WO2023085061A1 - 樹脂膜及び表示装置 - Google Patents
樹脂膜及び表示装置 Download PDFInfo
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- WO2023085061A1 WO2023085061A1 PCT/JP2022/039471 JP2022039471W WO2023085061A1 WO 2023085061 A1 WO2023085061 A1 WO 2023085061A1 JP 2022039471 W JP2022039471 W JP 2022039471W WO 2023085061 A1 WO2023085061 A1 WO 2023085061A1
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/0001—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems
- G02B6/0011—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems the light guides being planar or of plate-like form
- G02B6/0033—Means for improving the coupling-out of light from the light guide
- G02B6/005—Means for improving the coupling-out of light from the light guide provided by one optical element, or plurality thereof, placed on the light output side of the light guide
- G02B6/0053—Prismatic sheet or layer; Brightness enhancement element, sheet or layer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
-
- C—CHEMISTRY; METALLURGY
- 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
- 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
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- 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
- C08F8/00—Chemical modification by after-treatment
-
- C—CHEMISTRY; METALLURGY
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/372—Sulfides, e.g. R-(S)x-R'
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/372—Sulfides, e.g. R-(S)x-R'
- C08K5/3725—Sulfides, e.g. R-(S)x-R' containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/375—Thiols containing six-membered aromatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/62—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing gallium, indium or thallium
- C09K11/621—Chalcogenides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/70—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
- C09K11/881—Chalcogenides
- C09K11/883—Chalcogenides with zinc or cadmium
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
Definitions
- the present invention relates to a resin film containing semiconductor particles and a display device containing the resin film.
- Patent Document 1 describes a curable resin composition containing semiconductor particles, a polymer having a specific structural unit, a polymerizable unsaturated compound and a polymerization initiator, and a cured film formed using the curable resin composition. is described. This cured film is used as a wavelength conversion film or a light-emitting layer of a light-emitting display device.
- a cured film formed from a conventional curable resin composition has room for improvement in resistance to light (hereinafter also referred to as "light resistance").
- light resistance hereinafter also referred to as "light resistance”
- An object of the present invention is to provide a resin film containing semiconductor particles and having good light resistance, and a display device including the resin film.
- the present invention provides a resin film and a display device described below.
- a resin film containing semiconductor particles (A) When the resin film was subjected to a first exposure test in which the exposure amount was 200 mJ/cm 2 (based on the irradiation wavelength of 365 nm) in the atmosphere, the first emission intensity maintenance rate R1 represented by the following formula was obtained. is 95% or more, the resin film.
- First emission intensity maintenance rate R1 (%) 100 ⁇ (emission intensity after the first exposure test)/(emission intensity before the first exposure test) [2]
- the resin film subjected to the first exposure test was subjected to a second exposure test in which the exposure amount was 200 mJ/cm 2 (standard irradiation wavelength: 365 nm) in the atmosphere, the following formula was obtained:
- Second emission intensity maintenance rate R2 (%) 100 ⁇ (emission intensity after second exposure test)/(emission intensity after first exposure test) [3]
- the content of the polymerizable compound (C) and the polymerization initiator (D) in the resin composition is each 0.01% by mass or less with respect to the total solid content of the resin composition.
- the contents of the polymerizable compound (C) and the polymerization initiator (D) are each 0% by mass with respect to the total solid content of the resin composition, [ 4].
- a display device comprising the resin film according to any one of [1] to [6].
- the resin film according to the present invention (hereinafter also simply referred to as "resin film”) contains semiconductor particles (A), and when the first exposure test is performed, the first emission intensity maintenance rate R1 shown by the following formula is obtained. is 95% or more.
- First emission intensity maintenance rate R1 (%) 100 ⁇ (emission intensity after first exposure test)/(emission intensity before first exposure test)
- the resin film has a high emission intensity maintenance rate (first emission intensity maintenance rate R1) and good light resistance even after the first exposure test in which ultraviolet rays are irradiated.
- the resin film exhibits a first emission intensity retention rate R1 of preferably 96% or more, more preferably 97% or more, still more preferably 98% or more, and even more preferably 99% or more.
- the first exposure test is a test in which the resin film is irradiated with ultraviolet rays.
- the ultraviolet irradiation in the first exposure test is performed in the atmosphere under the condition of an exposure amount of 200 mJ/cm 2 (wavelength of 365 nm standard).
- the amount of exposure is represented by the product of the irradiation intensity (mW/cm 2 ) of ultraviolet rays and the irradiation time (s).
- the irradiation intensity of the ultraviolet rays irradiated in the first exposure test is, for example, 10 mW/cm 2 or more and 100 mW/cm 2 or less. If the exposure amount is the same even if the irradiation intensity and/or the irradiation time are different, the emission intensity before and after the first exposure test and the first emission intensity maintenance rate R1 usually have the same value or substantially the same value.
- the emission intensity of the resin film before the first exposure test is preferably 120 ⁇ W or higher, more preferably 150 ⁇ W or higher, even more preferably 170 ⁇ W or higher, even more preferably 180 ⁇ W or higher, and particularly preferably 190 ⁇ W or higher.
- the emission intensity of the resin film after the first exposure test is preferably 120 ⁇ W or more, more preferably 150 ⁇ W or more, even more preferably 170 ⁇ W or more, even more preferably 180 ⁇ W or more, and particularly preferably 190 ⁇ W or more.
- the luminescence intensity of the resin film before and after the first exposure test and the luminescence intensity of the resin film after the second exposure test described later are measured according to the measurement method described in Examples described later.
- the resin film preferably has a second emission intensity maintenance rate R2 of 85% or more, which is represented by the following formula when the second exposure test is performed on the resin film that has been subjected to the first exposure test.
- the resin film exhibits a second emission intensity maintenance rate R2 of more preferably 90% or more, still more preferably 94% or more, even more preferably 96% or more, particularly preferably 98% or more, and most preferably 99% or more.
- Second emission intensity maintenance rate R2 (%) 100 ⁇ (emission intensity after second exposure test)/(emission intensity after first exposure test)
- the second exposure test is a test in which the resin film after the first exposure test is irradiated with ultraviolet rays.
- the ultraviolet irradiation in the second exposure test is performed in the air under the condition of an exposure amount of 200 mJ/cm 2 (wavelength of 365 nm standard).
- the amount of exposure is represented by the product of the irradiation intensity (mW/cm 2 ) of ultraviolet rays and the irradiation time (s).
- the irradiation intensity and irradiation time of the ultraviolet rays irradiated in the second exposure test are the same as those in the first exposure test.
- the emission intensity after the first exposure test and after the second exposure test, and the second emission intensity maintenance rate R2 are usually the same value or substantially essentially the same value.
- the emission intensity of the resin film after the second exposure test is preferably 120 ⁇ W or more, more preferably 150 ⁇ W or more, even more preferably 170 ⁇ W or more, even more preferably 180 ⁇ W or more, and particularly preferably 190 ⁇ W or more.
- the resin film is preferably formed from a resin composition containing semiconductor particles (A) and resin (B).
- a resin film formed from the resin composition contains semiconductor particles (A) and a resin (B).
- the resin film is not particularly limited, but can be produced by a method described in ⁇ Method for producing resin film>> described later.
- the resin composition contains semiconductor particles (A) and a resin (B).
- the semiconductor particles (A) emit light of a wavelength different from the primary light, and preferably convert the wavelength of blue light, which is the primary light, into a wavelength of light of a different color.
- the semiconductor particles (A) preferably emit green or red light, and more preferably absorb blue light and emit green or red light.
- the semiconductor particles (A) may be, for example, red light-emitting semiconductor particles that emit light having an emission peak wavelength in a wavelength range of 605 nm or more and 665 nm or less, and have an emission peak wavelength in a wavelength range of 500 nm or more and 560 nm or less. They may be green light-emitting semiconductor particles that emit light, or blue light-emitting semiconductor particles that emit light having an emission peak wavelength in the wavelength range of 420 nm or more and 480 nm or less.
- the semiconductor particles (A) are preferably red-emitting semiconductor particles and/or green-emitting semiconductor particles.
- the emission peak wavelength of the semiconductor particles (A) can be confirmed, for example, in the emission spectrum measured using an ultraviolet-visible spectrophotometer.
- the full width at half maximum of the emission spectrum of the semiconductor particles (A) is preferably 60 nm or less, more preferably 55 nm or less, still more preferably 50 nm or less, and particularly preferably 45 nm or less. Thereby, light with higher color purity can be emitted.
- the lower limit of the full width at half maximum of the emission spectrum of the semiconductor particles (A) is not particularly limited, it may be 5 nm or more, or 15 nm or more.
- the semiconductor particles (A) are particles made of semiconductor crystals, preferably nanoparticles made of semiconductor crystals.
- the semiconductor particles (A) include particles of semiconductor quantum dots (hereinafter also referred to as “quantum dots”) and compounds having a perovskite crystal structure (hereinafter also referred to as “perovskite compounds”), Quantum dots are more preferred.
- the average particle size of the quantum dots is, for example, 0.5 nm or more and 20 nm or less, preferably 1 nm or more and 15 nm or less (for example, 2 nm or more and 15 nm or less). Since the energy state of quantum dots depends on their size, it is possible to freely select the emission wavelength by changing the particle diameter. For example, in the case of quantum dots composed only of CdSe, the peak wavelengths of the emission spectrum when the particle diameters are 2.3 nm, 3.0 nm, 3.8 nm, and 4.6 nm are 528 nm, 570 nm, 592 nm, and 637 nm, respectively. is.
- the average particle size of the semiconductor particles (A) can be measured using a scanning transmission electron microscope.
- Quantum dots are, for example, selected from the group consisting of Group 2 elements, Group 11 elements, Group 12 elements, Group 13 elements, Group 14 elements, Group 15 elements and Group 16 elements of the periodic table. It can be composed of a semiconductor material containing a species or two or more elements.
- semiconductor materials that can form quantum dots include: Compounds of Group 14 elements and Group 16 elements such as SnS 2 , SnS, SnSe, SnTe, PbS, PbSe, PbTe; Compounds of Group 13 elements and Group 15 elements such as GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, InGaN, InGaP; Group 13 elements and Group 16 elements such as Ga2O3 , Ga2S3 , Ga2Se3 , Ga2Te3 , In2O3 , In2S3 , In2Se3 , In2Te3 a compound with; Group 12 and Group 16 elements such as ZnO, ZnS, ZnSe, ZnTe, CdO, CdS, CdSe, CdTe, HgO, HgS, HgSe, HgTe, ZnSTe, ZnSeS, ZnSeTe, C, C
- Quantum dots may have a single-layer structure made of a single semiconductor material, or the surface of a core particle (core layer) made of a single semiconductor material is composed of one or more semiconductors different from this. It may have a core-shell structure covered with a coating layer (shell layer) made of a material. In the latter case, the semiconductor material forming the shell layer usually has a higher bandgap energy than the semiconductor material forming the core layer.
- a quantum dot may have two or more kinds of shell layers.
- the shape of the quantum dot is not particularly limited, and may be, for example, spherical or substantially spherical, rod-like, disk-like, or the like.
- a perovskite compound is a compound having A, B and X as components and having a perovskite crystal structure.
- A is a component located at each vertex of a hexahedron centered on B in the perovskite crystal structure, and is a monovalent cation.
- X represents a component located at each vertex of an octahedron centered on B in the perovskite crystal structure, and is at least one type of ion selected from the group consisting of halide ions and thiocyanate ions.
- B is a metal ion, which is a component located at the center of the hexahedron with A at its vertex and the octahedron with X at its vertex in the perovskite crystal structure.
- the average particle size of the semiconductor particles made of the perovskite compound is preferably 3 nm or more, more preferably 4 nm or more, still more preferably 5 nm or more, and usually 50 nm or less, from the viewpoint of maintaining the crystal structure well.
- the perovskite compound having A, B and X as components is not particularly limited, and may be a compound having any of a three-dimensional structure, a two-dimensional structure and a pseudo-two-dimensional structure.
- perovskite compounds are represented by ABX (3+ ⁇ ) .
- perovskite compounds are represented by A 2 BX (4+ ⁇ ) .
- ⁇ is a number that can be appropriately changed according to the charge balance of B, and is from -0.7 to 0.7.
- Preferred specific examples of perovskite compounds having a two-dimensional perovskite-type crystal structure represented by A 2 BX (4+ ⁇ ) include: ( C4H9NH3 ) 2PbBr4 , ( C4H9NH3 ) 2PbCl4 , ( C4H9NH3 ) 2PbI4 , ( C7H15NH3 ) 2PbBr4 , ( C 7H15NH3 ) 2PbCl4 , ( C7H15NH3 ) 2PbI4 , ( C4H9NH3 ) 2Pb (1-a) LiaBr ( 4 + ⁇ ) (0 ⁇ a ⁇ 0.
- the resin composition may contain only one type of semiconductor particles (A) that emit light of a specific wavelength when emitted from a light source, or may contain two types of semiconductor particles (A) that emit light of different wavelengths. It may contain a combination of more than one species.
- the resin composition may contain only one type of quantum dot that emits light of a specific wavelength by light emitted from the light source, and two or more types of quantum dots that emit light of different wavelengths are combined. may contain. Examples of the light of the specific wavelength include red light, green light, and blue light.
- the content of the semiconductor particles (A) in the resin composition is, for example, 1% by mass or more and 60% by mass or less, preferably 10% by mass or more and 50% by mass or less, relative to the total solid content of the resin composition. It is preferably 10% by mass or more and 40% by mass or less, more preferably 10% by mass or more and 30% by mass or less, and even more preferably 10% by mass or more and 20% by mass or less.
- the total amount of solids means the total amount of components contained in the resin composition, excluding the solvent (G).
- the content in the solid content of the resin composition can be measured by known analysis means such as liquid chromatography or gas chromatography. The content of each component in the solid content of the resin composition may be calculated from the formulation when the resin composition is prepared.
- Organic ligand (F) The semiconductor particles (A) may be present in the resin composition in a coordinated state with an organic ligand.
- semiconductor particles to which organic ligands are coordinated are also referred to as ligand-containing semiconductor particles.
- the organic ligand that coordinates to the semiconductor particles is, for example, an organic compound having a polar group that exhibits coordinating ability to the semiconductor particles.
- the organic ligand may be an organic ligand added due to synthetic restrictions of the ligand-containing semiconductor particles or for stabilization.
- ligand-containing semiconductor particles contain hexanoic acid as an organic ligand from the viewpoint of particle size control, and an organic ligand for post-synthesis stabilization.
- the organic ligands can coordinate, for example, to the surfaces of the semiconductor particles (A).
- the resin composition can contain one or more organic ligands (F).
- a resin film formed from a resin composition containing an organic ligand (F) contains an organic ligand (F).
- the polar group of the organic ligand is, for example, preferably at least one group selected from the group consisting of a thiol group (--SH), a carboxy group (--COOH) and an amino group ( --NH.sub.2 ).
- a polar group selected from the group can be advantageous in enhancing coordination to the semiconductor particles (A).
- a high coordinating property can contribute to improving the stability and dispersibility of the semiconductor particles (A) in the resin composition, improving the emission intensity of the resin film, and the like.
- the polar group is more preferably at least one group selected from the group consisting of thiol groups and carboxy groups.
- the organic ligand (F) may have one or more polar groups.
- the organic ligand is, for example, the following formula (X): X A -R X (X) It can be an organic compound represented by In the formula, X A is the above polar group, and R X is a monovalent hydrocarbon group optionally containing a heteroatom (N, O, S, halogen atom, etc.).
