a monovalent cation, for example, an ammonium cation (NH ₄ ⁺ ), an alkylammonium cation having 6 or less carbon atoms, a formamidinium cation (HC(NH ₂ ) ₂ ⁺ ), a guanidinium cation (C( NH ₂ ) ₃ ⁺ ), imidazolium cations, pyridinium cations, nitrogen-containing organic compound cations such as pyrrolidinium cations; or lithium cations (Li ⁺ ), sodium cations (Na ⁺ ), potassium cations (K ⁺ ), rubidium cations (Rb ⁺ ), and alkali metal cations such as cesium cations (Cs ⁺ ); Since these cations have a small ion diameter and are of a size that can be accommodated in the crystal lattice, the perovskite compound can form a stable three-dimensional crystal.

Preferred examples of alkylammonium cations having 6 or less carbon atoms include methylammonium cation (CH ₃ NH ₃ ⁺ ), ethylammonium cation (C ₂ H ₅ NH ₃ ⁺ ), and propylammonium cation (C ₃ H ₇ NH ₃ ⁺ ). etc.

A is preferably a methylammonium cation, a formamidinium cation, or a cesium cation from the viewpoint of obtaining high luminous efficiency, and more preferably a cesium cation from the viewpoint of suppressing color change. These cations may be used in combination of two or more.

When A is a cesium cation, raw materials for synthesizing semiconductor nanoparticles described later include cesium chloride, cesium bromide, cesium iodide, cesium hydroxide, cesium carbonate, cesium hydrogen carbonate, cesium bicarbonate, cesium formate, Salts such as cesium acetate, cesium propionate, cesium pivalate, and cesium oxalate can be mentioned, and suitable ones can be used depending on the synthesis method.
When A is another alkali metal cation, a salt or the like obtained by replacing the cesium element of the above cesium compound with another alkali metal cation element can be used as a raw material.
When A is a nitrogen-containing organic compound cation such as methylammonium cation, for example, neutral compounds other than salts such as methylamine can be used as raw materials. These raw materials may be used in combination of two or more.

[B (divalent cation)]
B is a divalent cation such as scandium cation (Sc ²⁺ ), titanium cation (Ti ²⁺ ), vanadium cation (V ²⁺ ), chromium cation (Cr ²⁺ ), manganese cation (Mn ²⁺ ), iron cation (Fe ²⁺ ), cobalt cation (Co ²⁺ ), nickel cation (Ni ²⁺ ), copper cation (Cu ²⁺ ), palladium cation (Pd ²⁺ ), europium cation (Eu ²⁺ ), ytterbium cation (Yb ²⁺ ), etc. metal cation; or magnesium cation (Mg ²⁺ ), calcium cation (Ca ²⁺ ), strontium cation (Sr ²⁺ ), barium cation (Ba ²⁺ ), zinc cation (Zn ²⁺ ), cadmium cation (Cd ²⁺ ), germanium cation ( Ge ²⁺ ), tin cations (Sn ²⁺ ), lead cations (Pb ²⁺ ) and other typical divalent metal cations;
Among these, divalent typical metal cations are preferred from the viewpoint of growing stable three-dimensional crystals, tin cations or lead cations are more preferred, and lead cations are particularly preferred from the viewpoint of obtaining strong light emission. These cations may be used in combination of two or more.

When B is a lead cation, lead chloride, lead bromide, lead iodide, lead oxide, lead hydroxide, lead sulfide, lead carbonate, lead formate, and lead acetate are used as raw materials for synthesizing semiconductor nanoparticles, which will be described later. , lead 2-ethylhexanoate, lead oleate, lead stearate, lead naphthenate, lead citrate, lead maleate, lead acetylacetonate, etc., and suitable salts can be used depending on the synthesis method. . When B is another divalent metal cation, a salt or the like obtained by replacing the lead element of the above lead compound with another divalent metal cation element can be used as a raw material. These raw materials may be used in combination of two or more.

[X (monovalent anions including halide anions)]
X is a monovalent anion including halide anions, and the halide anions include fluoride anion (F ⁻ ), chloride anion (Cl ⁻ ), bromide anion (Br ⁻ ), iodide anion (I ⁻ ) and the like. Among them, a chloride anion, a bromide anion, or an iodide anion is preferable from the viewpoint of forming a stable three-dimensional crystal and exhibiting strong light emission in the visible light region. The emission color is blue when chloride anions are used, green when bromide anions are used, and red when iodide anions are used.
Two or more halide anions may be used in combination. Especially when chloride anions, bromide anions, and iodide anions are used in combination, depending on the ratio of the anion species, the emission of the semiconductor nanoparticles can be made at the desired wavelength, and the emission from blue to red can be achieved while maintaining a narrow full width at half maximum. It is preferable because it is possible to obtain an emission spectrum that covers almost the entire region of visible light.
X may contain monovalent anions other than halide anions, such monovalent anions include cyanide anion (CN ⁻ ), thiocyanate anion (SCN ⁻ ), isothiocyanate anion (CNS ^- ) and other pseudohalide anions.

Raw materials for synthesizing semiconductor nanoparticles described later include salts with the aforementioned A and B as counter cations, such as cesium chloride and lead bromide, and salts with other cations, depending on the synthesis method. You can choose the appropriate one accordingly. Among them, salts having tetraalkylammonium as a counter cation are preferable from the viewpoint of dispersion stability of raw materials and semiconductor nanoparticles. The four alkyl groups constituting the tetraalkylammonium can be independently selected from alkyl groups having any carbon length, and may have further substituents such as alicyclic, aromatic rings and polar groups, The alkyl groups may form a ring together.

When the raw material of X is a salt of a tetraalkylammonium cation and a halide anion, examples of the raw material of X include tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, tetrapentylammonium chloride, and benzyltriethylammonium chloride. , benzyltributyl ammonium chloride, salts with chloride anions such as (2-methoxyethoxymethyl) triethylammonium chloride; Salts with bromide anions such as tetraheptylammonium bromide, tetraoctylammonium bromide, tetra(decyl)ammonium bromide, tetradodecylammonium bromide, benzyltriethylammonium bromide, benzyltributylammonium bromide, allyltriethylammonium bromide; Propyl ammonium iodide, tetrabutylammonium iodide, tetrapentylammonium iodide, tetrahexylammonium iodide, tetraheptylammonium iodide, tetraoctylammonium iodide, ethyltripropylammonium iodide, benzyltriethylammonium iodide, benzyl salts with iodide anions such as tributylammonium iodide, triethylphenylammonium iodide, 5-azoniaspiro[4.4]nonane iodide;
These raw materials may be used in combination of two or more different types.

Specific examples of the semiconductor nanoparticles having the perovskite crystal structure include structures described in paragraphs 0036 to 0038 of [Patent Document 6] International Publication No. 2019/022195, but the present invention is not limited thereto. not something.

Semiconductor nanoparticles in the present invention are produced by a hot injection method in which a raw material solution is mixed at a high temperature, and then rapidly cooled after fine particle formation to obtain a stable product. Ligand-assisted reprecipitation method for obtaining fine particles. Under mild conditions at about room temperature, a raw material mixture of A and B, which is a non-halide containing no X component, is mixed with a separately prepared raw material solution of X. room-temperature synthesis method to obtain fine particles, mechanochemical method to obtain product fine particles by reacting solid raw materials by mechanical mixing such as milling or ultrasonic treatment, electronic devices, etc. directly after coating the raw material liquid on the substrate It can be produced by using an in situ synthesis method or the like in which a reactant is obtained by crystal growth. Among them, the room temperature synthesis method is preferably used from the viewpoint of producing fine particles stably.

Specific synthesis methods include ACS Nano, 10 (3), 3648-3657 (2016), Adv. Funct. Mater., 26 (15), 2435-2445 (2016), Chem. ), 7265-7268 (2016), ACS Nano, 10(8), 7943-7954(2016), Adv. Funct. Mater., 26(47), 8757-8763(2016), ChemistrySelect, 1(13), 3479-3482 (2016), Adv. Funct. Mater., 26 (34), 6238-6245 (2016), Phys. No., International Publication No. 2017/106979, International Publication No. 2016/180364, International Publication No. 2017/166871, International Publication No. 2017/020137, International Publication No. 2017/077523, International Publication No. 2018/168638 , JP-A-2017-108129, JP-A-2017-142486, International Publication No. 2019/022195, International Publication No. 2019/142089, etc., but are limited to these isn't it.

<ligand>
The luminescent material of the present invention is characterized by having a ligand bound to the surface of a core containing semiconductor nanoparticles having a perovskite crystal structure, and containing an organic acid salt as the ligand. Stability such as dispersion stability and spectral characteristics can be improved by these ligands.
The organic acid in the organic acid salt includes, for example, an organic compound having a carboxyl group and an organic compound having a sulfo group. From the viewpoint of synthesis, an organic compound having a carboxyl group is preferable. The organic compound having a carboxyl group is preferably a branched or linear fatty acid salt having 1 to 30 carbon atoms, and may be either saturated or unsaturated.

Specific examples of linear saturated fatty acid salts include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, and tridecylic acid. , myristic acid, pentadecyl acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, heptacosanoic acid, montanic acid, melisic acid, and laxeric acid.
Linear unsaturated fatty acids include, for example, acrylic acid, crotonic acid, isocrotonic acid, undecylenic acid, oleic acid, elaidic acid, cetoleic acid, erucic acid, nervonic acid, sapienic acid, brassic acid, sorbic acid, and linoleic acid. , linolenic acid, stearidonic acid, eicosapentaenoic acid, docosapentaenoic acid, docosahexaenoic acid, arachidonic acid, propiolic acid, stearolic acid, palmitoleic acid, vaccenic acid, pauric acid.

