CN116375930A - Curable resin composition containing luminescent particles, light-converting layer, color filter, wavelength conversion film, and light-emitting element - Google Patents

Curable resin composition containing luminescent particles, light-converting layer, color filter, wavelength conversion film, and light-emitting element Download PDF

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CN116375930A
CN116375930A CN202211585929.6A CN202211585929A CN116375930A CN 116375930 A CN116375930 A CN 116375930A CN 202211585929 A CN202211585929 A CN 202211585929A CN 116375930 A CN116375930 A CN 116375930A
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meth
acrylate
curable resin
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延藤浩一
野中祐贵
堀口雅弘
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DIC Corp
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
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    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
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    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
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    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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    • C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
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    • C09K11/665—Halogenides with alkali or alkaline earth metals
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    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements
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    • H01L33/502—Wavelength conversion materials
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    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

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Abstract

The purpose of the present invention is to provide a curable resin composition containing luminescent particles, which has excellent stability to light in the presence of water and oxygen, and a light conversion layer, a color filter, a wavelength conversion film and a light-emitting element using the composition. The light-emitting particle-containing curable resin composition of the present invention is characterized by comprising: luminescent particles comprising semiconductor nanocrystals and an inorganic coating layer, organic-inorganic composite particles, and photopolymerizable compounds. The light conversion layer of the present invention is characterized by comprising the polymer of the light-emitting particle-containing curable resin composition. The light emitting element of the present invention is characterized by comprising the light conversion layer.

Description

Curable resin composition containing luminescent particles, light-converting layer, color filter, wavelength conversion film, and light-emitting element
Technical Field
The invention relates to a curable resin composition containing luminescent particles, a light conversion layer, a color filter, a wavelength conversion film and a light-emitting element.
Background
Conventionally, color filter pixel portions in displays such as liquid crystal display devices are manufactured by photolithography using a curable resist material containing, for example, red organic pigment particles or green organic pigment particles, and an alkali-soluble resin and/or an acrylic monomer.
In recent years, there has been a strong demand for lower power consumption of displays, and studies have been actively made on light conversion layers such as light conversion sheets and color filter pixel portions, in which luminescent nanoparticles such as quantum dots, quantum rods, and other inorganic phosphor particles are used instead of the red organic pigment particles or the green organic pigment particles to extract red light or green light.
The luminescent nanoparticle has a characteristic that it emits fluorescence or phosphorescence and has a narrow half width of a luminescence wavelength. CdSe was used as the luminescent nanocrystals in the beginning, but InP and a material having a perovskite structure have recently been used to avoid the harmful effects. As luminescent nanoparticles having a perovskite structure, for example, csPbX is known 3 (X is a halogen elementAnd represents Cl, br or I).
Luminescent nanoparticles such as semiconductor nanocrystals are susceptible to degradation by light irradiation in the presence of water vapor, oxygen, and the like. In particular, since the light conversion layer is heated by intense light from the backlight, there is a problem in that the luminescent nanoparticles are degraded by light irradiation at high temperature, and the luminescent intensity is lowered. To solve this problem, for example, a technique of improving light resistance by coating the particle surface with a silane coupling agent such as TEOS has been proposed (see non-patent document 1).
The luminescent nanocrystals having a perovskite structure have an advantage of excellent productivity because the luminescent wavelength can be controlled by adjusting the type of halogen element and the ratio of the halogen element present. Further, for example, a composition and a luminescent member containing a luminescent crystal having a perovskite structure and a solid polymer derived from an acrylate polymer are disclosed (patent document 1). As a composition capable of improving the light absorption efficiency and quantum yield without deteriorating the perovskite compound, a composition and a film containing inorganic fine particles such as a perovskite compound and alumina are disclosed (patent document 2).
Prior art literature
Patent literature
Patent document 1: international publication No. 2018/028870
Patent document 2: international publication No. 2019/022194
Non-patent literature
Non-patent document 1: journal of Materials Chemistry C,2019,7,9813
Disclosure of Invention
Problems to be solved by the invention
However, since luminescent nanoparticles having a perovskite structure are easily degraded by light in the presence of moisture and oxygen, there is a problem that these compositions and films cannot suppress the decrease in emission intensity with time when the composition or a light conversion layer formed from the composition is exposed to light.
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a light-emitting particle-containing curable resin composition capable of realizing a composition having excellent stability to light under moisture and oxygen and excellent optical characteristics and dispersibility and long-term storage property. Further, a light conversion layer and a light emitting element using the curable resin composition are provided.
Means for solving the problems
The present inventors have conducted intensive studies and as a result, have found that a composition containing a semiconductor nanocrystal and containing a specific organic-inorganic composite particle in a light-emitting particle-containing curable resin composition has excellent dispersibility, and a cured film obtained by polymerizing the composition has excellent light resistance, thereby leading to the present invention.
Specifically, the curable resin composition containing luminescent particles according to the present invention is characterized by comprising luminescent particles, organic-inorganic composite particles, and a photopolymerizable compound, wherein the luminescent particles comprise semiconductor nanocrystals and an inorganic coating layer that covers the surfaces of the semiconductor nanocrystals and contains an inorganic material.
The organic-inorganic composite particle is characterized by comprising a polymer Z having a structural unit represented by the general formula (Z1-1) or (Z1-2).
Figure BDA0003991136830000031
(wherein R is 1 、R 2 And R is 3 Each independently represents a hydrogen atom or a methyl group, R Z1 Represents a basic 1-valent group selected from the group consisting of primary amino, secondary amino, tertiary amino, quaternary ammonium group, imino, pyridyl, pyrimidinyl, piperazinyl, piperidinyl, imidazolyl, pyrrolidinyl and imidazolidinyl, X 1 And X 2 Each independently represents-COO-, -OCO-, an alkyl chain having 1 to 8 carbon atoms which may be substituted with a nitrogen atom, or a single bond. ) The organic-inorganic composite particles preferably contain a polymer represented by the following general formula (G).
Figure BDA0003991136830000032
(wherein R is G1 And R is G2 Each independently represents alkyl, R G3 And R is G4 Each independently represents a hydrogen atom or an alkyl group, n1 represents 0 or 1, and m1 represents an integer of 1 or more. )
The semiconductor nanocrystals described above comprise A, M and X,
the A is selected from Cs, rb, methyl ammonium, formamidine, ammonium, 2-phenylethyl ammonium and pyrrolidine
Figure BDA0003991136830000033
Piperidine->
Figure BDA0003991136830000034
1-butyl-1-methylpiperidine->
Figure BDA0003991136830000035
More than 1 cation selected from the group consisting of tetramethyl ammonium, tetraethyl ammonium, benzyl trimethyl ammonium and benzyl triethyl ammonium,
m represents 1 or more metal ions selected from the group consisting of Ag, au, bi, ca, ce, co, cr, cu, eu, fe, ga, ge, hf, in, ir, mg, mn, mo, na, nb, nd, ni, os, pb, pd, pt, re, rh, ru, sb, sc, sm, sn, sr, ta, te, ti, V, W, zn and Zr,
The above X preferably represents 1 or more halide ions selected from the group consisting of F, cl, br and I.
The semiconductor nanocrystals preferably have a perovskite structure.
The inorganic coating layer preferably has a siloxane bond.
Another aspect of the present invention relates to a light-converting layer comprising the polymer containing a luminescent particle-curable resin composition described above.
Another aspect of the present invention relates to a color filter using the above light conversion layer.
Another aspect of the present invention relates to a wavelength conversion film using the above light conversion layer.
Another aspect of the present invention relates to a light-emitting element provided with the above color filter.
Another aspect of the present invention relates to a light-emitting element including the above wavelength conversion film.
Effects of the invention
According to the present invention, it is possible to provide a light-emitting particle having a composition excellent in stability with respect to light and excellent in optical characteristics and dispersibility and long-term storage property, a light-emitting particle-containing curable resin composition containing the light-emitting particle, a light-converting layer using the resin composition, and a light-emitting element.
Drawings
Fig. 1 is a cross-sectional view showing one embodiment of a light-emitting particle including semiconductor nanocrystals of the present invention.
Fig. 2 is a schematic cross-sectional view showing one embodiment of the organic-inorganic composite particle of the present invention.
Fig. 3 is a schematic cross-sectional view showing one embodiment of a light-emitting element of the present invention.
Fig. 4 is a schematic cross-sectional view showing one embodiment of a light-emitting element of the present invention.
Fig. 5 is a schematic diagram showing the configuration of an active matrix circuit.
Fig. 6 is a schematic diagram showing the configuration of an active matrix circuit.
Symbol description
100. Light-emitting element
200 EL light source unit
1. Lower substrate
2. Anode
3. Hole injection layer
4. Hole transport layer
5. Light-emitting layer
6. Electron transport layer
7. Electron injection layer
8. Cathode electrode
9. Sealing layer
10. Filling layer
11. Protective layer
12. Light conversion layer
13. Upper base plate
14 EL layer
20. Pixel unit
20a first pixel portion
20b second pixel portion
20c third pixel portion
21a first light scattering particles
21b second light scattering particles
21c third light scattering particles
22a first curing component
22b second curing component
22c third curing component
91a first luminescent particle
91b second luminescent particles
30. Light shielding part
40. Laminated structure
41. First substrate
42. Second substrate
43. Sealing layer
44. Wavelength conversion film
441. Light scattering particles
442. Luminescent particles
500. Organic-inorganic composite particles
501. Polymers having structural units comprising basic groups
502. Inorganic oxide layer
91. Luminescent particles
911. Semiconductor nanocrystals
912. First shell layer
913. Second shell layer (inorganic coating layer)
701. Capacitor with a capacitor body
702. Driving transistor
705. Common electrode
706. Signal line
707. Scanning line
708. Switching transistor
C1 Signal line driving circuit
C2 Scanning line driving circuit
C3 Control circuit
PE, R, G, B pixel electrodes.
Detailed Description
The curable resin composition containing luminescent particles, the light-converting layer, and the light-emitting element according to the present invention will be described in detail below based on preferred embodiments shown in the drawings.
1. Curable resin composition containing luminescent particles
The curable resin composition containing luminescent particles, which contains semiconductor nanocrystals, is characterized by containing luminescent particles, organic-inorganic composite particles, and a photopolymerizable compound, wherein the luminescent particles comprise semiconductor nanocrystals and an inorganic coating layer that covers the surfaces of the semiconductor nanocrystals and contains an inorganic material. As described later, the light-emitting particle-containing curable resin composition containing semiconductor nanocrystals according to one embodiment can be suitably used for the purpose of forming a light conversion layer of a light-emitting display element using an organic EL. The composition is preferably appropriately prepared and used in order to be more suitable for the inkjet method than for the photolithography method, in that the material such as light-emitting particles including relatively expensive semiconductor nanocrystals, curable resin, and the like can be consumed without waste, and the pixel portion (light conversion layer) can be formed only in a necessary amount at a necessary portion. In addition, the composition is preferably supported between barrier films or glass films, and is used as a wavelength conversion film.
1-1 luminescent particles
The luminescent particles containing semiconductor nanocrystals in the luminescent particle-containing curable resin composition of the present invention are, for example, nanoparticles containing semiconductor nanocrystals having luminescence that can emit light (fluorescence or phosphorescence) of a wavelength different from the wavelength absorbed by absorbing light of a predetermined wavelength. That is, the luminescence is preferably a property of luminescence by excitation of electrons, and more preferably a property of luminescence by excitation of electrons by excitation light. The semiconductor nanocrystals having luminescence may be nanocrystals having red luminescence that emit light having a luminescence peak wavelength (red light) in the range of 605 to 665nm, nanocrystals having green luminescence that emit light having a luminescence peak wavelength (green light) in the range of 500 to 560nm, or nanoparticles having blue luminescence that emit light having a luminescence peak wavelength (blue light) in the range of 420 to 480 nm.
The semiconductor nanocrystals having luminescence may be luminescent nanocrystal particles (luminescent semiconductor nanocrystals) comprising a semiconductor material. Examples of the semiconductor nanocrystals having luminescence include quantum dots and quantum rods. Among them, quantum dots are preferable from the viewpoints of easy control of the emission spectrum, ensuring reliability, reducing production cost, and improving mass productivity. Further, from the viewpoint of obtaining a luminescence peak having a narrower half-value width, the luminescent nanocrystals are preferably quantum dots composed of metal halides. In the present embodiment, nanoparticles formed of quantum dots made of metal halides are described below, but the present invention is not limited thereto and can be applied to various nanoparticles including semiconductor nanocrystals having luminescence.
Fig. 1 shows 1 embodiment of a light-emitting particle including a semiconductor nanocrystal in the present invention. The light-emitting particles 91 include a semiconductor nanocrystal (hereinafter, also simply referred to as "nanocrystal 911") formed of a metal halide and having light-emitting properties, and a ligand coordinated to the surface of the nanocrystal 911. By coordinating the ligand to the surface of the nanocrystal 911, dispersibility can be ensured. As the ligand, for example, oleic acid, caprylic acid, oleylamine, octylamine, trioctylphosphine, etc. can be used.
As the ligand, a compound capable of forming a siloxane bond is used in combination in addition to the above oleic acid and the like. Thus, a shell layer 912 containing siloxane bonds (hereinafter referred to as "first shell layer 912") is formed on the surface of the nanocrystals 911. The nanocrystals 911 can be protected from heat, air, moisture, and the like by the first shell layer 912.
In this embodiment mode, a shell layer 913 in which siloxane bonds are formed between molecules of a silane compound having a hydrolyzable silyl group (hereinafter referred to as "second shell layer 913". Corresponding to the "inorganic coating layer" of the present invention) is further provided as an inorganic coating layer on the surface of the first shell layer 912. With the second shell layer 913, the nanocrystals 911 can be more reliably protected from heat, air, moisture, or the like than the case of only the first shell layer 912.
The light-emitting particles 91 can be obtained, for example, as follows. The first shell layer 912 is formed by mixing a precursor of the nanocrystal 911, a ligand such as oleic acid or oleylamine, and a ligand having a site capable of forming a siloxane bond, allowing the ligand to coordinate to the surface of the nanocrystal 911 while precipitating the nanocrystal 911, and then subsequently forming a siloxane bond. Then, after adsorbing a polymer containing a structural unit having a basic group on the surface of the first shell layer 912, a silane compound having a hydrolyzable silyl group is mixed to generate a siloxane bond, thereby forming the second shell layer 913. Since the nanocrystals 911 are protected by the first shell layer 912 and the second shell layer 913 located on the surface of the first shell layer 912, the luminescent particles 91 can have excellent stability to light under moisture and oxygen, and as a result, excellent luminescent characteristics can be obtained.
The light-emitting particles 91 themselves may be used alone as the light-emitting particles, but are preferably added to the resin composition for use.
< nanocrystal 911 >)
Nanocrystals 911 are nano-sized crystals (nanocrystal particles) formed from metal halides that absorb excitation light and fluoresce or phosphoresce. The nanocrystals 911 are crystals having a maximum particle diameter of 100nm or less as measured by, for example, a transmission electron microscope or a scanning electron microscope. Nanocrystals 911 can be excited by light energy or electric energy of a predetermined wavelength, for example, and emit fluorescence or phosphorescence.
Nanocrystals 911 composed of metal halides are semiconductors containing A, M and X, are of the general formula A a M b X c The compound represented.
Wherein A represents a 1-valent cation, and is at least one of an organic cation and a metal cation. Examples of the organic cation include ammonium, methyl ammonium, formamidine (formamidine), guanidine (guanidium), and imidazole
Figure BDA0003991136830000081
Pyridine->
Figure BDA0003991136830000082
Pyrrolidine compounds
Figure BDA0003991136830000083
Examples of the metal cation include cations such as Cs, rb, K, na, li.
M represents a metal ion, and is at least one metal cation. Examples of the metal cation include metal cations selected from groups 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 13, 14, and 15. More preferably, the cation may be Ag, au, bi, ca, ce, co, cr, cu, eu, fe, ga, ge, hf, in, ir, mg, mn, mo, na, nb, nd, ni, os, pb, pd, pt, re, rh, ru, sb, sc, sm, sn, sr, ta, te, ti, V, W, zn, zr.
X is at least one anion. Examples of the anions include halide ions such as chloride ions, bromide ions, iodide ions, and cyanide ions.
a is 1 to 7, b is 1 to 4, and c is 1 to 16.
The nanocrystals 911 can control the emission wavelength (emission color) by adjusting the particle size, the type and the presence ratio of anions constituting the X site.
General formula A a M b X c The compounds represented are preferably AMX, A 4 MX、AMX 2 、AMX 3 、A 2 MX 3 、AM 2 X 3 、A 2 MX 4 、A 2 MX 5 、A 3 MX 5 、A 3 M 2 X 5 、A 3 MX 6 、A 4 MX 6 、AM 2 X 6 、A 2 MX 6 、A 4 M 2 X 6 、A 3 MX 8 、A 3 M 2 X 9 、A 3 M 3 X 9 、A 2 M 2 X 10 、A 7 M 3 X 16 The compound represented.
Wherein A is at least one of an organic cation and a metal cation. Examples of the organic cation include ammonium, methyl ammonium, formamidine, guanidine, and imidazole
Figure BDA0003991136830000091
Pyridine->
Figure BDA0003991136830000092
Pyrrolidine->
Figure BDA0003991136830000093
Examples of the metal cation include cations such as Cs, rb, K, na, li.
Wherein M is at least one metal cation. Specifically, 1 metal cation (M 1 ) 2 metal cations (M) 1 α M 2 β ) 3 metal cations (M) 1 α M 2 β M 3 γ ) 4 metal cations (M) 1 α M 2 β M 3 γ M 4 δ ) Etc. Wherein α, β, γ, δ each represent a real number of 0 to 1, and α+β+γ+δ=1. Examples of the metal cation include metal cations selected from groups 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 13, 14, and 15. More preferably, the cation may be Ag, au, bi, ca, ce, co, cr, cu, eu, fe, ga, ge, hf, in, ir, mg, mn, mo, na, nb, nd, ni, os, pb, pd, pt, re, rh, ru, sb, sc, sm, sn, sr, ta, te, ti, V, W, zn, zr.
Wherein X is an anion comprising at least 1 halogen. Specifically, 1 halogen anion (X 1 ) 2 halogen anions (X) 1 α X 2 β ) Etc. Examples of the anions include chloride ion, bromide ion, iodide ion, cyanide ion, and the like, and include at least one halideAnd (3) an object ion.
In order to improve the light-emitting characteristics, the above formula A a M b X c A metal ion such as Bi, mn, ca, eu, sb, yb may be added (doped) to the compound composed of the metal halide.
In the general formula A a M b X c Among the compounds represented as metal halides, compounds having a perovskite crystal structure can be particularly preferably used as semiconductor nanocrystals in that the emission wavelength (emission color) can be controlled by adjusting the particle size, the kind and the existing ratio of metal cations constituting the M site, and further the kind and the existing ratio of anions constituting the X site. Specifically, AMX is preferable 3 、A 3 MX 5 、A 3 MX 6 、A 4 MX 6 、A 2 MX 6 The compound represented. A, M and X in the formula are as described above. In addition, a metal ion such as Bi, mn, ca, eu, sb, yb may be added (doped) to the compound having a perovskite crystal structure as described above.
Among the compounds exhibiting a perovskite crystal structure, a is preferably a cation selected from the group consisting of Cs, rb, K, na, li, methylammonium, and formamidine, more preferably a cation selected from Cs, rb, methylammonium, and formamidine, and particularly preferably a cation selected from Cs and formamidine, from the viewpoints of ease of synthesis, good light-emitting characteristics, and firmness of crystal structure. M is 1 metal cation (M 1 ) Or 2 metal cations (M) 1 α M 2 β (wherein α and β each represent a real number of 0 to 1, α+β=1)), a metal ion selected from the group consisting of Pb, sn, ge, bi, sb, ag, in, cu, yb, ti, pd, mn, eu, zr and Tb is preferable, a metal ion selected from the group consisting of Pb, sn, bi, sb, ag, in, cu, mn and Zr is more preferable, a metal ion selected from the group consisting of Pb, sn and Cu is more preferable, and Pb ion is particularly preferable from the viewpoints of easiness of synthesis, good light emission characteristics and firmness of crystal structure. X is preferably chloride ion, bromide ion,Iodide ions. From the viewpoints of ease of synthesis, good light-emitting characteristics, and firmness of crystal structure, X is preferably a halide ion selected from the group consisting of F, cl, br, and I, X is more preferably a halide ion selected from the group consisting of Cl, br, and I, X is even more preferably a halide ion selected from the group consisting of Br and I, and X is particularly preferably a Br ion.