- the hydrocarbon group may have one or more unsaturated bonds such as carbon-carbon double bonds.
- the hydrocarbon group may have a linear, branched or cyclic structure.
- the number of carbon atoms in the hydrocarbon group is, for example, 1 or more and 40 or less, and may be 1 or more and 30 or less.
- the group R X may contain a polar group.
- the polar group the above description of the polar group XA is cited.
- organic ligands having a carboxy group as the polar group X A include formic acid, acetic acid, propionic acid, and saturated or unsaturated fatty acids.
- saturated or unsaturated fatty acids include butyric acid, pentanoic acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, behenic acid, and lignoserine.
- saturated fatty acids such as acids; monounsaturated fatty acids such as myristoleic acid, palmitoleic acid, oleic acid, icosenoic acid, erucic acid, nervonic acid; linoleic acid, ⁇ -linolenic acid, ⁇ -linolenic acid, stearic acid, dihomo- It contains polyunsaturated fatty acids such as ⁇ -linolenic acid, arachidonic acid, eicosatetraenoic acid, docosadienoic acid and adrenic acid (docosatetraenoic acid).
- a specific example of the organic ligand having a thiol group or an amino group as the polar group XA is the above-exemplified organic ligand having a carboxy group as the polar group XA , in which the carboxy group is replaced with a thiol group or an amino group. Contains organic ligands.
- examples of the organic ligand represented by formula (X) include compound (F-1) and compound (F-2).
- Compound (F-1) is a compound having a first functional group and a second functional group.
- the first functional group is a carboxy group (--COOH) and the second functional group is a carboxy group or a thiol group (--SH). Since the compound (F-1) has a carboxy group and/or a thiol group, it can serve as a ligand that coordinates to the semiconductor particles (A).
- Including the compound (F-1) in the resin composition is advantageous for improving the stability and dispersibility of the semiconductor particles (A) and the emission intensity of the resin film.
- the resin composition may contain only one kind of compound (F-1) or two or more kinds thereof.
- Compound (F-1) is a compound represented by the following formula (F-1a).
- Compound (F-1) may be an acid anhydride of the compound represented by formula (F-1a).
- RB represents a divalent hydrocarbon group. When multiple RBs are present, they may be the same or different.
- the hydrocarbon group may have one or more substituents. When there are multiple substituents, they may be the same or different, and they may be bonded together to form a ring with the atoms to which each is attached.
- -CH 2 - contained in the above hydrocarbon group may be replaced with at least one of -O-, -S-, -SO 2 -, -CO- and -NH-.
- p represents an integer from 1 to 10; ]
- Examples of the divalent hydrocarbon group represented by RB include chain hydrocarbon groups, alicyclic hydrocarbon groups and aromatic hydrocarbon groups.
- chain hydrocarbon groups include linear or branched alkanediyl groups, which usually have 1 to 50 carbon atoms, preferably 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms.
- the alicyclic hydrocarbon group includes, for example, a monocyclic or polycyclic cycloalkanediyl group, which usually has 3 to 50 carbon atoms, preferably 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms. is.
- the aromatic hydrocarbon group includes, for example, a monocyclic or polycyclic arenediyl group, which usually has 6 to 20 carbon atoms.
- Examples of the substituent that the hydrocarbon group may have include an alkyl group having 1 to 50 carbon atoms, a cycloalkyl group having 3 to 50 carbon atoms, an aryl group having 6 to 20 carbon atoms, a carboxy group, an amino groups, halogen atoms, and the like.
- the substituent which the hydrocarbon group may have is preferably a carboxy group, an amino group or a halogen atom.
- —CH 2 — contained in the hydrocarbon group is replaced with at least one of —O—, —CO— and —NH—
- —CH 2 — is preferably replaced with —CO— and —NH—. It is at least one, more preferably -NH-.
- p is preferably 1 or 2;
- Examples of compounds represented by formula (F-1a) include compounds represented by formulas (1-1) to (1-9) below.
- Specific examples of the compound represented by formula (F-1a) by chemical name include mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutanoic acid, 4-mercaptobutanoic acid, mercaptosuccinic acid, mercaptostearic acid, mercaptooctanoic acid, 4-mercaptobenzoic acid, 2,3,5,6-tetrafluoro-4-mercaptobenzoic acid, L-cysteine, N-acetyl-L-cysteine, 3-mercapto 3-methoxybutyl propionate, 3-mercapto-2-methylpropionic acid and the like. Among them, 3-mercaptopropionic acid and mercaptosuccinic acid are preferred.
- Another example of the compound (F-1) is a polyvalent carboxylic acid compound, preferably a compound represented by the above formula (F-1a), wherein —SH in formula (F-1a) is a carboxy group ( —COOH) is substituted with a compound (F-1b).
- Examples of the compound (F-1b) include the following compounds. Succinic acid, glutaric acid, adipic acid, octafluoroadipic acid, azelaic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, dodecafluorosuberic acid, 3-ethyl- 3-methylglutaric acid, hexafluoroglutaric acid, trans-3-hexenedioic acid, sebacic acid, hexadecafluorosebacic acid, acetylenedicarboxylic acid, trans-aconitic acid, 1,3-adamantanedicarboxylic acid, bicyclo [2.2 .2] octane-1,4-dicarboxylic acid, cis-4-cyclohe
- the molecular weight of the compound (F-1) is preferably 3000 or less, more preferably 2500 or less, and still more preferably 2000. 1000 or less, particularly preferably 800 or less, and most preferably 500 or less.
- the molecular weight of compound (F-1) is usually 100 or more.
- the above molecular weight may be a number average molecular weight or a weight average molecular weight.
- the number-average molecular weight and weight-average molecular weight are the number-average molecular weight and weight-average molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC), respectively.
- At least part of the molecules of the compound (F-1) in the resin composition are preferably coordinated to the semiconductor particles (A), and all or substantially all of the molecules are coordinated to the semiconductor particles (A).
- the resin composition preferably contains the compound (F-1) coordinated to the semiconductor particles (A), but together with the compound (F-1) coordinated to the semiconductor particles (A), It may contain a compound (F-1) that is not coordinated to the semiconductor particles (A).
- Inclusion of the compound (F-1) coordinated to the semiconductor particles (A) can be advantageous from the viewpoint of improving the stability and dispersibility of the semiconductor particles (A) and the emission intensity of the resin film.
- the compound (F-1) can usually coordinate to the semiconductor particles (A) via the first functional group and/or the second functional group.
- the compound (F-1) can be coordinated to the surface of the semiconductor particle (A), for example.
- the content ratio of the compound (F-1) to the semiconductor particles (A) in the resin composition is preferably 0.001 or more and 1 or less, It is more preferably 0.01 or more and 0.5 or less, and still more preferably 0.02 or more and 0.45 or less.
- the content ratio is within this range, it can be advantageous from the viewpoint of improving the stability and dispersibility of the semiconductor particles (A) and the emission intensity of the resin film.
- the content of the compound (F-1) in the resin composition improves the stability and dispersibility of the semiconductor particles (A) and the emission intensity of the resin film. From the viewpoint of increasing the solid % or more and 10 mass % or less, more preferably 0.5 mass % or more and 10 mass % or less, and particularly preferably 0.5 mass % or more and 8 mass % or less.
- the compound (F-2) is a compound different from the compound (F-1), containing a polyalkylene glycol structure and having a polar group at the end of the molecule.
- the molecular terminal is preferably the terminal of the longest carbon chain (a carbon atom in the carbon chain may be replaced with another atom such as an oxygen atom) in the compound (F-2).
- the resin composition may contain only one type of compound (F-2), or may contain two or more types.
- the resin composition may contain the compound (F-1) or the compound (F-2), or may contain the compound (F-1) and the compound (F-2).
- the compound containing a polyalkylene glycol structure and having the first functional group and the second functional group belongs to the compound (F-1).
- the polyalkylene glycol structure is the following formula:
- R 1 C is an alkylene group such as an ethylene group and a propylene group.
- compound (F-2) include polyalkylene glycol-based compounds represented by the following formula (F-2a).
- X is a polar group
- Y is a monovalent group
- Z C is a divalent or trivalent group.
- n is an integer of 2 or more.
- At least part of the molecules of the compound (F-2) in the resin composition are preferably coordinated to the semiconductor particles (A), and all or substantially all of the molecules are coordinated to the semiconductor particles (A).
- the resin composition preferably contains the compound (F-2) coordinated to the semiconductor particles (A), but together with the compound (F-2) coordinated to the semiconductor particles (A), It may contain a compound (F-2) that is not coordinated to the semiconductor particles (A).
- the compound (F-2a) can usually be coordinated to the semiconductor particles (A) via the polar group X.
- the compound (F-2a) may be coordinated to the semiconductor particle (A) via the polar group of the group Y or via the polar group X and the polar group of the group Y. can.
- the compound (F-2) can be coordinated to the surface of the semiconductor particle (A), for example.
- the polar group X is preferably at least one group selected from the group consisting of a thiol group (--SH), a carboxy group (--COOH) and an amino group ( --NH.sub.2 ).
- a polar group selected from the group can be advantageous in enhancing coordination to the semiconductor particles (A).
- the polar group X is at least one group selected from the group consisting of thiol groups and carboxy groups. It is more preferable to have
- the group Y is a monovalent group.
- the group Y is not particularly limited, and may be a monovalent hydrocarbon group optionally having a substituent (N, O, S, halogen atom, etc.).
- the number of carbon atoms in the hydrocarbon group is, for example, 1 or more and 12 or less.
- the hydrocarbon group may have an unsaturated bond.
- Examples of the group Y include an alkyl group having 1 to 12 carbon atoms having a linear, branched or cyclic structure; an alkoxy group having 1 to 12 carbon atoms having a linear, branched or cyclic structure, and the like. mentioned.
- the number of carbon atoms in the alkyl group and alkoxy group is preferably 1 or more and 8 or less, more preferably 1 or more and 6 or less, and still more preferably 1 or more and 4 or less.
- the group Y is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms, and is preferably a linear alkoxy group having 1 to 4 carbon atoms. more preferred.
- Group Y may contain a polar group.
- the polar group includes at least one group selected from the group consisting of a thiol group (--SH), a carboxy group (--COOH) and an amino group ( --NH.sub.2 ).
- the compound containing the polyalkylene glycol structure and having the first functional group and the second functional group belongs to the compound (F-1).
- the polar group is preferably arranged at the end of the group Y.
- the group Z C is a divalent or trivalent group.
- the group Z C is not particularly limited, and may be a divalent or trivalent hydrocarbon group optionally containing a heteroatom (N, O, S, halogen atom, etc.).
- the carbon number of the hydrocarbon group is, for example, 1 or more and 24 or less.
- the hydrocarbon group may have an unsaturated bond.
- the divalent group Z C is an alkylene group having 1 to 24 carbon atoms having a linear, branched or cyclic structure; and 1 or more carbon atoms having a linear, branched or cyclic structure.
- Examples include alkenylene groups of 24 or less.
- the number of carbon atoms in the alkyl group and alkenylene group is preferably 1 or more and 12 or less, more preferably 1 or more and 8 or less, and still more preferably 1 or more and 4 or less.
- Examples of the trivalent group Z C include groups obtained by removing one hydrogen atom from the above divalent group Z C .
- the group Z C may have a branched structure.
- the group Z C having a branched structure has a polyalkylene glycol structure represented by the above formula (F-2a) in a branched chain different from the branched chain containing the polyalkylene glycol structure represented by the above formula (F-2a). may have another polyalkylene glycol structure.
- the group Z C is preferably a linear or branched alkylene group having 1 to 6 carbon atoms, and is a linear alkylene group having 1 to 4 carbon atoms. is more preferred.
- R C is an alkylene group, preferably a linear or branched alkylene group having 1 to 6 carbon atoms, and a linear alkylene group having 1 to 4 carbon atoms. is more preferable.
- n in formula (F-2a) is an integer of 2 or more, preferably 2 or more and 540 or less, more preferably 2 or more and 120 or less, and still more preferably 2 or more and 60 or less.
- the molecular weight of the compound (F-2) can be, for example, about 150 to 10,000, and from the viewpoint of improving the stability and dispersibility of the semiconductor particles (A) and the emission intensity of the resin film, the molecular weight is 150 to 5,000. and more preferably 150 or more and 4000 or less.
- the above molecular weight may be a number average molecular weight or a weight average molecular weight.
- the number-average molecular weight and weight-average molecular weight are the number-average molecular weight and weight-average molecular weight in terms of standard polystyrene measured by GPC, respectively.
- the content ratio of the compound (F-2) to the semiconductor particles (A) in the resin composition is preferably 0.001 or more and 2 or less, in terms of mass ratio. It is more preferably 0.01 or more and 1.5 or less, still more preferably 0.1 or more and 1 or less. When the content ratio is within this range, it can be advantageous from the viewpoint of improving the stability and dispersibility of the semiconductor particles (A) and the emission intensity of the resin film.
- the content of the compound (F-2) in the resin composition improves the stability and dispersibility of the semiconductor particles (A) and the emission intensity of the resin film. From the viewpoint of increasing It is 15 mass % or less, still more preferably 2 mass % or more and 10 mass % or less.
- the content ratio of the compound (F-2) to the compound (F-1) in the resin composition is preferably a mass ratio. is 1 or more and 50 or less, more preferably 5 or more and 40 or less, and still more preferably 10 or more and 25 or less. When the content ratio is within this range, it can be advantageous from the viewpoint of improving the stability and dispersibility of the semiconductor particles (A) and the emission intensity of the resin film.
- the resin composition may further contain a compound (F-3), which is a compound other than the compound (F-1) and the compound (F-2) and has coordinating ability to the semiconductor particles (A).
- a compound (F-3) include organic acids, organic amine compounds, thiol compounds and the like.
- the compound (F-3) may be a silicone oil or the like modified with a carboxy group and an amino group or a thiol group, and by including such a compound (F-3) in the resin composition, a resin film properties (such as contact angle, surface properties such as surface tension, etc.) can be adjusted.
- the compound (F-3), the resin (B), the polymerizable compound (C), the polymerization initiator (D), the polymerization initiation aid (D1), Light scattering agent (E), solvent (G), antioxidant (H) and leveling agent (I) are not included.
- the content ratio of the compound (F-3) to the semiconductor particles (A) in the resin composition is preferably 0.001 or more and 2 or less, in terms of mass ratio. It is more preferably 0.01 or more and 1.5 or less, still more preferably 0.1 or more and 1 or less. When the content ratio is within this range, it can be advantageous from the viewpoint of improving the stability and dispersibility of the semiconductor particles (A) and the emission intensity of the resin film.
- the content of the compound (F-3) in the resin composition improves the stability and dispersibility of the semiconductor particles (A) and the emission intensity of the resin film. From the viewpoint of increasing the solid % or more and 15 mass % or less, and still more preferably 0.2 mass % or more and 10 mass % or less.
- the content ratio of the organic ligand (F) to the semiconductor particles (A) in the resin composition is preferably 0.001 or more in mass ratio. 1 or less, more preferably 0.01 or more and 0.8 or less, and still more preferably 0.02 or more and 0.5 or less. When the content ratio is within this range, it can be advantageous from the viewpoint of improving the stability and dispersibility of the semiconductor particles (A) and the emission intensity of the resin film.
- the content of the organic ligand (F) referred to here is the total content of all organic ligands contained in the resin composition.