Examples of branched fatty acids include 2-ethylhexanoic acid, 2-ethylisohexanoic acid, 2-propylheptanoic acid, 2-butyloctanoic acid, 2-isobutylisooctanoic acid, 2-pentylnonanoic acid, and 2-isopentylnonane. acid, 2-hexyldecanoic acid, 2-hexylisodecanoic acid, 2-butyldodecanoic acid, 2-isobutyldodecanoic acid, 2-heptylundecanoic acid, 2-isoheptylundecanoic acid, 2-isopeptylisoundecanoic acid, 2- Dodecylhexanoic acid, 2-isododecylhexanoic acid, 2-octyldodecanoic acid, 2-isooctyldodecanoic acid, 2-octylisododecanoic acid, 2-nonyltridecanoic acid, 2-isononylisotridecanoic acid, 2-decyldodecane acid, 2-isodecyldodecanoic acid, 2-decylisododecanoic acid, 2-decyltetradecanoic acid, 2-octylhexadecanoic acid, 2-isooctylhexadecanoic acid, 2-undecylpentadecanoic acid, 2-isoundecylpentadecanoic acid, 2-dodecylheptadecanoic acid, 2-isododecylisoheptadecanoic acid, 2-decyloctadecanoic acid, 2-decylisooctadecanoic acid, 2-tridecylheptadecanoic acid, 2-isotridecylisoheptadecanoic acid, 2-tetra Decyloctadecanoic acid, 2-isotetradecyloctadecanoic acid, 2-hexadecylhexadecanoic acid, 2-hexadecyltetradecanoic acid, 2-hexadecylisohexadecanoic acid, 2-isohexadecylisohexadecanoic acid, 2-pentadecylnonadecanoic acid , 2-isopentadecylisononadecanoic acid, 2-tetradecylbehenic acid, 2-isotetradecylbehenic acid, 2-tetradecylisobehenic acid, and 2-isotetradecylisobehenic acid.
Tertiary fatty acids include, for example, pivalic acid, neononanoic acid, neodecanoic acid, isononanoic acid and the like.

Among them, linear fatty acids are preferred from the viewpoint of solubility and stability in solvents, and more preferably at least one selected from caproic acid, enanthic acid, caprylic acid, myristic acid, stearic acid and oleic acid. and more preferably oleic acid, which is a linear unsaturated fatty acid.

These organic acids may be used singly or in combination of two or more.

The cation in the organic acid salt is preferably a metal cation, more preferably an alkali metal cation or an alkaline earth metal cation, and still more preferably an alkali metal cation. Among alkali metal cations, sodium and potassium are preferred, and sodium is more preferred.

Ligands containing organic acid salts bind to the core either through ionic interactions or through physical interactions that fill defects in the core, and are particularly likely to bind selectively to perovskite compounds. Therefore, when the ligand and the perovskite compound are brought into contact with each other, such as in a solution state, the ligand easily binds to the core. Examples of the method for binding the core to the surface of the ligand include a method in which an organic acid salt is directly acted after core synthesis, or a method in which an organic acid is reacted as a precursor during core synthesis and then converted to an organic acid salt. be done.
As the ligand, an organic acid salt may be used alone or in combination of two or more kinds, and another known ligand may be used in combination as long as the effect of the above ligand is not impaired.
The content of the total ligand is preferably 0.1 to 20 mol, more preferably 0.5 to 10 mol, still more preferably 1 to 5 mol, per 1 mol of A (monovalent cation) in the semiconductor nanoparticles. Mole.

<Shell>
The luminescent material of the present invention is characterized in that at least part of the core to which the ligand is bound is covered with a shell containing a basic group-containing compound. Since the ligand is more strongly immobilized by the shell, not only is the stability of the light-emitting material significantly improved, but also the light-emitting properties are improved.

The basic group of the basic group-containing compound includes an amino group, an amide group, a pyridyl group, a pyrrolyl group, a nitrile group and the like. An amino group is preferred from the viewpoint of raw material availability, synthesis, and functionality as a shell, and a group represented by the following general formula (1) is preferred from the viewpoint of performance and stability as a light-emitting material.

general formula 1

[In general formula (1), R ¹ to R ⁴ each independently represent an alkyl group having 1 to 10 carbon atoms. R ⁵ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an aryl group. n is an integer of 0-2. ]

Examples of alkyl groups having 1 to 10 carbon atoms include methyl group, ethyl group, butyl group, propyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, isopropyl group and 2-ethylhexyl group. A linear or branched alkyl group such as is mentioned.

Examples of alkoxy groups having 1 to 10 carbon atoms include methoxy, ethoxy, butoxy, propoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, and isopropyloxy groups. , 2-ethylhexyloxy group.

In the group represented by general formula (1), R ¹ to R ⁴ are preferably each independently an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group. Further, the nitrogen atom in the general formula (1) is preferably a tertiary amine, and R ⁵ is preferably an alkyl group having 1 to 10 carbon atoms or a phenyl group, more preferably an alkyl group having 1 to 3 carbon atoms. group, more preferably a methyl group. n is preferably 1.

The basic group-containing compound is not particularly limited as long as it is a compound containing the above basic group, and may be either a low-molecular-weight compound or a high-molecular-weight compound.
Examples of basic group-containing low-molecular-weight compounds include primary to tertiary amines having saturated or unsaturated alkyl groups of 1 to 30 carbon atoms.
Examples of basic group-containing polymer compounds include poly(meth)acrylates, poly-α-alkyl acrylates, polyamides, polyvinyl acetals, polyformaldehydes, polyurethanes, polycarbonates, polystyrene, which have the basic group. Polyvinyl esters, polyesters, polyvinyl chloride, polyepoxies, cellulose derivatives (e.g., ethyl cellulose, cellulose acetate, nitrocellulose), vinyl chloride vinyl acetate copolymers, polyamide resins, diallyl phthalate resins, silicone resins, butadiene - Polymers such as acrylonitrile copolymers, copolymer resins, synthetic rubbers, and the like.

The basic group-containing compound is preferably a polymer compound from the viewpoint of function as a shell, and preferably contains a repeating unit derived from a monomer containing a basic group from the viewpoint of the function as a shell and resin design. It is a copolymer.
The copolymer may be a copolymer obtained by copolymerizing a monomer containing a basic group and another known monomer, or a copolymer containing a repeating unit derived from a monomer, A basic group may be introduced by reacting a compound having a basic group. A copolymer with is preferred.

Examples of monomers containing a basic group include N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N , N-dimethylaminobutyl (meth)acrylate, (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl (meth)acrylamide, N,N-dimethylaminoethyl (meth)acrylate, N, N-dimethylaminopropyl (meth)acrylate, N,N-dimethylaminopropyl acrylamide, morpholinoethyl (meth)acrylate, 1,2,2,6,6-pentamethyl-4-piperidyl (meth)acrylate, 2,2, 6,6-tetramethyl-4-piperidyl (meth)acrylate, 1-methoxy-2,2,6,6-toteramethyl-4-piperidyl (meth)acrylate, 4-vinylpyridine, 4-(meth)acryloyloxypyridine , acrylonitrile.
Among them, preferably 1,2,2,6,6-pentamethyl-4-piperidyl (meth)acrylate and 2,2,6,6-tetramethyl having a group represented by the above general formula (1) -4-piperidyl (meth)acrylate, 1-methoxy-2,2,6,6-toteramethyl-4-piperidyl (meth)acrylate and the like.

Other known monomers other than the monomer containing a basic group may be used singly or in combination of two or more in an arbitrary ratio. The content of the monomer containing a basic group with respect to 100 parts by mass of the total monomers constituting the copolymer is preferably 1 to 99 parts by mass, more preferably 5 to 90 parts by mass, More preferably 10 to 80 parts by mass.
Preferred monomers are those described below, but are not limited thereto.

Examples of other known monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, ) acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, cetyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate ) acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, hexadecyl (meth)acrylate, behenyl (meth)acrylate, isomyristyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate Linear or branched alkyl (meth)acrylates such as acrylates, isostearyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, and adamantyl (meth)acrylate;

cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, cyclic alkyl (meth)acrylates or cyclic alkenyl (meth)acrylates such as dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and isobornyl (meth)acrylate;

2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-chloropropyl (meth)acrylate, 2 -hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxy-3-allyloxypropyl (meth)acrylate, 2-hydroxy-3-allyloxypropyl (meth)acrylate, 2-(meth)acryloyloxyethyl -2-hydroxypropyl phthalate, glycerin mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, 4-hydroxyvinylbenzene, polypropylene glycol mono (meth) acrylate, and caprolactone adducts of these monomers (addition mole number is 1 to (meth)acrylates having a hydroxyl group such as 5);

(2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 1H-hexafluoroisopropyl (meth)acrylate, 1H,1H,5H-octafluoropentyl (Meth)acrylate, 1H,1H,2H,2H-heptadecafluorodecyl (meth)acrylate, 2,6-dibromo-4-butylphenyl (meth)acrylate, 2,4,6-tribromophenoxyethyl (meth) fluoroalkyl (meth)acrylates such as acrylates, 2,4,6-tribromophenol-3EO addition (meth)acrylates, and perfluorooctylethyl (meth)acrylate;

Tetrahydrofurfuryl (meth)acrylate, dioxolane (meth)acrylate, acryloylfurfuryl (meth)acrylate, 2-isocyanatoethyl (meth)acrylate-modified furfuryl alcohol, 2-isocyanatoethyl (meth)acrylate-modified furfurylamine, 2 - (meth)acrylates having a heterocyclic ring such as bromofuran EO addition (meth)acrylate and 3-methyl-3-oxetanyl (meth)acrylate;

benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, paracumylphenoxyethyl (meth)acrylate, paracumylphenoxypolyethyleneglycol (meth)acrylate, nonylphenoxypolyethyleneglycol (meth)acrylate, etc. (meth) acrylates having an aromatic ring of;

2-Methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, n-butoxydiethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, 1,3-butylene glycol methyl ether (meth)acrylate, methoxytri Ethylene glycol (meth) acrylate, methoxy polyethylene glycol mono (meth) acrylate, methoxy polyethylene glycol #400 (meth) acrylate, methoxy polyethylene glycol #100 (meth) acrylate, methoxy polyethylene glycol #1000 (meth) acrylate, methoxy polyethylene glycol # 4000 (meth)acrylate, methoxypolyethylene glycol #200 (meth)acrylate, methoxydipropylene glycol (meth)acrylate, methoxytripropylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, ethyl Carbitol (meth)acrylate, 2-ethylhexylcarbitol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, cresyl polyethylene Glycol (meth)acrylate, 2-(vinyloxyethoxy)ethyl (meth)acrylate, p-nonylphenoxyethyl (meth)acrylate, p-nonylphenoxypolyethylene glycol (meth)acrylate, glycidyl (meth)acrylate, β- Carboxyethyl (meth)acrylate, succinic acid mono(meth)acryloyloxyethyl ester, ω-carboxypolycaprolactone mono(meth)acrylate, 2-(meth)acryloyloxyethyl hydrogen phthalate, 2-(meth)acryloyloxypropyl hydrogen phthalate , 2-(meth)acryloyloxypropyl hexahydrohydrogen phthalate, 2-(meth)acryloyloxypropyl tetrahydrohydrogen phthalate, octoxy polyethylene glycol polypropylene glycol mono (meth) acrylate, lauroxy polyethylene glycol mono (meth) acrylate, stearoxy Polyethylene glycol mono (meth) acrylate, phenoxy polyethylene glycol mono (meth) acrylate, phenoxy polyethylene glycol polypropylene glycol mono (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, nonylphenoxy polyethylene glycol mono (meth) acrylate, nonylphenoxy polypropylene (meth)acrylates having an ether group such as glycol mono(meth)acrylate, nonylphenoxy polyethylene glycol polypropylene glycol mono(meth)acrylate, n-butoxyethyl (meth)acrylate, and 2-ethoxyethyl (meth)acrylate;