As a specific composition of the nanocrystal 911 having a perovskite crystal structure formed of a metal halide, csPbBr is preferable in terms of excellent light intensity and excellent quantum efficiency 3 、CH 3 NH 3 PbBr 3 、CHN 2 H 4 PbBr 3 、CsPbI 3 And the like using Pb as nanocrystals 911 of M. In addition, csSnBr is preferable in terms of low toxicity and small influence on the environment 3 、CsSnCl 3 、CsSnBr 1.5 Cl 1.5 、Cs 3 Sb 2 Br 9 、(CH 3 NH 3 ) 3 Bi 2 Br 9 、(C 4 H 9 NH 3 ) 2 AgBiBr 6 And the like, a metal cation other than Pb is used as the nanocrystal 911 of M.
As the nanocrystals 911, a crystal that emits red light (red light) having a light emission peak in a wavelength range of 605 to 665nm, a crystal that emits green light (green light) having a light emission peak in a wavelength range of 500 to 560nm, and a crystal that emits blue light (blue light) having a light emission peak in a wavelength range of 420 to 480nm can be selected. In addition, in one embodiment, a plurality of these nanocrystals may also be used in combination.
The wavelength of the luminescence peak of the nanocrystals 911 can be confirmed, for example, in a fluorescence spectrum or a phosphorescence spectrum measured using an absolute PL quantum yield measurement device.
The red light-emitting nanocrystals 911 preferably have light-emitting peaks in the wavelength ranges of 665nm or less, 663nm or less, 660nm or less, 658nm or less, 655nm or less, 653nm or less, 651nm or less, 650nm or less, 647nm or less, 645nm or less, 643nm or less, 640nm or less, 637nm or less, 635nm or less, 632nm or less, or 630nm or less, preferably in the wavelength ranges of 628nm or more, 625nm or more, 623nm or more, 620nm or more, 615nm or more, 610nm or more, 607nm or more, or 605nm or more.
These upper and lower limits may be arbitrarily combined. In the same manner as described below, the upper limit value and the lower limit value described separately may be arbitrarily combined.
The green luminescent nanocrystals 911 preferably have luminescent peaks in the wavelength range of 560nm or less, 557nm or less, 555nm or less, 550nm or less, 547nm or less, 545nm or less, 543nm or less, 540nm or less, 537nm or less, 535nm or less, 532nm or less, or 530nm or less, and preferably have luminescent peaks in the wavelength range of 528nm or more, 525nm or more, 523nm or more, 520nm or more, 515nm or more, 510nm or more, 507nm or more, 505nm or more, 503nm or more, or 500nm or more.
The blue light-emitting nanocrystals 911 preferably have light-emitting peaks in the wavelength ranges of 480nm or less, 477nm or less, 475nm or less, 470nm or less, 467nm or less, 465nm or less, 463nm or less, 460nm or less, 457nm or less, 455nm or less, 452nm or less, or 450nm or less, and preferably have light-emitting peaks in the wavelength ranges of 450nm or more, 445nm or more, 440nm or more, 435nm or more, 430nm or more, 428nm or more, 425nm or more, 422nm or more, or 420nm or more.
The shape of the nanocrystals 911 is not particularly limited, and may be any geometric shape or any irregular shape. Examples of the shape of the nanocrystals 911 include rectangular parallelepiped, cube, sphere, regular tetrahedron, ellipsoid, pyramid, disk, dendrite, net, and rod. The nanocrystals 911 are preferably rectangular parallelepiped, cube, or sphere.
The average particle diameter (volume average diameter) of the nanocrystals 911 is preferably 40nm or less, more preferably 30nm or less, and even more preferably 20nm or less. The average particle diameter of the nanocrystals 911 is preferably 1nm or more, more preferably 1.5nm or more, and even more preferably 2nm or more. Nanocrystals 911 having the above average particle diameter are preferable because they easily emit light having a desired wavelength. The average particle diameter of the nanocrystals 911 can be obtained by measuring and calculating the volume average diameter by using a transmission electron microscope or a scanning electron microscope.
< first Shell 912 >
The first shell layer 912 is formed of a ligand including a compound that can be coordinated to the surface of the nanocrystal 911 and that can form siloxane bonds with each other.
The ligand is a compound having a binding group that binds to a cation or anion contained in the nanocrystal 911, and includes a compound containing Si and having a reactive group that forms a siloxane bond. The binding group is preferably at least one of a carboxyl group, a carboxylic anhydride group, an amino group, an ammonium group, a mercapto group, a phosphine oxide group, a phosphate group, a phosphonate group, a phosphinate group, a sulfonate group, a borate group, and salts thereof, and more preferably at least one of a carboxyl group, an amino group, a mercapto group, a sulfonate group, and salts thereof. The ligand may be a carboxyl group-containing compound, an amino group-containing compound, a sulfonic acid group-containing compound or a salt thereof, and 1 or 2 or more of them may be used singly or in combination. As the ligand, 1 or more of a carboxyl group-containing compound, an amino group-containing compound, a sulfonic acid group-containing compound, and salts thereof, and 1 or more of a compound containing Si and having a reactive group capable of forming a siloxane bond are preferably used in order to improve stability of the nanocrystal 911. The ligand is preferably used when synthesizing the nanocrystal 911, or is replaced with a ligand formed of a compound different from the ligand used when synthesizing the nanocrystal 911 after the formation of the nanocrystal 911.
Examples of the carboxyl group-containing compound include linear or branched aliphatic carboxylic acids having 1 to 30 carbon atoms. As a specific example of the above-mentioned carboxyl group-containing compound, examples thereof include arachidonic acid, crotonic acid, trans-2-decenoic acid, erucic acid, 3-decenoic acid, cis-4, 7,10,13,16, 19-docosahexaenoic acid, 4-decenoic acid, all-cis-5, 8,11,14, 17-eicosapentaenoic acid, all-cis-8, 11, 14-eicosatrienoic acid, cis-9-hexadecenoic acid, trans-3-hexenoic acid, trans-2-hexenoic acid, 2-heptenoic acid, 3-heptenoic acid, 2-hexadecenoic acid, linolenic acid, linoleic acid, gamma-linolenic acid, 3-nonenoic acid, 2-nonenoic acid, trans-2-octenoic acid, petroselinic acid, elaidic acid, oleic acid, 3-octenoic acid, trans-2-pentenoic acid, 3-octenoic acid trans-3-pentenoic acid, ricinoleic acid, sorbic acid, 2-tridecenoic acid, cis-15-tetradecenoic acid, 10-undecenoic acid, 2-undecenoic acid, acetic acid, butyric acid, behenic acid, cerotic acid, capric acid, eicosanoic acid, heneicosanoic acid, heptadecanoic acid, heptanoic acid, caproic acid, heptadecanoic acid, lauric acid, myristic acid, melissic acid, octacosanoic acid, nonadecanoic acid, n-octanoic acid, palmitic acid, pentadecanoic acid, propionic acid, eicosanoic acid, nonanoic acid, stearic acid, tetracosanoic acid, tricosanoic acid, tridecanoic acid, undecanoic acid, valeric acid, and the like.
Examples of the amino group-containing compound include linear or branched aliphatic amines having 1 to 30 carbon atoms. Specific examples of the amino group-containing compound include 1-aminoheptadecane, 1-aminononadecane, heptadecane-9-amine, stearylamine, oleylamine, 2-n-octyl-1-dodecylamine, allylamine, pentylamine, 2-ethoxyethylamine, 3-ethoxypropylamine, isobutylamine, isopentylamine, 3-methoxypropylamine, 2-methoxyethylamine, 2-methylbutylamine, neopentylamine, propylamine, methylamine, ethylamine, butylamine, hexylamine, heptylamine, n-octylamine, 1-aminodecane, nonylamine, 1-aminoundecane, dodecylamine, 1-aminopentadecane, 1-aminotridecane, hexadecylamine, and dodecylamine.
Examples of the thiol-group-containing compound include n-dodecyl mercaptan, t-dodecyl mercaptan, 1-dodecyl mercaptan, n-octane mercaptan, and 1-octadecyl mercaptan.
Examples of the sulfonic acid group-containing compound and its salt include sodium dodecylbenzenesulfonate, sodium 4-n-octylbenzenesulfonate, sodium 4-dodecylbenzene-1-sulfonate, sodium 4-undecylbenzenesulfonate, sodium 4-tetradecylbenzene-1-sulfonate, sodium 4-tridecylbenzene-1-sulfonate, sodium 1-decanesulfonate, sodium 1-dodecylbenzenesulfonate, sodium lauryl sulfate and the like.
In addition, the silane compound a containing Si and having a reactive group forming a siloxane bond preferably has a binding group that binds to a cation or anion contained in the nanocrystal 911.
The reactive group is preferably a hydrolyzable silyl group such as a silanol group or an alkoxysilyl group having 1 to 6 carbon atoms, more preferably a silanol group or an alkoxysilyl group having 1 to 2 carbon atoms, because a siloxane bond is easily formed.
Examples of the binding group include a carboxyl group, an amino group, an ammonium group, a mercapto group, a phosphine oxide group, a phosphate group, a phosphonate group, a phosphinate group, a sulfonate group, and a borate group. Among them, at least one of a carboxyl group, a mercapto group and an amino group is preferable as the binding group. These binding groups have a higher affinity for the cations or anions contained in the nanocrystals 911 than the reactive groups described above. Therefore, the ligand coordinates to the side of the nanocrystal 911 with a binding group, and the first shell layer 912 can be formed more easily and reliably.
The compound containing Si and having a reactive group forming a siloxane bond may contain 1 or more kinds of silicon compounds containing a binding group, or 2 or more kinds of silicon compounds may be used in combination.
It is preferable to use any one of the carboxyl group-containing silicon compound, amino group-containing silicon compound and mercapto group-containing silicon compound in combination of 2 or more.
Specific examples of the carboxyl group-containing silicon compound include 3- (trimethoxysilyl) propionic acid, 3- (triethoxysilyl) propionic acid, 2-carboxyethylphenyl bis (2-methoxyethoxy) silane, N- [3- (trimethoxysilyl) propyl ] -N ' -carboxymethylethylenediamine, N- [3- (trimethoxysilyl) propyl ] phthalic acid amide, N- [3- (trimethoxysilyl) propyl ] ethylenediamine-N, N ', N ' -triacetic acid, (6-triethoxysilyl) -3- [ [ [3- (triethoxysilyl) propyl ] amino ] carbonyl ] hexanoic acid, and the like.
On the other hand, specific examples of the amino-containing silicon compound include 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, N- (2-aminoethyl) -3-aminopropyl methyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyl methyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyl methyldipropoxysilane, N- (2-aminoethyl) -3-aminopropyl methyldiisopropyloxysilane, N- (2-aminoethyl) -3-aminopropyl trimethoxysilane, N- (2-aminoethyl) -3-aminopropyl triethoxysilane, N- (2-aminoethyl) -3-aminopropyl tripropoxysilane, N- (2-aminoethyl) -3-aminopropyl triisopropoxysilane, N- (2-aminoethyl) -3-aminoisobutyl dimethylmethoxysilane, N- (2-aminoethyl) -3-aminoisobutyl methyldimethoxysilane, N- (2-aminoethyl) -11-aminoundecyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylsilane, 3-triethoxysilyl-N- (1, 3-butanetriol-dimethylpropylamine, N-phenyl-3-aminopropyl trimethoxysilane, N-bis [3- (trimethoxysilyl) propyl ] ethylenediamine, (aminoethylaminoethyl) phenyl trimethoxysilane, (aminoethylaminoethyl) phenyl triethoxysilane, (aminoethylaminoethyl) phenyl tripropoxysilane, (aminoethylaminoethyl) phenyl triisopropoxysilane, (aminoethylaminomethyl) phenyl trimethoxysilane, (aminoethylaminomethyl) phenyl triethoxysilane, (aminoethylaminomethyl) phenyl tripropoxysilane, (aminoethylaminomethyl) phenyl triisopropoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyl trimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyl methyldimethoxysilane, N-beta- (N-vinylbenzyl aminoethyl) -N-gamma- (N-vinylbenzyl) -gamma-aminopropyl trimethoxysilane, N-beta- (N-di (vinylbenzyl) aminoethyl) -gamma-aminopropyl trimethoxysilane, N-beta- (N-di (vinylbenzyl) amino ethyl) -N-gamma- (N-vinylbenzyl) -gamma-aminopropyl trimethoxysilane, methyl benzyl amino ethyl amino propyl trimethoxy silane, dimethyl benzyl amino ethyl amino propyl trimethoxy silane, benzyl amino ethyl amino propyl triethoxy silane, 3-ureido propyl triethoxy silane, 3- (N-phenyl) amino propyl trimethoxy silane, N, N-bis [3- (trimethoxysilyl) propyl ] ethylenediamine, (aminoethylaminoethyl) phenethyltrimethoxysilane, (aminoethylaminoethyl) phenethyltriethoxysilane, (aminoethylaminoethyl) phenethyltripropoxysilane, (aminoethylaminoethyl) phenethyl triisopropoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, (aminoethylaminomethyl) phenethyltriethoxysilane, (aminoethylaminomethyl) phenethyltripropoxysilane, (aminoethylaminomethyl) phenethyl triisopropoxysilane, N- [2- [3- (trimethoxysilyl) propylamino ] ethyl ] ethylenediamine, N- [2- [3- (triethoxysilyl) propylamino ] ethyl ] ethylenediamine, N- [2- [3- (tripropoxysilyl) propylamino ] ethyl ] ethylenediamine, N- [2- [3- (triisopropoxysilyl) propylamino ] ethyl ] ethylenediamine, and the like.
Specific examples of the mercapto-containing silicon compound include 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl triethoxysilane, 3-mercaptopropyl methyl dimethoxysilane, 3-mercaptopropyl methyl diethoxysilane, 2-mercaptoethyl trimethoxysilane, 2-mercaptoethyl triethoxysilane, 2-mercaptoethyl methyl dimethoxysilane, 2-mercaptoethyl methyl diethoxysilane, 3- [ ethoxybis (3, 6,9,12, 15-pentaoxadioctadec-1-yloxy) silyl ] -1-propanethiol, and the like.
The first shell layer 912 can be formed by further reacting 3-aminopropyl trimethoxysilane using, for example, oleic acid, 3-aminopropyl trimethoxysilane as a ligand and locating it on the surface of the nanocrystal 911.
The thickness of the first shell layer 912 is preferably 0.5 to 50nm, more preferably 1.0 to 30nm. If the luminescent particle has the first shell layer 912 having the above thickness, the stability of the nanocrystals 911 against heat can be sufficiently improved.
The thickness of the first shell layer 912 may be changed by adjusting the number of atoms (chain length) of the linking structure linking the binding group of the ligand to the reactive group.
In addition to the ligands, the luminescent particles of the present invention may have additives coordinated to the surface of the nanocrystals 911. Examples of the additive include ammonium salts. Examples of the ammonium salt include Didodecyl Dimethyl Ammonium Bromide (DDAB), phenethyl ammonium bromide (pea), phenethyl ammonium iodide (pea), methyltrioctyl ammonium bromide, didecyl dimethyl ammonium bromide, ditetradecyl dimethyl ammonium bromide, and tetraoctyl ammonium bromide (TOAB).
Specifically, the light-emitting particle including the first shell layer 912 can be easily produced by mixing a solution containing a raw material compound of the nanocrystals 911, a solution containing a compound having a binding group to a cation or anion contained in the nanocrystals 911 and a compound containing Si and having a reactive group capable of forming a siloxane bond, and then condensing the reactive group in the compound containing Si and having a reactive group capable of forming a siloxane bond, which is coordinated to the surface of the precipitated nanocrystals 911. In this case, there are a method of manufacturing without heating and a method of manufacturing without heating.
First, a method of manufacturing a light-emitting particle having the first shell layer 912 by heating will be described. The following methods are mentioned: separately preparing solutions containing 2 raw material compounds for synthesizing semiconductor nanocrystals by reaction, at this time, a compound having a binding group to a cation contained in nanocrystal 911 is added in advance to any one of the 2 solutions, and a compound containing Si and having a reactive group capable of forming a siloxane bond is added to the other; then, they are mixed under the inert gas atmosphere and reacted at the temperature of 140-260 ℃; then, the mixture is cooled to-20 to 30 ℃ and stirred, whereby nanocrystals are precipitated. The precipitated nanocrystals are nanocrystals in which a first shell layer 912 having siloxane bonds is formed on the surface of nanocrystals 911, and can be obtained by a conventional method such as centrifugation.
Specifically, for example, a solution containing cesium carbonate, oleic acid, and an organic solvent is prepared. As the organic solvent, 1-octadecene, dioctyl ether, diphenyl ether and the like can be used. In this case, the addition amounts of cesium carbonate and oleic acid are preferably adjusted so that the amount of cesium carbonate is 0.2 to 2g and the amount of oleic acid is 0.1 to 10mL, respectively, relative to 40mL of the organic solvent. The resulting solution was dried under reduced pressure at 90 to 150℃for 10 to 180 minutes, and then heated to 100 to 200℃under an inert gas atmosphere such as argon or nitrogen, to thereby obtain a cesium-oleic acid solution.
On the other hand, a solution containing lead (II) bromide and the same organic solvent as described above was prepared. At this time, 20 to 100mg of lead (II) bromide was added to 5mL of the organic solvent. The resulting solution was dried under reduced pressure at 90 to 150℃for 10 to 180 minutes, and then 0.1 to 2mL of 3-aminopropyl triethoxysilane was added under an inert gas atmosphere such as argon or nitrogen.
Then, the cesium-oleic acid solution was added in a state where a solution containing lead (II) bromide and 3-aminopropyl triethoxysilane was heated to 140 to 260 ℃, and the mixture was heated and stirred for 1 to 10 seconds to react, and then the obtained reaction solution was cooled in an ice bath. In this case, it is preferable to add 0.1 to 1mL of cesium-oleic acid solution to 5mL of the solution containing lead (II) bromide and 3-aminopropyl triethoxysilane. During the stirring process at-20 to 30 ℃, nanocrystals 911 are precipitated, and 3-aminopropyl triethoxysilane and oleic acid coordinate to the surface of nanocrystals 911.
Then, the obtained reaction solution was stirred at room temperature (10 to 30 ℃ C., humidity 5 to 60%) under atmospheric pressure for 5 to 300 minutes, and then 0.1 to 50mL of ethanol was added thereto, thereby obtaining a suspension. The alkoxysilyl group of 3-aminopropyl triethoxysilane is condensed under stirring at room temperature under atmospheric pressure to form a first shell layer 912 having siloxane bonds on the surface of the nanocrystal 911.
The obtained suspension is centrifuged to collect a solid material, and the solid material is added to hexane, whereby a luminescent particle dispersion in which luminescent particles having a first shell layer 912 having siloxane bonds on the surface of nanocrystals 911 composed of lead cesium tribromide are dispersed in toluene can be obtained.
Next, a method for manufacturing the light-emitting particle having the first shell layer 912 without heating will be described. The following methods are mentioned: a solution containing a raw material compound of a semiconductor nanocrystal and a compound having a binding group to a cation contained in the nanocrystal 911 (a compound containing no Si and having a reactive group capable of forming a siloxane bond) is added dropwise under an atmosphere, and the mixture is mixed with a solution in which a compound containing Si and having a reactive group capable of forming a siloxane bond is dissolved in an organic solvent which is a poor solvent for the nanocrystal, whereby the nanocrystal is precipitated. The amount of the organic solvent to be used is preferably 10 to 1000 times the amount of the semiconductor nanocrystals on a mass basis. The precipitated nanocrystals are nanocrystals in which a first shell layer 912 having siloxane bonds is formed on the surface of nanocrystals 911, and can be obtained by a conventional method such as centrifugation.
Specifically, as a solution of a raw material compound containing semiconductor nanocrystals, for example, a solution containing lead (II) bromide, cesium bromide, oleic acid, oleylamine, and an organic solvent is prepared. The organic solvent may be any good solvent for nanocrystals, but is preferably dimethyl sulfoxide, N-dimethylformamide, N-methylformamide, or a mixed solvent thereof, in terms of compatibility. In this case, the amounts of the respective additives are preferably adjusted so that 10 to 50mg of lead (II) bromide, 5 to 25mg of cesium bromide, 0.2 to 2mL of oleic acid and 0.05 to 0.5mL of oleylamine are added to 10mL of the organic solvent.
On the other hand, as a solution containing a compound containing Si and having a reactive group that can form a siloxane bond and an organic solvent that is a poor solvent for nanocrystals, for example, 3-aminopropyl triethoxysilane and a poor solvent are prepared. As the poor solvent, isopropyl alcohol, toluene, hexane, or the like can be used. In this case, the addition amount of each of the solvents is preferably adjusted so that 5mL of 3-aminopropyl triethoxysilane is 0.01 to 0.5mL relative to the poor solvent.