- the total content of the semiconductor particles (A) and the organic ligand (F) in the resin composition is determined from the viewpoint of improving the stability and dispersibility of the semiconductor particles (A) and the emission intensity of the resin film. It is preferably 10% by mass or more and 75% by mass or less, more preferably 12% by mass or more and 70% by mass or less, and still more preferably 15% by mass or more and 65% by mass or less, relative to the total solid content of the product.
- Resin (B) may contain one or more resins.
- the resin (B) include the following resins [K1] to [K4].
- Resin [K1] at least one (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter also referred to as "(a)"), and copolymerizable with (a) A copolymer with a monomer (c) (but different from (a)) (hereinafter also referred to as "(c)”);
- Resin [K3] a resin obtained by reacting (a) with a copolymer of (b) and (c);
- (a) includes, for example, (meth)acrylic acid, crotonic acid, and unsaturated monocarboxylic acids such as o-, m-, and p-vinylbenzoic acid; Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexenedicarboxylic acid; methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-eth
- (meth)acrylic acid as used herein means acrylic acid and/or methacrylic acid.
- (meth)acryloyl means acrylic acid and/or methacrylic acid.
- (meth)acrylate means acrylic acid and/or methacrylic acid.
- (b) is, for example, a monomer having a cyclic ether structure having 2 to 4 carbon atoms (eg, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond; be.
- (b) is preferably a monomer having a cyclic ether structure with 2 to 4 carbon atoms and a (meth)acryloyloxy group.
- Examples of (b) include glycidyl (meth)acrylate, ⁇ -methylglycidyl (meth)acrylate, ⁇ -ethylglycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p -vinylbenzyl glycidyl ether, ⁇ -methyl-o-vinylbenzyl glycidyl ether, ⁇ -methyl-m-vinylbenzyl glycidyl ether, ⁇ -methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyloxymethyl)styrene , 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxy
- (c) includes, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth) Acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 2,6 ]decane-8-yl (meth)acrylate (in the technical field, it is commonly referred to as "dicyclopentanyl (meth)acrylate”.
- tricyclodecyl (meth)acrylate tricyclo[5.2.1.0 2,6 ]decen-8-yl (meth)acrylate (in the art, it is commonly called “dicyclopentenyl (meth)acrylate”.
- dicyclopentanyloxyethyl (meth)acrylate isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth)acrylic acid ester such as (meth)acrylate; Hydroxy group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5- Hydroxybicyclo[2.2.1]hept-2-ene, 5-
- styrene vinyltoluene
- N-phenylmaleimide N-cyclohexylmaleimide
- N-benzylmaleimide bicyclo[2.2.1]hept- 2-ene and the like are preferred.
- the ratio of the structural units of the resin [K1] is within the above range, the storage stability of the resin composition and the solvent resistance of the obtained resin film tend to be excellent.
- the resin (B) contains a structural unit derived from (a), it may contain two or more structural units derived from (a). In this case, the ratio of the structural units derived from (a) (Content on a molar basis) is the sum of the ratios of the respective structural units. The same applies to structural units derived from other monomers such as (b) and (c).
- the resin [K1] is, for example, the method described in the document "Experimental Methods for Polymer Synthesis” (written by Takayuki Otsu, Published by Kagaku Dojin, 1st Edition, 1st Edition, March 1, 1972) and the document It can be manufactured with reference to the cited document described in .
- a polymerization initiator e.g., a polymerization initiator, a solvent, and the like are placed in a reaction vessel, and, for example, by replacing oxygen with nitrogen, a deoxygenated atmosphere is created, and while stirring, A method of heating and keeping warm can be mentioned.
- the polymerization initiator, solvent, and the like to be used are not particularly limited, and those commonly used in the field can be used.
- polymerization initiators include azo compounds (2,2′-azobisisobutyronitrile, 2,2′-azobis(2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.).
- the solvent any solvent can be used as long as it dissolves each monomer, and examples of the solvent (G) that may be contained in the resin composition include the solvents described later.
- the obtained copolymer may be used as a solution after the reaction as it is, may be used as a concentrated or diluted solution, or may be taken out as a solid (powder) by a method such as reprecipitation. may be used. If the solvent (G) described below is used as the solvent for polymerization, the solution after the reaction can be used as it is for preparing the resin composition, so that the production process of the resin composition can be simplified.
- Resin [K2] is a copolymer of (a) and (c), and the cyclic ether having 2 to 4 carbon atoms of (b) is added to the carboxylic acid and/or carboxylic anhydride of (a). It can be manufactured by First, a copolymer of (a) and (c) is produced in the same manner as the method for producing resin [K1]. In this case, the ratio of structural units derived from each is preferably the same as the ratio described for resin [K1].
- part of the carboxylic acid and/or carboxylic acid anhydride derived from (a) in the copolymer is reacted with the cyclic ether having 2 to 4 carbon atoms of (b).
- the atmosphere in the flask was replaced from nitrogen to air, and (b) a reaction catalyst (e.g., organic phosphorus compound, metal complex, amine compound, etc.) and a polymerization inhibitor (e.g., hydroquinone, etc.), for example, at a temperature of 60° C. or higher and 130° C. or lower for 1 to 10 hours to produce the resin [K2].
- a reaction catalyst e.g., organic phosphorus compound, metal complex, amine compound, etc.
- a polymerization inhibitor e.g., hydroquinone, etc.
- the amount of (b) used is preferably 5 mol or more and 80 mol or less per 100 mol of (a), It is more preferably 10 mol or more and 75 mol or less. Within this range, the storage stability of the resin composition and the solvent resistance, heat resistance and mechanical strength of the resulting resin film tend to be well balanced.
- the amine compound as the reaction catalyst for example, an aliphatic tertiary amine compound or an aliphatic quaternary ammonium salt compound can be used. Specific examples thereof include tris(dimethylaminomethyl)phenol, triethylamine, tetrabutylammonium bromide, tetrabutylammonium chloride and the like.
- the reaction catalyst is preferably an organophosphorus compound.
- the amount of the reaction catalyst used is preferably 0.001 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the total amount of (a), (b) and (c).
- the amount of the polymerization inhibitor used is preferably 0.001 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the total amount of (a), (b) and (c).
- Reaction conditions such as the preparation method, reaction temperature and time can be appropriately adjusted in consideration of the production equipment and the amount of heat generated by polymerization.
- the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.
- a copolymer of (b) and (c) is obtained in the same manner as in the method for producing resin [K1] described above.
- the obtained copolymer may be used as a solution after the reaction as it is, may be used as a concentrated or diluted solution, or may be converted into a solid (powder) by a method such as reprecipitation. You may use what was taken out as.
- the ratio of structural units derived from (b) and (c) to the total number of moles of all structural units constituting the copolymer is, respectively, Structural units derived from (b); 5 mol% or more and 95 mol% or less Structural units derived from (c); preferably 5 mol% or more and 95 mol% or less, Structural units derived from (b): 10 mol % or more and 90 mol % or less Structural units derived from (c): More preferably 10 mol % or more and 90 mol % or less.
- Resin [K3] is prepared by adding a carboxylic acid or It can be obtained by reacting a carboxylic acid anhydride.
- the amount of (a) to be reacted with the copolymer is preferably 5 mol or more and 80 mol or less per 100 mol of (b).
- Resin [K4] is a resin obtained by reacting resin [K3] with a carboxylic acid anhydride.
- the hydroxy group generated by the reaction of the cyclic ether with the carboxylic acid or carboxylic anhydride is reacted with the carboxylic anhydride.
- carboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, and 3,4,5,6-tetrahydrophthalic anhydride.
- the amount of carboxylic acid anhydride to be used is preferably 0.5 to 1 mol per 1 mol of (a).
- resin [K1], resin [K2], resin [K3] and resin [K4] include benzyl (meth)acrylate/(meth)acrylic acid copolymer, styrene/(meth)acrylic acid copolymer, etc.
- Resin (B) preferably contains at least one selected from the group consisting of resin [K2], resin [K3] and resin [K4].
- the resin (B) include resins described in JP-A-2018-123274.
- the resin has a double bond in its side chain, and has, in its main chain, a structural unit ( ⁇ ) represented by the following formula (I) and a structural unit ( ⁇ ) represented by the following formula (II). and further containing an acid group (hereinafter also referred to as “resin (Ba)”).
- the acid group is, for example, the resin (Ba) that is introduced into the resin by including a structural unit ( ⁇ ) derived from an acid group-containing monomer (for example, (meth)acrylic acid, etc.). can.
- the resin (Ba) preferably contains structural units ( ⁇ ), ( ⁇ ) and ( ⁇ ) in its main chain skeleton.
- R A and R B are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms.
- n represents the average number of repeating units of the structural unit represented by formula (I), and is a number of 1 or more.
- R 2 C is the same or different and represents a hydrogen atom or a methyl group.
- RD which may be the same or different, represents a linear or branched hydrocarbon group having 4 to 20 carbon atoms.
- m represents the average number of repeating units of the structural unit represented by formula (II), and is a number of 1 or more.
- the content of the structural unit ( ⁇ ) is 100 mass of the total amount of all monomer units that provide the main chain skeleton of the resin (Ba). %, for example, 0.5% by mass or more and 50% by mass or less, preferably 1% by mass or more and 40% by mass or less, more preferably 5% by mass or more and 30% by mass or less.
- n in formula (I) represents the average number of repeating units of the structural unit ( ⁇ ) in the resin (Ba), and n can be set so that the content of the structural unit ( ⁇ ) is within the above range. can.
- the content of the structural unit ( ⁇ ) is, for example, 10% by mass or more and 90% by mass with respect to 100% by mass of the total amount of all monomer units that provide the main chain skeleton of the resin (Ba). %, preferably 20% by mass or more and 80% by mass or less, more preferably 30% by mass or more and 75% by mass or less.
- m in the formula (II) represents the average number of repeating units of the structural unit ( ⁇ ) in the resin (Ba), and is set so that the content of the structural unit ( ⁇ ) is within the range described above. can be done.
- the content of the structural unit ( ⁇ ) is For example, it is 0.5% by mass or more and 50% by mass or less, preferably 2% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 45% by mass or less.
- the resin (B) can contain one or more selected from the group consisting of the above resin [K1], resin [K2], resin [K3], resin [K4] and resin (Ba).
- the resin (B) preferably has a weight average molecular weight Mw ratio (Mw/acid value) to an acid value [unit: mgKOH/g] of 150 or less, more preferably 120 or less, still more preferably 100 or less, and even more preferably 100 or less. is 90 or less, particularly preferably 85 or less, most preferably 70 or less.
- Mw/acid value is advantageous for improving the emission intensity of the resin film. This is probably because the dispersibility of the semiconductor particles (A) in the resin composition is enhanced. It is considered that the higher the dispersibility, the higher the emission intensity of the resin film.
- Mw/acid value is usually 20 or more, and may be 30 or more or 40 or more.
- the Mw of the resin (B) can be adjusted by appropriately combining reaction conditions such as selection of raw materials to be used, preparation method, reaction temperature and time.
- the acid value of resin (B) can be adjusted by the content of the monomer component having an acid group (for example, (a) above).
- the Mw of the resin (B) is the weight average molecular weight in terms of standard polystyrene measured by GPC. Specifically, it can be measured according to the measuring method described in the section of Examples below. Alternatively, the Mw of the resin (B) contained in the resin composition may be measured using GPC.
- the acid value of the resin (B) is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and is determined by titration with an aqueous potassium hydroxide solution, for example. be able to. Specifically, it can be measured according to the measuring method described in the section of Examples below. Alternatively, the acid value may be obtained by, for example, structural analysis of the resin (B) contained in the resin composition.
- the Mw of the resin (B) is usually over 2900. From the viewpoint of making the Mw/acid value within the above range, and from the viewpoint of increasing the emission intensity of the resin film, it is preferably 3000 or more and 12000 or less, more preferably 3000 or more and 10000 or less, still more preferably 3000 or more and 9000 or less, still more preferably 3500 or more. 8500 or less.
- the molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (B) measured by GPC is, for example, 1.0 or more and 6.0 or less. , preferably from 1.2 to 4.0.
- the acid value of the resin (B) is preferably 90 mgKOH/g or more and 150 mgKOH/g or less, more preferably 90 mgKOH/g or more and 140 mgKOH, from the viewpoint of making the Mw/acid value within the above range and from the viewpoint of increasing the emission intensity of the resin film. /g or less, more preferably 90 mgKOH/g or more and 130 mgKOH/g or less, even more preferably 90 mgKOH/g or more and 120 mgKOH/g or less, particularly preferably 95 mgKOH/g or more and 110 mgKOH/g or less. Having an acid value within the above range for the resin (B) is also advantageous for enhancing the solvent resistance of the resin film.
- the resin (B) preferably contains a resin having a double bond equivalent of 300 g/eq or more and 2000 g/eq or less, and a resin having a double bond equivalent of 500 g/eq or more and 1500 g/eq or less. It is more preferable to include Resins having a double bond equivalent weight of 300 g/eq or more and 2000 g/eq or less include (meth)acrylic resins.
- the resin (B) preferably consists of a (meth)acrylic resin.
- the content of the resin (B) in the resin composition is, for example, 5% by mass or more and 85% by mass or less, preferably 10% by mass or more and 85% by mass or less, more preferably 10% by mass or more and 85% by mass or less, based on the total solid content of the resin composition. is 20% by mass or more and 85% by mass or less, and may be 30% by mass or more and 80% by mass or less.
- the content of the resin (B) is within the above range, the semiconductor particles (A) are easily dispersed, and the emission intensity of the resin film tends to be high.
- the resin composition preferably does not substantially contain the polymerizable compound (C) and the polymerization initiator (D).
- substantially free means that the content of the total solid content of the resin composition is 0.01% by mass or less.
- the contents of the polymerizable compound (C) and the polymerization initiator (D) are each preferably 0.005% by mass or less, more preferably 0% by mass.
- the resin composition does not substantially contain the polymerizable compound (C) and the polymerization initiator (D), the first and second emission intensity retention ratios R1 and R2 are good and a resin film with high light resistance is obtained. is advantageous.
- the resin film according to the present invention has excellent resistance to ultraviolet rays.
- a resin film containing semiconductor particles such as quantum dots is conventionally coated with a curable composition containing semiconductor particles, a resin, a polymerizable compound and a polymerization initiator, cured by light or heat, and optionally It was made by developing.
- the present inventor's studies have revealed that the resin film formed from the conventional curable composition described above may cause a decrease in emission intensity when subjected to an exposure test.
- This decrease in emission intensity is due to the active component derived from the polymerizable compound remaining in the resin film and/or the polymerization initiator generated by light irradiation in the exposure test (for example, active radicals generated from the polymerization initiator and acid etc.).
- the active component derived from the polymerizable compound remaining in the resin film and/or the polymerization initiator generated by light irradiation in the exposure test for example, active radicals generated from the polymerization initiator and acid etc.
- the fact that the resin composition does not substantially contain the polymerizable compound (C) and the polymerization initiator (D) is also advantageous for obtaining a resin film with reduced tackiness.
- a resin film with reduced tackiness refers to a resin film with reduced tackiness on the surface of the resin film, and the tackiness can be evaluated by the method described in Examples below. By reducing the tackiness, unevenness on the surface of the resin film can be made less likely to occur.
- the resin composition does not substantially contain the polymerizable compound (C) and the polymerization initiator (D) means that in a display device including a resin film formed therefrom, the layer adjacent to the resin film contains the polymerizable compound (C ) and the polymerization initiator (D) are also advantageous in preventing migration.