3-(Acryloyloxymethyl) 3-methyloxetane, 3-(Methacryloyloxymethyl) 3-methyloxetane, 3-(Acryloyloxymethyl) 3-ethyloxetane, 3-(Methacryloyloxymethyl) 3-ethyloxetane, 3- Oxetanyl groups such as (acryloyloxymethyl)3-butyloxetane, 3-(methacryloyloxymethyl)3-butyloxetane, 3-(acryloyloxymethyl)3-hexyloxetane, and 3-(methacryloyloxymethyl)3-hexyloxetane (meth)acrylates having

Styrene, α-methylstyrene, p-hydroxystyrene, p-chlorostyrene, p-bromostyrene, p-methylstyrene, p-methoxystyrene, pt-butoxystyrene, pt-butoxycarbonylstyrene, pt -butoxycarbonyloxystyrene, 2,4-diphenyl-4-methyl-1-pentene vinyl acetate, vinyl (meth)acrylate and allyl (meth)acrylate, vinyl acetate, vinyl monochloroacetate, vinyl benzoate, pivalic acid vinyls such as vinyl, vinyl butyrate, vinyl laurate, vinyl 2-ethylhexanoate, N-vinylcarbazole, N-vinylpyrrolidone;

Nitriles such as (meth)acrylonitrile;
vinyl ethers having an ether group such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether;
fluoroalkyl (meth)acrylates such as trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, and tetrafluoropropyl (meth)acrylate;

JNC Co., Ltd. trade names "Silaplane FM-0711", "Silaplane FM-0721", "Silaplane FM-0725", and Shin-Etsu Silicone Co., Ltd. trade names "X-22-174DX", " X-22-2426", "X-22-174ASX" and other polysiloxane (meth)acrylates;

(meth)acrylates having an isocyanate group such as 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate, 4-isocyanatobutyl methacrylate, and 4-isocyanatobutyl acrylate; The isocyanate groups also include blocked isocyanate groups. The blocked isocyanate group refers to a group in which the isocyanate group is protected with another functional group and the reactivity is suppressed under non-heating conditions, while the protective group is deprotected by heating to regenerate the active isocyanate group. . Commercially available monomers having such a blocked isocyanate group include, for example, 2-[(3,5-dimethylpyrazolyl)carboxyamino]ethyl methacrylate (Karenzu MOI-BP, manufactured by Showa Denko), methacrylic acid 2- (0-[1'Methylpropylideneamino]carboxyamino)ethyl (Karenzu MOI-BM, manufactured by Showa Denko).

The copolymer can be produced by known radical polymerization methods, such as free radical polymerization and living radical polymerization.
In the living radical polymerization method, side reactions that occur in general radical polymerization are suppressed, and moreover, polymerization growth occurs uniformly, so that block polymers and polymers with well-defined molecular weights can be easily obtained. Among them, the atom transfer radical polymerization method, which uses an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst, can be applied to a wide range of monomers and has a polymerization temperature that can be adapted to existing equipment. It is preferable in that it can be adopted.
The polymerization temperature can be appropriately adjusted according to the type of polymerization initiator used and the boiling point of the solvent, preferably 20°C to 150°C, more preferably 40°C to 120°C, and still more preferably 50°C to 100°C. is. The reaction time can be appropriately adjusted depending on the type of polymerization initiator and monomers used, and is preferably 2 to 30 hours, more preferably 3 to 15 hours. In addition, the polymerization reaction is desirably carried out in an inert gas atmosphere in order to prevent coloration reduction and deactivation of the polymerization initiator, etc., and is preferably carried out in a nitrogen gas atmosphere from the viewpoint of availability, cost, etc. However, it is not limited to these.

As a polymerization initiator, an azo compound or an organic peroxide can be used.
Examples of azo compounds include 2,2′-azobisisobutyronitrile, 2,2′-azobis(2-methylbutyronitrile), 1,1′-azobis(cyclohexane 1-carbonitrile), 2 ,2′-azobis(2,4-dimethylvaleronitrile), 2,2′-azobis(2,4-dimethyl-4-methoxyvaleronitrile), 2,2′-azobis(4-methoxy-2,4- dimethylvaleronitrile), dimethyl 2,2'-azobis (2-methylpropionate), 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis (2-hydroxymethylpropionitrile ), 2,2′-azobis[N-(2-propenyl)-2-methylpropionamide], 2,2′-azobis(N-butyl-2-methylpropionamide), dimethyl 1,1′-azobis ( 1-cyclohexanecarboxylate) and 2,2′-azobis[2-(2-imidazolin-2-yl)propane].

Examples of organic peroxides include benzoyl peroxide, t-butylperbenzoate, cumene hydroperoxide, diisopropylperoxydicarbonate, di-n-propylperoxydicarbonate, di(2-ethoxyethyl)peroxy dicarbonate, t-butyl peroxy 2-ethylhexaate, t-butyl peroxyneodecanoate, t-butyl peroxy-2-ethylhexanoate, dilauroxyperoxide, peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl)peroxide, dipropionylperoxide, and diacetylperoxide.

The polymerization initiator is not limited to the above, and may be used alone or in combination of two or more. The amount of polymerization initiator to be used is preferably in the range of 0.001 to 20 parts by mass with respect to 100 parts by mass of the total monomers.

A chain transfer agent may be used for the purpose of adjusting the molecular weight during the polymerization. The amount of the chain transfer agent used is preferably 0.001 to 15 parts by mass with respect to 100 parts by mass of the total monomers.
The chain transfer agent is not particularly limited as long as it is a compound capable of adjusting the molecular weight, and known chain transfer agents can be used. n-tetradecylmercaptan, mercaptoethanol, 1-thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate methoxybutyl-3-mercaptopropionate, stearyl-3-mercaptopropionate, trimethylolpropane tris(3-mercaptopropionate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate , pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), thiomalic acid, octyl thioglycolate, 3- mercaptans such as octyl mercaptopropionate, 2-mercaptoethanesulfonic acid, butyl thioglycolate; disulfides such as dimethylxanthogen disulfide, diethylxanthogen disulfide, diisopropyl xanthogen disulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide Halogenated hydrocarbons such as carbon tetrachloride, methylene chloride, bromoform, bromotrichloroethane, carbon tetrabromide, and ethylene bromide; secondary alcohols such as isopropanol and glycerin; phosphorous acid, hypophosphorous acid, and their Salts (sodium hypophosphite, potassium hypophosphite, etc.), sulfurous acid, hydrogen sulfite, dithionous acid, metabisulfite, and their salts (sodium hydrogen sulfite, potassium hydrogen sulfite, sodium dithionite, potassium dithionite, sodium metabisulfite, potassium metabisulfite, etc.), lower oxides and salts thereof; and allyl alcohol, 2-ethylhexylthioglycolate, α-methylstyrene dimer, terpinolene, α-terpinene , γ-terpinene, dipentene, and anisole. These can be used alone or in combination of two or more.

An organic solvent can be used as a polymerization solvent during the polymerization. Examples of organic solvents include ethyl acetate, n-butyl acetate, isobutyl acetate, n-propyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, diethoxydiethylene glycol, and Examples include, but are not limited to, 3-methoxy-1-butanol. Two or more kinds of polymerization solvents may be mixed and used.

The shell can be formed by coating the ligand-bound semiconductor nanoparticles. A shell containing a basic group-containing compound accelerates the coating of the particle surface by acid-base interaction, and the shell can be easily coated by coexisting in a solution.

The amine value of the basic group-containing compound is preferably from 1 to 400 mgKOH/g, more preferably from 20 to 300 mgKOH/g, from the viewpoint of function as a shell.

The number average molecular weight (Mn) of the basic group-containing compound is preferably 500 or more and 50,000 or less, and the solubility of the basic group-containing compound, the optical properties of the perovskite compound coated with the basic group-containing compound, or From the viewpoint of stability and the like, it is more preferably 1,000 or more and 15,000 or less.

The amount of the basic group-containing compound to be coated is preferably 1 to 5000 parts by mass, more preferably 2 to 1000 parts by mass with respect to 100 parts by mass of the total of the core and the ligand.

<Luminescent material composition>
The luminescent material composition of the present invention contains the above-described luminescent material and solvent.
The solvent is not particularly limited as long as it does not affect the dispersibility and optical properties of the luminescent material, and known organic solvents can be used.
In addition, since the core of the luminescent material of the present invention is protected by a specific ligand and shell, even a solvent with a strong polarity that would roughen or destroy the surface of the core in a conventional perovskite compound Can be used in combination. In addition, since the luminescent material of the present invention has improved solubility mainly due to the action of the shell, it can be used in combination with solvents that do not dissolve conventional perovskite compounds.