Then, 0.1 to 1mL of the solution containing lead (II) bromide, cesium bromide, oleic acid and oleylamine was added to 5mL of the solution containing 3-aminopropyl triethoxysilane and a poor solvent under atmospheric conditions at 0 to 30℃and immediately stirred under atmospheric conditions for 5 to 180 seconds, followed by centrifugation to collect a solid substance. When the mixture is added to a poor solvent, nanocrystals 911 are precipitated, and 3-aminopropyl triethoxysilane, oleic acid, and oleylamine coordinate to the surfaces of nanocrystals 911. Then, the alkoxysilyl group of 3-aminopropyl triethoxysilane is condensed while stirring under the atmosphere, and a first shell layer 912 having siloxane bonds is formed on the surface of the nanocrystal 911.
By adding the recovered solid material to toluene, a luminescent particle dispersion in which luminescent particles having a first shell layer 912 having siloxane bonds on the surface of nanocrystals 911 composed of lead cesium tribromide crystals are dispersed in toluene can be obtained.
< second Shell 913 >
In order to uniformly form the above-mentioned shell layer 913 on the surface of the first shell layer 912, the second shell layer 913 is preferably derived from the polymer B having a structural unit containing a basic group and the silane compound C having a hydrolyzable silyl group. This is because, in order to uniformly coat the second shell layer 913 on the surface of the first shell layer 912, a reaction field of the silane compound is preferably present on the surface of the first shell layer 912. First, the basic group of the polymer B is adsorbed on the surface of the first shell layer 912, and a reaction field is formed on the surface of the first shell layer 912. Then, the silane compound C is mixed, and the siloxane bond is formed by hydrolysis of the hydrolyzable silyl group in the reaction field, so that the second shell 913 can be uniformly formed on the surface of the first shell 912. The luminescent particle having the second shell 913 can reliably obtain excellent stability to light under moisture and oxygen, and as a result, excellent light emission characteristics can be obtained.
The polymer B is a compound having a structural unit containing a basic group, and is a polymer having a first structural unit containing a basic group and a second structural unit containing no basic group and having a solphilicity excellent in affinity to a dispersion medium. The dispersion medium is a compound for dispersing the light-emitting particles, and may be various organic solvents, photopolymerisable compounds, and other resins.
The first structural unit having a basic group is more preferably a structural unit represented by the following formulas (B1) and (B2) from the viewpoint of adsorptivity to a semiconductor nanocrystal.
Figure BDA0003991136830000181
Wherein R is B11 、R B21 And R is B22 Each independently represents a hydrogen atom or a methyl group, R B12 Represents a basic group having a basic valence of 1, including, for example, a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium group, an imino group, a pyridyl group, a pyrimidinyl group, a piperazinyl group, a piperidinyl group, an imidazolyl group, a pyrrolidinyl group, an imidazolidinyl group,
X B11 and X B12 Each independently represents-COO-, -OCO-, an alkyl chain having 1 to 8 carbon atoms which may be substituted with a nitrogen atom, or a single bond.
Specific examples of the compound providing the first structural unit represented by the above formula (B1) include 2-vinylpyridine, 4-aminostyrene, 4-dimethylaminostyrene, 1-vinylimidazole, N-vinyl-2-pyrrolidone, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dimethylaminobutyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) acrylate, dimethylaminopropyl acrylamide, diethylaminopropyl acrylamide, allylamine, and the like. In the present specification, "(meth) acrylate" means one or both of methacrylate and acrylate.
Examples of the compound providing the first structural unit represented by the above formula (B2) include ethyleneimine and propyleneimine.
The second structural unit having the solvophilicity is more preferably a structural unit represented by the following formulas (B3) and (B4) from the viewpoint of dispersibility in the semiconductor nanocrystal particle.
Figure BDA0003991136830000191
Wherein R is B21 And R is B41 Represents a hydrogen atom or a methyl group, R B32 Represents a linear or branched alkyl group having 2 to 15 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms which may have a substituent, a polyoxyalkylene group having 10 to 50 carbon atoms which is a hydroxyl group or an alkoxy group at the end, an aromatic group which may have a substituent, or a group represented by the general formula (B3), X B31 And X B41 represents-COO-, -OCO-, an alkyl chain having 1 to 8 carbon atoms, a single bond,
R B42 a group represented by the general formula (B4-1),
Figure BDA0003991136830000192
R B43 a represents a linear or branched saturated or unsaturated 2-valent hydrocarbon group having 1 to 20 carbon atoms, a represents 0 or 1, and b represents 1 to 100.
The polyester skeleton in the general formula (B4-1) can be obtained by self-condensation of hydroxycarboxylic acid, lactone, or mixed condensation of hydroxycarboxylic acid and lactone. Examples of the hydroxycarboxylic acid include 12-hydroxystearic acid, and examples of the lactone include epsilon-caprolactone, beta-propiolactone, gamma-butyrolactone, and delta-valerolactone, but it is preferable that the lactone has at least one structural unit derived from 12-hydroxystearic acid, valerolactone, or caprolactone.
Examples of the compound providing the second structural unit represented by the above formula (B3) include (meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, and the like; aromatic (meth) acrylates such as benzyl (meth) acrylate and phenylethyl (meth) acrylate; (meth) acrylic esters having an alicyclic structure such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate; alkyl-terminated polyalkylene glycol (meth) acrylates such as methoxypolyethylene glycol (meth) acrylate, octyloxypolyethylene glycol (meth) acrylate, octyloxypolypropylene glycol (meth) acrylate, lauroxypolypropylene glycol (meth) acrylate, stearoxypolyethylene glycol (meth) acrylate, stearoxypolypropylene glycol (meth) acrylate, allyloxypolyethylene glycol (meth) acrylate, allyloxypolypropylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, and the like; glycidyl (meth) acrylate, dicyclopentenyl (meth) acrylate, tricyclodecyl (meth) acrylate, and the like; styrene derivative monomers such as styrene, α -methylstyrene, 4-t-butylstyrene, 2, 5-dimethylstyrene, and p-isobutylstyrene; condensates of allylamine with polyesters, and the like.
Examples of the compound providing the second structural unit represented by the above formula (B4) include a condensate of ethyleneimine and polyester, a condensate of propyleneimine and polyester, and the like.
In the polymer B, at least one or more of the structural units represented by the formulas (B1) and (B2) may be used, and at least one or more of the structural units represented by the formulas (B3) and (B4) may be used. The polymer B may be a block copolymer having the first structural unit represented by the formula (B1) as a first polymer block and the second structural unit represented by the formula (B3) as a second polymer block, a random polymer having the first structural unit represented by the formula (B1) and the second structural unit represented by the formula (B3) randomly, or a graft polymer having the first structural unit represented by the formula (B2) and the second structural unit represented by the formula (B4). The polymer B is preferably a block copolymer or a graft polymer from the viewpoint of the adsorptivity to the surface of the light-emitting particle having the first shell layer 912.
The content of the first structural unit in the polymer B is, for example, preferably 3 mol% or more, 4 mol% or more, or 5 mol% or more, and preferably 50 mol% or less, 30 mol% or less, or 20 mol% or less, based on the total structural units constituting the polymer B.
The content of the second structural unit in the polymer B is, for example, preferably 70 mol% or more, 75 mol% or more, or 80 mol% or more, and preferably 97 mol% or less, 96 mol% or less, or 95 mol% or less, based on the total structural units constituting the polymer B.
The polymer B may contain other structural units in addition to the first structural unit and the second structural unit. In this case, the total content of the first structural unit and the second structural unit in the polymer B is preferably 70 mol% or more, 80 mol% or more, or 90 mol% or more based on the total structural units constituting the polymer B.
For example, the polymer B may have a structural unit having an acidic group in addition to the first structural unit and the second structural unit.
Examples of the acidic group include a carboxyl group (-COOH) and a sulfonic acid group (-SO) 3 H) Sulfuric acid group (-OSO) 3 H) Phosphonic acid groups (-PO (OH) 3 ) Phosphate (-OPO (OH)) 3 ) Phosphinic acid groups (-PO (OH) -) and mercapto groups (-SH).
Examples of the nonionic functional group include a hydroxyl group, an ether group, a thioether group, a sulfinyl group (-SO-), and a sulfonyl group (-SO- 2 (-), carbonyl, formyl, ester, carbonate, amide, carbamoyl, ureido, thioamide, thiourea, sulfamoyl, cyano, alkenyl, alkynyl, phosphine oxide, phosphine sulfide.
Examples of the compound providing a structural unit having an acidic group include a (meth) acrylate having a carboxyl group, a (meth) acrylate having a phosphate group, and a (meth) acrylate having a sulfonate group. Examples of the (meth) acrylic acid ester having a carboxyl group include monomers obtained by reacting an acid anhydride such as maleic anhydride, succinic anhydride, or phthalic anhydride with a (meth) acrylic acid ester having a hydroxyl group such as carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl maleate, or 2- (meth) acryloyloxyethyl phthalate, and (meth) acrylic acid. Examples of the (meth) acrylic acid ester having a sulfonic acid group include ethyl (meth) acrylate sulfonate. Examples of the (meth) acrylate having a phosphate group include 2- (phosphonooxy) ethyl (meth) acrylate.
The weight average molecular weight (Mw) of the polymer B is a value measured by Gel Permeation Chromatography (GPC), expressed as a standard polystyrene conversion value. From the viewpoint of dispersibility of the luminescent particles, the range is preferably 3,000 to 200,000, more preferably 4,000 to 100,000, and even more preferably 5,000 to 80,000. The measurement conditions were the same as those in examples of the present specification.
The silane compound C is preferably a compound represented by the following formula (C1), for example.
Figure BDA0003991136830000221
Wherein R is C1 And R is C2 Each independently represents alkyl, R C3 And R is C4 Each independently represents a hydrogen atom or an alkyl group, n represents 0 or 1, and m represents an integer of 1 or more. m is preferably an integer of 10 or less.
Specific examples of the compound represented by the formula (C1) include tetrabutoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane, vinyltriethoxysilane, n-propyltrimethoxysilane, isopropyltrimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane, n-dodecyltrimethoxysilane, n-dodecyltriethoxysilane, n-hexadecyltrimethoxysilane, n-octadecyltrimethoxysilane, trimethoxy (3, 3-trifluoropropyl) silane, trimethoxy (pentafluorophenyl) silane, trimethoxy (11-pentafluorophenoxyundecyl) silane, trimethoxy (1H, 2H-nonafluorohexyl) silane, partially hydrolyzed oligomers of tetramethoxysilane (product name: methyl silicate 51, methyl silicate 53A, product of Colat) and partially hydrolyzed product of tetraethoxysilane (product of Colat-40) of Colco-Co.K.K.K., and the like.
The silane compound C may be a compound represented by the following formula (C2) or a compound represented by the following formula (C3) in addition to the compound represented by the above formula (C1).
Figure BDA0003991136830000222
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Figure BDA0003991136830000223
Wherein R is C21 、R C22 、R C31 Each independently represents alkyl, R C23 、R C24 、R C32 、R C33 And R is C34 Each independently represents a hydrogen atom, an alkyl group which may have a substituent, a phenyl group, or a cyclohexyl group, wherein a carbon atom in the alkyl group may be substituted with an oxygen atom or a nitrogen atom, and m2 represents an integer of 1 to 10.
Specific examples of the compound represented by the formula (C2) and the compound represented by the formula (C3) include dimethyldiethoxysilane, diphenyldimethoxysilane, methylethyldimethoxysilane, and trimethylmethoxysilane. The compound represented by the formula (C1) may be used alone or in combination of 1 or more than 2. The compound represented by the formula (C2) and the compound represented by the formula (C3) may be used in combination with 1 or 2 or more of the compounds represented by the general formula (C1).
As a method for forming the second shell layer 913, for example, a light-emitting particle including the first shell layer 912, a polymer solution containing the polymer B and the solvent, and a solution containing the silane compound C are mixed. The hydrolyzable silyl group of the silane compound C is condensed to form a siloxane bond, and thereby a second shell layer 913, which is a layer containing the polymer B and the silane compound C, is formed on the surface of the light-emitting particle having the first shell layer 912. As a result, luminescent particles having the first shell layer 912 and the second shell layer 913 containing Si are formed on the surface of the semiconductor nanocrystal particle. The shell layer contains polysiloxane derived from silane compound A, polymer B and polysiloxane derived from silane compound C. Then, the obtained reaction solution was centrifuged to collect a supernatant. And adding a poor solvent to the recovered supernatant to perform centrifugal separation, thereby obtaining a residue from which the supernatant is removed. The photopolymerizable compound is added to the residue, homogenized, and centrifuged to collect the supernatant, thereby obtaining a solution in which the luminescent particles are dispersed in the photopolymerizable compound.
Specifically, for example, the solution containing the silane compound C is added to the polymer solution so that the silane compound C is, for example, 0.1 to 50 parts by mass per 1 part by mass of the light-emitting particles including the polysiloxane derived from the silane compound a in the polymer solution B, and stirred for, for example, 5 to 300 minutes.
After mixing the polymer solution with the solution containing the silane compound C, water (e.g., ion-exchanged water) may be further added from the viewpoint of controlling hydrolysis. The amount of water to be added may be, for example, 1 to 100 parts by mass per 100 parts by mass of the silane compound C. After adding water, the mixture is stirred for, for example, 5 to 300 minutes.
Subsequently, the obtained reaction solution is centrifuged at, for example, 3000 to 15000 rpm for 1 to 30 minutes, and then the supernatant (for example, 70 to 100% by volume based on the total amount of the reaction solution) is recovered. After adding 2-fold volume% cyclohexane to the recovered supernatant and stirring with shaking, for example, centrifugation is performed at 3000 to 15000 rpm for 1 to 30 minutes, and then the supernatant is removed. By recovering the residue after the supernatant is removed, luminescent particles having the first shell layer 912 and the second shell layer 913 on the surface of the luminescent nanocrystals 911 can be obtained.
The total thickness of the first shell layer 912 and the second shell layer 913 is preferably 0.5 to 50nm, more preferably 1.0 to 30nm. In the case of the luminescent particle 91 having the first shell layer 912 and the second shell layer 913 having the above thicknesses, the light stability of the nanocrystals 911 can be sufficiently improved. The thickness may be measured by, for example, a high-resolution electron microscope.
The total thickness of the first shell layer 912 and the second shell layer 913 may be changed by adjusting the number of atoms (chain length) of the linking structure linking the binding group of the ligand and the reactive group.
The average particle diameter (volume average diameter) of the luminescent particles of the present invention is preferably 200nm or less, more preferably 150nm or less, further preferably 100nm or less, particularly preferably 50nm or less. The average particle diameter of the luminescent particles is preferably 1nm or more, more preferably 1.5nm or more, further preferably 2nm or more, and particularly preferably 5nm or more. The luminescent particles having the above average particle diameter are preferable because they easily emit light of a desired wavelength. The average particle diameter (volume average diameter) of the light-emitting particles is obtained by measuring the particle diameter of each particle by a transmission electron microscope or a scanning electron microscope, and calculating the volume average diameter.
The luminescent particles of the present invention can be produced using a batch reactor. In addition, from the viewpoints of reducing the variation in particle size, preventing contamination, manufacturing efficiency, temperature control, and the like, it is more preferable to manufacture using a continuous laminar flow, a flow reactor based on liquid droplets, a forced film, or the like. In order to promote the formation of siloxane bonds in the ligand layer, the silica layer and the organic layer, water may be added at the time of the reaction. In addition, the siloxane bond may be formed by using a small amount of water contained in the reaction solvent or the reaction atmosphere without adding water. In addition, the formation of siloxane bonds may also be promoted by heating. In this case, the heating temperature is preferably 20 ℃ to 120 ℃, more preferably 30 ℃ to 100 ℃, and particularly preferably 40 ℃ to 80 ℃.
The luminescent particles of the present invention can be obtained as a colloidal solution dispersed in a solvent. The resulting colloidal solution containing luminescent particles is preferably purified to remove excess production raw materials or precursors, ligands, impurities, particles having undesirable particle sizes, and the like. Examples of the purification method include filtration, reprecipitation, extraction, centrifugal separation, adsorption, recrystallization, and column chromatography. From the viewpoints of ease of operation and cost, it is preferable to purify the colloidal solution containing the obtained luminescent particles by centrifugation. The purified luminescent particles may be redispersed in an organic solvent or may be dried and then taken out as a solid. In the case of not immediately being used in the next step, the purified light-emitting particles are preferably prepared as a colloidal solution from the viewpoints of stability of optical characteristics and dispersion stability. The organic solvent used to disperse the purified luminescent particles is preferably a low-polarity solvent. Specific examples of the organic solvent include toluene, hexane, heptane, cyclohexane and methylcyclohexane. From the viewpoint of stability of optical properties, the colloidal solution containing the obtained luminescent particles preferably contains as little impurities as possible such as water and alcohol. In the colloidal solution containing the obtained luminescent particles, water or alcohol is preferably 1.0% or less, more preferably 0.1% or less, and particularly preferably 100ppm or less. In addition, from the viewpoint of dispersion stability of the colloidal solution, the obtained colloidal solution containing light-emitting particles is preferably stored under light shielding at a low temperature. In this case, the storage temperature is preferably from-70℃to 40℃and more preferably from-50℃to 30℃and even more preferably from-30℃to 20℃and particularly preferably from-20℃to 10 ℃.
1-2. Organic-inorganic composite particles
The organic-inorganic composite particles contain an inorganic component and contain an organic component. The organic component is excellent in affinity not only for the luminescent particles but also for the photopolymerizable compound. Therefore, the organic-inorganic composite particles can be present in the light-emitting particle-containing curable resin composition without forming aggregates, and thus the composition is excellent in dispersion stability. In addition, when a coating film is formed using the composition, the organic-inorganic composite particles are likely to be localized in the vicinity of the light-emitting particles having good affinity along with polymerization of the photopolymerizable compound by irradiation with ultraviolet rays, and therefore the organic-inorganic composite particles act as a virtual surface layer of the light-emitting particles, and as a result, the light resistance of the light-emitting particles can be improved.
The organic component of the organic-inorganic composite particles is a component derived from a polymer, and the inorganic component is a component derived from a silane compound. The polymer is not particularly limited, and is preferably a polymer having a structural unit containing a basic group. The silane compound is not particularly limited, but is preferably a silane compound having a hydrolyzable silyl group.
Fig. 2 shows 1 morphology of the organic-inorganic composite particles. The organic-inorganic composite particle 500 includes: a polymer 501 having a structural unit containing a basic group, and an inorganic oxide site 502 in which a siloxane bond is formed between molecules as a silane compound. The organic-inorganic composite particles 500 can be obtained by dissolving the polymer 501 in a solvent, and mixing a silane compound having a hydrolyzable silyl group to form a siloxane bond. Since the organic-inorganic composite particles 500 are formed by disposing the organic chains derived from the polymer 501 in the direction from the particle surface to the outside, excellent dispersion stability can be obtained.
Specifically, for example, first, a polymer is added to a solvent so as to have a concentration of 0.1 to 100mg/mL, and dissolved at a temperature of 20 to 80 ℃. Then, the silane compound is added to the polymer solution so that the silane compound is, for example, 0.1 to 50 parts by mass, and stirred for, for example, 5 to 300 minutes. After mixing the polymer solution with the silane compound, water (e.g., ion-exchanged water) may be further added from the viewpoint of controlling hydrolysis. The amount of water to be added may be, for example, 1 to 100 parts by mass per 100 parts by mass of the silane compound. After adding water, the mixture is stirred for, for example, 5 to 300 minutes. The obtained solution is subjected to centrifugal separation at a speed of, for example, 3000 to 10000 rpm for 1 to 30 minutes, and then the supernatant (for example, 70 to 100% by volume based on the total amount of the solution) is recovered, whereby organic-inorganic composite particles dispersed in a solvent can be obtained.
The polymer is not particularly limited as long as it is a polymer having a structural unit containing a basic group, and the polymer may be a polymer used in the light-emitting particle. From the viewpoint of controlling the particle size of the organic-inorganic composite particles, the polymer Z having a structural unit containing a basic group represented by the general formula (Z1-1) or (Z1-2) is preferable.
Figure BDA0003991136830000261
Wherein R is 1 、R 2 And R is 3 Each independently represents a hydrogen atom or a methyl group, R Z1 Represents a basic group having a basic valence of 1, including, for example, a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium group, an imino group, a pyridyl group, a pyrimidinyl group, a piperazinyl group, a piperidinyl group, an imidazolyl group, a pyrrolidinyl group, an imidazolidinyl group,
X 1 and X 2 Each independently represents-COO-, -OCO-, an alkyl chain having 1 to 8 carbon atoms which may be substituted with a nitrogen atom, or a single bond.
Specific examples of the compound providing the first structural unit represented by the above formula (Z1-1) include 2-vinylpyridine, 4-aminostyrene, 4-dimethylaminostyrene, 1-vinylimidazole, N-vinyl-2-pyrrolidone, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dimethylaminobutyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) acrylate, dimethylaminopropyl acrylamide, diethylaminopropyl acrylamide, and allylamine.
Examples of the compound providing the first structural unit represented by the above formula (Z1-2) include ethyleneimine and propyleneimine.