- the polymerizable compound (C) is a compound that can be polymerized by an active radical generated from the polymerization initiator (D), an acid, etc., and has a weight average molecular weight of 2900 or less.
- Examples of the polymerizable compound (C) having a weight average molecular weight of 2900 or less include photopolymerizable compounds such as compounds having an ethylenically unsaturated bond, such as (meth)acrylate compounds.
- the weight average molecular weight of the polymerizable compound (C) is the weight average molecular weight in terms of standard polystyrene measured by GPC.
- the weight average molecular weight of the polymerizable compound (C) is usually 150 or more.
- a compound having an ethylenically unsaturated bond is, for example, a polymerizable compound having three or more ethylenically unsaturated bonds.
- polymerizable compounds include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa( meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tris(2-(meth)acryloyloxyethyl ) isocyanurate, ethylene glycol
- the polymerizable compound (C) is a thermally polymerizable compound.
- the resin composition does not substantially contain a thermally polymerizable compound either.
- the meaning of "substantially free” is as described above, and the content of the thermally polymerizable compound is more preferably 0.005% by mass or less, more preferably 0.005% by mass or less, more preferably It is 0% by mass.
- the thermally polymerizable compound includes known thermally polymerizable compounds.
- the thermally polymerizable compound as used herein refers to a compound having a weight average molecular weight of 2900 or less.
- the polymerization initiator (D) is a compound that initiates polymerization of the polymerizable compound (C).
- the polymerization initiator (D) is, for example, a compound that generates active radicals, acids, etc. by the action of light or heat.
- Examples of the polymerization initiator (D) include photopolymerization initiators such as oxime compounds, biimidazole compounds, triazine compounds and acylphosphine compounds, and thermal polymerization initiators such as azo compounds and organic peroxides.
- oxime compounds examples include oxime compounds having a partial structure represented by the following formula (d1). * represents a bond.
- Examples of the oxime compound having a partial structure represented by formula (d1) include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1 -[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethan-1-imine, N-acetoxy-1-[9-ethyl-6- ⁇ 2-methyl-4-( 3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl ⁇ -9H-carbazol-3-yl]ethan-1-imine, N-acetoxy-1-[9-ethy
- biimidazole compounds examples include compounds represented by formula (d5).
- R E to R J represent an aryl group having 6 to 10 carbon atoms which may have a substituent.
- Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a toluyl group, a xylyl group, an ethylphenyl group and a naphthyl group.
- substituents include halogen atoms and alkoxy groups having 1 to 4 carbon atoms.
- alkoxy groups having 1 to 4 carbon atoms include methoxy, ethoxy, propoxy and butoxy groups.
- Biimidazole compounds include, for example, 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetraphenylbiimidazole, 2,2′-bis(2,3-dichlorophenyl)-4 ,4′,5,5′-tetraphenylbiimidazole (see, for example, JP-A-06-75372 and JP-A-06-75373), 2,2′-bis(2-chlorophenyl)-4, 4′,5,5′-tetraphenylbiimidazole, 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetra(alkoxyphenyl)biimidazole, 2,2′-bis( 2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-t
- triazine compounds examples include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxy naphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl )-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4- Bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-tri
- acylphosphine compounds include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and (2,4,6-trimethylbenzoyl)diphenylphosphine oxide.
- Photopolymerization initiators other than the above include, for example, benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzoyl-4'-methyldiphenylsulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, 4,4'-bis(diethylamino)benzophenone, etc.
- benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether
- benzoyl-4'-methyldiphenylsulfide 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophen
- quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compounds and the like.
- the polymerization initiator (D) is a thermal polymerization initiator.
- the resin composition does not substantially contain a thermal polymerization initiator either.
- the meaning of "substantially free” is as described above, and the content of the thermal polymerization initiator is more preferably 0.005% by mass or less, more preferably 0.005% by mass or less, more preferably It is 0% by mass.
- Thermal polymerization initiators include known thermal polymerization initiators.
- the resin composition preferably does not substantially contain the polymerization initiation aid (D1).
- the polymerization initiation aid (D1) is a compound or a sensitizer used to accelerate the polymerization of the polymerizable compound (C) initiated by the polymerization initiator (D).
- Polymerization initiation aids (D1) include photopolymerization initiation aids such as amine compounds, alkoxyanthracene compounds, thioxanthone compounds and carboxylic acid compounds, and thermal polymerization initiation aids.
- amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N- dimethyl p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone and the like.
- alkoxyanthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10- dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene and the like.
- thioxanthone compounds include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like.
- carboxylic acid compounds include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, and dichlorophenylsulfanylacetic acid.
- N-phenylglycine phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.
- the resin composition can contain a light scattering agent (E).
- a resin film formed from the resin composition may contain a light scattering agent (E) and exhibit light scattering properties.
- the resin composition and resin film may contain two or more light scattering agents (E).
- Examples of the light scattering agent (E) include inorganic particles such as metal or metal oxide particles and glass particles.
- metal oxides include TiO 2 , SiO 2 , BaTiO 3 , ZnO, etc. TiO 2 particles are preferable because they efficiently scatter light.
- the particle size of the light scattering agent (E) is, for example, about 0.03 ⁇ m or more and 20 ⁇ m or less, preferably 0.05 ⁇ m or more and 1 ⁇ m or less, more preferably 0.05 ⁇ m or more and 0.5 ⁇ m or less.
- a dispersing agent may be used in which the light scattering agent is previously dispersed in part or all of the solvent (G).
- a commercial item can be used as a dispersing agent. Examples of commercially available products include: BYK-Chemie Japan DISPERBYK-101, 102, 103, 106, 107, 108, 109, 110, 111, 116, 118, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 192, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155; ANTI-TERRA-U, U100, 203, 204, 250,; BYK-P104, P104S, P105, 220S, 6919; BYK-LPN6919, 21116; LACTIMON, LACTIMON-WS; SOLSPERSE-3
- the content of the light scattering agent (E) in the resin composition is, for example, 0.001% by mass or more and 50% by mass or less with respect to the total solid content of the resin composition, and the light scattering ability and emission intensity of the resin film are From the viewpoint of increasing the content, it is preferably 1% by mass or more and 30% by mass or less, more preferably 2% by mass or more and 20% by mass or less.
- the resin composition can contain a solvent (G).
- the solvent (G) is not particularly limited as long as it dissolves the resin (B), and solvents commonly used in this field can be used.
- ester solvent solvent (solvent containing -COO- in the molecule but not containing -O-)
- ether solvent solvent containing -O- in the molecule but not containing -COO-
- ether ester solvent solvent containing -COO- in the molecule solvent containing -COO- and -O-
- ketone solvent solvent containing -CO- in the molecule and not containing -COO-
- alcohol solvent containing OH in the molecule, -O-, - solvents containing no CO- and COO-
- aromatic hydrocarbon solvents amide solvents, dimethyl sulfoxide and the like.
- the solvent (G) may be used in combination of two or more.
- Ester solvents include methyl lactate, ethyl lactate, n-butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, and isopropyl butyrate.
- ethyl butyrate n-butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate and ⁇ -butyrolactone.
- Ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether.
- propylene glycol monopropyl ether propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetol, methylanisole and the like.
- Ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy ethyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy- Ethyl 2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether a
- Ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone and isophorone. etc.
- Alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol and glycerin.
- Aromatic hydrocarbon solvents include benzene, toluene, xylene and mesitylene.
- Amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and the like.
- solvent (G) examples include propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4- Methyl-2-pentanone or toluene or mixtures of two or more of these are preferred.
- the solvent (G) is a component other than the solid content.
- the solvent contained in the semiconductor particles (A), the resin (B), etc. is also included in the solvent (G).
- the content of the solvent (G) in the resin composition is the ratio of the total mass of all solvents contained in the composition to the total amount of the composition, and is, for example, 40% by mass or more and 95% by mass of the total amount of the resin composition. % by mass or less, preferably 55% by mass or more and 90% by mass or less.
- the solid content of the resin composition is preferably 5% by mass or more and 60% by mass or less, more preferably 10% by mass or more and 45% by mass or less.
- Antioxidant (H) The resin composition and the resin film formed therefrom can contain an antioxidant (H).
- the antioxidant (H) is not particularly limited as long as it is an antioxidant that is commonly used industrially, and includes phenol antioxidants, phosphorus antioxidants, phosphorus/phenol composite antioxidants and sulfur antioxidants. An antioxidant or the like can be used.
- Antioxidants (H) may be used in combination of two or more.
- the phosphorus/phenol composite antioxidant can be a compound having one or more phosphorus atoms and one or more phenol structures in the molecule. From the viewpoint of the emission intensity of the resin film, the antioxidant (H) preferably contains a phosphorus/phenol composite antioxidant.
- Phenolic antioxidants include, for example, Irganox (registered trademark) 1010 (Irganox 1010: pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], BASF Corporation) ), 1076 (Irganox 1076: octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, manufactured by BASF), 1330 (Irganox 1330: 3,3',3 '',5,5',5''-hexa-tert-butyl-a,a',a''-(mesitylene-2,4,6-triyl)tri-p-cresol, manufactured by BASF Corporation) , 3114 (Irganox 3114: 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine
- Phosphorus-based antioxidants include, for example, Irgafos (registered trademark) 168 (Irgafos 168: Tris (2,4-di-tert-butylphenyl) phosphite, manufactured by BASF Corporation), Irgafos 12 (Irgafos 12: Tris [2-[[2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphine-6-yl]oxy]ethyl]amine, BASF Corporation ), Irgafos 38 (Irgafos 38: bis(2,4-bis(1,1-dimethylethyl)-6-methylphenyl)ethyl ester phosphorous acid, manufactured by BASF Corporation), Adekastab (registered trademark) 329K, PEP36, PEP-8 (manufactured by ADEKA Co., Ltd.), Sandstab P-EP
- Phosphorus/phenol composite antioxidants include, for example, Sumilizer (registered trademark) GP (6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8, 10-tetra-tert-butyldibenz[d,f][1.3.2]dioxaphosphepin) (manufactured by Sumitomo Chemical Co., Ltd.) and the like.
- sulfur-based antioxidants include dialkylthiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl or distearyl, and ⁇ -alkylmercaptopropionate esters of polyols such as tetrakis[methylene(3-dodecylthio)propionate]methane. compounds and the like.
- the content of the antioxidant (H) in the resin composition is, for example, 0.01 parts by mass or more and 10.0 parts by mass with respect to 100 parts by mass of the resin (B). part by mass or less, preferably 0.1 to 8.0 parts by mass, more preferably 1.0 to 7.0 parts by mass, from the viewpoint of the light emission amount and heat resistance of the resin film, More preferably, it is 2.0 parts by mass or more and 6.0 parts by mass or less.
- the content of the antioxidant (H) in the resin composition is the total value of the semiconductor particles (A) and the organic ligand (F) in the resin composition.
- 100 parts by mass it is, for example, 0.01 to 0.5 parts by mass, and from the viewpoint of the light emission amount and heat resistance of the resin film, preferably 0.02 to 0.4 parts by mass, and more It is preferably 0.03 to 0.3 parts by mass, more preferably 0.03 to 0.2 parts by mass.
- the resin composition and the resin film formed therefrom may optionally contain polymerization inhibitors, fillers, other polymer compounds, adhesion promoters, light stabilizers, Additives known in the art, such as chain transfer agents and leveling agents, may also be included.
- the viscosity of the resin composition at 25° C. is, for example, 50 mPa ⁇ s or more and 30000 mPa ⁇ s or less, and from the viewpoint of improving the coating properties of the resin composition and the appearance of the resin film formed by coating, it is preferably 80 mPa ⁇ s. 30000 mPa ⁇ s or less, more preferably 100 mPa ⁇ s or more and 25000 mPa ⁇ s or less, and still more preferably 200 mPa ⁇ s or more and 20000 mPa ⁇ s or less.
- the viscosity of the resin composition can be measured using a Brookfield rotational viscometer.
- the resin composition can be produced by a method including a step of mixing predetermined components and other components used as necessary.
- the method for producing the resin composition can further include the step of preparing the resin (B).
- the resin film according to the present invention can be obtained, for example, by a method including a step of applying the above resin composition to a substrate and then drying the composition.
- the resin film may be formed over the entire surface of the substrate, or may be formed in a pattern on a portion of the substrate.
- methods for forming a resin film in a pattern include an inkjet method and a printing method.
- the printing method include a stencil printing method, a screen printing method, and printing coating using an applicator.
- the substrate examples include glass plates such as quartz glass, borosilicate glass, alumina silicate glass, and soda-lime glass whose surface is coated with silica; resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate; and aluminum, silver, silver/copper/palladium alloy thin films, and the like.
- a patterned resin film can be produced, for example, as follows. First, a resin composition is applied onto a substrate through a mask to form a patterned composition layer. Examples of methods for applying the resin composition include a spin coating method, a slit coating method, a slit and spin coating method, and the like.
- a resin film is obtained by drying the composition layer (removing volatile components such as solvents). Drying methods include heat drying, vacuum drying, or a combination thereof.
- the temperature for heat drying is preferably 30° C. or higher and 250° C. or lower, more preferably 50° C. or higher and 235° C. or lower.
- the heating time is preferably 10 seconds or more and 180 minutes or less, more preferably 30 seconds or more and 90 minutes or less.
- drying under reduced pressure it is preferable to perform under the pressure of 50 Pa or more and 150 Pa or less. Drying of the composition layer may be carried out in a plurality of stages such as carrying out a plurality of drying steps with different drying temperatures.
- the method for producing a resin film comprises A coating step of coating the above resin composition to form a composition layer; A first drying step of drying the composition layer at a first temperature; A second drying step of drying the composition layer after the first drying step at a second temperature; including. The second temperature is higher than the first temperature.
- the resin composition described in ⁇ Resin composition> above can be used.
- the resin composition includes a polymerizable compound (C) and a polymerization initiator. It is preferable to use one that does not substantially contain the agent (D).
- the resin composition used in the coating step contains at least semiconductor particles (A) and resin (B), and usually further contains solvent (G).
- the resin film is formed by a method including two drying steps, the first drying step and the second drying step.
- the second temperature which is the drying temperature in the second drying process
- the first temperature which is the drying temperature in the first drying process
- a resin film can be formed.
- the composition layer is heat-treated at a constant or substantially constant temperature, which is the first temperature and the second temperature, respectively, to remove volatile components such as solvents in the composition layer. refers to the process of removing
- substantially constant means that the drying temperature may fluctuate to the extent that the difference between the maximum temperature and the minimum temperature is, for example, within 10°C, preferably within 5°C.
- the heat treatment method is not particularly limited, and examples thereof include heat treatment methods using hot air, infrared rays, microwaves, electric resistance, etc., or combinations thereof. Heat treatment of the composition layer may be performed by heating the substrate.
- the first temperature is preferably a temperature within the range of 80° C. or higher and 120° C. or lower, and more preferably a temperature within the range of 90° C. or higher and 110° C. or lower. preferable.
- the second temperature is preferably a temperature within the range of 150° C. or higher and 200° C. or lower, and more preferably a temperature within the range of 160° C. or higher and 190° C. or lower.
- the first drying step and the second drying step are preferably performed under atmospheric pressure.
- the method for producing a resin film includes a first temperature raising step of raising the temperature of the composition layer to the first temperature, a second temperature raising step of raising the temperature of the composition layer to the second temperature, and after the second drying step.