[solvent]
Specific examples of solvents include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, pentanol, 3-methyl-1,3-butanediol, 1,3-butanediol, 1 ,3-butylene glycol, octanediol, 2,4-diethylpentanediol, butylethylpropanediol, 2-methyl-1,3-propanediol, 4-hydroxy-4-methyl-2-pentanone, 2-ethyl-1-hexanol , 3,5,5-trimethyl-1-hexanol, isodecanol, isotridecanol, 3-methoxy-3-methyl-1-butanol, 2-methoxybutanol, 3-methoxybutanol, cyclohexanol, furfuryl alcohol, tetrahydro Furfuryl alcohol, benzyl alcohol, methylcyclohexanol, ethylene glycol, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol mono- 2-ethylhexyl ether, diethylene glycol mono-2-ethylhexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-tert-butyl ether, ethylene glycol monopropyl ether, ethylene glycol monomethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether , tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol monophenyl ether, 1,3-butylene glycol, propylene glycol n-propyl ether, propylene glycol n-butyl ether, diethylene glycol monoethyl ether, dipropylene glycol n-propyl ether , dipropylene glycol n-butyl ether, tripropylene glycol methyl ether, tripropylene glycol n-butyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, 2-heptanone, 4-heptanone, 3,5 ,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone and other ketone solvents; methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, tert-butyl acetate, amyl acetate, isoamyl acetate, ethyl 3-ethoxypropionate, ethyl lactate ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, 3-methoxy-3-methylbutyl acetate, 3 - methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol dimethyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, cyclohexanol acetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene Glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol diacetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, 1,4-butanediol diacetate , 1,3-butylene glycol diacetate, 1,6-hyoxanediol diacetate and other ester solvents; diethyl ether, cyclopentyl methyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, Ether solvents such as diethylene glycol diethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol dibutyl ether, tetraethylene glycol dimethyl ether, polyethylene glycol dimethyl ether; benzene, toluene, ethylbenzene, o-xylene, m-xylene, p-xylene, o- Aromatic solvents such as diethylbenzene, m-diethylbenzene, p-diethylbenzene, n-butylbenzene, sec-butylbenzene, tert-butylbenzene; alicyclic solvents such as cycloheptane and cyclohexane; pentane, hexane, octane, isohexane , isooctane, and isononane; dichloromethane, chloroform, carbon tetrachloride, chlorobenzene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, m-dichlorobenzene, 1,2,3-trichloropropane, etc. chlorinated solvents; N,N-dimethylformamide, N,N-dimethylacetamide, amide solvents such as dimethylacetamide; acetonitrile, dimethylsulfoxide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, γ -butyrolactone, isophorone, triacetin, propylene glycol monomethyl ether propionate, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate and the like, but are not limited thereto. These solvents may be used singly or in combination of two or more.

The content of the light-emitting material in the composition is preferably 0.1 to 90 parts by mass, more preferably 0.5 to 60 parts by mass, and still more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the composition. be.

[Curing component]
The luminescent material composition can further contain a curing component. The curing component promotes a polymerization reaction or a cross-linking reaction to cure the light-emitting material composition and impart strength and resistance.

(Polymerization initiator)
In the polymerization reaction, generally a polymerization initiator and a polymerizable compound are used together. The polymerization initiator is a compound that generates active species for initiating a polymerization reaction by irradiation with active energy rays or heat, and known polymerization initiators can be used. Main active species for initiating the polymerization reaction include radical polymerization initiators that generate radicals and cationic polymerization initiators that generate acids, and these may be used in combination.

Photoradical polymerization initiators that generate radicals by active energy rays include, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl methyl ketal, 4-(2-hydroxyethoxy ) phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2 -dimethylamino-1-(4-morpholinophenyl)butane, oligo[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone], 2-hydroxy-1-[4-[ Acetophenones such as 4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl]-2-methylpropan-1-one; Benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether phosphines such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; and phenyl glyoxylic methyl esters.

Among photoradical polymerization initiators, acetophenones represented by aminoketones, phosphines, and oxime ester compounds are preferred. These may be used alone or in combination depending on the properties required for the cured product. When the radical polymerization initiator is used, the amount used is preferably 0.01 to 100 parts by mass, more preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the total solid content in the composition. .

Thermal radical polymerization initiators that generate radicals by heat include azo thermal polymerization initiators and organic peroxide polymerization initiators, and two or more of them may be used in combination.
Examples of azo thermal polymerization initiators include 2,2′-azobisisobutyronitrile, 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis(2 ,4-dimethylvaleronitrile), dimethyl 2,2′-azobis(2-methylpropionate), 2,2′-azobis(2-methylbutyronitrile), 1,1′-azobis(cyclohexane-1- carbonitrile), 1-[(1-cyano-1-methylethyl)azo]formamide, 2,2′-azobis(N-butyl-2-methylpropionamide), 2,2′-azobis(N-cyclohexyl -2-methylpropionamide).
Examples of organic peroxide polymerization initiators include benzoyl peroxide (BPO), lauroyl peroxide, di-t-butylperoxyhexahydroterephthalate, t-butylperoxy-2-ethylhexanoate, di-α -cumyl peroxide (DCPO), t-butylperoxyisopropyl carbonate, di-t-butylperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane (DDBH), 2,5,-dimethyl -2,5-di(t-butylperoxy)hexyne-3, 1,1,3,3-tetramethylbutyl hydroperoxide, t-butyl hydroperoxide.

The content of the azo thermal polymerization initiator and the organic peroxide polymerization initiator is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, with respect to 100 parts by mass of the total solid content in the composition. parts by mass, more preferably 1 to 3 parts by mass.

Examples of photocationic polymerization initiators that generate acid upon exposure to active energy rays include diazonium salts, sulfonium salts, iodonium salts, etc. Specifically, benzenediazonium hexafluoroantimonate, benzenediazonium hexafluorophosphate, benzenediazonium Diazonium salts such as hexafluoroborate; triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroborate, 4,4'-bis[bis(2-hydroxyethoxyphenyl)sulfonio]phenylsulfide bis Sulfonium salts such as hexafluorophosphate, diphenyl-4-thiophenoxyphenylsulfonium hexafluorophosphate; diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, bis(4-t-butylphenyl)iodonium hexafluorophosphate, bis(4 - iodonium salts such as t-butylphenyl)iodonium hexafluoroantimonate; Among them, iodonium salts are preferably used.

The content of the photocationic polymerization initiator is preferably 0.1 to 10 parts by mass, more preferably 1 to 5 parts by mass, per 100 parts by mass of the total solid content in the composition.

Thermal cationic polymerization initiators that generate acid by heat include, for example, diphenyliodonium hexafluoroarsenate, diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, triphenylsulfonium tetrafluoroborate, and tri-p-tolyl. sulfonium hexafluorophosphate, tri-p-tolylsulfonium trifluoromethanesulfonate, bis(cyclohexylsulfonyl)diazomethane, bis(tert-butylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, triphenylsulfonium trifluoromethanesulfonate, diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium-p-toluenesulfonate, and diphenyl-p-phenylthiophenylsulfonium hexafluorophosphate.

The content of the thermal cationic polymerization initiator is preferably 0.1 to 20 parts by mass, more preferably 1 to 5 parts by mass, per 100 parts by mass of the total solid content in the composition. When it is 0.1 part or more, the curing reaction proceeds sufficiently, and when it is 20 parts or less, it is possible to suppress coloring and deterioration of physical properties due to the thermal cationic polymerization initiator.

(Polymerizable compound)
Examples of the polymerizable compound include radically polymerizable compounds and cationic polymerizable compounds, and these can be used in any combination. A radically polymerizable compound refers to a compound having at least one or more radically polymerizable skeletons in the molecule, and includes liquid or solid monomers, oligomers, or polymers at normal temperature and normal pressure. The radically polymerizable compounds may be used singly or in combination of two or more in an arbitrary ratio.

<Radical polymerizable compound>
Examples of radically polymerizable compounds include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid, salts thereof, ester compounds, acid amides, and acid anhydrides, as well as urethanes. Examples include, but are not limited to, acrylates, acrylonitrile, styrene derivatives, various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, unsaturated polyurethanes. Specific examples of the radically polymerizable compound in the present invention are given below.

Examples of radically polymerizable compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, monofunctional alkyl (meth) acrylates such as benzyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate; ) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3-allyloxypropyl (meth) monofunctional hydroxy(meth)acrylates such as acrylates, 2-hydroxy-3-allyloxypropyl acrylate, 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate;

2-methoxyethyl (meth)acrylate, 1,3-butylene glycol methyl ether (meth)acrylate, butoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxypolyethylene glycol #400 (meth)acrylate, methoxydi Propylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate ) acrylate, cresyl polyethylene glycol (meth)acrylate, 2-(vinyloxyethoxy)ethyl acrylate, monofunctional ether-containing group (meth)acrylates such as glycidyl (meth)acrylate; β-carboxyethyl (meth) monofunctional carboxyl-containing (meth)acrylates such as acrylates, succinic acid mono(meth)acryloyloxyethyl ester, ω-carboxypolycaprolactone mono(meth)acrylate;
N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, morpholinoethyl (meth)acrylate, trimethylsiloxyethyl (meth)acrylate, diphenyl-2-(meth)acryloyloxyethyl phosphate , 2-hydroxy-1-(meth)acryloxy-3-methacryloxypropane; other monofunctional (meth)acrylates;

1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene Glycol di(meth)acrylate, polyethylene glycol #200 di(meth)acrylate, polyethylene glycol #300 di(meth)acrylate, polyethylene glycol #400 di(meth)acrylate, polyethylene glycol #600 di(meth)acrylate, dipropylene glycol Di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol #400 di (meth) acrylate, polypropylene glycol #700 di (meth) acrylate, neopentyl glycol di (meth) ) acrylate, neopentyl glycol PO-modified di(meth)acrylate, 1,6-hexanediol bis(2-hydroxy-3-(meth)acryloyloxypropyl) ether, bis(4-(meth)acryloxypolyethoxyphenyl) propane, 1,9-nonanediol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol di(meth)acrylate monobenzoate, bisphenol A di(meth)acrylate, EO-modified bisphenol A di(meth)acrylate, PO-modified bisphenol A di(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate, EO-modified hydrogenated bisphenol A di(meth)acrylate, PO-modified hydrogenated bisphenol A di(meth)acrylate, bisphenol F di(meth) Acrylate, EO-modified bisphenol F di(meth)acrylate, PO-modified bisphenol F di(meth)acrylate, tricyclodecanedimethylol di(meth)acrylate, isocyanuric acid EO-modified di(meth)acrylate, 2-hydroxy-1,3 - difunctional (meth)acrylates such as di(meth)acryloxypropane;

glycerin PO-modified tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, isocyanuric acid EO-modified tri(meth)acrylate, Isocyanuric acid EO-modified ε-caprolactone-modified tri(meth)acrylate, 1,3,5-tri(meth)acryloylhexahydro-s-triazine, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate tripropio Pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate monopropionate, dipentaerythritol hexa(meth)acrylate , tetramethylolmethane tetra(meth)acrylate, oligoester tetra(meth)acrylate, tris((meth)acryloyloxy)phosphate and other tetrafunctional or higher (meth)acrylates;

Allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, isocyanuric acid triarylate; acrylamide, N-methylol acrylamide, diacetone acrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N- Acid amides such as isopropylacrylamide, acryloylmorpholine, methacrylamide, N-methylolmethacrylamide, diacetonemethacrylamide, N,N-dimethylmethacrylamide, N,N-diethylmethacrylamide, N-isopropylmethacrylamide, methacryloylmorpholine styrene, p-hydroxystyrene, p-chlorostyrene, p-bromostyrene, p-methylstyrene, p-methoxystyrene, pt-butoxystyrene, pt-butoxycarbonylstyrene, pt-butoxycarbonyloxy Styrenes such as styrene, 2,4-diphenyl-4-methyl-1-pentene; vinyl acetate, vinyl monochloroacetate, vinyl benzoate, vinyl pivalate, vinyl butyrate, vinyl laurate, divinyl adipate, vinyl methacrylate , vinyl crotonate, vinyl 2-ethylhexanoate, N-vinylcarbazole, N-vinylpyrrolidone;

three-membered ring compounds such as vinylcyclopropanes, 1-phenyl-2-vinylcyclopropanes, 2-phenyl-3-vinyloxiranes, 2,3-divinyloxiranes; 2-methylene-1,3-dioxepane , dioxolanes, 2-methylene-4-phenyl-1,3-dioxepane, 4,7-dimethyl-2-methylene-1,3-dioxepane, 5,6-benzo-2-methylene-1,3-dioxepane Such cyclic ketene acetals; Shinzo Yamashita et al., "Crosslinking Agent Handbook" (1981, Taiseisha) and Kiyomi Kato, "UV/EB Curing Handbook (Raw Materials)" (1985, Kobunshi Publishing) Society), Edited by Radtech Study Group, edited by Kiyoshi Akamatsu, "Practical Technology of New Photosensitive Resin", (1987, CMC), Edited by Tsuyoshi Endo, "Precision of Thermosetting Polymer", (1986, CMC), Eiichiro Takiyama, "Polyester Resin Handbook", (1988, Nikkan Kogyo Shimbun), Radtech Study Group, "Application and Market of UV/EB Curing Technology", (2002, CMC), etc. described compounds;

As the radically polymerizable compound, oligomers and prepolymers can be used in addition to the above monomers.

<Cationically polymerizable compound>
A cationic polymerizable compound refers to a compound that undergoes polymerization or cross-linking under the action of an acid catalyst generated by irradiation with active energy rays or heat.
Cationically polymerizable compounds include, for example, various aminoplasts or phenoplasts, i.e. formaldehyde precursors such as urea-formaldehyde, melamine-formaldehyde, benzoguanamine-formaldehyde, glycoluril-formaldehyde resins and monomers or oligomers thereof. Methylolated or alkoxydimethylated phenol derivatives such as formaldehyde precursors; Compounds with silanol groups; Mixtures of polyenes and polythiols; Alkoxysilanes;
Epoxy compounds; oxetane compounds; styrenes; vinyl compounds; vinyl ethers; spiroorthoesters; bicycloorthoesters; cyclic acid anhydrides; lactams or aryldialdehydes;

The cationic polymerizable compound is preferably an epoxy compound, an oxetane compound, or a vinyl ether, and more preferably an epoxy compound or an oxetane compound. Since the polymerization reaction using an epoxy compound and an oxetane compound has relatively high reactivity and a short curing time, the curing process can be shortened.
Specific examples of epoxy compounds include bisphenol A type epoxy resins, bisphenol F type epoxy resins, naphthalene type epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins. Specific examples of oxetane compounds include phenoxymethyl Oxetane, 3,3-bis(methoxymethyl)oxetane, 3,3-bis(phenoxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-ethylhexyloxymethyl) Oxetane, 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane, di[1-ethyl(3-oxetanyl)]methyl ether, oxetanylsilsesquioxane, phenol novolac oxetane, 1,4 -bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene and the like.
The cationic polymerizable compounds may be used alone or in combination of two or more.

The amount of the polymerizable compound containing the radically polymerizable compound and the cationically polymerizable compound is preferably 1 to 99 parts by mass, more preferably 3 to 70 parts by mass, more preferably 100 parts by mass of the composition. 5 to 50 parts by mass.

The luminescent material composition of the present invention can be used in combination with a sensitizer for the purpose of further improving sensitivity and improving film properties after reaction curing.
Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, and anthraquinone derivatives. , xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives , naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, or Michler ketone derivatives, α-acyloxyesters , acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3′, or 4,4′ -tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-diethylaminobenzophenone and the like. These sensitizers can be used singly or as a mixture of two or more at any ratio as required.
The amount of the sensitizer used is preferably 0.01 to 100 parts by mass, more preferably 0.1 to 50 parts by mass, per 100 parts by mass of the polymerization initiator.

Furthermore, the luminescent material composition can introduce a crosslinked structure into the luminescent material by including a crosslinking agent. In that case, a compound having a substituent capable of reacting with the cross-linking agent may be used, or a substituent capable of reacting with the cross-linking agent may be introduced into the shell compound. You may react with an agent. Examples of cross-linking agents include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, aziridine-based cross-linking agents, melamine-based cross-linking agents, aldehyde-based cross-linking agents, amine-based cross-linking agents, and metal chelate-based cross-linking agents. may be used, or two or more may be used in combination.

The isocyanate cross-linking agent is capable of reacting with a hydroxyl group, an amino group or a carboxyl group, such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hydrogenated tolylene diisocyanate, 1,3-xylylene diisocyanate. , 1,4-xylylene diisocyanate, hexamethylene diisocyanate, diphenylmethane-4,4-diisocyanate, isophorone diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, tetramethylxylylene diisocyanate, 1,5-naphthalene diisocyanate, tri Examples include phenylmethane triisocyanate, adducts of these polyisocyanate compounds and polyol compounds such as trimethylolpropane, and burettes and isocyanurates of these polyisocyanate compounds.

Epoxy cross-linking agents are capable of reacting with hydroxyl groups, phenolic hydroxyl groups, amino groups, carboxyl groups, and the like, and examples thereof include bisphenol A/epichlorohydrin type epoxy resins, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and glycerol diglycidyl. Ether, glycerin triglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidylerythritol, diglycerol polyglycidyl ether.

Aziridine-based cross-linking agents are capable of reacting with carboxyl groups and the like. '-diphenylmethane-4,4'-bis(1-aziridinecarboxamide) and N,N'-hexamethylene-1,6-bis(1-aziridinecarboxamide).

The melamine-based cross-linking agent is capable of reacting with a hydroxyl group, an amino group, or the like. Examples include methyl melamine and melamine resin.
Aldehyde-based cross-linking agents are capable of reacting with hydroxyl groups, amino groups, and the like, and include, for example, glyoxal, malondialdehyde, succindialdehyde, maleindialdehyde, glutardialdehyde, formaldehyde, acetaldehyde, and benzaldehyde.

Amine-based cross-linking agents are capable of reacting with carboxyl groups, ester groups, formyl groups, epoxy groups, isocyanate groups, or the like. Examples include isophorone diamine, amino resins, and polyamides.
A metal chelate-based cross-linking agent can react with a hydroxyl group, an amino group, a carboxyl group, or the like. Examples include metal acetylacetone and acetoacetyl ester coordination compounds.

The content of the cross-linking agent is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and still more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the solid content in the luminescent material composition. 2 parts by mass. Within the above range, excellent cohesive strength and adhesive strength can be exhibited, and sufficient durability can be obtained.

Depending on the purpose, the luminescent material composition contains binder resins, dyes, organic and inorganic pigments, pigment dispersants, oxygen scavengers and reducing agents, antifoggants, antifading agents, antihalation agents, fluorescent brighteners, interfacial activator, colorant, extender, plasticizer, flame retardant, antioxidant, dye precursor, ultraviolet absorber, foaming agent, anti-mold agent, antistatic agent, magnetic material, dispersant, silane coupling agent, and 4 Storage stabilizers such as ammonium chloride, plasticizers, surface tension modifiers, slipping agents, anti-blocking agents, light stabilizers, leveling agents, antifoaming agents, infrared absorbers, surfactants, thixotropic agents, antibacterial agents It may be used by mixing with an agent, fine particles such as silica, an additive that imparts various properties, a diluent solvent, and the like.

<Wavelength conversion member>
The wavelength conversion member of the present invention has a wavelength conversion layer formed by forming the above-described luminescent material composition on a substrate. Specifically, a film or sheet obtained by applying a luminescent material composition onto a substrate and curing the composition can be used.

[Base material]
The substrate is not particularly limited, and examples thereof include inorganic substrates and resin substrates.
Examples of inorganic substrates include glass substrates; ceramic substrates; inorganic substrates such as calcium silicate plates, asbestos slate plates and cement slate plates; metal substrates such as aluminum plates, copper plates, stainless steel plates and plated steel plates; is mentioned.
Examples of the resin for the resin base material include (meth)acrylic resins such as polymethyl methacrylate; polystyrene, polyvinyl toluene, polystyrene, styrene-methyl methacrylate copolymer, styrene-acrylonitrile copolymer, acrylonitrile-butadiene- Styrene-based resins such as styrene block copolymers and poly(p-methylstyrene); polycarbonate; polyarylate; polyethersulfone; polyethylene, polypropylene, ethylene-propylene and other polyolefin-based resins; Halogen-containing resins such as vinyl chloride resins and chlorinated vinyl resins; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate and polycyclohexanedimethanol terephthalate; polyamides such as nylon 6, nylon 66 and nylon 610; cellulose triacetate , cellulose acetate propionate, cellulose acetate butyrate and other cellulose resins; polyacetal resins; polyvinyl fluoride, polyvinylidene fluoride, polychlorotrifluoroethylene, polyethylenetetrafluoroethylene, polytetrafluoroethylene, tetrafluoroethylene-per Fluorine resins such as fluoroalkyl vinyl ether copolymers and tetrafluoroethylene-hexafluoropropylene copolymers; polyphenylene oxide; polyphenylene sulfide; polyether ether ketone; polyether nitrile; imide; silicone resin; and the like. From the viewpoint of improving weather resistance and reducing costs, the resin is preferably a (meth)acrylic resin, a polyolefin resin, a cyclic olefin resin, a polyester resin, a polyamide, a cellulose resin, or a fluororesin, and more preferably. are polyester-based resins and fluororesins. The thickness of the resin base material is not particularly limited, and is preferably about 10 to 800 μm.
These substrates may be subjected to surface treatment such as corona treatment, flame treatment, plasma treatment, etc., if necessary.