The polymer Z may have a second structural unit as a solvent-philic group. The second structural unit is more preferably a structural unit represented by the following formulas (Z2-1) and (Z2-2) from the viewpoint of controlling the particle size of the organic-inorganic composite particles.
Figure BDA0003991136830000271
Wherein R is 4 And R is 5 Represents a hydrogen atom or a methyl group, R Z3 Represents a linear or branched alkyl group having 2 to 15 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms which may have a substituent, a polyoxyalkylene group having 10 to 50 carbon atoms which is a hydroxyl group or an alkoxy group at the end, an aromatic group which may have a substituent, or a group represented by the general formula (Z3),
X 3 and X 4 represents-COO-, -OCO, an alkyl chain having 1 to 8 carbon atoms, a single bond,
R Z4 a group represented by the general formula (Z3),
Figure BDA0003991136830000272
R 6 a represents a linear or branched saturated or unsaturated 2-valent hydrocarbon group having 1 to 20 carbon atoms, a represents 0 or 1, and b represents 1 to 100.
The polyester skeleton in the general formula (Z3) can be obtained by self-condensation of a hydroxycarboxylic acid, a lactone, or mixed condensation of a hydroxycarboxylic acid and a lactone. Examples of the hydroxycarboxylic acid include 12-hydroxystearic acid, and examples of the lactone include epsilon-caprolactone, beta-propiolactone, gamma-butyrolactone, and delta-valerolactone, but it is preferable that the lactone has at least one structural unit derived from 12-hydroxystearic acid, valerolactone, or caprolactone.
Examples of the compound providing the second structural unit represented by the above formula (Z2-1) include (meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, and the like; aromatic (meth) acrylates such as benzyl (meth) acrylate and phenyl ethyl (meth) acrylate, (meth) acrylates having an alicyclic structure such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate; alkyl-terminated polyalkylene glycol (meth) acrylates such as methoxypolyethylene glycol (meth) acrylate, octyloxypolyethylene glycol (meth) acrylate, octyloxypolypropylene glycol (meth) acrylate, lauroxypolypropylene glycol (meth) acrylate, stearoxypolyethylene glycol (meth) acrylate, stearoxypolypropylene glycol (meth) acrylate, allyloxypolyethylene glycol (meth) acrylate, allyloxypolypropylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, and the like; glycidyl (meth) acrylate, dicyclopentenyl (meth) acrylate, tricyclodecyl (meth) acrylate, and the like; styrene derivative monomers such as styrene, α -methylstyrene, 4-t-butylstyrene, 2, 5-dimethylstyrene, and p-isobutylstyrene, and condensates of allylamine and polyester.
Examples of the compound providing the second structural unit represented by the above formula (Z2-2) include a condensate of ethyleneimine and polyester, a condensate of propyleneimine and polyester, and the like.
In the polymer Z, 1 or 2 or more structural units represented by the formula (Z1) and the formula (Z2) may be used respectively. The polymer Z may be a block copolymer having the first structural unit represented by the formula (Z1) as the first polymer block and the second structural unit represented by the formula (Z2) as the second polymer block, a random polymer having the first structural unit represented by the formula (Z1) and the second structural unit represented by the formula (Z2) randomly, or a graft polymer having the first structural unit represented by the formula (Z1) and the second structural unit represented by the formula (Z2). The polymer Z is preferably a block copolymer or a graft polymer from the viewpoint of adsorptivity to the surface of a solid substance containing precursor particles.
In the polymer Z, at least one or more of the structural units represented by the formulas (Z1-1) and (Z1-2) may be used, and at least one or more of the structural units represented by the formulas (Z2-1) and (Z2-2) may be used. The polymer B may be a block copolymer having the first structural unit represented by the formula (Z1-1) as a first polymer block and the second structural unit represented by the formula (Z2-1) as a second polymer block, a random polymer having the first structural unit represented by the formula (Z1-2) and the second structural unit represented by the formula (Z2-2) randomly, or a graft polymer having the first structural unit represented by the formula (Z1-2) and the second structural unit represented by the formula (Z2-2). From the viewpoint of uniformity of the size of the organic-inorganic composite particles, the polymer Z is preferably a block copolymer or a graft polymer.
The content of the first structural unit in the polymer Z is, for example, preferably 3 mol% or more, 4 mol% or more, or 5 mol% or more, and preferably 50 mol% or less, 30 mol% or less, or 20 mol% or less, based on the total structural units constituting the polymer Z.
The content of the second structural unit in the polymer Z is, for example, preferably 70 mol% or more, 75 mol% or more, or 80 mol% or more, and preferably 97 mol% or less, 96 mol% or less, or 95 mol% or less, based on the total structural units constituting the polymer Z.
The polymer Z may contain other structural units in addition to the first structural unit and the second structural unit. In this case, the total content of the first structural unit and the second structural unit in the polymer Z is preferably 70 mol% or more, 80 mol% or more, or 90 mol% or more based on the total structural units constituting the polymer Z.
For example, the polymer Z may have a structural unit having an acidic group in addition to the first structural unit and the second structural unit.
Examples of the acidic group include a carboxyl group (-COOH) and a sulfonic acid group (-SO) 3 H) Sulfuric acid group (-OSO 3H), phosphonic acid group (-PO (OH) 3 ) Phosphate (-OPO (OH)) 3 ) Phosphinic acid groups (-PO (OH) -) and mercapto groups (-SH).
Examples of the nonionic functional group include a hydroxyl group, an ether group, a thioether group, a sulfinyl group (-SO-), and a sulfonyl group (-SO- 2 (-), carbonyl, formyl, ester, carbonate, amide, carbamoyl, ureido, thioamide, thiourea, sulfamoyl, cyano, alkenyl, alkynyl, phosphine oxide, phosphine sulfide.
Examples of the compound providing a structural unit having an acidic group include a (meth) acrylate having a carboxyl group, a (meth) acrylate having a phosphate group, and a (meth) acrylate having a sulfonate group. Examples of the (meth) acrylic acid ester having a carboxyl group include monomers obtained by reacting an acid anhydride such as maleic anhydride, succinic anhydride, or phthalic anhydride with a (meth) acrylic acid ester having a hydroxyl group such as carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl maleate, or 2- (meth) acryloyloxyethyl phthalate, and (meth) acrylic acid. Examples of the (meth) acrylic acid ester having a sulfonic acid group include ethyl (meth) acrylate sulfonate. Examples of the (meth) acrylate having a phosphate group include 2- (phosphonooxy) ethyl (meth) acrylate.
The weight average molecular weight (Mw) of the polymer Z is a value measured by Gel Permeation Chromatography (GPC) and expressed as a standard polystyrene equivalent. From the viewpoint of dispersibility of the luminescent particles, the range is preferably 3,000 to 200,000, more preferably 4,000 to 100,000, and even more preferably 5,000 to 80,000.
The silane compound is not particularly limited as long as the hydrolyzable silyl group of the silane compound is condensed to form a crosslinked structure by a siloxane bond, and the silane compound may be a silane compound C used in the light-emitting particles. The silane compound preferably contains, for example, a compound represented by the general formula (G) from the viewpoint of ease of formation of the organic-inorganic composite particles.
Figure BDA0003991136830000301
Wherein R is G11 And R is G12 Each independently represents alkyl, R G13 And R is G14 Each independently represents a hydrogen atom or an alkyl group, n11 represents 0 or 1, and m11 represents an integer of 1 or more, but m11 is preferably an integer of 10 or less.
Specific examples of the compound represented by the formula (G) include tetrabutoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane, vinyltriethoxysilane, n-propyltrimethoxysilane, isopropyltrimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane, n-dodecyltrimethoxysilane, n-dodecyltriethoxysilane, n-hexadecyltrimethoxysilane, n-octadecyltrimethoxysilane, trimethoxy (3, 3-trifluoropropyl) silane, trimethoxy (pentafluorophenyl) silane, trimethoxy (11-pentafluorophenoxyundecyl) silane, trimethoxy (1 h,2 h-nonafluorohexyl) silane, and partially hydrolyzed oligomers of tetramethoxysilane (product name: methyl silicate 51, methyl silicate 53A (above is made by Colcoat Co.), partially hydrolyzed oligomers of tetraethoxysilane (product name: ethyl silicate 40, ethyl silicate 48 (above is made by Colcoat Co.), partially hydrolyzed oligomers of a mixture of tetramethoxysilane and tetraethoxysilane (product name: EMS-485 (made by Colcoat Co.), etc.), and the like.
As the silane compound, in addition to the compound represented by the above formula (G), for example, a compound represented by the following formula (G2) and a compound represented by (G3) may be used in combination.
Figure BDA0003991136830000311
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Figure BDA0003991136830000312
Wherein R is G21 、R G22 、R G31 Each independently represents alkyl, R G23 、R G24 、R G32 、R G33 And R is G34 Each independently represents a hydrogen atom, an alkyl group which may have a substituent, a phenyl group, or a cyclohexyl group, wherein a carbon atom in the alkyl group may be substituted with an oxygen atom or a nitrogen atom, and m21 represents an integer of 1 to 10.
Specific examples of the compound represented by the formula (G2) and the compound represented by the formula (G3) include dimethyldiethoxysilane, diphenyldimethoxysilane, methylethyldimethoxysilane, and trimethylmethoxysilane. The compound represented by the formula (G1) may be used alone or in combination of 1 or more than 2. The compound represented by the formula (G2) and the compound represented by the formula (G3) may be used in combination with 1 or 2 or more of the compounds represented by the general formula (G).
The average particle diameter (volume average diameter) of the organic-inorganic composite particles is, for example, preferably 10nm or more, 15nm or more, or 20nm or more, and preferably 400nm or less, 300nm or less, or 200nm or less. The average particle diameter of the organic-inorganic composite particles means a volume average diameter measured by a dynamic light scattering method.
From the viewpoints of optical characteristics and dispersibility, the content of the organic-inorganic composite particles contained in the light-emitting particle-containing curable resin composition of the present invention is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.1% by mass or more and 8% by mass or less, still more preferably 0.5% by mass or more and 6% by mass or less, and particularly preferably 1% by mass or more and 5% by mass or less.
1-3 photopolymerizable compounds
The photopolymerizable compound contained in the light-emitting particle-containing curable resin composition of the present invention is a compound that functions as a binder in a cured product and is polymerized by irradiation of light (active energy rays), and a photopolymerizable monomer or oligomer may be used.
The photopolymerizable compound may be a radical polymerizable compound, a cation polymerizable compound, an anion polymerizable compound, or the like, but from the viewpoint of rapid curability, a radical polymerizable compound is preferably used.
The radical polymerizable compound is, for example, a compound having an ethylenically unsaturated group. In the present specification, an ethylenically unsaturated group means a group having an ethylenically unsaturated bond (polymerizable carbon-carbon double bond). The number of ethylenic unsaturated bonds (for example, the number of ethylenic unsaturated groups) in the compound having an ethylenic unsaturated group is, for example, 1 to 4.
Examples of the compound having an ethylenically unsaturated group include compounds having an ethylenically unsaturated group such as a vinyl group, a vinylidene group (vinyl) and a (meth) acryl group. From the viewpoint of further improving the external quantum efficiency, the compound having a (meth) acryloyl group is preferable, and a monofunctional or polyfunctional (meth) acrylate is more preferable, and a monofunctional or difunctional (meth) acrylate is still more preferable. In the present specification, "(meth) acryl" means "acryl" and "methacryl" corresponding thereto. The same applies to the expression "(meth) acrylate". In addition, the monofunctional (meth) acrylate means a (meth) acrylate having 1 (meth) acryloyl group, and the multifunctional (meth) acrylate means a (meth) acrylate having 2 or more (meth) acryloyl groups.
Examples of the monofunctional (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, dodecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, nonylphenoxyethyl (meth) acrylate, glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, isobornyl (meth) acrylate, dicyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, and mono (benzyl) acrylate N- [2- (acryloyloxy) ethyl ] phthalimide, N- [2- (acryloyloxy) ethyl ] tetrahydrophthalimide, and the like.
The multifunctional (meth) acrylate is 2-functional (meth) acrylate, 3-functional (meth) acrylate, 4-functional (meth) acrylate, 5-functional (meth) acrylate, 6-functional (meth) acrylate, or the like. For example, a di (meth) acrylate in which 2 hydroxyl groups of a diol compound are substituted with (meth) acryloyloxy groups, a di (meth) acrylate in which 2 or 3 hydroxyl groups of a triol compound are substituted with (meth) acryloyloxy groups, a tri (meth) acrylate, or the like can be used.
Specific examples of the 2-functional (meth) acrylate include 1, 3-butanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 5-pentanediol di (meth) acrylate, 3-methyl-1, 5-pentanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 8-octanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol hydroxypivalate di (meth) acrylate, di (meth) acrylate obtained by substituting 2 hydroxyl groups of tris (2-hydroxyethyl) isocyanurate with (meth) acryloyloxy groups, di (meth) acrylate obtained by adding more than 4 moles of ethylene oxide or ethylene oxide to 1 mole of neopentyl glycol, and di (meth) acrylate obtained by substituting 2 hydroxyl groups of ethylene oxide with acryloyloxy groups, and (3) a di (meth) acrylate in which 2 hydroxyl groups of a diol obtained by adding 2 moles of ethylene oxide or propylene oxide to 1 mole of bisphenol a are substituted with (meth) acryloyloxy groups, a di (meth) acrylate in which 2 hydroxyl groups of a triol obtained by adding 3 moles or more of ethylene oxide or propylene oxide to 1 mole of trimethylolpropane are substituted with (meth) acryloyloxy groups, a di (meth) acrylate in which 2 hydroxyl groups of a diol obtained by adding 4 moles or more of ethylene oxide or propylene oxide to 1 mole of bisphenol a are substituted with (meth) acryloyloxy groups.
Specific examples of the 3-functional (meth) acrylate include trimethylolpropane tri (meth) acrylate, glycerol triacrylate, pentaerythritol tri (meth) acrylate, and tri (meth) acrylate in which 3 hydroxyl groups of a triol obtained by adding 3 or more moles of ethylene oxide or propylene oxide to 1 mole of trimethylolpropane are substituted with (meth) acryloyloxy groups.
Specific examples of the 4-functional (meth) acrylate include pentaerythritol tetra (meth) acrylate and ditrimethylolpropane tetra (meth) acrylate.
Specific examples of the 5-functional (meth) acrylate include dipentaerythritol penta (meth) acrylate.
Specific examples of the 6-functional (meth) acrylate include dipentaerythritol hexa (meth) acrylate.
The polyfunctional (meth) acrylate may be at least one compound selected from the group consisting of a poly (meth) acrylate in which a plurality of hydroxyl groups of dipentaerythritol such as dipentaerythritol hexa (meth) acrylate are substituted with (meth) acryloyloxy groups, an aromatic urethane oligomer having 2 or more ethylenic double bonds in one molecule, an aliphatic urethane oligomer, an epoxy acrylate oligomer, a polyester acrylate oligomer, and other specific oligomers.
The (meth) acrylate compound may be an ethylene oxide-modified phosphoric acid (meth) acrylate, an ethylene oxide-modified alkyl phosphoric acid (meth) acrylate, or the like having a phosphoric acid group.
In the curable resin composition of the present invention, when the curable component is composed of only the photopolymerizable compound or the photopolymerizable compound as the main component, it is more preferable to use a photopolymerizable compound having 2 or more functions having 2 or more polymerizable functional groups in 1 molecule as an essential component, from the viewpoint that the durability (strength, heat resistance, etc.) of the cured product can be further improved.
From the viewpoint of excellent viscosity stability at the time of preparing the composition, more excellent discharge and coating properties, and the viewpoint of being able to suppress a decrease in smoothness of the coating film caused by curing shrinkage at the time of producing a light-emitting particle coating film, it is preferable to use a monofunctional (meth) acrylate in combination with a multifunctional (meth) acrylate.
The molecular weight of the photopolymerizable compound is, for example, 50 or more, and may be 100 or more or 150 or more. The molecular weight of the photopolymerizable compound is, for example, 500 or less, and may be 400 or less or 300 or less. When the composition is applied by the inkjet printing method, the composition is preferably 50 to 500, more preferably 100 to 400, from the viewpoint of easily achieving both the viscosity and the volatility resistance of the ink after discharge. When the composition is applied to a substrate such as a film using a printing system such as a roll coater, a gravure coater, a flexo coater, or a die coater, the composition is preferably 100 to 500, more preferably 150 to 400, from the viewpoint of easily achieving both viscosity and leveling property.
From the viewpoint of reducing the surface tackiness (tack) of a cured product of the composition, a radical polymerizable compound having a cyclic structure is preferably used as the photopolymerizable compound. The cyclic structure may be an aromatic ring structure or a non-aromatic ring structure. The number of cyclic structures (the total of the number of aromatic rings and non-aromatic rings) is 1 or 2 or more, preferably 3 or less. The number of carbon atoms constituting the cyclic structure is, for example, 4 or more, preferably 5 or more or 6 or more. The number of carbon atoms is, for example, 20 or less, preferably 18 or less.
The aromatic ring structure is preferably a structure having an aromatic ring having 6 to 18 carbon atoms. Examples of the aromatic ring having 6 to 18 carbon atoms include benzene ring, naphthalene ring, phenanthrene ring, and anthracene ring. The aromatic ring structure may have an aromatic heterocyclic ring structure. Examples of the aromatic heterocycle include a furan ring, a pyrrole ring, a pyran ring, and a pyridine ring. The number of aromatic rings may be 1 or 2 or more, and preferably 3 or less. The organic group may have a structure in which 2 or more aromatic rings are bonded by a single bond (for example, a biphenyl structure).
The non-aromatic ring structure is preferably an alicyclic structure having 5 to 20 carbon atoms, for example. Examples of the alicyclic ring having 5 to 20 carbon atoms include cycloalkane rings such as cyclopentane ring, cyclohexane ring, cycloheptane ring and cyclooctane ring, cycloalkene rings such as cyclopentene ring, cyclohexene ring, cycloheptene ring and cyclooctene ring. The alicyclic ring may be a condensed ring such as a bicycloundecane ring, a decalin ring, a norbornene ring, a norbornadiene ring, or an isobornyl ring. The non-aromatic ring structure may have a non-aromatic heterocyclic ring structure. Examples of the non-aromatic heterocyclic ring include a tetrahydrofuran ring, a pyrrolidine ring, a tetrahydropyran ring, and a piperidine ring.
The radically polymerizable compound having a cyclic structure is preferably a monofunctional or polyfunctional (meth) acrylate having a cyclic structure. Examples of the monofunctional (meth) acrylate having a cyclic structure include phenoxyethyl (meth) acrylate, phenoxybenzyl (meth) acrylate, biphenyl (meth) acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate. Examples of the polyfunctional (meth) acrylate having a cyclic structure include dimethylol-tricyclodecane diacrylate, EO-modified bisphenol A diacrylate, PO-modified bisphenol A diacrylate, and the like.
The content of the radical polymerizable compound having a cyclic structure is preferably 3 to 85% by mass, more preferably 5 to 65% by mass, even more preferably 10 to 45% by mass, and particularly preferably 15 to 35% by mass based on the total mass of the photopolymerizable compound in the curable resin composition, from the viewpoint of easily suppressing the surface tackiness (tack) of the curable resin composition.
As the photopolymerizable compound, 2 or more radical polymerizable compounds are preferably used, and a monofunctional (meth) acrylate and a multifunctional (meth) acrylate are preferably used in combination, from the viewpoint of excellent surface uniformity of the pixel portion, good curability of the curable resin composition, improvement in solvent resistance and abrasion resistance of the pixel portion (cured product of the curable resin composition), and obtaining more excellent optical characteristics (for example, external quantum efficiency). The amount of the photopolymerizable compound contained in the composition containing the luminescent particles is preferably 40 mass% or more and 95 mass% or less, more preferably 45 mass% or more and 94 mass% or less, and particularly preferably 50 mass% or more and 93 mass% or less.
The photopolymerizable compound is preferably alkali-insoluble from the viewpoint of easy obtaining of a pixel portion (cured product of the curable resin composition) excellent in reliability. In the present specification, the term "base-insoluble" as used herein means that the amount of the photopolymerizable compound dissolved in 1 mass% aqueous potassium hydroxide solution at 25 ℃ is 30 mass% or less based on the total mass of the photopolymerizable compound. The amount of the photopolymerizable compound dissolved is preferably 10 mass% or less, more preferably 3 mass% or less.
1-4 photopolymerization initiator
The photopolymerization initiator used in the light-emitting particle-containing curable resin composition of the present invention is, for example, a photo radical polymerization initiator. As the photo radical polymerization initiator, a molecular cleavage type or hydrogen abstraction type photo radical polymerization initiator is preferable.