- a step of lowering the temperature of the composition layer (resin film) to, for example, about room temperature can be further included.
- a process that does not correspond to any of these may be included between the first drying process and the second drying process.
- the step includes, for example, placing the composition layer at a third temperature lower than the first temperature and the second temperature, and may be a conveying step.
- the total amount of UV exposure (based on irradiation wavelength of 365 nm) to the composition layer between the first drying step and the second drying step is preferably 10 mJ/ cm2 or less, and 0 mJ/cm2. cm 2 is more preferred. As a result, it is possible to simplify the process of manufacturing the resin film and to suppress the decrease in the emission intensity of the resin film.
- the resin composition contains a slight amount of the polymerizable compound ( When C) and the polymerization initiator (D) are included, it is possible to particularly suppress the decrease in the emission intensity of the resin film.
- the composition layer is coated with the is preferably 10 mJ/cm 2 or less, more preferably 0 mJ/cm 2 .
- the film thickness of the resin film is not particularly limited, and may be appropriately selected according to the purpose. 20 ⁇ m or less. If the film thickness is too small, sufficient emission intensity cannot be obtained.
- the shape and dimensions of the patterned resin film are not particularly limited.
- the patterned resin film has, for example, a square shape in plan view.
- the resin film By irradiating the resin film with ultraviolet light or visible light, it is possible to emit light with a wavelength different from that of the irradiated light.
- the wavelength of emitted light can be selected by selecting the component and particle diameter of the semiconductor particles (A). Since the resin film has a function of converting the wavelength of irradiation light, it can be used as a color conversion layer of a display device.
- the resin film according to the present invention is useful as a color conversion layer (wavelength conversion layer) in display devices, particularly liquid crystal display devices, organic EL display devices or inorganic EL display devices.
- display devices include, for example, JP-A-2006-309219, JP-A-2006-310303, JP-A-2013-15812, JP-A-2009-251129, JP-A-2014-2363, etc. and the display device described in .
- a display device includes the resin film and usually further includes a light source.
- the display device is not particularly limited, but may further include layers such as a light absorbing layer, a light reflecting member (reflecting film, etc.), a diffusion film, a brightness enhancing portion, a prism sheet, a light guide plate, and a medium material layer between elements. You can
- a light absorption layer is a layer having wavelength selectivity that transmits light in a specific wavelength range and absorbs light in other wavelength ranges.
- the light absorbing layer is usually a layer containing a coloring agent such as dyes and pigments, and can be arranged on the resin film.
- a conventionally known color filter can be used as the light absorption layer.
- the light absorption layer is generally formed by curing a layer made of a photocurable resin composition by ultraviolet irradiation. At this time, when the adjacent resin film is irradiated with ultraviolet rays, the emission intensity of the resin film tends to decrease in the case of the conventional resin film. According to the resin film of the present invention, it is possible to suppress such a decrease in emission intensity.
- the light reflecting member is a member for reflecting light from the light source toward the resin film, and may be a reflecting mirror, a film of reflecting particles, a reflecting metal film, a reflector, or the like.
- the diffusion film is a film for diffusing light from a light source or light emitted from a resin film, and may be an amplifying diffusion film or the like.
- a brightness enhancer is a member for reflecting a portion of the light back toward the direction in which the light was transmitted.
- a prism sheet typically has a base portion and a prism portion.
- the base portion may be omitted depending on the adjacent member.
- the prism sheet can be attached to adjacent members via any appropriate adhesive layer (eg, adhesive layer, adhesive layer).
- the prism sheet is configured by arranging a plurality of unit prisms convex on the opposite side (back side) of the viewing side. By arranging the prism sheet so that the convex portion faces the back side, the light passing through the prism sheet can be easily condensed. In addition, by arranging the convex portion of the prism sheet facing the back side, compared to the case where the convex portion is arranged facing the viewer side, less light is reflected without entering the prism sheet, resulting in a high brightness display. You can get the device.
- any appropriate light guide plate is used as the light guide plate.
- a light guide plate in which a lens pattern is formed on the back side and a light guide plate in which a prism shape or the like is formed on the back side and/or the viewing side is used so that light from the lateral direction can be deflected in the thickness direction.
- the display device may include one or more media material layers on the optical path between adjacent elements (layers).
- One or more media materials such as vacuum, air, gas, optical materials, adhesives, optical adhesives, glasses, polymers, solids, liquids, gels, curable materials, optical bonding materials, refractive index matching or refractive index mismatching material, refractive index gradient material, cladding or anti-cladding material, spacer, silica gel, brightness enhancing material, scattering or diffusing material, reflective or anti-reflective material, wavelength selective material, wavelength selective anti-reflective material or in the art Any suitable material may be included, including, but not limited to, other known suitable media.
- display devices include those equipped with wavelength conversion materials for EL displays and liquid crystal displays.
- the resin film as the wavelength conversion layer is arranged between the blue light source and the light guide plate along the end surface (side surface) of the light guide plate, and the backlight emits white light (on-edge type backlight).
- a display device in which a light absorption layer is arranged on the light guide plate side;
- a display device in which a backlight (surface-mount type backlight) that emits light irradiated to the wavelength conversion layer as white light is used, and a light absorption layer is arranged on the wavelength conversion layer;
- a backlight on-chip type backlight that emits the irradiated light as white light, and a light absorption layer disposed on the wavelength conversion layer.
- Emission Intensity L of Resin Film and First and Second Emission Intensity Maintenance Rates R1 and R2 A resin film having a film thickness of 10 ⁇ m was formed on a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Incorporated) to obtain a substrate having a resin film.
- the resin film was manufactured according to the description of Examples and Comparative Examples described later.
- An LED lamp with an emission wavelength of 444 nm and a narrow directivity angle type sensing backlight (OPF series; manufactured by Optex FA Co., Ltd.) equipped with a scratch-resistant cover were prepared as backlights.
- a backlight was placed with the scratch-resistant cover facing upward, and an optical fiber for detecting light emission connected to the spectrometer described below was installed at a height of 4 cm from the surface of the scratch-resistant cover.
- a glass substrate (Eagle 2000; manufactured by Corning Incorporated) was placed as a reference on the surface of the scratch resistant cover of the backlight. In this state, the backlight was turned on, and the light amount of the backlight was adjusted so that the total radiant flux ( ⁇ W) of the backlight was 1500 ⁇ W through a reference glass substrate (Eagle 2000; manufactured by Corning Incorporated).
- the substrate having the resin film produced above was placed on the surface of the glass substrate.
- the backlight was turned on, and the emission intensity (unit: ⁇ W) of the light emitted from the resin film was measured as the integrated radiant flux in the wavelength range of 485 nm to 780 nm.
- a spectrometer Spectrum meter manufactured by Ocean Optics was used to measure the emission intensity.
- the emission intensity (%) of the resin film immediately after production was measured.
- the emission intensity of the resin film immediately after production is called "L0".
- a first exposure test was performed in which the resin film was exposed to ultraviolet rays immediately after production (before the first exposure test).
- the first exposure test was performed in the atmosphere at a temperature of 25° C. and an exposure amount of 200 mJ/cm 2 (wavelength of 365 nm).
- the irradiation intensity of the ultraviolet rays irradiated in the first exposure test was set to 30 mW/cm 2 .
- the emission intensity of the resin film after the first exposure test was measured using the apparatus described above. The emission intensity of the resin film after the first exposure test is called "L1".
- a first emission intensity maintenance rate R1 was obtained based on the following formula.
- First emission intensity maintenance rate R1 (%) 100 ⁇ (emission intensity after first exposure test)/(emission intensity before first exposure test)
- a second exposure test was performed in which the resin film after the first exposure test was exposed to ultraviolet rays.
- the second exposure test was performed in the atmosphere at a temperature of 25° C. and an exposure amount of 200 mJ/cm 2 (wavelength of 365 nm).
- the UV irradiation intensity and irradiation time were the same as in the first exposure test.
- the emission intensity of the resin film after the second exposure test was measured using the apparatus described above.
- the emission intensity of the resin film after the second exposure test is called "L2".
- Weight average molecular weight Mw of resin The weight-average molecular weight Mw of the resin was measured by the GPC method under the following conditions. Apparatus; K2479 (manufactured by Shimadzu Corporation) Column; SHIMADZU Shim-pack GPC-80M Column temperature; 40°C Solvent; Tetrahydrofuran Flow rate; 1.0 mL/min detector; RI Calibration standard material; TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)
- ⁇ Production Example 1 Preparation of dispersion liquid of semiconductor particles (A-1)> A toluene dispersion of InP/ZnSeS quantum dots coordinated with oleic acid as an organic ligand (F) was prepared. The dispersion was distilled under reduced pressure to remove toluene. 70 parts of cyclohexyl acetate was added to 30 parts of solid content to obtain a dispersion of semiconductor particles (A-1) (30% solid content).
- Resin (B-1) has a standard polystyrene equivalent weight average molecular weight Mw of 5200, a molecular weight distribution of 2.3, an acid value of 100 mgKOH/g, and a solid content in the resin (B-1) solution of 40% by mass. Met.
- Resin (B-4) Preparation of resin (B-4) solution> Resin (B-4 ) to give a solution.
- Resin (B-4) has a standard polystyrene equivalent weight average molecular weight Mw of 8400, a molecular weight distribution of 2.2, and an acid value of 100 mgKOH/g, and the solid content in the resin (B-4) solution is 40% by mass. Met.
- the content of each component in the resin composition obtained from the added amount is as shown in Table 1.
- the contents of the components other than the solvent (G) are in terms of solid content (unit: parts by mass).
- the unit for the content of the solvent (G) is parts by mass.
- the semiconductor particles (A-1) are blended as a dispersion of the semiconductor particles (A-1) in the preparation of the resin composition.
- (A-1) is the amount of itself.
- Solvent (G) in Table 1 includes the solvent contained in the dispersion or solution used for preparing the resin composition.
- the organic ligand (F) in the resin composition shown in Table 1 the organic ligand ( The concentration of F) was measured and calculated based on this. That is, after the dispersion of semiconductor particles (A-1) was vacuum-dried at 150° C. to remove the solvent, the weight change of the remaining solid content was measured using a thermogravimetric analyzer “TGDTA6200” at a heating rate of 5. It was measured from 50°C to 550°C at °C/min. The change in weight from 50° C. to 500° C. was taken as the weight of the organic ligand (F), and the concentration of the organic ligand (F) in the dispersion liquid of the semiconductor particles (A-1) was calculated.
- TGDTA6200 thermogravimetric analyzer
- a composition layer was formed by applying the same resin composition as the resin composition of Example 1 onto a glass substrate at a temperature of 25° C. using a film applicator (“AP75” manufactured by Taiyu Kizai Co., Ltd.). .
- a drying process including a second drying process was performed according to the following temperature profile to form a resin film having a thickness of 10 ⁇ m. [25°C ⁇ 180°C (1 minute)] - [180°C constant (10 minutes, second drying step)] - [180°C ⁇ 25°C (5 minutes)]
- the resin film of Reference Example was evaluated as A for tackiness, but as B for film appearance.
- Polymerizable compound (C-1) photopolymerizable compound "M-510" (polybasic modified acrylate, manufactured by Toagosei Co., Ltd., solid content 100%)
- Polymerization initiator (D-1) a compound represented by the following formula (photopolymerization initiator). It was produced by the method described in JP-A-2011-132215 (solid content 100%).