[Method of Forming Wavelength Conversion Layer]
The method for forming the wavelength conversion layer is not particularly limited. For example, after coating the light-emitting material composition on the substrate, pre-drying is performed as necessary, and heat treatment or activation energy is performed as necessary. A method of curing the film by irradiating with rays can be mentioned. The thickness of the wavelength conversion layer after curing is preferably 0.1 to 200 μm, more preferably 1 to 100 μm.

As the coating method, known methods can be used, for example, gravure coating method, gravure offset method, kiss coating method, rod coating method, reverse gravure coating method, roll coating method, comma coating method, top coating method. , die coating, knife coating, lip coating, spray coating, spin coating, bar coating, slit coating, gravure printing, offset printing, screen printing, transfer printing, sublimation transfer printing, and inkjet printing.

Pre-drying is mainly performed to remove the solvent contained in the coating film. Pre-drying is preferable because it promotes the subsequent curing reaction, suppresses foaming due to rapid drying, and makes poor film formation less likely to occur.
Examples of pre-drying methods include vacuum drying under reduced pressure using a vacuum dryer or the like, drying by baking using a convection oven (hot air dryer), IR oven, hot plate, or the like, or a combination thereof.

The heat treatment can be performed by selecting the temperature and time suitable for the curing reaction using the same equipment and facilities as those for the pre-drying.

The active energy ray in the active energy ray irradiation includes heat rays, ultraviolet rays, visible rays, near-infrared rays, electron beams, and the like. As a light source for applying active energy rays, a light source having a dominant wavelength of light emission in the wavelength range of 100 to 450 nm is preferable. Examples of such light sources include ultra-high pressure mercury lamps, high pressure mercury lamps, medium pressure mercury lamps, mercury xenon lamps, metal halide lamps, high power metal halide lamps, xenon lamps, pulse emission xenon lamps, deuterium lamps, fluorescent lamps, ND-YAG triple wave laser, HE-CD laser, nitrogen laser, XE-Cl excimer laser, XE-F excimer laser, semiconductor excitation solid-state laser, and LED lamp light sources having emission wavelengths of 365 nm, 375 nm and 385 nm. In this specification, the definitions of ultraviolet rays, visible light, near-infrared rays, etc. are according to Ryogo Kubo et al.

The wavelength conversion member of the present invention may have another layer in addition to the substrate and the wavelength conversion layer.
Additional layers include, but are not limited to, known barrier layers and light scattering layers to improve stability and optical properties.
From the viewpoint of extracting emitted light, the barrier layer is preferably transparent, and a polymer such as polyethylene terephthalate, a glass film, or the like can be used. The light scattering layer is preferably transparent from the viewpoint of extracting emitted light, and a layer containing light scattering particles such as silica particles, an amplifying diffusion film, or the like can be used.

The wave power conversion member of the present invention may be a film or sheet molding having a wavelength conversion layer. Examples of molding methods include vacuum molding, air pressure molding, membrane press molding, in-mold molding, insert molding, insert mold molding, and overlay vacuum molding, but are not limited to these.

<Backlight unit>
The backlight unit of the present invention includes at least the above-described wavelength conversion member and a light source, and irradiates the wavelength conversion member installed in the subsequent stage with light emitted by the light source to cause the wavelength conversion member to emit light, It is a device that extracts light. The backlight unit may further comprise optional layers such as light reflecting members, brightness enhancements, prism sheets, light guide plates, media material layers between elements, and the like.

The light source is not particularly limited, and from the viewpoint of causing the semiconductor nanoparticles having a perovskite crystal structure contained in the wavelength conversion member to emit light, one having an emission wavelength of 600 nm or less is preferable, such as a blue light emitting diode. A known light source such as a light emitting diode (LED), laser, EL, or the like can be used.

In order to achieve high color reproducibility in the liquid crystal display device described later, the backlight unit is
blue light having an emission center wavelength in a wavelength band of 430 to 480 nm and an emission intensity peak with a half width of 50 nm or less;
Green light having an emission center wavelength in a wavelength band of 500 to 600 nm and an emission intensity peak with a half width of 50 nm or less;
It is preferable to emit red light having an emission center wavelength in a wavelength band of 600 to 680 nm and a peak of emission intensity with a half-value width of 50 nm or less, and white light having both.

As one aspect of the backlight unit, for example, a blue light emitting diode having an emission center wavelength in a wavelength band of 430 to 480 nm is used as a light source, and semiconductor nanoparticles having a perovskite crystal structure that emit green and red light are used as wavelength conversion members. , the blue light emitted from the light source and transmitted through the light conversion member and the red light and the green light emitted from the light conversion member are used to realize white light.
In another aspect, an ultraviolet light emitting diode having an emission central wavelength in a wavelength band of 300 nm to 430 nm is used as a light source, and semiconductor nanoparticles having a perovskite crystal structure that emit blue, green, and red light are used as a wavelength conversion member. white light is realized by blue light, red light and green light emitted from the light conversion member.

From the viewpoint of high color reproducibility, it is preferable to use semiconductor nanoparticles having a perovskite crystal structure characterized by light emission with a narrow half-width to emit blue, green, and red light. Other light-emitting materials such as quantum dots may be used for other colors as long as structured semiconductor nanoparticles are used. Examples of quantum dots include, but are not limited to, known quantum dots such as cadmium-based and indium-based quantum dots.

The light reflecting member is not particularly limited, but may be a reflective film. As the reflective film, for example, known reflective films such as a reflective mirror, a film of reflective particles, a reflective metal film, and a reflector can be used. The invention may also include a backlight unit that includes a brightness enhancer for the purpose of reflecting a portion of the light back toward the direction in which the light was transmitted.
A prism sheet usually has a substrate portion and a prism portion, but the substrate portion may be omitted depending on the adjacent members. The prism sheet can be attached to adjacent members via any appropriate adhesive layer. The prism sheet is configured by arranging a plurality of unit prisms convex on the opposite side (back side) of the viewing side. By arranging the prism sheet so that the convex portion faces the back side, the light passing through the prism sheet can be easily condensed. In addition, by arranging the convex portion of the prism sheet toward the back side, compared to the case where the convex portion is arranged toward the viewing side, less light is reflected without entering the prism sheet, resulting in a display with high brightness. can be obtained.
As the light guide plate, for example, a light guide plate having a lens pattern formed on the back side so that light from the lateral direction can be deflected in the thickness direction, or a prism shape or the like is formed on the back side and/or the viewing side. A light guide plate or the like can be used.
The one or more media contained in the media material layer between the elements are not particularly limited and include vacuum, air, gas, optical materials, adhesives, optical adhesives, glass, polymers, solids, liquids, gels, curable materials, Optical coupling materials, index matching or index mismatching materials, refractive index gradient materials, cladding or anti-cladding materials, spacers, silica gel, brightness enhancing materials, scattering or diffusing materials, reflective or anti-reflective materials, wavelength selective materials , wavelength-selective anti-reflective materials, color filters, or suitable media known in the art.

<Liquid crystal display device>
A liquid crystal display device of the present invention includes at least the backlight unit and the liquid crystal cell described above. Further, it may comprise a liquid crystal cell, a viewing side polarizing plate arranged on the viewing side of the liquid crystal cell, and a rear side polarizing plate arranged on the rear side of the liquid crystal cell. The viewer-side polarizing plate and the back-side polarizing plate are arranged such that their absorption axes are substantially orthogonal or parallel.

A liquid crystal cell has a pair of substrates and a liquid crystal layer as a display medium sandwiched between the substrates. In a general configuration, one substrate is provided with a color filter and a black matrix, and the other substrate is provided with a switching element for controlling the electro-optical characteristics of the liquid crystal and a scanning line for applying a gate signal to the switching element. and a signal line for supplying a source signal, a pixel electrode, and a counter electrode. The distance between the substrates (cell gap) can be controlled by a spacer or the like. An alignment film made of polyimide, for example, can be provided on the side of the substrate that is in contact with the liquid crystal layer.

A polarizing plate typically has a polarizer and protective layers disposed on both sides of the polarizer. The polarizer is typically an absorptive polarizer. Any appropriate polarizer is used as the polarizer. For example, a hydrophilic polymer film such as a polyvinyl alcohol film, a partially formalized polyvinyl alcohol film, or a partially saponified ethylene/vinyl acetate copolymer film is allowed to adsorb a dichroic substance such as iodine or a dichroic dye. Polyene-based oriented films such as those uniaxially stretched by stretching, polyvinyl alcohol dehydrated products, polyvinyl chloride dehydrochlorinated products, and the like. Among these, a polarizer obtained by adsorbing a dichroic substance such as iodine to a polyvinyl alcohol film and uniaxially stretching the film is particularly preferable because of its high polarization dichroic ratio.

EXAMPLES The present invention will be specifically described below with reference to examples, but the following examples are not intended to limit the scope of rights of the present invention. "Parts" and "%" represent "mass parts" and "mass%" unless otherwise specified.

<Number average molecular weight>
The number average molecular weight was measured using GPC (gel permeation chromatography) "GPC-8020" manufactured by Tosoh Corporation. Two SHODEX KF-806L columns, one KF-804L column, and one KF-802 column were used, tetrahydrofuran was used as the solvent, and values converted to standard polystyrene were used.

<Shell: Synthesis of Basic Group-Containing Compound>
(Synthesis Example 1: Copolymer (1))
A reaction vessel equipped with a stirrer, a thermometer, a reflux condenser and a gas inlet tube was charged with 80 parts of toluene as a solvent, and the temperature was raised to 70° C. under a nitrogen atmosphere.
Then, 80 parts of 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 20 parts of octyl methacrylate, and 6 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) as an initiator, and toluene After 41 parts of the monomer liquid which had been mixed in advance was added dropwise over 2 hours, the mixture was reacted at 70° C. for 1 hour.
Then, after performing a step of adding 0.6 parts of 2,2′-azobis(2,4-dimethylvaleronitrile) as an additional initiator and reacting for 1 hour until the addition rate of the monomer reaches 98% or more. , toluene was used to adjust the solid content concentration to 50% to obtain a solution of copolymer (1) containing repeating units derived from a monomer containing a basic group. The copolymer obtained had a number average molecular weight of 8,000.