As the molecular cleavage type photo-radical polymerization initiator, benzoin isobutyl ether, 2, 4-diethylthioxanthone, 2-isopropylthioxanthone, 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, bis (2, 6-dimethoxybenzoyl) -2, 4-trimethylpentylphosphine oxide, (2, 4, 6-trimethylbenzoyl) ethoxyphenylphosphine oxide and the like are suitably used. As the molecular cleavage type photo radical polymerization initiator other than these, 1-hydroxycyclohexyl phenyl ketone, benzoin diethyl ether, benzildimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one may be used in combination.
Examples of the hydrogen abstraction type photo radical polymerization initiator include benzophenone, 4-phenylbenzophenone, m-xylyl benzophenone (isophthalophenone), 4-benzoyl-4' -methyl-diphenyl sulfide, and the like. A combination of a molecular cleavage type photo radical polymerization initiator and a hydrogen abstraction type photo radical polymerization initiator may also be used.
The photopolymerization initiator used in the curable resin composition of the present invention preferably contains an initiator having photobleaching properties. In this case, the light transmittance of the cured product is easily improved. The photobleaching initiator contains, for example, at least one of an oxime ester compound and an acylphosphine oxide compound having photobleaching properties.
Examples of the oxime ester compound having photobleaching properties include 1- [4- (phenylthio) phenyl ] -1, 2-octanedione 2- (O-benzoyl oxime), ethanone, and 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ]1- (O-acetyl oxime).
Examples of the photobleaching acyl phosphine oxide compound include 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide and bis (2, 4, 6-trimethylbenzoyl) phenyl phosphine oxide.
The photopolymerization initiator used in the curable resin composition of the present invention preferably contains at least one or more acyl phosphine oxide compounds. Thus, a coating film having excellent internal curability and a cured film having a small initial coloration can be formed. Particularly, when at least one or more acyl phosphine oxide compound is contained, it is preferable to use an ultraviolet light emitting diode (UV-LED) having a narrow spectral output in a region of ±15 nm centered on a predetermined wavelength such as 365 nm, 385 nm, 395 nm or 405 nm.
The content of the photopolymerization initiator is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, even more preferably 1 to 15% by mass, and particularly preferably 3 to 7% by mass, relative to 100% by mass of the photopolymerizable compound, from the viewpoints of solubility in the photopolymerizable compound, curability of the curable resin composition, and stability over time (stability in maintaining external quantum efficiency) of the pixel portion (cured product of the composition).
From the viewpoint of curability of the curable resin composition, the content of the acylphosphine oxide compound in the photopolymerization initiator is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, and particularly preferably 70 to 100% by mass.
1-5 other ingredients
The curable resin composition of the present invention may further contain components other than the above components within a range that does not inhibit the effects of the present invention. Specifically, polymerization inhibitors, antioxidants, dispersants, surfactants, light scattering particles, chain transfer agents, solvents, and the like can be cited.
Specific examples of the polymerization inhibitor include quinone compounds such as p-methoxyphenol, cresol, t-butylcatechol, and 3, 5-di-t-butyl-4-hydroxytoluene; amine compounds such as p-phenylenediamine, 4-aminodiphenylamine and N, N' -diphenyl-p-phenylenediamine; thioether compounds such as phenothiazine and distearyl thiodipropionate; 2, 6-tetramethylpiperidine-1-oxyl, 2, 6-tetramethylpiperidine N-oxy compounds such as 4-hydroxy-2, 6-tetramethylpiperidine-1-oxyl; nitroso compounds such as N-nitrosodiphenylamine, N-nitrosophenyl naphthylamine and N-nitrosodinaphthyl amine. The amount of the polymerization inhibitor to be added is preferably 0.01 to 1.0 mass%, particularly preferably 0.02 to 0.5 mass%, based on the total amount of the photopolymerizable compound contained in the light-emitting particle-containing curable resin composition.
Examples of the antioxidant include conventionally known compounds used as antioxidants, such as phenol antioxidants, amine antioxidants, phosphorus antioxidants, and sulfur antioxidants. Specifically, pentaerythritol tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ("IRGANOX 1010" (IRGANOX is a registered trademark)), thiodiethylenebis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ("IRGAFNOX 1035"), and octadecyl-3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ("IRGANOX 1076"). The amount of the antioxidant to be added is preferably 0.01 to 2.0 mass%, particularly preferably 0.02 to 1.0 mass%, based on the total amount of the photopolymerizable compound contained in the light-emitting particle-containing curable resin composition.
Specific examples of the dispersant include phosphorus atom-containing compounds such as TOP (trioctylphosphine), TOPO (trioctylphosphine oxide) and hexylphosphonic acid (HPA); nitrogen atom-containing compounds such as oleylamine, octylamine, and trioctylamine; sulfur atom-containing compounds such as 1-decanethiol, octanethiol and dodecanethiol; a polymer dispersant such as an acrylic resin, a polyester resin, and a polyurethane resin; DISPERBYK (registered trademark of Pick chemical Co.), TEGO Dispers (registered trademark of Evonik Co.), EFKA (registered trademark of Basoff Co.), SOLSPERSE (registered trademark of Japanese road-run chemical Co.), AJISPER (registered trademark of Ajinomoto Fine-Techno Co.), DISPARRON (registered trademark of Nanye chemical Co.), FLOWLEN (co-Rong chemical Co.). The amount of the dispersant to be added is preferably 0.05 mass% to 10 mass%, particularly preferably 0.1 mass% to 5 mass%, based on the total amount of the photopolymerizable compound contained in the light-emitting particle-containing curable resin composition.
In the case of forming a thin film containing the light-emitting particles 91, the surfactant is preferably a compound capable of reducing film thickness unevenness. Examples thereof include anionic surfactants such as dialkylsulfosuccinates, alkylnaphthalenesulfonates and fatty acid salts; nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylenic diols, and polyoxyethylene-polyoxypropylene block copolymers; cationic surfactants such as alkylamine salts and quaternary ammonium salts; and an organosilicon-based and fluorine-based surfactant. Specifically, examples thereof include "MEGAFAC F-114", "MEGAFAC F-251", "MEGAFAC F-281" (the above is made by DIC corporation), MEGAFAC is made by registered trademark), "FTERGENT 100", "FTERGENT 100C", "FTERGENT 110" (the above is made by NEOS corporation), BYK-300"," BYK-302"," BYK-306 "(the above is made by Pick corporation, BYK is registered trademark)," TEGO Rad2100"," TEGO Rad2011"," TEGO Rad2200N "(the above is made by Evonik corporation), TEGO is made by registered trademark)," DISPARON OX-880 "," DISPARON OX-881"," DISPARRON OX-883 "(the above is made by WLEN) and" POLYW No.7"," FLOAC-300 "," FLOEN AC-303 "(the above is made by FLOO Co., ltd.). The amount of the surfactant to be added is preferably 0.005 mass% to 2 mass%, particularly preferably 0.01 mass% to 0.5 mass%, based on the total amount of the photopolymerizable compound contained in the light-emitting particle-containing curable resin composition.
The light scattering particles are preferably optically inactive inorganic particles. The light scattering particles can scatter light from the light source unit that is irradiated to the light emitting layer (light conversion layer). Examples of the material constituting the light scattering particles include elemental metals such as tungsten, zirconium, titanium, platinum, bismuth, rhodium, palladium, silver, tin, platinum, and gold; silica, barium sulfate, barium carbonate, calcium carbonate, talc, titanium oxide, clay, kaolin, barium sulfate, barium carbonate, calcium carbonate; metal oxides such as alumina white, titanium oxide, magnesium oxide, barium oxide, aluminum oxide, bismuth oxide, zirconium oxide, and zinc oxide; metal carbonates such as magnesium carbonate, barium carbonate, bismuth subcarbonate and calcium carbonate; metal hydroxides such as aluminum hydroxide; and metal salts such as barium zirconate, calcium titanate, barium titanate, strontium titanate and the like.
Among them, the material constituting the light scattering particles preferably contains at least one selected from the group consisting of titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, calcium carbonate, barium sulfate, and silicon dioxide, more preferably contains at least one selected from the group consisting of titanium oxide, barium sulfate, and calcium carbonate, and particularly preferably titanium oxide, from the viewpoint of more excellent effect of reducing light leakage.
In the case where the light scattering particle-containing curable resin composition of the present invention is used as a material for forming a color filter layer, the content of the light scattering particles is preferably 1 to 10 parts by mass, more preferably 2 to 7.5 parts by mass, and particularly preferably 3 to 5 parts by mass, based on 100 parts by mass of the composition, from the viewpoint of suppressing blue light transmission of a backlight. In the case where the curable resin composition containing luminescent particles of the present invention is used as a material for forming a light conversion sheet, the amount of the luminescent particles is preferably 0.1 to 5 parts by mass, more preferably 0.15 to 3 parts by mass, and particularly preferably 0.2 to 1.5 parts by mass, based on 100 parts by mass of the composition, from the viewpoint of taking out blue light from a backlight.
The chain transfer agent is a component used for the purpose of further improving the adhesion between the composition and a substrate, and the like. Examples of the chain transfer agent include aromatic hydrocarbons; halogenated hydrocarbons such as chloroform, carbon tetrachloride, carbon tetrabromide and bromotrichloromethane; thiol compounds such as octyl thiol, n-butyl thiol, n-pentyl thiol, n-hexadecyl thiol, n-tetradecyl thiol, n-dodecyl thiol, t-tetradecyl thiol, and t-dodecyl thiol; thiol compounds such as hexanedithiol, decanedithiol, 1, 4-butanediol dithiopropionate, 1, 4-butanediol dithioglycolate, ethylene glycol dithiopropionate, trimethylolpropane trithioglycolate, trimethylolpropane trithiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrathioglycolate, pentaerythritol tetrathiopropionate, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), trimercapto-propionic tris (2-hydroxyethyl) isocyanurate, 1, 4-dimethylmercapto benzene, 2,4, 6-trimercapto-s-triazine, and 2- (N, N-dibutylamino) -4, 6-dimercapto-s-triazine; a thioether compound such as dimethyl xanthate (dimethyl xanthogen disulfide), diethyl xanthate, diisopropyl xanthate, tetramethylthiuram disulfide (tetramethyl thiuram disulfide), tetraethylthiuram disulfide, and tetrabutylthiuram disulfide; n, N-dimethylaniline, N-divinylbenzene, pentaphenyl ethane, α -methylstyrene dimer, acrolein, allyl alcohol, terpinolene (terpinolene), α -terpinene, γ -terpinene, dipentene and the like are preferred, 2, 4-diphenyl-4-methyl-1-pentene, thiol compounds are more preferred, trimethylolpropane trithioglycolate, trimethylolpropane trithiopropionate, trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrathioglycolate, pentaerythritol tetrathiopropionate, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), trimercapto-propionic tris (2-hydroxyethyl) isocyanurate, and particularly preferred are trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate).
The amount of the chain transfer agent to be added is preferably 0.1 mass% to 30 mass%, more preferably 1.0 mass% to 25 mass%, and particularly preferably 5.0 mass% to 20 mass%, based on the total amount of the photopolymerizable compound contained in the light-emitting particle-containing curable resin composition.
Examples of the solvent include cyclohexane, hexane, heptane, chloroform, toluene, octane, chlorobenzene, tetrahydronaphthalene, diphenyl ether, propylene glycol monomethyl ether acetate, butyl carbitol acetate, and mixtures thereof. Since the solvent needs to be removed from the composition before the composition is cured when forming the pixel portion, the boiling point of the solvent is preferably 300 ℃ or less, more preferably 200 ℃ or less, and even more preferably 150 ℃ or less, from the viewpoint of easy removal of the solvent. When the light-emitting particle-containing curable resin composition contains a solvent, the content of the solvent is preferably 0 to 5 mass% or less based on the total mass of the composition (including the solvent).
1-5 Process for producing curable resin composition containing luminescent particles
The curable resin composition of the present invention, for example, an active energy ray curable resin composition, can be prepared by mixing the above components. In a specific method for preparing the composition, the above-mentioned luminescent particles 91 are synthesized in an organic solvent, the organic solvent is removed from the precipitate separated by centrifugation, and then dispersed in a photopolymerizable compound. The organic-inorganic composite particles are synthesized in an organic solvent, and after the organic solvent is separated and removed by centrifugation, the particles are dispersed in a photopolymerizable compound. The dispersion of the light-emitting particles 91 and the organic-inorganic composite particles can be performed by using a dispersing machine such as a ball mill, a sand mill, a bead mill, a three-roll mill, a paint conditioner, an attritor, a dispersing mixer, or ultrasonic waves, for example. Further, the composition can be prepared by adding a photopolymerization initiator, light-emitting particles, organic-inorganic composite particles, a photopolymerizable compound, and a component other than the photopolymerization initiator, if necessary, to a solution in which these dispersions are mixed, and stirring and mixing the mixture. In the case of using light-scattering particles, the light-scattering particles may be prepared by separately preparing a polishing material comprising the light-scattering particles and a polymer dispersant, dispersing the mixture in the photopolymerizable compound by a bead mill, and mixing the photopolymerizable compound, a photopolymerization initiator, and the light-emitting particles.
2. Use examples of light-emitting particle-containing curable resin composition
The curable resin composition containing luminescent particles of the present invention is suitable for use as a wavelength conversion film. Examples of the method for supporting the curable resin composition containing luminescent particles of the present invention on a substrate include spin coating, die coating, extrusion coating, roll coating, bar coating, gravure coating, spray coating, dipping, inkjet method, and printing method. In addition, an organic solvent may be added to the composition containing the luminescent particles at the time of coating. The organic solvent may be a hydrocarbon solvent, a halogenated hydrocarbon solvent, an ether solvent, an alcohol solvent, a ketone solvent, an ester solvent, or an aprotic solvent, but is preferably a hydrocarbon solvent, a halogenated hydrocarbon solvent, or an ester solvent from the viewpoint of stability of the luminescent particles. Specific examples of the organic solvent include toluene, hexane, heptane, cyclohexane, and methylcyclohexane. These may be used alone or in combination, as long as they are appropriately selected in consideration of vapor pressure and solubility of the light-emitting particle-containing composition. As a method for volatilizing the added organic solvent, natural drying, heat drying, reduced pressure heat drying can be used. The film thickness of the film can be appropriately adjusted depending on the application, and is preferably, for example, 0.1 μm to 10mm, particularly preferably, 1 μm to 1 mm.
The substrate shape of the curable resin composition containing light-emitting particles of the present invention when supported on a substrate may have a curved surface as a constituent part, in addition to a flat plate. The material constituting the substrate may be any of organic materials and inorganic materials. Examples of the organic material to be used as the substrate material include polyethylene terephthalate, polycarbonate, polyimide, polyamide, polymethyl methacrylate, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polychlorotrifluoroethylene, polyarylate, polysulfone, triacetylcellulose, cellulose, and polyether ether ketone, and examples of the inorganic material include silicon, glass, and calcite.
In the case of supporting and polymerizing the curable resin composition containing light-emitting particles of the present invention on a substrate, it is desirable to rapidly polymerize the composition, and therefore, a method of polymerizing the composition by irradiation with active energy rays such as ultraviolet rays or electron beams is preferable. The temperature at the time of irradiation is preferably within a temperature range in which the particle shape of the luminescent particle of the present invention is maintained. In the case where a film is to be produced by photopolymerization, it is preferable to carry out the polymerization at a temperature as close to room temperature as possible, that is, typically 25 ℃, in the sense of avoiding the induction of undesired thermal polymerization. The intensity of the active energy ray is preferably 0.1mW/cm 2 Above 2.0W/cm 2 The following is given. At an intensity of less than 0.1mW/cm 2 In the case of (C), a large amount of time is required for completion of photopolymerization, and productivity becomes poor, at a concentration of more than 2.0W/cm 2 In the presence of luminescent particles or luminescent particle-containing combinationsRisk of deterioration of the object.
The wavelength conversion film using the curable resin composition containing luminescent particles of the present invention obtained by polymerization as a forming material may be subjected to a heat treatment for the purpose of reducing initial characteristic changes and achieving stable characteristic performance. The temperature of the heat treatment is preferably in the range of 50 to 250 ℃, and the heat treatment time is preferably in the range of 30 seconds to 12 hours.
The wavelength conversion film using the light-emitting particle-containing composition of the present invention produced by such a method as a forming material may be used alone by being peeled off from a substrate, or may be used without being peeled off. The obtained wavelength conversion film may be laminated or may be bonded to another substrate for use.
When the wavelength conversion film containing the luminescent particle-containing curable resin composition of the present invention as a forming material is used in a laminated structure, the laminated structure may have any layer such as a substrate, a barrier layer, and a light scattering layer. Examples of the material constituting the substrate include the above materials. As an example of a structure of the laminated structure, a structure in which a light conversion layer containing the light emitting particle-containing composition of the present invention as a forming material is sandwiched between 2 substrates is given. In this case, the outer peripheral portions between the substrates may be sealed with a sealing material in order to protect the light conversion layer made of the light emitting particle-containing composition from moisture and oxygen in the air. Examples of the barrier layer include polyethylene terephthalate and glass. In order to uniformly scatter light, a light scattering layer may be provided. Examples of the light scattering layer include a layer containing the light scattering particles and a light scattering film. Fig. 3 is a cross-sectional view schematically showing the structure of the laminated structure of the present embodiment. In fig. 3, hatching showing a cross section is omitted to avoid complicating the drawing. The laminated structure 40 includes the wavelength conversion film 44 according to the present embodiment sandwiched between the first substrate 41 and the second substrate 42. The wavelength conversion film 44 is formed using a light-emitting particle-containing composition containing light-scattering particles 441 and light-emitting particles 442 as a forming material, and the light-scattering particles 441 and the light-emitting particles 442 are uniformly dispersed in the wavelength conversion film. The wavelength conversion film 44 is sealed by a sealing layer 43 formed of a sealing material.
The laminate structure using the curable resin composition containing luminescent particles of the present invention as a forming material is suitable for use in a light-emitting device. Examples of the structure of the light-emitting device include a prism sheet, a light guide plate, a laminated structure including the light-emitting particles of the present invention, and a light source. Examples of the light source include a light emitting diode, a laser, and an electroluminescent device.
The laminated structure using the luminescent particle-containing curable resin composition of the present invention as a forming material is preferably used as a wavelength conversion member for a display. As an example of a structure for use as a wavelength conversion member, there is a structure in which a laminated structure in which a wavelength conversion film made of the light-emitting particle-containing curable resin composition of the present invention is sealed between 2 barrier layers is provided on a light guide plate. In this case, blue light from the light emitting diode provided on the side surface of the light guide plate is converted into green light and red light by passing through the laminated structure, and the blue light, green light, and red light are mixed to obtain white light, which can be used as a backlight for a display.
The curable resin composition containing light-emitting particles can be obtained by forming a coating film on a substrate by various methods such as an inkjet printer, photolithography, spin coater, and the like, and curing the coating film by heating. Hereinafter, a case where a color filter pixel portion including a light emitting element of a blue organic LED backlight is formed from a light emitting particle-containing curable resin composition will be described as an example.
Fig. 4 is a cross-sectional view showing an embodiment of a light-emitting element of the present invention, and fig. 5 and 6 are schematic diagrams showing the configuration of an active matrix circuit, respectively. In fig. 4, the dimensions of each part and the ratio thereof are shown enlarged for convenience, and may be different from the actual ones. The materials, dimensions, and the like shown below are examples, and the present invention is not limited thereto, and may be appropriately modified within a range not changing the gist thereof. Hereinafter, for convenience of explanation, the upper side of fig. 4 will be referred to as "upper side" or "upper side", and the lower side will be referred to as "lower side" or "lower side". In fig. 4, hatching showing a cross section is omitted to avoid complicating the drawing.
As shown in fig. 4, the light-emitting element 100 has a structure in which a lower substrate 1, an EL light source unit 200, a filler layer 10, a protective layer 11, a light conversion layer 12 containing light-emitting particles 91 and functioning as a light-emitting layer, and an upper substrate 13 are stacked in this order. The light-emitting particles 91 contained in the light conversion layer 12 may be polymer-coated light-emitting particles 91 or may be light-emitting particles 91 not coated with a polymer layer. The EL light source section 200 includes, in order, an anode 2, an EL layer 14 composed of a plurality of layers, a cathode 8, a polarizing plate not shown, and a sealing layer 9. The EL layer 14 includes a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, an electron transport layer 6, and an electron injection layer 7, which are laminated in this order from the anode 2 side.
The light emitting element 100 is a photoluminescent element that absorbs, re-emits, or transmits light emitted from the EL light source section 200 (EL layer 14) by the light conversion layer 12, and is extracted from the upper substrate 13 side to the outside. At this time, light of a predetermined color is converted by the light emitting particles 91 contained in the light conversion layer 12. The respective layers will be described in order below.