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Abstract
Description
[1] 半導体粒子(A)を含む樹脂膜であって、
前記樹脂膜に対して、大気中、露光量200mJ/cm2(照射波長365nm基準)の条件で露光を行う第1露光試験を実施したとき、下記式で示される第1の発光強度維持率R1が95%以上である、樹脂膜。
第1の発光強度維持率R1(%)=100×(前記第1露光試験後の発光強度)/(前記第1露光試験前の発光強度)
[2] 前記第1露光試験が実施された樹脂膜に対して、大気中、露光量200mJ/cm2(照射波長365nm基準)の条件で露光を行う第2露光試験を実施したとき、下記式で示される第2の発光強度維持率R2が85%以上である、[1]に記載の樹脂膜。
第2の発光強度維持率R2(%)=100×(前記第2露光試験後の発光強度)/(前記第1露光試験後の発光強度)
[3] 前記半導体粒子(A)と、樹脂(B)とを含む樹脂組成物から形成される、[1]又は[2]に記載の樹脂膜。
[4] 前記樹脂組成物は、重合性化合物(C)及び重合開始剤(D)の含有量が、それぞれ、前記樹脂組成物の固形分の総量に対して0.01質量%以下である、[3]に記載の樹脂膜。
[5] 前記樹脂組成物は、前記重合性化合物(C)及び前記重合開始剤(D)の含有量が、それぞれ、前記樹脂組成物の固形分の総量に対して0質量%である、[4]に記載の樹脂膜。
[6] 光散乱剤(E)をさらに含む、[1]~[5]のいずれかに記載の樹脂膜。
[7] [1]~[6]のいずれかに記載の樹脂膜を含む表示装置。
本発明に係る樹脂膜(以下、単に「樹脂膜」ともいう。)は、半導体粒子(A)を含み、第1露光試験を実施したときに下記式で示される第1の発光強度維持率R1が95%以上である樹脂膜である。
第1の発光強度維持率R1(%)=100×(第1露光試験後の発光強度)/(第1露光試験前の発光強度)
第2の発光強度維持率R2(%)=100×(第2露光試験後の発光強度)/(第1露光試験後の発光強度)
樹脂組成物は、半導体粒子(A)と、樹脂(B)とを含む。
半導体粒子(A)は、一次光とは異なる波長の光を発し、好ましくは、一次光である青色の光の波長を、これとは異なる色の光の波長に変換する。半導体粒子(A)は、緑色又は赤色を発光することが好ましく、青色光を吸収して緑色又は赤色を発光することがより好ましい。
SnS2、SnS、SnSe、SnTe、PbS、PbSe、PbTe等の第14族元素と第16族元素との化合物;
GaN、GaP、GaAs、GaSb、InN、InP、InAs、InSb、InGaN、InGaP等の第13族元素と第15族元素との化合物;
Ga2O3、Ga2S3、Ga2Se3、Ga2Te3、In2O3、In2S3、In2Se3、In2Te3等の第13族元素と第16族元素との化合物;
ZnO、ZnS、ZnSe、ZnTe、CdO、CdS、CdSe、CdTe、HgO、HgS、HgSe、HgTe、ZnSTe、ZnSeS、ZnSeTe、CdSTe、CdSeTe、HgSTe、HgSeS、HgSeTe等の第12族元素と第16族元素との化合物;
As2O3、As2S3、As2Se3、As2Te3、Sb2O3、Sb2S3、Sb2Se3、Sb2Te3、Bi2O3、Bi2S3、Bi2Se3、Bi2Te3等の第15族元素と第16族元素との化合物;
MgS、MgSe、MgTe、CaS、CaSe、CaTe、SrS、SrSe、SrTe、BaS、BaSe、BaTe等
の第2族元素と第16族元素との化合物;
Si、Ge等の第14族元素、第15族元素又は第16族元素の単体
を含む。
Aは、ペロブスカイト型結晶構造において、Bを中心とする6面体の各頂点に位置する成分であって、1価の陽イオンである。
Xは、ペロブスカイト型結晶構造において、Bを中心とする8面体の各頂点に位置する成分を表し、ハロゲン化物イオン及びチオシアン酸イオンからなる群より選ばれる少なくとも一種のイオンである。
Bは、ペロブスカイト型結晶構造において、Aを頂点に配置する6面体及びXを頂点に配置する8面体の中心に位置する成分であって、金属イオンである。
3次元構造の場合には、ペロブスカイト化合物は、ABX(3+δ)で表される。
2次元構造の場合には、ペロブスカイト化合物は、A2BX(4+δ)で表される。
ここで、δは、Bの電荷バランスに応じて適宜変更が可能な数であり、-0.7以上0.7以下である。
CH3NH3PbBr3、CH3NH3PbCl3、CH3NH3PbI3、CH3NH3PbBr(3-y)Iy(0<y<3)、CH3NH3PbBr(3-y)Cly(0<y<3)、(H2N=CH-NH2)PbBr3、(H2N=CH-NH2)PbCl3、(H2N=CH-NH2)PbI3、
CH3NH3Pb(1-a)CaaBr3(0<a≦0.7)、CH3NH3Pb(1-a)SraBr3(0<a≦0.7)、CH3NH3Pb(1-a)LaaBr(3+δ)(0<a≦0.7,0<δ≦0.7)、CH3NH3Pb(1-a)BaaBr3(0<a≦0.7)、CH3NH3Pb(1-a)DyaBr(3+δ)(0<a≦0.7,0<δ≦0.7)、
CH3NH3Pb(1-a)NaaBr(3+δ)(0<a≦0.7,-0.7≦δ<0)、CH3NH3Pb(1-a)LiaBr(3+δ)(0<a≦0.7,-0.7≦δ<0)、
CsPb(1-a)NaaBr(3+δ)(0<a≦0.7,-0.7≦δ<0)、CsPb(1-a)LiaBr(3+δ)(0<a≦0.7,-0.7≦δ<0)、
CH3NH3Pb(1-a)NaaBr(3+δ-y)Iy(0<a≦0.7,-0.7≦δ<0,0<y<3)、CH3NH3Pb(1-a)LiaBr(3+δ-y)Iy(0<a≦0.7,-0.7≦δ<0,0<y<3)、CH3NH3Pb(1-a)NaaBr(3+δ-y)Cly(0<a≦0.7,-0.7≦δ<0,0<y<3)、CH3NH3Pb(1-a)LiaBr(3+δ-y)Cly(0<a≦0.7,-0.7≦δ<0,0<y<3)、
(H2N=CH-NH2)Pb(1-a)NaaBr(3+δ)(0<a≦0.7,-0.7≦δ<0)、(H2N=CH-NH2)Pb(1-a)LiaBr(3+δ)(0<a≦0.7,-0.7≦δ<0)、(H2N=CH-NH2)Pb(1-a)NaaBr(3+δ-y)Iy(0<a≦0.7,-0.7≦δ<0,0<y<3)、(H2N=CH-NH2)Pb(1-a)NaaBr(3+δ-y)Cly(0<a≦0.7,-0.7≦δ<0,0<y<3)、
CsPbBr3、CsPbCl3、CsPbI3、CsPbBr(3-y)Iy(0<y<3)、CsPbBr(3-y)Cly(0<y<3)、CH3NH3PbBr(3-y)Cly(0<y<3)、
CH3NH3Pb(1-a)ZnaBr3(0<a≦0.7)、CH3NH3Pb(1-a)AlaBr(3+δ)(0<a≦0.7,0≦δ≦0.7)、CH3NH3Pb(1-a)CoaBr3(0<a≦0.7)、CH3NH3Pb(1-a)MnaBr3(0<a≦0.7)、CH3NH3Pb(1-a)MgaBr3(0<a≦0.7)、
CsPb(1-a)ZnaBr3(0<a≦0.7)、CsPb(1-a)AlaBr(3+δ)(0<a≦0.7,0<δ≦0.7)、CsPb(1-a)CoaBr3(0<a≦0.7)、CsPb(1-a)MnaBr3(0<a≦0.7)、CsPb(1-a)MgaBr3(0<a≦0.7)、
CH3NH3Pb(1-a)ZnaBr(3-y)Iy(0<a≦0.7,0<y<3)、CH3NH3Pb(1-a)AlaBr(3+δ-y)Iy(0<a≦0.7,0<δ≦0.7,0<y<3)、CH3NH3Pb(1-a)CoaBr(3-y)Iy(0<a≦0.7,0<y<3)、CH3NH3Pb(1-a)MnaBr(3-y)Iy(0<a≦0.7,0<y<3)、CH3NH3Pb(1-a)MgaBr(3-y)Iy(0<a≦0.7,0<y<3)、CH3NH3Pb(1-a)ZnaBr(3-y)Cly(0<a≦0.7,0<y<3)、CH3NH3Pb(1-a)AlaBr(3+δ-y)Cly(0<a≦0.7,0<δ≦0.7,0<y<3)、CH3NH3Pb(1-a)CoaBr(3+δ-y)Cly(0<a≦0.7,0<y<3)、CH3NH3Pb(1-a)MnaBr(3-y)Cly(0<a≦0.7,0<y<3)、CH3NH3Pb(1-a)MgaBr(3-y)Cly(0<a≦0.7,0<y<3)、
(H2N=CH-NH2)ZnaBr3(0<a≦0.7)、(H2N=CH-NH2)MgaBr3(0<a≦0.7)、(H2N=CH-NH2)Pb(1-a)ZnaBr(3-y)Iy(0<a≦0.7,0<y<3)、(H2N=CH-NH2)Pb(1-a)ZnaBr(3-y)Cly(0<a≦0.7,0<y<3)等が挙げられる。
(C4H9NH3)2PbBr4、(C4H9NH3)2PbCl4、(C4H9NH3)2PbI4、(C7H15NH3)2PbBr4、(C7H15NH3)2PbCl4、(C7H15NH3)2PbI4、(C4H9NH3)2Pb(1-a)LiaBr(4+δ)(0<a≦0.7,-0.7≦δ<0)、(C4H9NH3)2Pb(1-a)NaaBr(4+δ)(0<a≦0.7,-0.7≦δ<0)、(C4H9NH3)2Pb(1-a)RbaBr(4+δ)(0<a≦0.7,-0.7≦δ<0)、
(C7H15NH3)2Pb(1-a)NaaBr(4+δ)(0<a≦0.7,-0.7≦δ<0)、(C7H15NH3)2Pb(1-a)LiaBr(4+δ)(0<a≦0.7,-0.7≦δ<0)、(C7H15NH3)2Pb(1-a)RbaBr(4+δ)(0<a≦0.7,-0.7≦δ<0)、
(C4H9NH3)2Pb(1-a)NaaBr(4+δ-y)Iy(0<a≦0.7,-0.7≦δ<0,0<y<4)、(C4H9NH3)2Pb(1-a)LiaBr(4+δ-y)Iy(0<a≦0.7,-0.7≦δ<0,0<y<4)、(C4H9NH3)2Pb(1-a)RbaBr(4+δ-y)Iy(0<a≦0.7,-0.7≦δ<0,0<y<4)、
(C4H9NH3)2Pb(1-a)NaaBr(4+δ-y)Cly(0<a≦0.7,-0.7≦δ<0,0<y<4)、(C4H9NH3)2Pb(1-a)LiaBr(4+δ-y)Cly(0<a≦0.7,-0.7≦δ<0,0<y<4)、(C4H9NH3)2Pb(1-a)RbaBr(4+δ-y)Cly(0<a≦0.7,-0.7≦δ<0,0<y<4)、
(C4H9NH3)2PbBr4、(C7H15NH3)2PbBr4、
(C4H9NH3)2PbBr(4-y)Cly(0<y<4)、(C4H9NH3)2PbBr(4-y)Iy(0<y<4)、
(C4H9NH3)2Pb(1-a)ZnaBr4(0<a≦0.7)、(C4H9NH3)2Pb(1-a)MgaBr4(0<a≦0.7)、(C4H9NH3)2Pb(1-a)CoaBr4(0<a≦0.7)、(C4H9NH3)2Pb(1-a)MnaBr4(0<a≦0.7)、
(C7H15NH3)2Pb(1-a)ZnaBr4(0<a≦0.7)、(C7H15NH3)2Pb(1-a)MgaBr4(0<a≦0.7)、(C7H15NH3)2Pb(1-a)CoaBr4(0<a≦0.7)、(C7H15NH3)2Pb(1-a)MnaBr4(0<a≦0.7)、
(C4H9NH3)2Pb(1-a)ZnaBr(4-y)Iy(0<a≦0.7,0<y<4)、(C4H9NH3)2Pb(1-a)MgaBr(4-y)Iy(0<a≦0.7,0<y<4)、(C4H9NH3)2Pb(1-a)CoaBr(4-y)Iy(0<a≦0.7,0<y<4)、(C4H9NH3)2Pb(1-a)MnaBr(4-y)Iy(0<a≦0.7,0<y<4)、
(C4H9NH3)2Pb(1-a)ZnaBr(4-y)Cly(0<a≦0.7,0<y<4)、(C4H9NH3)2Pb(1-a)MgaBr(4-y)Cly(0<a≦0.7,0<y<4)、(C4H9NH3)2Pb(1-a)CoaBr(4-y)Cly(0<a≦0.7,0<y<4)、(C4H9NH3)2Pb(1-a)MnaBr(4-y)Cly(0<a≦0.7,0<y<4)等が挙げられる。
本明細書において固形分の総量とは、樹脂組成物に含まれる成分のうち、溶剤(G)を除いた成分の合計を意味する。樹脂組成物の固形分中の含有率は、液体クロマトグラフィ又はガスクロマトグラフィ等の公知の分析手段で測定することができる。樹脂組成物の固形分中における各成分の含有率は、該樹脂組成物調製時の配合から算出されてもよい。
半導体粒子(A)は、有機配位子が配位した状態で樹脂組成物中に存在していてもよい。以下、有機配位子が配位している半導体粒子を配位子含有半導体粒子ともいう。半導体粒子に配位する有機配位子は、例えば、半導体粒子に対する配位能を示す極性基を有する有機化合物である。有機配位子は、配位子含有半導体粒子の合成上の制約から、又は、安定化のために添加した有機配位子であってもよい。例えば、特表2015-529698号公報において、配位子含有半導体粒子は、粒子サイズ制御の観点から有機配位子としてヘキサン酸を含み、また、合成後の安定化のために有機配位子をDDSA(ドデセニルコハク酸)に置換している。
有機配位子は、例えば半導体粒子(A)の表面に配位することができる。樹脂組成物は、1種又は2種以上の有機配位子(F)を含むことができる。有機配位子(F)を含む樹脂組成物から形成される樹脂膜は、有機配位子(F)を含む。
XA-RX (X)
で表される有機化合物であることができる。式中、XAは上記の極性基であり、RXはヘテロ原子(N、O、S、ハロゲン原子等)を含んでいてもよい1価の炭化水素基である。該炭化水素基は、炭素-炭素二重結合等の不飽和結合を1個又は2個以上有していてもよい。該炭化水素基は、直鎖状、分岐鎖状又は環状構造を有していてもよい。該炭化水素基の炭素数は、例えば1以上40以下であり、1以上30以下であってもよい。該炭化水素基に含まれるメチレン基は、-O-、-S-、-C(=O)-、-C(=O)-O-、-O-C(=O)-、-C(=O)-NH-、-NH-等で置換されていてもよい。
化合物(F-1)は、第1官能基及び第2官能基を有する化合物である。第1官能基はカルボキシ基(-COOH)であり、第2官能基はカルボキシ基又はチオール基(-SH)である。化合物(F-1)は、カルボキシ基及び/又はチオール基を有しているため、半導体粒子(A)に配位する配位子となり得る。化合物(F-1)を樹脂組成物に含有させることは、半導体粒子(A)の安定性及び分散性、並びに、樹脂膜の発光強度を向上させるうえで有利である。
樹脂組成物は、化合物(F-1)を1種のみ含んでいてもよいし2種以上含んでいてもよい。
[式中、RBは、2価の炭化水素基を表す。複数のRBが存在する場合、それらは同一でも異なっていてもよい。上記炭化水素基は1以上の置換基を有していてもよい。置換基が複数存在する場合、それらは同一でも異なっていてもよく、それらは互いに結合して、それぞれが結合する原子とともに環を形成していてもよい。上記炭化水素基に含まれる-CH2-は-O-、-S-、-SO2-、-CO-及び-NH-の少なくとも1つに置き換わっていてもよい。
pは、1~10の整数を表す。]