(Synthesis Examples 2 to 8, Comparative Synthesis Example 1: Copolymers (2) to (8), Comparative Polymer (1))
The same procedure as in Synthesis Example 1 was performed except that the monomer was changed to the type and amount shown in Table 1, and the repeating unit derived from a monomer containing a basic group having a solid content concentration of 50% was included. Solutions of copolymers (2) to (8) and a solution of comparative polymer (1) containing no repeating unit derived from a monomer containing a basic group were obtained.

Table 1 shows the obtained copolymer and the like.

<Ligand: Preparation of organic acid salt solution>
(Adjustment example 1: sodium caproate)
90 parts of caproic acid and 20 parts of sodium hydroxide were introduced into a reaction vessel equipped with a stirrer, thermometer, reflux condenser and gas inlet tube, heated to 120° C. under reduced pressure, and heated for 30 minutes. After confirming that the sodium hydroxide was completely dissolved, the vacuum was released and a nitrogen atmosphere was created. After lowering the temperature to 60° C., 110 parts of toluene was charged to obtain a sodium caproate solution.

(Adjustment Example 2: sodium oleate)
100 parts of oleic acid and 10 parts of sodium hydroxide were introduced into a reaction vessel equipped with a stirrer, thermometer, reflux condenser and gas inlet tube, heated to 120° C. under reduced pressure, and heated for 30 minutes. After confirming that the sodium hydroxide was completely dissolved, the vacuum was released and a nitrogen atmosphere was created. After lowering the temperature to 60° C., 120 parts of toluene was charged to obtain a sodium oleate solution.

(Adjustment Example 3: Sodium lignocerate)
140 parts of oleic acid and 5 parts of sodium hydroxide were introduced into a reaction vessel equipped with a stirrer, thermometer, reflux condenser and gas inlet tube, heated to 120° C. under reduced pressure, and heated for 30 minutes. After confirming that the sodium hydroxide was completely dissolved, the vacuum was released and a nitrogen atmosphere was created. After lowering the temperature to 60° C., 140 parts of toluene was charged to obtain a sodium lignocerinate solution.

<Production of luminescent material composition>
[Example 1]
(core synthesis)
1.68 parts of cesium hydroxide, 2.23 parts of lead(II) oxide and 45 parts of oleic acid were placed in a flask and dissolved by heating to a liquid temperature of 130° C. under a stream of dry nitrogen. After holding the temperature for a while and removing generated water from the system, 325 parts of toluene previously dehydrated and oxygen-degassed with dry nitrogen was added and cooled to room temperature to obtain a cation raw material liquid.
Separately, 2.73 parts of tetraoctylammonium bromide, 1.67 parts of tetraamyl ammonium chloride, and 5.6 parts of oleic acid were dissolved in 32.5 parts of toluene at room temperature to obtain an anion raw material solution.
At a liquid temperature of 20° C. under dry nitrogen, the anion raw material solution was quickly added to the cation raw material solution and stirred. After 20 seconds, 160 parts of ethanol was added, followed by centrifugation to collect the supernatant.
The same volume of acetone was added to the resulting supernatant, and centrifugation was performed again to collect the sediment. The resulting sediment was dispersed in toluene to adjust the solid content concentration to 5% to obtain a solution of CsPb(Br/Cl) ₃ semiconductor nanoparticles having a perovskite crystal structure.

(ligand binding)
20 parts of the semiconductor nanoparticle solution and 100 parts of toluene were put into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a gas inlet pipe at room temperature and in a nitrogen atmosphere, and diluted.
Then, 3 parts of sodium oleate solution was added and stirred for 1 hour. After adding 100 parts of acetone, centrifugation was performed to collect the precipitate. The sediment was dispersed in toluene to prepare a solid content concentration of 5% to obtain a solution of a compound having a ligand bound to the core surface.

(shell coating)
Into a reactor equipped with a stirrer, a thermometer, a reflux condenser, and a gas inlet tube, 20 parts of the solution of the compound having the ligand bound to the core surface and 100 parts of toluene were charged and diluted at room temperature and in a nitrogen atmosphere.
Then, 2 parts of the copolymer (1) solution was added and stirred for 1 hour. After adding 100 parts of acetone, centrifugation was performed to collect the precipitate. A light-emitting material composition comprising the light-emitting material of the present invention, in which the sediment is dispersed in toluene to prepare a solid content concentration of 5%, and at least a portion of the core to which the ligand is bound is coated with a compound containing a basic group, and a solvent. got 1.

[Examples 2 to 8]
Light-emitting material compositions 2 to 8 were obtained in the same manner as in Example 1, except that the copolymer (1) solution was changed to the copolymer solution shown in Table 2.

[Example 9]
2.73 parts of tetraoctylammonium bromide and 1.67 parts of tetraamyl ammonium chloride in the synthesis of the core in Example 1 were changed to 5.47 parts of tetraoctylammonium bromide to produce a semiconductor having a perovskite crystal structure of _CsPbBr3 A luminescent material composition 9 was obtained in the same manner as in Example 1, except that a nanoparticle solution was obtained.

[Examples 10 to 16]
Luminescent material compositions 10 to 16 were obtained in the same manner as in Example 9, except that the sodium oleate solution and the copolymer (1) solution were changed to solutions of the compounds shown in Table 2.

[Example 17]
2.73 parts of tetraoctylammonium bromide and 1.67 parts of tetraamyl ammonium chloride in the core synthesis of Example 1 were changed to 4.82 parts of tetrahexylammonium iodide to have a perovskite crystal structure of _CsPbI3 A light-emitting material composition 17 was obtained in the same manner as in Example 1, except that a solution of semiconductor nanoparticles was obtained.

[Examples 18 to 24]
Luminescent material compositions 18 to 24 were obtained in the same manner as in Example 17, except that the sodium oleate solution and the copolymer (1) solution were changed to solutions of the compounds shown in Table 2.

[Comparative Example 1]
The solution of semiconductor nanoparticles having a perovskite crystal structure of CsPb(Br/Cl) ₃ obtained in Example 1 was used as the light-emitting material composition 25 .

[Comparative Example 2]
A core was synthesized in the same manner as in Example 1 to obtain a solution of semiconductor nanoparticles having a perovskite crystal structure of CsPb(Br/Cl) ₃ . Next, the shell coating step was performed in the same manner as in Example 1, except that the solution of the compound in which the ligand was bound to the core surface was changed to the solution of the semiconductor nanoparticles, and a luminescent material composition 26 was obtained.

[Comparative Example 3]
A luminescent material composition 27 was obtained in the same manner as in Comparative Example 2, except that the copolymer (1) solution of Comparative Example 2 was changed to the comparative polymer (1) solution.

[Comparative Example 4]
A luminescent material composition 28 was obtained in the same manner as in Example 1, except that the copolymer (1) solution was changed to the solution of the comparative polymer (1).

[Comparative Example 5]
The solution of the compound having the ligand bound to the core surface obtained in Example 1 was used as the luminescent material composition 29 .

[Comparative Example 6]
20 parts of the semiconductor nanoparticle solution obtained in the core synthesis of Example 1 and 100 parts of toluene were placed in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a gas inlet tube at room temperature and in a nitrogen atmosphere. diluted with
Then, 2 parts of tri-n-octylphosphine was added and stirred for 1 hour. After adding 100 parts of acetone, centrifugation was performed to collect the precipitate. The sediment was dispersed in toluene to prepare a solid content concentration of 5%, thereby obtaining a light-emitting material composition 30 in which a ligand was bound to the core surface.

[Comparative Example 7]
The solution of semiconductor nanoparticles having a perovskite crystal structure of CsPbBr ₃ obtained in Example 9 was used as the light-emitting material composition 31 .

[Comparative Example 8]
The solution of semiconductor nanoparticles having a perovskite crystal structure of CsPbI ₃ obtained in Example 17 was used as the light-emitting material composition 32 .

<Evaluation of luminescent material composition>
The following evaluations were performed on the obtained composition containing a light-emitting material. Table 2 shows the results.

[Evaluation of light emission characteristics]
The emission peak wavelength, full width at half maximum, and internal quantum efficiency (hereinafter referred to as QY) of the luminescent material-containing composition were measured immediately after preparation and after being left at room temperature (25° C.) in the air for 2 weeks.
The emission peak wavelength and full width at half maximum are the values of the emission spectrum that are the basis for calculating the internal quantum efficiency, and the internal quantum efficiency is the number of photons of fluorescence emission when the number of excitation photons absorbed by the semiconductor nanoparticles is 1. be. Each luminescent material-containing composition was diluted with toluene so that the light absorptance at the excitation light wavelength was between 0.2 and 0.3, and then measured. Measurement conditions are shown below.
≪Measurement conditions≫
Measuring device: Otsuka Electronics Co., Ltd. quantum efficiency measuring device QE-2000
Excitation light wavelength: 350 nm (emission peak wavelength is less than 450 nm)
400 nm (emission peak wavelength is 450 nm or more and less than 600 nm)
550 nm (emission peak wavelength is 600 nm or more)
Excitation light integration range: Excitation light wavelength ±25 nm
Emission integration range: (excitation light wavelength + 30) nm ~ 800 nm

According to Table 2, the composition containing the luminescent material of the present invention has high quantum efficiency and narrow half-width, which can be maintained for a long period of time, regardless of the types of cores having various wavelengths. In particular, Examples 1 to 8 have a narrow half width and exhibit extremely high internal quantum efficiencies for blue light with an emission wavelength of 450 nm. In particular, Examples 1 to 5, 9 to 13, 17 to 21 coated with a shell containing a compound having a group represented by the general formula (1) have a small change in internal quantum efficiency before and after aging, and are more stable. Excellent in nature.
On the other hand, as in Comparative Examples 1, 7, and 8, the composition containing a light-emitting material that does not have the specific ligand and shell of the present application, only Comparative Example 7 had a high internal quantum efficiency immediately after preparation, but was significantly deactivated over time. Moreover, in Comparative Examples 1 and 8, the internal quantum efficiency was low immediately after production and was deactivated over time.
As in Comparative Examples 2 and 5, the compositions containing only the ligand specific to the present application or the luminescent material having only the shell specific to the present application had low internal quantum efficiencies immediately after preparation and were deactivated over time.
In addition, as in Comparative Examples 3 and 4, the compositions containing a light-emitting material having a polymer having no basic group in the shell have low internal quantum efficiencies immediately after preparation, regardless of the presence or absence of ligands. It was inactivated, indicating that the effect of the present application is exhibited by the combination of the ligand and the shell.
Furthermore, as shown in Comparative Example 6, a composition containing a light-emitting material having a known general ligand also had a low internal quantum efficiency immediately after preparation and was deactivated over time.
In some of the comparative examples, the measured values were below the lower measurement limit of the apparatus and no significant values were obtained, so the measurement was not possible. Precipitation and the like were also observed in such samples, suggesting that the quantum efficiency was remarkably lowered due to the deactivation and aggregation of the semiconductor nanoparticles.