< lower substrate 1 and upper substrate 13 >)
The lower substrate 1 and the upper substrate 13 have a function of supporting and/or protecting each layer constituting the light emitting element 100, respectively. In the case where the light-emitting element 100 is of a top emission type, the upper substrate 13 is constituted by a transparent substrate. On the other hand, in the case where the light-emitting element 100 is of the bottom emission type, the lower substrate 1 is constituted by a transparent substrate. The transparent substrate herein refers to a substrate that transmits light having a wavelength in the visible light range, and transparent includes colorless transparent, colored transparent, and translucent.
As the transparent substrate, for example, a transparent glass substrate such as quartz glass, pyrex (registered trademark) glass, or a synthetic quartz plate, a quartz substrate, a plastic substrate (resin substrate) composed of polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyether sulfone (PES), polyimide (PI), polycarbonate (PC), or the like, a metal substrate composed of iron, stainless steel, aluminum, copper, or the like, a silicon substrate, a gallium arsenide substrate, or the like can be used. Among them, a glass substrate made of alkali-free glass containing no alkali component in the glass is preferably used. Specifically, "7059 glass", "1737 glass", "Eagle 2000" and "Eagle XG (registered trademark)", made by Kaning corporation, "AN 100" made by Asahi Nitsu corporation, and "OA-10G" and "OA-11" made by Nitro corporation are preferable. These materials have a small thermal expansion coefficient, and are excellent in dimensional stability and workability in high-temperature heating treatment. In addition, when flexibility is provided to the light-emitting element 100, a plastic substrate (a substrate made of a polymer material) and a metal substrate having a small thickness are selected for the lower substrate 1 and the upper substrate 13, respectively.
The thickness of the lower substrate 1 and the upper substrate 13 is not particularly limited, but is preferably in the range of 100 to 1,000 μm, and more preferably in the range of 300 to 800 μm.
In addition, depending on the manner of use of the light-emitting element 100, either or both of the lower substrate 1 and the upper substrate 13 may be omitted.
As shown in fig. 4, the lower substrate 1 includes: a signal line driver circuit C1 and a scanning line driver circuit C2 which control current supply to the anode 2 constituting the pixel electrode PE indicated by R, G, B; a control circuit C3 that controls the operation of these circuits; a plurality of signal lines 706 connected to the signal line driving circuit C1; and a plurality of scanning lines 707 connected to the scanning line driving circuit C2. As shown in fig. 5, a capacitor 701, a driving transistor 702, and a switching transistor 708 are provided near the intersection of each signal line 706 and each scanning line 707.
One electrode of the capacitor 701 is connected to the gate electrode of the driving transistor 702, and the other electrode is connected to the source electrode of the driving transistor 702. The gate electrode of the driving transistor 702 is connected to one electrode of the capacitor 701, the source electrode is connected to the other electrode of the capacitor 701 and the power supply line 703 for supplying a driving current, and the drain electrode is connected to the anode 4 of the EL light source section 200.
A gate electrode of the switching transistor 708 is connected to the scanning line 707, a source electrode is connected to the signal line 706, and a drain electrode is connected to a gate electrode of the driving transistor 702. In the present embodiment, the common electrode 705 forms the cathode 8 of the EL light source unit 200. The driving transistor 702 and the switching transistor 708 can be formed, for example, by thin film transistors or the like.
The scanning line driving circuit C2 supplies or blocks a scanning voltage corresponding to a scanning signal to the gate electrode of the switching transistor 708 via the scanning line 707, and turns on or off the switching transistor 708. Thereby, the scanning line driving circuit C2 adjusts timing of writing the signal voltage to the signal line driving circuit C1. On the other hand, the signal line driving circuit C1 supplies or blocks a signal voltage corresponding to the video signal to the gate electrode of the driving transistor 702 via the signal line 706 and the switching transistor 708, and adjusts the amount of signal current supplied to the EL light source unit 200.
Accordingly, if the scanning voltage is supplied from the scanning line driving circuit C2 to the gate electrode of the switching transistor 708 and the switching transistor 708 is turned on, the signal voltage is supplied from the signal line driving circuit C1 to the gate electrode of the switching transistor 708. At this time, a leakage current corresponding to the signal voltage is supplied as a signal current from the power supply line 703 to the EL light source section 200. As a result, the EL light source unit 200 emits light according to the supplied signal current.
< EL light source portion 200 >)
[ Anode 2]
The anode 2 has a function of supplying holes from an external power source to the light-emitting layer 5. The constituent material (anode material) of the anode 2 is not particularly limited, and examples thereof include metals such as gold (Au), halogenated metals such as copper iodide (CuI), indium Tin Oxide (ITO), and tin oxide (SnO) 2 ) Metal oxides such as zinc oxide (ZnO), and the like. The number of these may be 1 alone or 2 or more.
The thickness of the anode 2 is not particularly limited, but is preferably in the range of 10 to 1,000nm, more preferably in the range of 10 to 200 nm.
The anode 2 can be formed by a dry film forming method such as a vacuum deposition method or a sputtering method. At this time, the anode 2 having a predetermined pattern may be formed by a photolithography method using a mask.
[ cathode 8]
The cathode 8 has a function of supplying electrons from an external power source to the light-emitting layer 5. As a constituent material of the cathode 8 (cathodeThe electrode material) is not particularly limited, and examples thereof include lithium, sodium, magnesium, aluminum, silver, sodium-potassium alloy, magnesium/aluminum mixture, magnesium/silver mixture, magnesium/indium mixture, aluminum/aluminum oxide (Al) 2 O 3 ) Mixtures, rare earth metals, and the like. The number of these may be 1 alone or 2 or more.
The thickness of the cathode 8 is not particularly limited, but is preferably in the range of 0.1 to 1,000nm, and more preferably in the range of 1 to 200 nm.
The cathode 8 may be formed by a dry film forming method such as a vapor deposition method or a sputtering method.
[ hole injection layer 3]
The hole injection layer 3 has a function of receiving holes supplied from the anode 2 and injecting the holes into the hole transport layer 4. The hole injection layer 3 may be provided as needed, or may be omitted.
The constituent material (hole injection material) of the hole injection layer 3 is not particularly limited, and examples thereof include: phthalocyanine compounds such as copper phthalocyanine; triphenylamine derivatives such as 4,4' -tris [ phenyl (m-tolyl) amino ] triphenylamine; cyano compounds such as 1,4,5,8,9, 12-hexaazatriphenylhexacarbonitrile, 2,3,5, 6-tetrafluoro-7, 8-tetracyano-quinone dimethane; metal oxides such as vanadium oxide and molybdenum oxide; amorphous carbon; polyaniline (emerald), poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT-PSS), and polymer such as polypyrrole. Among them, the hole injection material is preferably a polymer, more preferably PEDOT-PSS. The hole injecting material may be used alone or in combination of 1 or 2 or more kinds.
The thickness of the hole injection layer 3 is not particularly limited, but is preferably in the range of 0.1 to 500mm, more preferably in the range of 1 to 300nm, and even more preferably in the range of 2 to 200 nm. The hole injection layer 3 may have a single-layer structure or a stacked structure in which 2 or more layers are stacked.
Such a hole injection layer 3 can be formed by a wet film forming method or a dry film forming method. When the hole injection layer 3 is formed by a wet film formation method, an ink containing the hole injection material is generally applied by various coating methods, and the resulting coating film is dried. The coating method is not particularly limited, and examples thereof include an inkjet printing method (droplet discharge method), a spin coating method, a casting method, an LB method, a relief printing method, a gravure printing method, a screen printing method, a nozzle printing method, and the like. On the other hand, in the case of forming the hole injection layer 3 by a dry film forming method, a vacuum deposition method, a sputtering method, or the like can be preferably used.
[ hole transport layer 4]
The hole transport layer 4 has a function of receiving holes from the hole injection layer 3 and efficiently transporting the holes to the light emitting layer 5. The hole transport layer 4 may have a function of preventing electron transport. The hole transport layer 4 may be provided as needed, or may be omitted.
The constituent material (hole transporting material) of the hole transporting layer 4 is not particularly limited, and examples thereof include low-molecular triphenylamine derivatives such as TPD (N, N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine), α -NPD (4, 4 '-bis [ N- (1-naphthyl) -N-phenylamino ] biphenyl), and m-MTDATA (4, 4',4 "-tris (3-methylphenyl phenylamino) triphenylamine); polyvinylcarbazole; conjugated compound polymers such as Poly [ N, N ' -bis (4-butylphenyl) -N, N ' -bis (phenyl) -benzidine ] (Poly-TPA), polyfluorene (PF), poly [ N, N ' -bis (4-butylphenyl) -N, N ' -bis (phenyl) benzidine (Poly-TPD), poly [ (9, 9-dioctylfluorenyl-2, 7-diyl) -co- (4, 4' - (N- (sec-butylphenyl) diphenylamine)) (TFB), and polyphenylene vinylene (PPV); and copolymers containing these monomer units.
Among them, the hole transporting material is preferably a polymer compound obtained by polymerizing a triphenylamine derivative or a triphenylamine derivative having a substituent introduced therein, and more preferably a polymer compound obtained by polymerizing a triphenylamine derivative having a substituent introduced therein. The hole transport material may be used alone or in combination of 1 or more than 2 kinds.
The thickness of the hole transport layer 4 is not particularly limited, but is preferably in the range of 1 to 500nm, more preferably in the range of 5 to 300nm, and even more preferably in the range of 10 to 200 nm. The hole transport layer 4 may have a single-layer structure or a laminated structure in which 2 or more layers are laminated.
Such a hole transport layer 4 can be formed by a wet film forming method or a dry film forming method. When the hole transport layer 4 is formed by a wet film formation method, an ink containing the hole transport material is generally applied by various coating methods, and the resulting coating film is dried. The coating method is not particularly limited, and examples thereof include an inkjet printing method (droplet discharge method), a spin coating method, a casting method, an LB method, a relief printing method, a gravure printing method, a screen printing method, a nozzle printing method, and the like. On the other hand, in the case of forming the hole transport layer 4 by a dry film forming method, a vacuum deposition method, a sputtering method, or the like can be preferably used.
[ Electron injection layer 7]
The electron injection layer 7 has a function of receiving electrons supplied from the cathode 8 and injecting the electrons into the electron transport layer 6. The electron injection layer 7 may be provided as needed, or may be omitted.
The constituent material (electron injection material) of the electron injection layer 7 is not particularly limited, and examples thereof include: li (Li) 2 O、LiO、Na 2 S、Na 2 Alkali metal chalcogenides such as Se and NaO; an alkaline earth metal chalcogenide such as CaO, baO, srO, beO, baS, mgO, caSe; an alkali metal halide such as CsF, liF, naF, KF, liCl, KCl, naCl; alkali metal salts such as lithium 8-hydroxyquinoline (Liq); caF (CaF) 2 、BaF 2 、SrF 2 、MgF 2 、BeF 2 Such as alkaline earth metal halides. Among them, alkali metal chalcogenides, alkaline earth metal halides and alkali metal salts are preferable. The electron injection material may be used alone or in combination of 1 or 2 or more.
The thickness of the electron injection layer 7 is not particularly limited, but is preferably in the range of 0.1 to 100nm, more preferably in the range of 0.2 to 50nm, and even more preferably in the range of 0.5 to 10 nm. The electron injection layer 7 may have a single-layer structure or a laminated structure in which 2 or more layers are laminated.
Such an electron injection layer 7 can be formed by a wet film forming method or a dry film forming method. When the electron injection layer 7 is formed by a wet film formation method, the ink containing the electron injection material is generally applied by various coating methods, and the obtained coating film is dried. The coating method is not particularly limited, and examples thereof include an inkjet printing method (droplet discharge method), a spin coating method, a casting method, an LB method, a relief printing method, a gravure printing method, a screen printing method, a nozzle printing method, and the like. On the other hand, in the case of forming the electron injection layer 7 by a dry film forming method, a vacuum deposition method, a sputtering method, or the like may be applied.
[ Electron transport layer 6]
The electron transport layer 6 has a function of receiving electrons from the electron injection layer 7 and efficiently transporting to the light emitting layer 5. The electron transport layer 6 may have a function of preventing hole transport. The electron transport layer 6 may be provided as needed, or may be omitted.
The constituent material (electron transport material) of the electron transport layer 6 is not particularly limited, and examples thereof include: tris (8-hydroxyquinoline) aluminum (Alq 3), tris (4-methyl-8-hydroxyquinoline) aluminum (Almq 3), bis (10-hydroxybenzo [ h ]]Quinoline) beryllium (BeBq 2), bis (2-methyl-8-hydroxyquinoline) (p-phenylphenoxy) aluminum (BAlq), bis (8-hydroxyquinoline) zinc (Znq), and other metal complexes having a quinoline skeleton or a benzoquinoline skeleton; bis [2- (2' -hydroxyphenyl) benzoxazolyl]Metal complexes having a benzoxazoline skeleton such as zinc (Zn (BOX) 2); bis [2- (2' -hydroxyphenyl) benzothiazolyl]Metal complexes having a benzothiazoline skeleton such as zinc (Zn (BTZ) 2); 2- (4-Biphenyl) -5- (4-tert-butylphenyl) -1,3, 4-oxadiazole (PBD), 3- (4-Biphenyl) -4-phenyl-5- (4-tert-butylphenyl) -1,2, 4-Triazole (TAZ), 1, 3-bis [5- (p-tert-butylphenyl) -1,3, 4-oxadiazol-2-yl ]Benzene (OXD-7), 9- [4- (5-phenyl-1, 3, 4-oxadiazol-2-yl) phenyl]Triazole derivatives or diazole derivatives such as carbazole (CO 11); 2,2' - (1, 3, 5-benzenetriyl) tris (1-phenyl-1H-benzimidazole) (TPBI), 2- [3- (dibenzothiophen-4-yl) phenyl]-imidazole derivatives such as 1-phenyl-1H-benzimidazole (mdtbim-II); quinoline derivatives; perylene derivatives; pyridine derivatives such as 4, 7-diphenyl-1, 10-phenanthroline (BPhen); pyrimidine derivatives; triazine derivatives; quinoxaline derivatives; diphenylA quinone derivative; nitro-substituted fluorene derivatives; zinc oxide (ZnO), titanium oxide (TiO 2 ) Such metal oxides, and the like. Among them, the electron transport material is preferably an imidazole derivative, a pyridine derivative, a pyrimidine derivative, a triazine derivative, or a metal oxide (inorganic oxide). The electron transport material may be used alone or in combination of 1 or more than 2.
The thickness of the electron transport layer 6 is not particularly limited, but is preferably in the range of 5 to 500nm, and more preferably in the range of 5 to 200 nm. The electron transport layer 6 may be a single layer or may be formed by stacking 2 or more layers.
Such an electron transport layer 6 can be formed by a wet film forming method or a dry film forming method. In the case of forming the electron transport layer 6 by a wet film forming method, an ink containing the electron transport material is generally applied by various coating methods, and the obtained coating film is dried. The coating method is not particularly limited, and examples thereof include an inkjet printing method (droplet discharge method), a spin coating method, a casting method, an LB method, a relief printing method, a gravure printing method, a screen printing method, a nozzle printing method, and the like. On the other hand, in the case where the electron transport layer 6 is formed by a dry film forming method, a vacuum deposition method, a sputtering method, or the like may be applied.
[ light-emitting layer 5]
The light-emitting layer 5 has a function of generating light emission by using energy generated by recombination of holes and electrons injected into the light-emitting layer 5. The light-emitting layer 5 of the present embodiment emits blue light having a wavelength in the range of 400 to 500nm, and more preferably in the range of 420 to 480 nm.
The light emitting layer 5 preferably contains a light emitting material (guest material or dopant material) and a host material. In this case, the mass ratio of the host material to the light-emitting material is not particularly limited, and is preferably 10:1 to 300: 1. As the light-emitting material, a compound capable of converting singlet excitation energy into light or a compound capable of converting triplet excitation energy into light can be used. The light-emitting material preferably contains at least one selected from the group consisting of an organic low-molecular fluorescent material, an organic high-molecular fluorescent material, and an organic phosphorescent material.
Examples of the compound capable of converting singlet excitation energy into light include an organic low-molecular fluorescent material or an organic high-molecular fluorescent material that emits fluorescence.
As the organic low-molecular fluorescent material, preferably has an anthracene structure, a naphthacene structure,
Figure BDA0003991136830000491
A compound of structure, phenanthrene structure, pyrene structure, perylene structure, stilbene (stinlbene) structure, acridone structure, coumarin structure, phenoxazine structure or phenothiazine structure.
Specific examples of the organic low-molecular fluorescent material include 5, 6-bis [4- (10-phenyl-9-anthryl) phenyl ] phenyl]-2,2 '-bipyridine, 5, 6-bis [4' - (10-phenyl-9-anthryl) biphenyl-4-yl]-2,2 '-bipyridine, N' -bis [4- (9H-carbazol-9-yl) phenyl ]]-N, N '-diphenylstilbene-4, 4' -diamine, 4- (9H-carbazol-9-yl) -4'- (10-phenyl-9-anthryl) triphenylamine, 4- (9H-carbazol-9-yl) -4' - (9, 10-diphenyl-2-anthryl) triphenylamine, N, 9-diphenyl-N- [4- (10-phenyl-9-anthryl) phenyl]-9H-carbazol-3-amine, 4- (10-phenyl-9-anthryl) -4' - (9-phenyl-9H-carbazol-3-yl) triphenylamine, 4- [4- (10-phenyl-9-anthryl) phenyl]-4' - (9-phenyl-9H-carbazol-3-yl) triphenylamine, perylene, 2,5,8, 11-tetra (t-butyl) perylene, N ' -diphenyl-N, N ' -bis [4- (9-phenyl-9H-fluoren-9-yl) phenyl ]]Pyrene-1, 6-diamine, N '-bis (3-methylphenyl) -N, N' -bis [3- (9-phenyl-9H-fluoren-9-yl) phenyl ]]-pyrene-1, 6-diamine, N ' -bis (dibenzofuran-2-yl) -N, N ' -diphenylpyrene-1, 6-diamine, N ' -bis (dibenzothiophene-2-yl) -N, N ' -diphenylpyrene-1, 6-diamine, N ' - (2-tert-butylanthracene-9, 10-diyl-4, 1-phenylene) bis [ N, N ', N ' -triphenylene-1, 4-phenylenediamine]N, 9-diphenyl-N- [4- (9, 10-diphenyl-2-anthracenyl) phenyl group ]-9H-carbazol-3-amine, N- [4- (9, 10-diphenyl-2-anthracenyl) phenyl ]]-N, N ', N ' -triphenyl-1, 4-phenylenediamine, N, N, N ', N ' ", N ' -octaphenyldibenzo [ g, p]
Figure BDA0003991136830000501
-2,7,10,15-tetramine, coumarin 30, N- (9, 10-diphenyl-2-anthryl) -N, 9-diphenyl-9H-carbazole-3-amine, N- (9, 10-diphenyl-2-anthryl) -N, N ' -triphenylanthracene-1, 4-phenylenediamine, N, 9-triphenylanthracene-9-amine, coumarin 6, coumarin 545T, N, N ' -diphenylquinacridone, rubrene, 5, 12-bis (1, 1' -biphenyl-4-yl) -6, 11-diphenyltetracene, 2- (2- {2- [4- (dimethylamino) phenyl ]]Vinyl } -6-methyl-4H-pyran-4-ylidene) malononitrile, 2- { 2-methyl-6- [2- (2, 3,6, 7-tetrahydro-1H, 5H-benzo [ ij ]]Quinolizin-9-yl) vinyl]-4H-pyran-4-ylidene } malononitrile, N, N, N ', N' -tetrakis (4-methylphenyl) naphthacene-5, 11-diamine, 7,14-diphenyl-N, N, N ', N' -tetrakis (4-methylphenyl) acenaphtho [1,2-a]Fluoranthene-3,10-diamine (7, 14-diphenyl-N, N, N ', N' -tetrakis (4-methylphenyl) aceaphtho [1, 2-a)]fluoroantane-3, 10-diamine), 2- { 2-isopropyl-6- [2- (1, 7-tetramethyl-2, 3,6, 7-tetrahydro-1H, 5H-benzo [ ij ]]Quinolizin-9-yl) vinyl]-4H-pyran-4-ylidene } malononitrile, 2- { 2-tert-butyl-6- [2- (1, 7-tetramethyl-2, 3,6, 7-tetrahydro-1H, 5H-benzo [ ij ] ]Quinolizin-9-yl) vinyl]-4H-pyran-4-ylidene } malononitrile, 2- (2, 6-bis {2- [4- (dimethylamino) phenyl)]Vinyl } -4H-pyran-4-ylidene) malononitrile, 2- {2, 6-bis [2- (8-methoxy-1, 7-tetramethyl-2, 3,6, 7-tetrahydro-1H, 5H-benzo [ ij ]]Quinolizin-9-yl) vinyl]-4H-pyran-4-ylidene } malononitrile, 5,10,15, 20-tetraphenylbisbenzo [5,6 ]]Indeno [1,2,3-cd:1',2',3' -lm]Perylene, and the like.