コハク酸、グルタル酸、アジピン酸、オクタフルオロアジピン酸、アゼライン酸、ドデカン二酸、テトラデカン二酸、ヘキサデカン二酸、ヘプタデカン二酸、オクタデカン二酸、ノナデカン二酸、ドデカフルオロスベリン酸、3-エチル-3-メチルグルタル酸、ヘキサフルオログルタル酸、trans-3-ヘキセン二酸、セバシン酸、ヘキサデカフルオロセバシン酸、アセチレンジカルボン酸、trans-アコニット酸、1,3-アダマンタンジカルボン酸、ビシクロ[2.2.2]オクタン-1,4-ジカルボン酸、cis-4-シクロヘキセン-1,2-ジカルボン酸、1,1-シクロプロパンジカルボン酸、1,1-シクロブタンジカルボン酸、cis-又はtrans-1,3-シクロヘキサンジカルボン酸、cis-又はtrans-1,4-シクロヘキサンジカルボン酸、1,1-シクロペンタン二酢酸、1,2,3,4-シクロペンタンテトラカルボン酸、デカヒドロ-1,4-ナフタレンジカルボン酸、2,3-ノルボルナンジカルボン酸、5-ノルボルネン-2,3-ジカルボン酸、フタル酸、3-フルオロフタル酸、イソフタル酸、テトラフルオロイソフタル酸、テレフタル酸、テトラフルオロテレフタル酸、2,5-ジメチルテレフタル酸、2,6-ナフタレンジカルボン酸、2,3-ナフタレンジカルボン酸、1,4-ナフタレンジカルボン酸、1,1’-フェロセンジカルボン酸、2,2’-ビフェニルジカルボン酸、4,4’-ビフェニルジカルボン酸、2,5-フランジカルボン酸、ベンゾフェノン-2,4’-ジカルボン酸一水和物、ベンゾフェノン-4,4’-ジカルボン酸、2,3-ピラジンジカルボン酸、2,3-ピリジンジカルボン酸、2,4-ピリジンジカルボン酸、3,5-ピリジンジカルボン酸、2,5-ピリジンジカルボン酸、2,6-ピリジンジカルボン酸、3,4-ピリジンジカルボン酸、ピラゾール-3,5-ジカルボン酸一水和物、4,4’-スチルベンジカルボン酸、アントラキノン-2,3-ジカルボン酸、4-(カルボキシメチル)安息香酸、ケリドン酸一水和物、アゾベンゼン-4,4’-ジカルボン酸、アゾベンゼン-3,3’-ジカルボン酸、クロレンド酸、1H-イミダゾール-4,5-ジカルボン酸、2,2-ビス(4-カルボキシフェニル)ヘキサフルオロプロパン、1,10-ビス(4-カルボキシフェノキシ)デカン、ジプロピルマロン酸、ジチオジグリコール酸、3,3’-ジチオジプロピオン酸、4,4’-ジチオジブタン酸、4,4’-ジカルボキシジフェニルエーテル、4,4’-ジカルボキシジフェニルスルホン、エチレングリコール ビス(4-カルボキシフェニル)エーテル、3,4-エチレンジオキシチオフェン-2,5-ジカルボン酸、4,4’-イソプロピリデンジフェノキシ酢酸、1,3-アセトンジカルボン酸、メチレンジサリチル酸、5,5’-チオジサリチル酸、トリス(2-カルボキシエチル)イソシアヌレート、テトラフルオロコハク酸、α,α,α’,α’-テトラメチル-1,3-ベンゼンジプロピオン酸、1,3,5-ベンゼントリカルボン酸等。
化合物(F-2)は、化合物(F-1)とは異なる化合物であって、ポリアルキレングリコール構造を含み、かつ極性基を分子末端に有する化合物である。分子末端とは、化合物(F-2)中、最も長い炭素鎖(炭素鎖中の炭素原子は、酸素原子等の他の原子に置き換わっていてもよい。)の末端であることが好ましい。
樹脂組成物は、化合物(F-2)を1種のみ含んでいてもよいし2種以上含んでいてもよい。樹脂組成物は、化合物(F-1)又は化合物(F-2)を含んでいてもよいし、化合物(F-1)及び化合物(F-2)を含んでいてもよい。
なお、ポリアルキレングリコール構造を含み、上記第1官能基及び第2官能基を有する化合物は、化合物(F-1)に属するものとする。
基Yとしては、直鎖状、分岐鎖状又は環状構造を有する炭素数1以上12以下のアルキル基;直鎖状、分岐鎖状又は環状構造を有する炭素数1以上12以下のアルコキシ基等が挙げられる。該アルキル基及びアルコキシ基の炭素数は、好ましくは1以上8以下であり、より好ましくは1以上6以下であり、さらに好ましくは1以上4以下である。該アルキル基及びアルコキシ基に含まれる-CH2-は、-O-、-S-、-C(=O)-、-C(=O)-O-、-O-C(=O)-、-C(=O)-NH-、-NH-等で置換されていてもよい。中でも、基Yは、炭素数が1以上4以下である直鎖状又は分岐鎖状のアルコキシ基であることが好ましく、炭素数が1以上4以下である直鎖状のアルコキシ基であることがより好ましい。
光散乱剤(E)、溶剤(G)、酸化防止剤(H)及びレベリング剤(I)は含まれない。
樹脂(B)は、1種又は2種以上の樹脂を含むことができる。樹脂(B)としては、以下の樹脂[K1]~[K4]等が挙げられる。
樹脂[K1];不飽和カルボン酸及び不飽和カルボン酸無水物からなる群より選ばれる少なくとも1種(a)(以下、「(a)」ともいう。)と、(a)と共重合可能な単量体(c)(ただし、(a)とは異なる。)(以下、「(c)」ともいう。)との共重合体;
樹脂[K2];(a)と(c)との共重合体に炭素数2~4の環状エーテル構造とエチレン性不飽和結合とを有する単量体(b)(以下、「(b)」ともいう。)を反応させた樹脂;
樹脂[K3];(b)と(c)との共重合体に(a)を反応させた樹脂;
樹脂[K4];(b)と(c)との共重合体に(a)を反応させ、さらにカルボン酸無水物を反応させた樹脂。
マレイン酸、フマル酸、シトラコン酸、メサコン酸、イタコン酸、3-ビニルフタル酸、4-ビニルフタル酸、3,4,5,6-テトラヒドロフタル酸、1,2,3,6-テトラヒドロフタル酸、ジメチルテトラヒドロフタル酸、1,4-シクロヘキセンジカルボン酸等の不飽和ジカルボン酸;
メチル-5-ノルボルネン-2,3-ジカルボン酸、5-カルボキシビシクロ[2.2.1]ヘプト-2-エン、5,6-ジカルボキシビシクロ[2.2.1]ヘプト-2-エン、5-カルボキシ-5-メチルビシクロ[2.2.1]ヘプト-2-エン、5-カルボキシ-5-エチルビシクロ[2.2.1]ヘプト-2-エン、5-カルボキシ-6-メチルビシクロ[2.2.1]ヘプト-2-エン、5-カルボキシ-6-エチルビシクロ[2.2.1]ヘプト-2-エン等のカルボキシ基を含有するビシクロ不飽和化合物;
無水マレイン酸、シトラコン酸無水物、イタコン酸無水物、3-ビニルフタル酸無水物、4-ビニルフタル酸無水物、3,4,5,6-テトラヒドロフタル酸無水物、1,2,3,6-テトラヒドロフタル酸無水物、ジメチルテトラヒドロフタル酸無水物、5,6-ジカルボキシビシクロ[2.2.1]ヘプト-2-エン無水物等の不飽和ジカルボン酸無水物;
こはく酸モノ〔2-(メタ)アクリロイルオキシエチル〕、フタル酸モノ〔2-(メタ)アクリロイルオキシエチル〕等の2価以上の多価カルボン酸の不飽和モノ〔(メタ)アクリロイルオキシアルキル〕エステル;
α-(ヒドロキシメチル)(メタ)アクリル酸のような、同一分子中にヒドロキシ基及びカルボキシ基を含有する不飽和(メタ)アクリレート
等が挙げられる。
これらのうち、共重合反応性等の観点から、(メタ)アクリル酸、無水マレイン酸等が好ましい。
本明細書において(メタ)アクリル酸とは、アクリル酸及び/又はメタクリル酸を意味する。「(メタ)アクリロイル」、「(メタ)アクリレート」等においても同様である。
3-メチル-3-メタクリルロイルオキシメチルオキセタン、3-メチル-3-アクリロイルオキシメチルオキセタン、3-エチル-3-メタクリロイルオキシメチルオキセタン、3-エチル-3-アクリロイルオキシメチルオキセタン、3-メチル-3-メタクリロイルオキシエチルオキセタン、3-メチル-3-アクリロイルオキシエチルオキセタン、3-エチル-3-メタクリロイルオキシエチルオキセタン、3-エチル-3-アクリロイルオキシエチルオキセタン等のオキセタン環とエチレン性不飽和結合とを有する単量体;
テトラヒドロフルフリルアクリレート(例えば、ビスコートV#150、大阪有機化学工業(株)製)、テトラヒドロフルフリルメタクリレート等のテトラヒドロフラン環とエチレン性不飽和結合とを有する単量体
等が挙げられる。
樹脂[K2]~[K4]の製造時の反応性が高く、未反応の(b)が残存しにくいことから、(b)としては、オキシラン環とエチレン性不飽和結合とを有する単量体が好ましい。
2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート等のヒドロキシ基含有(メタ)アクリル酸エステル;
マレイン酸ジエチル、フマル酸ジエチル、イタコン酸ジエチル等のジカルボン酸ジエステル;
ビシクロ[2.2.1]ヘプト-2-エン、5-メチルビシクロ[2.2.1]ヘプト-2-エン、5-エチルビシクロ[2.2.1]ヘプト-2-エン、5-ヒドロキシビシクロ[2.2.1]ヘプト-2-エン、5-ヒドロキシメチルビシクロ[2.2.1]ヘプト-2-エン、5-(2’-ヒドロキシエチル)ビシクロ[2.2.1]ヘプト-2-エン、5-メトキシビシクロ[2.2.1]ヘプト-2-エン、5-エトキシビシクロ[2.2.1]ヘプト-2-エン、5,6-ジヒドロキシビシクロ[2.2.1]ヘプト-2-エン、5,6-ジ(ヒドロキシメチル)ビシクロ[2.2.1]ヘプト-2-エン、5,6-ジ(2’-ヒドロキシエチル)ビシクロ[2.2.1]ヘプト-2-エン、5,6-ジメトキシビシクロ[2.2.1]ヘプト-2-エン、5,6-ジエトキシビシクロ[2.2.1]ヘプト-2-エン、5-ヒドロキシ-5-メチルビシクロ[2.2.1]ヘプト-2-エン、5-ヒドロキシ-5-エチルビシクロ[2.2.1]ヘプト-2-エン、5-ヒドロキシメチル-5-メチルビシクロ[2.2.1]ヘプト-2-エン、5-tert-ブトキシカルボニルビシクロ[2.2.1]ヘプト-2-エン、5-シクロヘキシルオキシカルボニルビシクロ[2.2.1]ヘプト-2-エン、5-フェノキシカルボニルビシクロ[2.2.1]ヘプト-2-エン、5,6-ビス(tert-ブトキシカルボニル)ビシクロ[2.2.1]ヘプト-2-エン、5,6-ビス(シクロヘキシルオキシカルボニル)ビシクロ[2.2.1]ヘプト-2-エン等のビシクロ不飽和化合物;
N-フェニルマレイミド、N-シクロヘキシルマレイミド、N-ベンジルマレイミド、N-スクシンイミジル-3-マレイミドベンゾエート、N-スクシンイミジル-4-マレイミドブチレート、N-スクシンイミジル-6-マレイミドカプロエート、N-スクシンイミジル-3-マレイミドプロピオネート、N-(9-アクリジニル)マレイミド等のジカルボニルイミド誘導体;
スチレン、α-メチルスチレン、m-メチルスチレン、p-メチルスチレン、ビニルトルエン、p-メトキシスチレン、アクリロニトリル、メタクリロニトリル、塩化ビニル、塩化ビニリデン、アクリルアミド、メタクリルアミド、酢酸ビニル、1,3-ブタジエンイソプレン、2,3-ジメチル-1,3-ブタジエン
等が挙げられる。
これらのうち、共重合反応性及び樹脂(C)の耐熱性の点から、スチレン、ビニルトルエン、N-フェニルマレイミド、N-シクロヘキシルマレイミド、N-ベンジルマレイミド、ビシクロ[2.2.1]ヘプト-2-エン等が好ましい。
(c)に由来する構造単位;40モル%以上98モル%以下
であることが好ましく、
(a)に由来する構造単位;10モル%以上50モル%以下
(c)に由来する構造単位;50モル%以上90モル%以下
であることがより好ましい。
樹脂[K1]の構造単位の比率が上記の範囲にあると、樹脂組成物の保存安定性及び得られる樹脂膜の耐溶剤性に優れる傾向がある。
なお、樹脂(B)が(a)に由来する構造単位を含む場合、(a)に由来する構造単位を2種以上を含むことができ、この場合、(a)に由来する構造単位の比率(モル基準の含有率)は、各構造単位の比率の総和である。(b)、(c)等の他の単量体に由来する構造単位についても同様である。
用いられる重合開始剤及び溶剤等は、特に限定されず、当該分野で通常使用されているものを使用することができる。例えば、重合開始剤としては、アゾ化合物(2,2’-アゾビスイソブチロニトリル、2,2’-アゾビス(2,4-ジメチルバレロニトリル)等)や有機過酸化物(ベンゾイルペルオキシド等)が挙げられ、溶剤としては、各モノマーを溶解するものであればよく、樹脂組成物に含まれていてもよい溶剤(G)として後述する溶剤等が挙げられる。
まず(a)と(c)との共重合体を、樹脂[K1]の製造方法として記載した方法と同様にして製造する。この場合、それぞれに由来する構造単位の比率は、樹脂[K1]について述べた比率と同じであることが好ましい。
(a)と(c)との共重合体の製造に引き続き、フラスコ内雰囲気を窒素から空気に置換し、(b)、カルボン酸又はカルボン酸無水物と環状エーテルとの反応触媒(例えば有機リン化合物、金属錯体、アミン化合物等)及び重合禁止剤(例えばハイドロキノン等)等の存在下、例えば60℃以上130℃以下で、1~10時間反応することにより、樹脂[K2]を製造することができる。
より好ましくは10モル以上75モル以下である。この範囲にすることにより、樹脂組成物の保存安定性、並びに、得られる樹脂膜の耐溶剤性、耐熱性及び機械強度のバランスが良好になる傾向がある。
重合禁止剤の使用量は、(a)、(b)及び(c)の合計量100質量部に対して、好ましくは0.001質量部以上5質量部以下である。
(b)に由来する構造単位;5モル%以上95モル%以下
(c)に由来する構造単位;5モル%以上95モル%以下
であることが好ましく、
(b)に由来する構造単位;10モル%以上90モル%以下
(c)に由来する構造単位;10モル%以上90モル%以下
であることがより好ましい。
上記共重合体に反応させる(a)の使用量は、(b)100モルに対して、5モル以上80モル以下が好ましい。
カルボン酸無水物としては、例えば、無水マレイン酸、シトラコン酸無水物、イタコン酸無水物、3-ビニルフタル酸無水物、4-ビニルフタル酸無水物、3,4,5,6-テトラヒドロフタル酸無水物、1,2,3,6-テトラヒドロフタル酸無水物、ジメチルテトラヒドロフタル酸無水物、5,6-ジカルボキシビシクロ[2.2.1]ヘプト-2-エン無水物等が挙げられる。
カルボン酸無水物の使用量は、(a)の使用量1モルに対して、0.5~1モルが好ましい。
ベンジル(メタ)アクリレート/(メタ)アクリル酸共重合体にグリシジル(メタ)アクリレートを付加させた樹脂、トリシクロデシル(メタ)アクリレート/スチレン/(メタ)アクリル酸共重合体にグリシジル(メタ)アクリレートを付加させた樹脂、トリシクロデシル(メタ)アクリレート/ベンジル(メタ)アクリレート/(メタ)アクリル酸共重合体にグリシジル(メタ)アクリレートを付加させた樹脂等の樹脂[K2];
トリシクロデシル(メタ)アクリレート/グリシジル(メタ)アクリレートの共重合体に(メタ)アクリル酸を反応させた樹脂、トリシクロデシル(メタ)アクリレート/スチレン/グリシジル(メタ)アクリレートの共重合体に(メタ)アクリル酸を反応させた樹脂等の樹脂[K3];
トリシクロデシル(メタ)アクリレート/グリシジル(メタ)アクリレートの共重合体に(メタ)アクリル酸を反応させた樹脂にさらにテトラヒドロフタル酸無水物を反応させた樹脂等の樹脂[K4]等が挙げられる。
樹脂(B)は、樹脂[K2]、樹脂[K3]及び樹脂[K4]からなる群より選ばれる少なくとも1種を含むことが好ましい。
酸基は、例えば樹脂(Ba)が、酸基含有単量体(例えば(メタ)アクリル酸等)に由来する構成単位(γ)を含むことで、樹脂中に導入されたものであることができる。樹脂(Ba)は、好ましくは、主鎖骨格に構成単位(α)、(β)及び(γ)を含む。
[式中、RCは、同一又は異なって、水素原子又はメチル基を表す。RDは、同一又は異なって、炭素数4~20の直鎖状又は分岐鎖状炭化水素基を表す。mは、式(II)で表される構成単位の平均繰り返し単位数を表し、1以上の数である。]
樹脂組成物は、重合性化合物(C)及び重合開始剤(D)を実質的に含まないことが好ましい。本明細書において、「実質的に含まない」とは、樹脂組成物の固形分の総量に対する含有率が0.01質量%以下であることをいう。重合性化合物(C)及び重合開始剤(D)の含有率は、それぞれ、好ましくは0.005質量%以下、より好ましくは0質量%である。
トリイソプロパノールアミン、4-ジメチルアミノ安息香酸メチル、4-ジメチルアミノ安息香酸エチル、4-ジメチルアミノ安息香酸イソアミル、安息香酸2-ジメチルアミノエチル、4-ジメチルアミノ安息香酸2-エチルヘキシル、N,N-ジメチルパラトルイジン、4,4’-ビス(ジメチルアミノ)ベンゾフェノン(通称ミヒラーズケトン)、4,4’-ビス(ジエチルアミノ)ベンゾフェノン、4,4’-ビス(エチルメチルアミノ)ベンゾフェノン等が挙げられる。
樹脂組成物は、光散乱剤(E)を含むことができる。該樹脂組成物から形成される樹脂膜は、光散乱剤(E)を含み、光散乱性を示し得る。樹脂組成物及び樹脂膜は、光散乱剤(E)を2種以上含んでもよい。