In addition, a large change in the peak wavelength between Example 1 and Comparative Examples 1 and 4 was confirmed, which indicates that the specific ligand and shell of the present invention do not simply protect the core, but act on the core. This suggests that the light emission characteristics are improved by
Therefore, the luminescent material of the present invention having a specific ligand and shell exhibits luminescence with a narrow half-width and high color purity, and has unexpectedly excellent internal quantum efficiency and long-term stability of the internal quantum efficiency. and has good emission characteristics and long-term stability.

<Manufacture of wavelength conversion member>
[Examples 25 to 48, Comparative Examples 10 to 13]
A luminescent material composition, a polymerizable compound, a polymerization initiator, and a solvent were blended according to the blending composition shown in Table 3 to obtain a curable composition. The obtained curable composition was spin-coated onto a glass substrate (10 cm×10 cm), and then dried at 80° C. for 1 minute using a hot air dryer. Next, using a belt-conveyor type ultraviolet irradiator (120 W/ ^cm2 high-pressure mercury lamp), ultraviolet rays are irradiated so that the integrated light amount becomes 400 mJ/ ^cm2 , forming a cured film having a thickness of 10 μm on the glass substrate. Then, wavelength conversion members 1 to 28 were obtained.

<Evaluation of Wavelength Conversion Member>
The obtained wavelength conversion member was evaluated as follows. Table 3 shows the results.

[Appearance evaluation and external quantum efficiency evaluation]
The obtained wavelength conversion member was subjected to visual evaluation of appearance and measurement of external quantum efficiency, which was used as an initial evaluation. Next, the same member was left to stand at 70% RH and 25 ° C. for 1 week using a constant temperature and humidity chamber, and then external appearance evaluation and external quantum efficiency measurement were performed in the same manner as in the initial evaluation. did. The external quantum efficiency was judged according to the following criteria.
≪Measurement conditions≫
Measuring device: Quantum efficiency measurement system QE-2000 (manufactured by Otsuka Electronics Co., Ltd.)
Excitation light wavelength: 450 nm, fluorescence integration range: 500-800 nm
(Evaluation criteria)
○: External quantum efficiency is 5% or more △: External quantum efficiency is 1% or more and less than 5% ×: External quantum efficiency is less than 1%

Abbreviations in Table 3 are shown below.
Polymerizable compound A: Dipentaerythritol triacrylate Esacure One: "ESACURE ONE" manufactured by Lambarti (photo radical initiator)

According to the evaluation results, the wavelength conversion member using the light-emitting material of the present invention is less likely to deteriorate in appearance and external quantum efficiency over time as compared to the wavelength conversion member using the light-emitting material that does not have the structure of the present invention. showed an inhibitory effect. It is presumed that this is because the luminescent material of the present invention is coated with a specific ligand and shell, and thus has excellent stability without using a barrier layer or the like.
Comparative Examples 10, 11, and 13 have low initial external quantum efficiencies, suggesting that the deterioration of the light-emitting material has already progressed in the cured film formation process, but in Examples 25 to 48 of the present invention, No such degradation is seen. Therefore, the luminescent material of the present invention has stability that can withstand the film forming process.

<Manufacture and Evaluation of Backlight Unit>
First, in order to manufacture a backlight unit, the following luminescent material composition and light diffusion layer coating solution were manufactured.

[Production of luminescent material composition]
The curable compositions used in the production of the wavelength conversion member were mixed according to the formulations shown in Table 4 to obtain curable luminescent material compositions 33 and 34. Table 4 shows the results of visual observation of the appearance of the obtained composition.

[Production of Light Diffusion Layer Coating Solution]
・ 30 parts of pentaerythritol triacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD-PET-30)
・ Urethane acrylate 70 parts (manufactured by Nippon Synthetic Chemical Co., Ltd., UV1700B)
- Photopolymerization initiator 5 parts (manufactured by BASF, Irgacure 184)
・ Silicone leveling agent 0.1 part (TSF4460, manufactured by Momentive Performance Materials)
・Acrylic resin diffusion particles 100 parts (average particle diameter 3 μm)
・ Dilution solvent 500 parts (methyl isobutyl ketone: cyclohexanone = 1: 1 (mass ratio))

[Example 49, Comparative Example 14]
A 20 nm-thick inorganic barrier layer was formed by vapor-depositing SiO _X on one side of a 12 μm-thick biaxially stretched polyethylene terephthalate (hereinafter referred to as PET) film by PVD to prepare a barrier film.
Next, on one surface of a biaxially stretched PET film having a thickness of 50 μm, a light diffusion layer coating solution having the following formulation is applied so that the thickness after drying becomes 11 μm, dried, and then irradiated with ultraviolet rays to form a light diffusion layer. A light diffusion film was produced.
Next, a 50 μm-thick biaxially stretched PET film, the above barrier film, and a light diffusion film were laminated in this order via a 3 μm-thick adhesive layer to obtain a laminate sheet. The barrier film and the light diffusing film were bonded together so that the surfaces on the sides of the biaxially stretched PET film of both faced each other. The same operation as above was repeated to obtain a total of two laminate sheets.
Next, on the surface of one of the laminate sheets facing the biaxially stretched PET film, the luminescent material composition 33 or 34 shown in Table 4 was applied so that the thickness after drying was 100 μm, dried, and then applied to the coated surface. The surface of the biaxially stretched PET film side of the other laminate sheet is bonded together, and ultraviolet rays (high-pressure mercury lamp 120 W/cm ² lamp, integrated light amount 1000 mJ/cm ² ) are irradiated from the light diffusion layer side of one laminate sheet. Thus, wavelength conversion members 29 and 30 having a wavelength conversion layer formed by curing the luminescent material composition were obtained.

A commercially available liquid crystal display device (diagonal: 7 inches) using a blue LED (450 nm) as a light source was disassembled and the backlight was taken out. The backlight was of the edge light type, and had a reflecting plate below the light guide plate, a light diffusion film and two prism sheets above the light guide plate. The stripe lines of the two prism sheets were perpendicular to each other between the lower one and the upper one.
The light diffusion film was removed from the backlight, and the wavelength conversion member 29 or 30 was arranged between the light guide plate and the prism sheet to obtain the backlight. In the backlight, a light guide plate is arranged so that one side of the light guide plate serves as a light entrance surface, and a wavelength conversion member and a prism sheet are arranged in this order on the light exit surface of the light guide plate. Backlight units 1 and 2 were obtained by arranging a reflective sheet on the back surface. Table 4 shows the result of visual confirmation of color development by causing the backlight unit to emit light.

According to the results in Table 4, a backlight unit comprising a wavelength-converting layer containing the light-emitting material of the present invention having a specific ligand and a shell exhibited white light emission (Example 49), whereas the specific ligand A backlight unit using a light-emitting material that does not have a shell does not function as a wavelength conversion layer, and blue light emission as a light source was confirmed (Comparative Example 14).

Composition 33, which is a mixture of two types of curable compositions, was transparent in appearance evaluation, while composition 34 was slightly turbid. This turbidity is presumed to be due to a halogen exchange reaction between perovskite particles with different compositions. When the halogen exchange reaction occurs, turbidity and agglomeration occur along with wavelength shifts and rapid changes in composition, indicating that the luminescent nanoparticles are deactivated at the stage of composition. On the other hand, in Composition 33 containing the luminescent material of the present invention, since the core is protected by a specific ligand and shell, the halogen exchange reaction is suppressed, and each luminescent material exists independently in the composition. it is conceivable that.

That is, since the luminescent material of the present invention itself has high stability, it can be applied to a wavelength conversion material composition, and a wavelength conversion member and a backlight unit using the composition, without being limited to the mode of use. We were able to.

Therefore, the light-emitting material of the present invention, which has excellent light-emitting properties and excellent stability, can be used not only for light wavelength conversion members, but also for electronic devices such as security inks or electroluminescent elements that utilize fluorescence response at specific wavelengths. can be applied.

Claims (9)

a core containing semiconductor nanoparticles having a perovskite crystal structure;
a ligand bound to the surface of the core;
a shell covering at least a portion of the core to which the ligand is bound;
the ligand comprises an organic acid salt;
A light-emitting material in which the shell contains a basic group-containing compound,
A luminescent material, wherein the basic group of the basic group-containing compound is a group represented by the following general formula (1).
General formula (1)
[In general formula (1), R ¹ to R ⁴ each independently represent an alkyl group having 1 to 10 carbon atoms. R ⁵ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an aryl group. n is an integer of 0-2. ] 2. The luminescent material according to claim 1, wherein the organic acid salt is a fatty acid salt having 1 to 30 carbon atoms. The luminescent material according to claim 1 or 2, wherein the organic acid salt is a sodium salt. The luminescent material according to any one of claims 1 to 3, wherein the basic group-containing compound is a polymer containing a repeating unit derived from a basic group-containing monomer. The luminescent material according to any one of claims 1 to 4 , wherein the basic group-containing compound has an amine value of 1 to 400 mgKOH/g. A luminescent material composition comprising the luminescent material according to any one of claims 1 to 5 and a solvent. A wavelength conversion member having a wavelength conversion layer formed from the luminescent material composition according to claim 6 . A backlight unit comprising the wavelength conversion member according to claim 7 and a light source. A liquid crystal display comprising the backlight unit according to claim 8 and a liquid crystal cell.