Specific examples of the organic polymer fluorescent material include: homopolymers of units based on fluorene derivatives, copolymers of units based on fluorene derivatives and units based on tetraphenylphenylenediamine derivatives, homopolymers of units based on biphenyl derivatives, homopolymers of units based on diphenylbenzofluorene derivatives, and the like.
As the compound capable of converting triplet excitation energy into light, an organic phosphorescent material that emits phosphorescence is preferable. Specific examples of the organic phosphorescent material include metal complexes containing at least one metal atom selected from the group consisting of iridium, rhodium, platinum, ruthenium, osmium, scandium, yttrium, gadolinium, palladium, silver, gold, and aluminum. Among them, the organic phosphorescent material is preferably a metal complex containing at least one metal atom selected from the group consisting of iridium, rhodium, platinum, ruthenium, osmium, scandium, yttrium, gadolinium, and palladium, more preferably a metal complex containing at least one metal atom selected from the group consisting of iridium, rhodium, platinum, and ruthenium, and still more preferably an iridium complex or a platinum complex.
As the host material, at least one compound having an energy gap larger than that of the light-emitting material is preferably used. Further, in the case where the light-emitting material is a phosphorescent material, a compound having a triplet excitation energy larger than the triplet excitation energy (energy difference between the ground state and the triplet excitation state) of the light-emitting material is preferably selected as the host material.
Examples of the host material include tris (8-hydroxyquinoline) aluminum (III), tris (4-methyl-8-quinoline) aluminum (III), and bis (10-hydroxybenzo [ h ]]Quinoline) beryllium (II), bis (2-methyl-8-quinoline) (4-phenylphenoxy) aluminum (III), bis (8-hydroxyquinoline) zinc (II), bis [2- (2-benzoxazolyl) phenol]Zinc (II), bis [2- (2-benzothiazolyl) phenol]Zinc (II), 2- (4-biphenyl) -5- (4-tert-butylphenyl) -1,3, 4-oxadiazole, 1, 3-bis [5- (p-tert-butylphenyl) -1,3, 4-oxadiazol-2-yl]Benzene, 3- (4-biphenyl) -4-phenyl-5- (4-tert-butylphenyl) -1,2, 4-triazole, 2' - (1, 3, 5-benzenetriyl) tris (1-phenyl-1H-benzimidazole), bathophenanthroline (Bathophenanthroline), bathocuproine (Bathocuproine), 9- [4- (5-phenyl-1, 3, 4-oxadiazol-2-yl) phenyl]-9H-carbazole, 9, 10-diphenylanthracene, N-diphenyl-9- [4- (10-phenyl-9-anthracenyl) phenyl ]-9H-carbazol-3-amine, 4- (10-phenyl-9-anthryl) triphenylamine, N, 9-diphenyl-N- {4- [4- (10-phenyl-9-anthryl) phenyl ]]Phenyl } -9H-carbazol-3-amine, 6, 12-dimethoxy-5, 11-diphenyl
Figure BDA0003991136830000511
9- [4- (10-phenyl-9-anthracenyl) phenyl group]-9H-carbazole, 3, 6-diphenyl-9- [4- (10-phenyl-9-anthracenyl) phenyl ]]-9H-carbazole, 9-phenyl-3- [4- (10-phenyl-9-anthryl) phenyl ]]-9H-carbazole, 7- [4- (10-phenyl-9-anthracenyl) phenyl ]]-7H-dibenzo [ c, g]Carbazole, 6- [3- (9, 10-diphenyl-2-anthryl) phenyl group]Benzo [ b ]]Naphtho [1,2-d]Furan, 9-phenyl-10- {4- (9-phenyl-9H-fluoren-9-yl) biphenyl-4 '-yl } anthracene, 9, 10-bis (3, 5-diphenylphenyl) anthracene, 9, 10-bis (2-naphthyl) anthracene, 2-tert-butyl-9, 10-bis (2-naphthyl) anthracene, 9' -bianthracene,9,9'- (stilbene-3, 3' -diyl) biphenanthrene, 9'- (stilbene-4, 4' -diyl) biphenanthrene, 1,3, 5-tris (1-pyrenyl) benzene, 5, 12-diphenyl tetracene, or 5, 12-bis (biphenyl-2-yl) tetracene, and the like. These host materials may be used alone or in combination of 2 or more.
The thickness of the light-emitting layer 5 is not particularly limited, but is preferably in the range of 1 to 100nm, and more preferably in the range of 1 to 50 nm.
Such a light-emitting layer 5 can be formed by a wet film forming method or a dry film forming method. When the light-emitting layer 5 is formed by a wet film formation method, an ink containing the light-emitting material and the host material is generally applied by various application methods, and the obtained coating film is dried. The coating method is not particularly limited, and examples thereof include an inkjet printing method (droplet discharge method), a spin coating method, a casting method, an LB method, a relief printing method, a gravure printing method, a screen printing method, a nozzle printing method, and the like. On the other hand, in the case where the light-emitting layer 5 is formed by a dry film forming method, a vacuum deposition method, a sputtering method, or the like may be applied.
The EL light source unit 200 may further include banks (partition walls) that divide the hole injection layer 3, the hole transport layer 4, and the light emitting layer 5, for example. The height of the bank (bank) is not particularly limited, but is preferably in the range of 0.1 to 5. Mu.m, more preferably in the range of 0.2 to 4. Mu.m, and still more preferably in the range of 0.2 to 3. Mu.m.
The width of the opening of the bank is preferably in the range of 10 to 200. Mu.m, more preferably in the range of 30 to 200. Mu.m, and even more preferably in the range of 50 to 100. Mu.m. The length of the opening of the bank is preferably in the range of 10 to 400. Mu.m, more preferably in the range of 20 to 200. Mu.m, and even more preferably in the range of 50 to 200. Mu.m. The inclination angle of the bank is preferably in the range of 10 to 100 °, more preferably in the range of 10 to 90 °, and even more preferably in the range of 10 to 80 °.
< light conversion layer 12 >)
The light conversion layer 12 converts light emitted from the EL light source unit 200 to re-emit the light, or transmits the light emitted from the EL light source unit 200. As shown in fig. 4, the pixel unit 20 includes: a first pixel unit 20a that converts light having a wavelength in the above range and emits red light; a second pixel unit 20b that converts light having a wavelength in the above range and emits green light; and a third pixel portion 20c that transmits light having a wavelength in the above range. The plurality of first, second and third pixel portions 20a, 20b and 20c are arranged in a lattice shape in such a manner that the order is repeated. A light shielding portion 30 for shielding light is provided between adjacent pixel portions, that is, between the first pixel portion 20a and the second pixel portion 20b, between the second pixel portion 20b and the third pixel portion 20c, and between the third pixel portion 20c and the first pixel portion 20 a. In other words, these adjacent pixel portions are separated from each other by the light shielding portion 30. The first pixel portion 20a and the second pixel portion 20b may contain coloring materials corresponding to respective colors.
Each of the first pixel portion 20a and the second pixel portion 20b contains the cured product of the light-emitting particle-containing curable resin composition of the above embodiment. The cured product preferably contains light-emitting particles 91 and a curing component, and further preferably contains light-scattering particles in order to scatter light and reliably take out the light to the outside. The curing component is a cured product of a thermosetting resin, for example, a cured product obtained by polymerizing an epoxy group-containing resin. That is, the first pixel portion 20a includes the first cured component 22a, and the first light emitting particles 91a and the first light scattering particles 21a dispersed in the first cured component 22a, respectively. Similarly, the second pixel portion 20b includes the second cured component 22b, and the second light-emitting particles 91b and the second light-scattering particles 21b dispersed in the second cured component 22b, respectively. In the first pixel portion 20a and the second pixel portion 20b, the first curing component 22a and the second curing component 22b may be the same or different, and the first light scattering particles 21a and the second light scattering particles 21b may be the same or different.
The first light-emitting particles 91a are red light-emitting particles that absorb light having a wavelength in the range of 420 to 480nm and emit light having a light emission peak wavelength in the range of 605 to 665 nm. That is, the first pixel portion 20a may be modified to be a red pixel portion for converting blue light into red light. The second light-emitting particles 91b are green light-emitting particles that absorb light having a wavelength in the range of 420 to 480nm and emit light having a light emission peak wavelength in the range of 500 to 560 nm. That is, the second pixel portion 20b may be modified to be a green pixel portion for converting blue light into green light.
The content of the luminescent particles 91 in the pixel portions 20a and 20b containing the cured product of the luminescent particle-containing curable resin composition is preferably 0.1 mass% or more based on the total mass of the cured product of the luminescent particle-containing curable resin composition, from the viewpoint that the effect of improving the external quantum efficiency is more excellent and excellent light-emitting intensity can be obtained. From the same viewpoint, the content of the luminescent particles 91 is preferably 1 mass% or more, 2 mass% or more, 3 mass% or more, or 5 mass% or more based on the total mass of the cured product of the luminescent particle-containing curable resin composition. The content of the luminescent particles 91 is preferably 30 mass% or less based on the total mass of the luminescent particle-containing curable resin composition from the viewpoint of excellent reliability of the pixel portions 20a, 20b and excellent light emission intensity. From the same viewpoint, the content of the luminescent particles 91 is preferably 25 mass% or less, 20 mass% or less, 15 mass% or less, or 10 mass% or less based on the total mass of the cured product of the luminescent particle-containing curable resin composition.
From the viewpoint of further excellent effect of improving external quantum efficiency, the content of the first light scattering particles 21a and the second light scattering particles 21b in the first pixel portion 20a and the second pixel portion 20b including the cured product of the light-emitting particle-containing curable resin composition is preferably 0.1 mass% or more, 1 mass% or more, 5 mass% or more, 7 mass% or more, 10 mass% or more, or 12 mass% or more based on the total mass of the cured product of the curable resin composition. The content of the first light scattering particles 21a and the second light scattering particles 21b is preferably 60 mass% or less, 50 mass% or less, 40 mass% or less, 30 mass% or less, 25 mass% or less, 20 mass% or less, or 15 mass% or less based on the total mass of the cured product of the curable resin composition, from the viewpoint of further excellent effect of improving external quantum efficiency and the viewpoint of excellent reliability of the pixel portion 20.
The third pixel portion 20c has a transmittance of 30% or more with respect to light having a wavelength in the range of 420 to 480 nm. Therefore, when a light source that emits light having a wavelength in the range of 420 to 480nm is used, the third pixel portion 20c functions as a blue pixel portion. The third pixel portion 20c includes, for example, a cured product of a composition containing the thermosetting resin. The cured product contains a third curing component 22c. The third curing component 22c is a cured product of a thermosetting resin, specifically, a cured product obtained by polymerizing a resin containing an epoxy group. That is, the third pixel portion 20c includes the third curing component 22c. When the third pixel portion 20c includes the cured product, the composition containing the thermosetting resin may further contain components other than the thermosetting resin, the curing agent, and the solvent among the components contained in the composition containing the luminescent particles, as long as the transmittance of the composition containing the thermosetting resin with respect to light having a wavelength in a range of 420 to 480nm is 30% or more. The transmittance of the third pixel portion 20c can be measured by a microscopic spectroscopic device.
The thickness of the pixel portions (the first pixel portion 20a, the second pixel portion 20b, and the third pixel portion 20 c) is not particularly limited, and is preferably 1 μm or more, 2 μm or more, or 3 μm or more, for example. The thickness of the pixel portions (the first pixel portion 20a, the second pixel portion 20b, and the third pixel portion 20 c) is preferably 30 μm or less, 25 μm or less, or 20 μm or less, for example.
[ method of Forming light-converting layer 12 ]
The light conversion layer 12 including the first to third pixel portions 20a to 20c described above can be formed by drying and heating a coating film formed by a wet film forming method to cure the coating film. The first pixel portion 20a and the second pixel portion 20b may be formed using the light-emitting particle-containing curable resin composition of the present invention, and the third pixel portion 20c may be formed using the curable resin composition that does not contain the light-emitting particles 91 contained in the light-emitting particle-containing curable resin composition. Hereinafter, a method for forming a coating film using the light-emitting particle-containing curable resin composition of the present invention will be described in detail, but the same can be performed also in the case of using the light-emitting particle-containing curable resin composition of the present invention.
The coating method for obtaining the coating film of the light-emitting particle-containing curable resin composition of the present invention is not particularly limited, and examples thereof include an inkjet printing method (a piezo-electric or thermal droplet discharge method), a spin coating method, a casting method, an LB method, a relief printing method, a gravure printing method, a screen printing method, a nozzle printing method, and the like. Here, the nozzle printing method is a method of applying a curable resin composition containing light-emitting particles in a stripe form from nozzle holes in the form of a liquid column. Among them, the coating method is preferably an inkjet printing method (particularly a piezoelectric droplet discharge method). This can reduce the heat load when the curable resin composition containing the light-emitting particles is discharged, and can prevent deterioration due to heat of the light-emitting particles 91.
The conditions of the inkjet printing method are preferably set as follows. The discharge amount of the light-emitting particle-containing curable resin composition is not particularly limited, but is preferably 1 to 50 pL/time, more preferably 1 to 30 pL/time, and still more preferably 1 to 20 pL/time.
The opening diameter of the nozzle hole is preferably in the range of 5 to 50. Mu.m, more preferably in the range of 10 to 30. Mu.m. This can prevent clogging of the nozzle hole and improve the discharge accuracy of the curable resin composition containing the luminescent particles.
The temperature at the time of forming the coating film is not particularly limited, but is preferably in the range of 10 to 50 ℃, more preferably in the range of 15 to 40 ℃, and even more preferably in the range of 15 to 30 ℃. When the droplets are discharged at this temperature, crystallization of various components contained in the light-emitting particle-containing curable resin composition can be suppressed.
The relative humidity at the time of forming the coating film is not particularly limited, and is preferably in the range of 0.01ppm to 80%, more preferably in the range of 0.05ppm to 60%, even more preferably in the range of 0.1ppm to 15%, particularly preferably in the range of 1ppm to 1%, and most preferably in the range of 5ppm to 100%. If the relative humidity is not less than the lower limit, it is easy to control the conditions at the time of forming the coating film. On the other hand, if the relative humidity is equal to or less than the upper limit value, the amount of moisture adsorbed to the coating film, which may adversely affect the obtained light conversion layer 12, can be reduced.
In the case where the light-emitting particle-containing curable resin composition contains an organic solvent, the organic solvent is preferably removed from the coating film by drying before the coating film is cured. The drying may be carried out at room temperature (25 ℃) or by heating, but is preferably carried out by heating from the viewpoint of productivity. In the case of drying by heating, the drying temperature is not particularly limited, and is preferably a temperature considering the boiling point and vapor pressure of the organic solvent used in the light-emitting particle-containing curable resin composition. The pre-baking step for removing the organic solvent in the coating film is preferably performed at a drying temperature of 50 to 130 ℃, more preferably 60 to 120 ℃, and particularly preferably 70 to 110 ℃. If the drying temperature is 50 ℃ or lower, the organic solvent may not be removed, whereas if the drying temperature is 130 ℃ or higher, the removal of the organic solvent occurs instantaneously, and the appearance of the coating film may be significantly deteriorated, which is not preferable. The drying is preferably performed under reduced pressure, more preferably under reduced pressure of 0.001 to 100 Pa. Further, the drying time is preferably 1 to 30 minutes, more preferably 1 to 15 minutes, and particularly preferably 1 to 10 minutes. By drying the coating film under such drying conditions, the organic solvent can be reliably removed from the coating film, and the external quantum efficiency of the obtained light conversion layer 12 can be further improved.
The light-emitting particle-containing curable resin composition of the present invention can be cured by irradiation with active energy rays (for example, ultraviolet rays). As the irradiation source (light source), for example, a mercury lamp, a metal halide lamp, a xenon lamp, an LED, or the like is used, but an LED is preferable from the viewpoints of reducing the heat load on the coating film and low power consumption.
The wavelength of the irradiated light is preferably 200nm or more, more preferably 440nm or less. The intensity of light is preferably 0.2 to 2kW/cm 2 More preferably 0.4 to 1kW/cm 2 . The intensity of the light is less than 0.2kW/cm 2 In the case where the coating film was not sufficiently cured, the intensity of light was 2kW/cm 2 In the above cases, the degree of hardening varies between the surface and the inside of the coating film, and the smoothness of the coating film surface is poor, which is not preferable. The irradiation amount (exposure amount) of light is preferably 10mJ/cm 2 Above, more preferably 4000mJ/cm 2 The following is given.
The curing of the coating film may be carried out in air or in an inert gas, and is more preferably carried out in an inert gas in order to inhibit oxygen inhibition on the surface of the coating film and oxidation of the coating film. Examples of the inert gas include nitrogen, argon, and carbon dioxide. By curing the coating film under such conditions, the coating film can be completely cured, and thus the external quantum efficiency of the obtained light conversion layer 12 can be further improved.
As described above, the light-emitting particle-containing curable resin composition of the present invention is excellent in heat stability, and therefore can realize good light emission even in the pixel portion 20 as a molded body after heat curing. Further, the light-emitting particle composition of the present invention is excellent in dispersibility, so that the light-emitting particles 91 are excellent in dispersibility, and the flat pixel portion 20 can be obtained.
Further, since the light-emitting particles 91 included in the first pixel portion 20a and the second pixel portion 20b include semiconductor nanocrystals having a perovskite type, absorption in a wavelength region of 300 to 500nm is large. Therefore, in the first pixel portion 20a and the second pixel portion 20b, blue light incident on the first pixel portion 20a and the second pixel portion 20b can be prevented from transmitting to the side of the substrate 13, that is, blue light leaks to the side of the substrate 13. Therefore, according to the first pixel portion 20a and the second pixel portion 20b of the present invention, red light and green light having high color purity can be extracted without mixing blue light.
The light shielding portion 30 is a so-called black matrix provided for the purpose of separating adjacent pixel portions 20 to prevent color mixing and for the purpose of preventing light leakage from the light source. The material constituting the light shielding portion 30 is not particularly limited, and a cured product of an ink composition containing light shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments in a binder polymer may be used in addition to metals such as chromium. As the binder polymer used herein, a polyimide resin, an acrylic resin, an epoxy resin, a polyacrylamide, a polyvinyl alcohol, gelatin, casein, a cellulose or other resin mixed with 1 or 2 or more kinds of resin, a photosensitive resin, an O/W emulsion type ink composition (for example, a substance obtained by liquefying reactive silicone emulsion), or the like can be used. The thickness of the light shielding portion 30 is preferably, for example, 1 μm or more and 15 μm or less.
The light-emitting element 100 may be configured to emit light in a bottom emission manner instead of the top emission manner. In addition, the light emitting element 100 may use another light source instead of the EL light source unit 200.
The above description has been made of the curable resin composition containing light-emitting particles, the method for producing the same, and the light-emitting element including the light-converting layer produced using the composition of the present invention, but the present invention is not limited to the configuration of the above embodiment. For example, the light-emitting particles, the light-emitting particle dispersion, the light-emitting particle-containing curable resin composition, and the light-emitting element of the present invention may have any other structure in addition to the structures of the above embodiments, or may be replaced with any structure that exhibits the same function. The method for producing a light-emitting particle according to the present invention may have any other process for the same purpose or may be replaced with any process for the same purpose in the above-described embodiment.
Examples
The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" and "%" are based on mass.
[ preparation of light-emitting particle-containing Dispersion ]
(preparation of light-emitting particle-containing Dispersion 1)
First, 0.12g of cesium carbonate, 5mL of 1-octadecene, and 0.5mL of oleic acid were mixed to obtain a mixed solution. Subsequently, the mixture was dried at 120℃under reduced pressure for 30 minutes, and then heated at 150℃under an argon atmosphere. Thus, cesium-oleic acid solution was obtained.
On the other hand, 0.2g of lead (II) bromide, 15mL of 1-octadecene and 1.5mL of oleic acid were mixed to obtain a mixed solution. Subsequently, the mixture was dried at 90℃under reduced pressure for 10 minutes, and 1.5mL of 3-aminopropyl triethoxysilane (APTES) was added to the mixture under an argon atmosphere. Then, after further drying under reduced pressure for 20 minutes, heating was performed at 140℃under an argon atmosphere.
Then, 1.5mL of the cesium-oleic acid solution was added to the above mixed solution containing lead (II) bromide at 150℃and stirred for 5 seconds with heating to effect reactionAfter this, the mixture was cooled with an ice bath. Then, 30mL of methyl acetate was added. After the obtained suspension was centrifuged (10,000 rpm, 1 minute), the supernatant was removed to obtain a solid (intermediate particle 1), and 20mL of toluene was added to the solid and stirred with shaking to disperse the solid. The resulting colloidal solution was centrifuged at 10,000rpm at 25℃for 3 minutes. By recovering the supernatant, csPbBr having a perovskite structure in the core is obtained 3 And a colloidal solution 1 having intermediate particles 1 containing a ligand layer having siloxane bonds. The nanocrystals constituting the intermediate particles 1 were analyzed by scanning transmission electron microscope observation, and as a result, the average particle diameter was 10nm.