ビックケミー・ジャパン社製のDISPERBYK-101、102、103、106、107、108、109、110、111、116、118、130、140、154、161、162、163、164、165、166、170、171、174、180、181、182、183、184、185、190、192、2000、2001、2020、2025、2050、2070、2095、2150、2155;ANTI-TERRA-U、U100、203、204、250、;BYK-P104、P104S、P105、220S、6919;BYK-LPN6919、21116;LACTIMON、LACTIMON-WS;Bykumen等;
日本ルーブリゾール社製のSOLSPERSE-3000、9000、13000、13240、13650、13940、16000、17000、18000、20000、21000、24000、26000、27000、28000、31845、32000、32500、32550、33500、32600、34750、35100、36600、38500、41000、41090、53095、55000、76500等;
BASF社製のEFKA-46、47、48、452、4008、4009、4010、4015、4020、4047、4050、4055、4060、4080、4400、4401、4402、4403、4406、4408、4300、4310、4320、4330、4340、450、451、453、4540、4550、4560、4800、5010、5065、5066、5070、7500、7554、1101、120、150、1501、1502、1503等;
味の素ファインテクノ社製のアジスパーPA111、PB711、PB821、PB822、PB824等が挙げられる。
樹脂組成物は、溶剤(G)を含むことができる。溶剤(G)は、樹脂(B)を溶解するものであれば特に限定されず、当該分野で通常使用される溶剤を用いることができる。例えば、エステル溶剤(分子内に-COO-を含み、-O-を含まない溶剤)、エーテル溶剤(分子内に-O-を含み、-COO-を含まない溶剤)、エーテルエステル溶剤(分子内に-COO-と-O-とを含む溶剤)、ケトン溶剤(分子内に-CO-を含み、-COO-を含まない溶剤)、アルコール溶剤(分子内にOHを含み、-O-、-CO-及びCOO-を含まない溶剤)、芳香族炭化水素溶剤、アミド溶剤、ジメチルスルホキシド等が挙げられる。溶剤(G)は、2種以上を併用してもよい。
2-メチルプロピオン酸エチル、3-メトキシブチルアセテート、3-メチル-3-メトキシブチルアセテート、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート、エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート及びジエチレングリコールモノブチルエーテルアセテート等が挙げられる。
樹脂組成物及びそれから形成される樹脂膜は、酸化防止剤(H)を含むことができる。酸化防止剤(H)としては、工業的に一般に使用される酸化防止剤であれば特に限定はなく、フェノール系酸化防止剤、リン系酸化防止剤、リン/フェノール複合型酸化防止剤及び硫黄系酸化防止剤等を用いることができる。酸化防止剤(H)は、2種以上を併用してもよい。
樹脂組成物及びそれから形成される樹脂膜は、必要に応じて、重合禁止剤、充填剤、他の高分子化合物、密着促進剤、光安定剤、連鎖移動剤、レベリング剤等、当該技術分野で公知の添加剤がさらに含まれていてもよい。
樹脂組成物は、所定の成分、並びに必要に応じて使用される他の成分を混合する工程を含む方法によって製造することができる。樹脂組成物の製造方法は、樹脂(B)を調製する工程をさらに含むことができる。
本発明に係る樹脂膜は、例えば、上述の樹脂組成物を基板に塗布した後に乾燥させる工程を含む方法によって得ることができる。樹脂膜は、上記基板全面に形成されていてもよいし、上記基板の一部にパターン状に形成されていてもよい。樹脂膜をパターン状に形成する方法としては、インクジェット法、印刷法等が挙げられる。印刷法としては、ステンシル印刷法、スクリーン印刷法、アプリケーターによる印刷塗工等が挙げられる。
上述の樹脂組成物を塗布して組成物層を形成する塗布工程と、
第1温度で組成物層の乾燥を行う第1乾燥工程と、
第2温度で第1乾燥工程後の組成物層の乾燥を行う第2乾燥工程と、
を含む。第2温度は、第1温度よりも高い。
熱処理の方法は特に制限されず、例えば、熱風、赤外線、マイクロ波、電気抵抗等を用いた熱処理方法、又はこれらの組み合わせが挙げられる。組成物層の熱処理は、上記基板を加熱することによって行われてもよい。
本発明に係る樹脂膜は、表示装置、特に、液晶表示装置、有機EL表示装置又は無機EL表示装置における色変換層(波長変換層)として有用である。このような表示装置としては、例えば、特開2006-309219号公報、特開2006-310303号公報、特開2013-15812号公報、特開2009-251129号公報、特開2014-2363号公報等に記載される表示装置が挙げられる。
(1)樹脂膜の発光強度L、並びに、第1及び第2の発光強度維持率R1、R2
5cm角のガラス基板(イーグル2000;コーニング社製)上に、膜厚10μmの樹脂膜を形成して、樹脂膜を有する基板を得た。樹脂膜は、後述する実施例及び比較例の記載に従って製造した。
第1の発光強度維持率R1(%)=100×(第1露光試験後の発光強度)/(第1露光試験前の発光強度)
第2の発光強度維持率R2(%)=100×(第2露光試験後の発光強度)/(第1露光試験後の発光強度)
5cm角のポリエチレンテレフタレート(PET)フィルム(東レ(株)製の「ルミラー75-T60」)に形成した膜厚10μmの樹脂膜を形成した。樹脂膜は、後述する実施例及び比較例の記載に従って製造した。放冷後、PETフィルム上に形成された樹脂膜に、別の5cm角PETフィルム(東レ(株)製の「ルミラー75-T60」)を押し付けた後、この押し付けたPETフィルムを剥がした。剥がした直後の樹脂膜の表面及び剥がしたPETフィルムを目視で観察し、下記の評価基準に従って評価した。
A:樹脂膜にムラがなく、剥がしたPETフィルムに膜の転写がない(タック性が見られない)
B:樹脂膜にムラがあり、剥がしたPETフィルムに膜の転写がある(タック性が見られる)
C:樹脂膜が得られなかった
後述する実施例及び比較例の記載に従ってガラス基板上に形成した直後の樹脂膜(膜厚10μm)の表面を目視観察し、下記の評価基準に従って評価した。
A:表面が平滑である
B:表面に凹凸がある
C:樹脂膜が得られなかった
樹脂の重量平均分子量Mwの測定は、GPC法により以下の条件で行った。
装置;K2479((株)島津製作所製)
カラム;SHIMADZU Shim-pack GPC-80M
カラム温度;40℃
溶媒;テトラヒドロフラン
流速;1.0mL/min
検出器;RI
校正用標準物質 ;TSK STANDARD POLYSTYRENE F-40、F-4、F-288、A-2500、A-500(東ソー(株)製)
樹脂溶液3gを精秤し、アセトン90gと水10gとの混合溶剤に溶解し、0.1規定のKOH水溶液を滴定液として用いて、自動滴定装置(平沼産業社製の商品名「COM-555」)により、樹脂溶液の酸価を測定し、溶液の酸価と溶液の固形分とから固形分1g当たりの酸価(mgKOH/g)を求めた。
樹脂溶液をアルミカップに約1gはかり取り、180℃で1時間乾燥した後、質量を測定した。その質量減少量から、樹脂溶液の固形分(質量%)を計算した。
有機配位子(F)としてオレイン酸が配位したInP/ZnSeS量子ドットのトルエン分散液を準備した。分散液を減圧蒸留し、トルエンを除去した。固形分30部に対しシクロヘキシルアセテート70部を添加して、半導体粒子(A-1)の分散液(固形分30%)を得た。
酸化チタンナノ粒子70部に、DISPERBYK21116(ビックケミー・ジャパン製)を固形分で3部、プロピレングリコールモノメチルエーテルアセテート(以下、「PGMEA」という。)を全量が100部になるように加えた後、ペイントシェイカーで十分に分散するまで撹拌して、光散乱剤(E-1)の分散液(固形分73%)を得た。
撹拌器、温度計付き還流冷却管、滴下ロート及び窒素導入管を具備したフラスコに、PGMEAを110部投入した後、窒素置換しながら撹拌し、80℃に昇温した。ジシクロペンタニルメタクリレート25部、メチルメタクリレート26部、メタクリル酸16部、2,2’-アゾビス(2,4-ジメチルバレロニトリル)14部をPGMEA110部に溶解した溶液を、滴下ロートからフラスコ中に滴下した後、80℃で3時間撹拌した。
次に、グリシジルメタクリレート16部、2、2’-メチレンビス(4-メチル-6-tert-ブチルフェノール)0.4部、トリフェニルホスフィン0.8部をフラスコ内に投入して110℃まで昇温、8時間撹拌することで重合体中のカルボン酸とエポキシ基とを反応させて、重合性不飽和結合を導入した。次いで、1,2,3,6-テトラヒドロフタル酸無水物17部を加え3時間反応を続けて、側鎖にカルボン酸基を導入した。反応液を室温まで冷却することで樹脂(B-1)溶液を得た。
樹脂(B-1)は、標準ポリスチレン換算の重量平均分子量Mwが5200、分子量分布が2.3、酸価が100mgKOH/gであり、樹脂(B-1)溶液中の固形分は40質量%であった。
2,2’-アゾビス(2,4-ジメチルバレロニトリル)を12.5質量部としたこと以外は製造例3と同様にして樹脂(B-2)溶液を得た。
樹脂(B-2)は、標準ポリスチレン換算の重量平均分子量Mwが6500、分子量分布が2.2、酸価が100mgKOH/gであり、樹脂(B-2)溶液中の固形分は40質量%であった。
2,2’-アゾビス(2,4-ジメチルバレロニトリル)を11質量部としたこと以外は製造例3と同様にして樹脂(B-3)溶液を得た。
樹脂(B-3)は、標準ポリスチレン換算の重量平均分子量Mwが7600、分子量分布が2.1、酸価が100mgKOH/gであり、樹脂(B-3)溶液中の固形分は40質量%であった。
メチルメタクリレートを23質量部、メタクリル酸を19質量部、2,2’-アゾビス
(2,4-ジメチルバレロニトリル)を10質量部としたこと以外は製造例3と同様にして樹脂(B-4)溶液を得た。
樹脂(B-4)は、標準ポリスチレン換算の重量平均分子量Mwが8400、分子量分布が2.2、酸価が100mgKOH/gであり、樹脂(B-4)溶液中の固形分は40質量%であった。
(1)樹脂組成物の調製
製造例1で得られた有機配位子(F)を含有する半導体粒子(A-1)の分散液、製造例2で得られた光散乱剤(E-1)の分散液、製造例3~6で得られた樹脂(B-1)溶液~樹脂(B-4)溶液のいずれか、並びに、表1に示される他の成分をそれぞれ所定量混合して、樹脂組成物を調製した。
ガラス基板上に、25℃の温度下、樹脂組成物をフィルムアプリケーター(太佑機材(株)製の「AP75」)を用いて塗布して組成物層を形成した。次いで、下記温度プロファイルに従う、第1乾燥工程及び第2乾燥工程を含む乾燥処理を行って、膜厚10μmの樹脂膜を形成した。
[25℃→100℃(1分)]-[100℃一定(3分、第1乾燥工程)]-[100℃→25℃(1分)]-[25℃一定(3分)]-[25℃→180℃(1分)]-[180℃一定(10分、第2乾燥工程)]-[180℃→25℃(5分)]
ガラス基板上に、25℃の温度下、実施例1の樹脂組成物と同じ樹脂組成物をフィルムアプリケーター(太佑機材(株)製の「AP75」)を用いて塗布して組成物層を形成した。次いで、下記温度プロファイルに従う、第2乾燥工程を含む乾燥処理(第1乾燥工程を有しない)を行って、膜厚10μmの樹脂膜を形成した。
[25℃→180℃(1分)]-[180℃一定(10分、第2乾燥工程)]-[180℃→25℃(5分)]
参考例の樹脂膜は、タック性の評価はAであったが、膜外観の評価はBであった。
〔1〕重合性化合物(C-1):光重合性化合物「M-510」(多塩基変性アクリレート、東亞合成社製、固形分100%)
〔2〕重合開始剤(D-1):下記式で表される化合物(光重合開始剤)。特開2011-132215号公報に記載される方法により製造した(固形分100%)。
〔4〕溶剤(G-1):PGMEA(プロピレングリコールモノメチルエーテルアセテート)
〔5〕溶剤(G-2):シクロヘキシルアセテート
〔6〕酸化防止剤(H-1):Sumilizer-GP(リン/フェノール複合型酸化防止剤、住友化学社製、固形分100%)
Claims (7)
- 半導体粒子(A)を含む樹脂膜であって、
前記樹脂膜に対して、大気中、露光量200mJ/cm2(照射波長365nm基準)の条件で露光を行う第1露光試験を実施したとき、下記式で示される第1の発光強度維持率R1が95%以上である、樹脂膜。
第1の発光強度維持率R1(%)=100×(前記第1露光試験後の発光強度)/(前記第1露光試験前の発光強度) - 前記第1露光試験が実施された樹脂膜に対して、大気中、露光量200mJ/cm2(照射波長365nm基準)の条件で露光を行う第2露光試験を実施したとき、下記式で示される第2の発光強度維持率R2が85%以上である、請求項1に記載の樹脂膜。
第2の発光強度維持率R2(%)=100×(前記第2露光試験後の発光強度)/(前記第1露光試験後の発光強度) - 前記半導体粒子(A)と、樹脂(B)とを含む樹脂組成物から形成される、請求項1に記載の樹脂膜。
- 前記樹脂組成物は、重合性化合物(C)及び重合開始剤(D)の含有量が、それぞれ、前記樹脂組成物の固形分の総量に対して0.01質量%以下である、請求項3に記載の樹脂膜。
- 前記樹脂組成物は、前記重合性化合物(C)及び前記重合開始剤(D)の含有量が、それぞれ、前記樹脂組成物の固形分の総量に対して0質量%である、請求項4に記載の樹脂膜。
- 光散乱剤(E)をさらに含む、請求項1~5のいずれか1項に記載の樹脂膜。
- 請求項1~5のいずれか1項に記載の樹脂膜を含む表示装置。
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| JP7406983B2 (ja) * | 2019-12-26 | 2023-12-28 | 住友化学株式会社 | 組成物および表示装置 |
-
2022
- 2022-10-19 JP JP2022167833A patent/JP2023070648A/ja active Pending
- 2022-10-24 US US18/707,818 patent/US20250012965A1/en active Pending
- 2022-10-24 EP EP22892561.6A patent/EP4431573A4/en active Pending
- 2022-10-24 KR KR1020247009622A patent/KR20240108371A/ko active Pending
- 2022-10-24 WO PCT/JP2022/039471 patent/WO2023085061A1/ja not_active Ceased
- 2022-10-24 CN CN202280073483.0A patent/CN118202003A/zh active Pending
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Also Published As
| Publication number | Publication date |
|---|---|
| EP4431573A4 (en) | 2025-10-08 |
| TW202319458A (zh) | 2023-05-16 |
| JP2023070648A (ja) | 2023-05-19 |
| EP4431573A1 (en) | 2024-09-18 |
| KR20240108371A (ko) | 2024-07-09 |
| CN118202003A (zh) | 2024-06-14 |
| US20250012965A1 (en) | 2025-01-09 |
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