0.8g of a block copolymer having a structure represented by the following formula (B4) (manufactured by S2VP, polymerSource. Co.) was added to 80mL of toluene, and the mixture was heated and dissolved at 60 ℃. 80mL of a toluene solution in which a block copolymer was dissolved was added to the colloidal solution 1, and after stirring for 15 minutes, the mixture was centrifuged to collect a supernatant, thereby obtaining a toluene dispersion 1 containing intermediate particles 1 and a block copolymer.
Figure BDA0003991136830000581
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To 2mL of the toluene dispersion 1, 0.01mL of a compound represented by the following formula (C4) (MS-51, manufactured by Colcoat Co., ltd., average value of m in the formula (C4)) was added, and the mixture was stirred at room temperature for 2 hours, and then 0.05mL of ion-exchanged water was further added and the mixture was stirred for 2 hours.
Figure BDA0003991136830000582
After the obtained solution was subjected to centrifugal separation at 9,000 rpm for 5 minutes, 2mL of the supernatant was recovered, thereby obtaining a luminescent particle-containing dispersion liquid 1 in which luminescent particles 1 having a silica layer on the surface of intermediate particles 1 were dispersed in toluene. The silica layer corresponds to the second shell layer 913 as the inorganic coating layer. As a result of evaluating the element distribution of the above-described luminescent particle 1 by energy dispersive X-ray analysis (STEM-EDS) using a scanning transmission electron microscope, it was confirmed that Si was contained in the surface layer of the luminescent particle. The thickness of the surface layer was measured and found to be about 4nm. Further, the light-emitting particles 1 were measured by thermogravimetric differential thermal analysis (TG-DTA; heating rate 10 ℃ C./min, under a nitrogen atmosphere), and the weight reduction was confirmed in the range of 200 to 550 ℃. On the other hand, the polymer B4 used was identified as a component as determined by thermal cracking gas chromatograph mass spectrometer (TD/Py-GC/MS).
(preparation of light-emitting particle-containing Dispersion 2)
To a three-necked flask, 0.06g of formamidine acetate, 0.50mL of oleic acid and 5mL of 1-octadecene were charged under an argon atmosphere. While the pressure was reduced (15.+ -.3 kPa) by a vacuum pump, the mixture was heated and stirred at 120℃for 30 minutes. The atmosphere was returned to atmospheric pressure under an argon atmosphere. Heating to 150 ℃, and stirring until the mixture becomes a uniform solution to obtain formamidine-oleic acid solution.
To a three-necked flask different from the above, 0.20g of lead (II) bromide, 1.50mL of oleic acid and 15mL of 1-octadecene were charged under an argon atmosphere. While the pressure was reduced (15.+ -.3 kPa) by a vacuum pump, the mixture was heated and stirred at 120℃for 30 minutes. Under an argon atmosphere, the atmosphere was returned to atmospheric pressure, and 1.5mL of 3-aminopropyl triethoxysilane (APTES) was added. Heating to 140 deg.C, and stirring until it becomes uniform solution. Then, 1.5mL of the formamidine-oleic acid solution was added to the above-mentioned mixed solution containing lead (II) bromide at 150℃and reacted by stirring for 5 seconds with heating, followed by cooling with an ice bath. Then, 30mL of methyl acetate was added. After the obtained suspension was centrifuged (10,000 rpm, 3 minutes), the supernatant was removed to obtain a solid (intermediate particles 2), and 20mL of toluene was added to the solid and the mixture was dispersed by stirring with shaking. The resulting colloidal solution was centrifuged at 10,000rpm at 25℃for 3 minutes. Recovering the supernatant to obtain FAPbBr having perovskite structure in the core 3 And a colloidal solution 2 of intermediate particles 2 having a ligand layer containing siloxane bonds. The intermediate particles 2 were separated by observation with a scanning transmission electron microscopeAs a result of the analysis, the average particle diameter was 11nm.
0.8g of a block copolymer having a structure represented by the formula (B4) (manufactured by S2VP, polymerSource. Co.) was added to 80mL of toluene, and the mixture was heated and dissolved at 60 ℃. 80mL of a toluene solution in which a block copolymer was dissolved was added to the colloidal solution 2, and after stirring for 15 minutes, the mixture was centrifuged to collect a supernatant, thereby obtaining a toluene dispersion liquid 2 containing intermediate particles 2 and a block copolymer.
To 2mL of the toluene dispersion liquid 2, 0.01mL of the compound represented by the formula (C4) (MS-51, manufactured by Colcoat Co., ltd., the average value of m in the formula (C4)) was added, and the mixture was stirred at room temperature for 2 hours, and then, 0.05mL of ion-exchanged water was further added and the mixture was stirred for 2 hours.
After the obtained solution was subjected to centrifugal separation at 9,000 rpm for 5 minutes, 2mL of the supernatant was recovered, thereby obtaining a luminescent particle-containing dispersion liquid 2 in which luminescent particles 2 having a silica layer on the surface of the intermediate particles 2 were dispersed in toluene. The silica layer corresponds to the second shell layer 913 as the inorganic coating layer. As a result of evaluating the element distribution of the above-described luminescent particle 2 by energy dispersive X-ray analysis (STEM-EDS) using a scanning transmission electron microscope, it was confirmed that Si was contained in the surface layer of the luminescent particle. The thickness of the surface layer was measured and found to be about 4nm.
(preparation of light-emitting particle-containing Dispersion 3)
To a glass vial equipped with a stirrer, 2mL of the colloidal solution of intermediate particles 1 was added. Dodecylbenzenesulfonic acid (DBSA) was added so as to be 0.3 μmol with respect to 1mg of intermediate particle 1, and stirred at room temperature for 1 hour. Then, 30mL of methyl acetate was added while stirring. The resulting suspension was centrifuged at 10,000rpm at 25℃for 1 minute using a high-speed cooling centrifuge Avanti J-E (manufactured by Beckman Coulter Co.). The supernatant was removed, and 20mL of toluene was added to the obtained solid material, followed by shaking and mixing to dissolve the solid material. The resulting colloidal solution was centrifuged at 10,000rpm at 25℃for 3 minutes. Recovering the supernatant to obtain a nucleus-containing intermediate particle 1 having a part of the ligand replaced with DBSACsPbBr with perovskite structure 3 And having a ligand layer containing siloxane bonds.
0.8g of a block copolymer having a structure represented by the formula (B4) (manufactured by S2VP, polymerSource. Co.) was added to 80mL of toluene, and the mixture was heated and dissolved at 60 ℃. 80mL of a toluene solution in which a block copolymer was dissolved was added to the colloidal solution 2, and after stirring for 15 minutes, the mixture was centrifuged to collect a supernatant, thereby obtaining a toluene dispersion 3 containing intermediate particles 3 and a block copolymer.
To 2mL of the toluene dispersion 3, 0.01mL of the compound represented by the formula (C4) (MS-51, manufactured by Colcoat Co., ltd., the average value of m in the formula (C4)) was added, and the mixture was stirred at room temperature for 2 hours, and then 0.05mL of ion-exchanged water was further added and the mixture was stirred for 2 hours.
After the obtained solution was subjected to centrifugal separation at 9,000 rpm for 5 minutes, 2mL of the supernatant was recovered, thereby obtaining a luminescent particle-containing dispersion liquid 3 in which luminescent particles 3 having a silica layer on the surface of the intermediate particles 3 were dispersed in toluene. The silica layer corresponds to the second shell layer 913 as the inorganic coating layer. As a result of evaluating the element distribution of the above-described luminescent particles 3 by energy dispersive X-ray analysis (STEM-EDS) using a scanning transmission electron microscope, it was confirmed that Si was contained in the surface layer of the luminescent particles. The thickness of the surface layer was measured and found to be about 4nm.
(preparation of light-emitting particle-containing Dispersion 4)
CsPbBr having a perovskite structure in the core was obtained by the same method except that dodecylbenzenesulfonic acid was replaced with octylphosphonic acid (OctPA) in the preparation of the luminescent particle-containing dispersion 3 3 And a colloidal solution of luminescent particles 4 having a ligand layer containing a siloxane bond and further having a silica layer on the surface thereof.
(preparation of light-emitting particle-containing Dispersion 5)
In the same manner as above except that the intermediate particles 1 were replaced with the intermediate particles 2 in the preparation of the dispersion liquid 3 containing luminescent particles, a core-in-core device was obtainedPreparation of FAPbBr with perovskite Structure 3 And a colloidal solution of luminescent particles 5 having a ligand layer containing a siloxane bond and further having a silica layer on the surface thereof.
< Synthesis of organic-inorganic composite particles >
(preparation of organic-inorganic composite particles 1)
As the polymer Z, 800mg of a block copolymer (S2 VP, the same product as B4) having a structure represented by the following formula (Z4) used for producing the above-mentioned light-emitting particles was added to 80mL of toluene, and heated and dissolved at 60 ℃.
Figure BDA0003991136830000611
To 80mL of the toluene solution, 400. Mu.L of a compound represented by the following formula (G4) (MS-51, product of Colcoat Co., ltd., average value of m in the formula (G4) was 4, the same as C4) was added, followed by stirring for 5 minutes, and then, 100. Mu.L of ion-exchanged water was further added and stirring was continued for 2 hours.
Figure BDA0003991136830000612
After the obtained solution was subjected to centrifugal separation at 9,000 rpm for 5 minutes, 80mL of the supernatant was recovered and dried, whereby organic-inorganic composite particles 1 were obtained. The composite particles were dispersed in methyl ethyl ketone, and the average particle diameter was measured using a dynamic light scattering Nanotrac particle size distribution meter, resulting in 165nm. The organic-inorganic composite particles 1 were sufficiently washed with acetone, and then subjected to thermogravimetric differential thermal analysis (TG-DTA; heating rate 10 ℃ C./min, under a nitrogen atmosphere), and as a result, weight loss was confirmed in the range of 200 to 550 ℃. On the other hand, the polymer B4 used was identified as a component as determined by thermal cracking gas chromatograph mass spectrometer (TD/Py-GC/MS).
(preparation of organic-inorganic composite particles 2)
15 parts of 12 hydroxystearic acid, 285 parts of epsilon-caprolactone and 0.05 part of monobutyl tin oxide as a catalyst were charged into a reaction vessel, replaced with nitrogen, and then heated and stirred at 120℃for 4 hours to obtain a polyester intermediate. Next, 100 parts of a 10% aqueous polyallylamine solution (PAA-1 LV, manufactured by Nito Kagaku Co., ltd., number average molecular weight of about 3,000) was stirred at 160℃and distilled off using a separating device, and 200 parts of a polyester intermediate was added thereto to raise the temperature to 160℃and reacted at 160℃for 2 hours to obtain a graft copolymer Z1. The weight average molecular weight (Mw) of the polymer obtained was determined by Gel Permeation Chromatography (GPC) under the following conditions, and was 44,000 as a pale yellow solid at ordinary temperature, based on polystyrene standards.
The resulting graft copolymer Z5 was added to 80mL of toluene, and heated at 60℃to dissolve. Then, 400. Mu.L of silane compound MS-51 (manufactured by Colcoat Co., ltd.) was added and stirred for 5 minutes, and then 100. Mu.L of ion-exchanged water was further added and stirred for 2 hours.
The obtained solution was subjected to centrifugal separation at 9,000 rpm for 5 minutes, and 80mL of the supernatant was recovered and dried to obtain organic-inorganic composite particles 2. The composite particles were dispersed in methyl ethyl ketone, and the average particle diameter was measured using a dynamic light scattering Nanotrac particle size distribution meter, resulting in 190nm. The organic-inorganic composite particles 2 were sufficiently washed with acetone, and then subjected to thermogravimetric differential thermal analysis (TG-DTA; heating rate 10 ℃ C./min, under a nitrogen atmosphere), and as a result, weight loss was confirmed in the range of 200 to 550 ℃. On the other hand, the polymer Z1 used was identified as a component as determined by thermal cracking gas chromatograph mass spectrometer (TD/Py-GC/MS).
(preparation of organic-inorganic composite particles 3)
An organic-inorganic composite particle 3 was obtained by the same method as that for the preparation of the organic-inorganic composite particle 1 except that MS-51 was replaced with Tetraethoxysilane (TEOS).
Preparation of light-emitting particle-containing curable resin composition
Example 1
(preparation of light-emitting particle-containing curable resin composition (1))
100mL of the above-obtained dispersion liquid containing luminescent particles 1 and 200mL of hexane were mixed, and the obtained suspension was centrifuged at 4,000rpm for 1 minute. To the residue obtained by removing the supernatant, 10. Mu.L of each of Light Acrylate PO-A (manufactured by Kagrong chemical Co., ltd.) and Light Acrylate DCPA (manufactured by Kagrong chemical Co., ltd.) was added, and the mixture was stirred at room temperature with shaking to uniformly disperse the mixture. Then, 1.1. Mu.g of Omnirad TPO (manufactured by Basfun Japanese Co., ltd.) was added and dissolved uniformly. After dissolution, 0.2. Mu.g of the organic-inorganic composite particles 1 was further added thereto, and the mixture was stirred with shaking, thereby obtaining a luminescent particle-containing curable resin composition (1).
(dispersion stability)
The obtained curable resin composition (1) containing luminescent particles was stored at 35℃for 3 months under light shielding. As a result of visual evaluation of the dispersion stability, no agglomerates of the precipitate were produced at all.
Evaluation criteria:
s: no agglomerates of precipitate were produced at all in the preserved luminescent particle-containing composition.
A: a very small amount of agglomerates of the precipitate is produced.
B: a condensate of a slightly more precipitate is produced.
C: a very large amount of agglomerates of precipitate is produced.
(production of light conversion layer 1)
The obtained luminescent particle-containing curable resin composition (1) was dropped onto glass substrate eaglxg (manufactured by corning corporation), and the other glass substrate eaglxg was placed on top of each other, and the cumulative light amount was 10J/cm under a nitrogen atmosphere 2 UV light having a dominant wavelength of 395nm was irradiated to produce a 50 μm thick light conversion layer 1 containing luminescent particles.
(evaluation of light resistance)
The obtained light conversion layer 1 was subjected to a light resistance tester (CCS Co.) at a stage temperature in airAt a temperature of 30 ℃ at 100mW/cm 2 Blue light having a peak emission wavelength of 450nm was irradiated for 100 hours. The absolute quantum yield (PLQY) of the film before and after light irradiation was measured, and the PLQY retention (%) after light irradiation was found to be 94%. The PLQY retention (%) after light irradiation was calculated by the following formula (2).
PLQY retention after light irradiation (%) = (PLQY of light conversion layer after light irradiation)/(PLQY of light conversion layer before light irradiation) ×100 (2)
Examples 2 to 12
(preparation of light-emitting particle-containing curable resin compositions (2) to (12) and (C1) to (C3))
Except that the addition amount of the organic-inorganic composite particles was changed to the addition amounts shown in the following tables 1 to 4, the light-emitting particle-containing curable resin compositions (2) to (12) of the present invention and the comparative light-emitting particle-containing curable resin compositions (C1) to (C3) were obtained under the same conditions as those for the preparation of the light-emitting particle-containing curable resin composition (1).
The dispersion stability of the obtained composition is shown in tables 1 to 4.
The photopolymerizable compound and photopolymerization initiator used in each resin composition were as follows.
(photopolymerizable Compound)
PhEA: phenoxyethyl acrylate (product name: light Acrylate PO-A, manufactured by Kagaku Co., ltd.)
DCPA: dimethylol-tricyclodecane diacrylate (product name: light Acrylate DCP-A, manufactured by Kagaku Co., ltd.)
(photopolymerization initiator)
TPO: diphenyl (2, 4, 6-trimethoxybenzoyl) phosphine oxide (product name: omnirad TPO, manufactured by Basv Japanese Co., ltd.)
(chain transfer compound)
PE1: pentaerythritol tetrakis (3-mercaptobutyrate) (product name: karenz MT PE1, manufactured by Zhaoyao electric Co., ltd.)
(preparation of light-converting layers 2 to 12 and C1 to C3)
Except that the light-emitting particle-containing curable resin composition (1) was changed to the compositions (2) to (12) and (C1) to (C3), the light conversion layers 2 to 12 and the comparative light conversion layers C1 to C3 of the present invention were produced under the same conditions as those for the production of the light conversion layer 1. The PLQY retention (%) after light irradiation for the obtained light conversion layers 2 to 12 and C1 to C3 is shown in tables 1 to 4 below.
TABLE 1
Figure BDA0003991136830000641
TABLE 2
Figure BDA0003991136830000651
TABLE 3
Figure BDA0003991136830000652
TABLE 4
Figure BDA0003991136830000661
As shown in examples 1 to 12, the curable resin compositions containing luminescent particles of the present invention were higher in dispersion stability after long-term storage than the compositions containing no organic-inorganic composite particles shown in comparative examples 1 to 3. Further, it was found that PLQY retention (%) after light irradiation was high, and thus stability against light was high in the presence of moisture and oxygen. It is assumed that this is because the organic component on the surface of the light-emitting particle and the organic component on the surface of the organic-inorganic composite particle easily interact with each other, and the organic-inorganic composite particle easily exists in the film in the vicinity of the surface of the light-emitting particle, and therefore the organic-inorganic composite particle functions as a virtual inorganic coating layer, whereby deterioration of the light-emitting particle can be suppressed.
As is clear from the above, the light-converting layers obtained from the light-emitting particle-containing curable resin compositions of examples 1 to 12 were excellent in light-emitting properties and light resistance. Therefore, when the light conversion layer is used to form a light conversion film or a color filter pixel portion of a light-emitting element, excellent light-emitting characteristics can be expected.

Claims (11)

1. A curable resin composition containing luminescent particles, which is characterized by comprising luminescent particles, organic-inorganic composite particles, and a photopolymerizable compound, wherein the luminescent particles comprise semiconductor nanocrystals and an inorganic coating layer that covers the surfaces of the semiconductor nanocrystals and that contains an inorganic material.
2. The luminescent particle-containing curable resin composition according to claim 1, wherein the organic-inorganic composite particles contain a polymer Z having a structural unit represented by the general formula (Z1-1) or (Z1-2),
Figure FDA0003991136820000011
wherein R is 1 、R 2 And R is 3 Each independently represents a hydrogen atom or a methyl group, R Z1 Represents a basic 1-valent group selected from the group consisting of primary amino, secondary amino, tertiary amino, quaternary ammonium group, imino, pyridyl, pyrimidinyl, piperazinyl, piperidinyl, imidazolyl, pyrrolidinyl and imidazolidinyl, X 1 And X 2 Each independently represents-COO-, -OCO-, an alkyl chain having 1 to 8 carbon atoms which may be substituted with a nitrogen atom, or a single bond.
3. The luminescent particle-containing curable resin composition according to claim 1 or 2, wherein the organic-inorganic composite particles comprise a polymer of a silane compound represented by the following general formula (G),
Figure FDA0003991136820000012
wherein R is G1 And R is G2 Each independently represents alkyl, R G3 And R is G4 Each independently represents a hydrogen atom or an alkyl group, n1 represents 0 or 1, and m1 represents an integer of 1 or more.
4. The luminescent particle-containing curable resin composition according to claim 1 or 2,
the semiconductor nanocrystals comprise A, M and X,
the A represents a compound selected from Cs, rb, methyl ammonium, formamidine, ammonium, 2-phenylethylammonium, and pyrrolidine
Figure FDA0003991136820000013
Piperidine->
Figure FDA0003991136820000014
1-butyl-1-methylpiperidine->
Figure FDA0003991136820000015
More than 1 cation selected from the group consisting of tetramethyl ammonium, tetraethyl ammonium, benzyl trimethyl ammonium and benzyl triethyl ammonium,
the M represents a metal ion selected from the group consisting of Pb, sn, ge, bi, sb, ag, in, cu, yb, ti, pd, mn, eu, zr and Tb,
the X represents more than 1 halide ion selected from the group consisting of F, cl, br and I.
5. The luminescent particle-containing curable resin composition according to claim 4, wherein the semiconductor nanocrystals have a perovskite structure.
6. The luminescent particle-containing curable resin composition according to claim 1 or 2, wherein the inorganic coating layer has a siloxane bond.
7. A light conversion layer comprising the polymer containing a luminescent particle-curable resin composition according to claim 1 or 2.
8. A color filter provided with the light conversion layer according to claim 7.
9. A wavelength conversion film comprising the light conversion layer according to claim 7.
10. A light-emitting element comprising the color filter according to claim 8.
11. A light-emitting element comprising the wavelength conversion film according to claim 9.
CN202211585929.6A 2021-12-23 2022-12-09 Curable resin composition containing luminescent particles, light-converting layer, color filter, wavelength conversion film, and light-emitting element Pending CN116375930A (en)

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