Compositions and methods of manufacturing thereof, thin films containing the composition and methods of manufacturing thereof, light-emitting devices, power-generating devices, and displays

Abstract

A composition is provided comprising: a quantum dot material having a perovskite-type crystalline structure and an olefin polymer. The olefin polymer is preferably a cycloolefin polymer, or a block copolymer comprising repeating units derived from aromatic ethylene compounds and repeating units derived from chain-like conjugated diene compounds. A thin film comprising the aforementioned composition, a light-emitting device and display using the aforementioned thin film as a light conversion element, a power-generating device using the aforementioned thin film as a power-generating element, and a method for manufacturing the aforementioned composition and the aforementioned thin film are also provided.

Description

Technical Field

[0001] This invention relates to a composition comprising a quantum dot material having a perovskite-type crystalline structure and a method for manufacturing the same, as well as a thin film comprising the composition and a method for manufacturing the same. Prior Technology

[0002] Quantum dot materials are nanoscale semiconductor materials that exhibit quantum effects by trapping electrons within the quantum dots. Quantum dot materials, as described in, for example, Patent Document 1, have been used as materials for light-emitting devices (Patent Document 1). Furthermore, quantum dot materials have also been used, for example, as materials for power-generating devices.

[0003] Patent Documents Patent Document 1: International Patent Publication No. 2012 / 102107 (corresponding publication: U.S. Patent Application Publication No. 2013 / 0334557). Summary of the Invention

[0004] As quantum dot materials, quantum dot materials with perovskite-type crystalline structures have attracted attention in recent years. These quantum dot materials are highly anticipated as materials for power generation and light-emitting devices due to their high luminescence quantum yield (luminescence efficiency) and high photoelectric conversion efficiency.

[0005] On the other hand, quantum dot materials with perovskite-type crystalline structures have low atmospheric stability.

[0006] The present invention was made in view of the above facts, and its purpose is to provide a composition comprising a quantum dot material having a perovskite-type crystalline structure and an atmospheric stability optimization thereof, as well as a thin film comprising the aforementioned composition and a method thereof for manufacturing the same.

[0007] The inventors have discovered that by combining quantum dot materials with perovskite-type crystalline structures with olefin polymers, the atmospheric stability of the quantum dot materials in the composition and in articles such as thin films formed from the composition can be improved, thereby completing the present invention. The present invention includes the following:

[0008] [1] A composition comprising: a quantum dot material having a perovskite-type crystalline structure and an olefin polymer.

[0009] [2] As described in [1], the aforementioned olefin polymers include cyclic olefin polymers.

[0010] [3] As described in [2], the aforementioned cyclic olefin polymer contains reduced Alkene polymers, the aforementioned degradation Alkene polymers include those selected from those with degradation Hydroxides of ring-opening polymers of monomers with olefin structures, possessing degrading properties At least one of the addition copolymers of an olefinic monomer and an α-olefin and its hydride.

[0011] [4] As described in [2], the aforementioned cyclic olefin polymer includes a hydrogenated block copolymer [E], which is a hydrogenated block copolymer formed by hydrogenating a block copolymer [D]. The block copolymer [D] is formed from "polymer blocks [A] with repeating units [I] derived from aromatic ethylene compounds as the main components" and "polymer blocks [B] with repeating units [I] derived from aromatic ethylene compounds and repeating units [II] derived from chain conjugated diene compounds as the main components" or "polymer blocks [C] with repeating units [II] derived from chain conjugated diene compounds as the main components".

[0012] [5] As described in [4], the aforementioned cyclic olefin polymers contain alkoxysilane groups.

[0013] [6] As described in [1], the aforementioned olefin polymer includes a block copolymer [D], which is composed of "polymer block [A] with repeating units [I] derived from aromatic ethylene compounds as the main component" and "polymer block [B] with repeating units [I] derived from aromatic ethylene compounds and repeating units [II] derived from chain conjugated diene compounds as the main components" or "polymer block [C] with repeating units [II] derived from chain conjugated diene compounds as the main component".

[0014] [7] The composition described in any of [1] to [6], wherein the quantum dot material contained in the aforementioned composition is 0.05 parts by weight or more and 50 parts by weight or less relative to 100 parts by weight of the aforementioned olefin polymer.

[0015] [8] A thin film comprising the composition described in any one of [1] to [7].

[0016] [9] A light-emitting device that uses a thin film as described in [8] as a light conversion element.

[0017]

[10] A power generation device that uses a thin film as described in [8] as a power generation element.

[0018]

[11] A display that uses a thin film as described in [8] as a light conversion element.

[0019]

[12] A method for manufacturing a composition, which is a method for manufacturing a composition of any one of the compositions described in [1] to [7], comprising: a first step of obtaining a dispersion of the aforementioned quantum dot material; a second step of obtaining a solution of the aforementioned olefin polymer; and a third step of mixing the dispersion of the aforementioned quantum dot material with the solution of the aforementioned olefin polymer.

[0020]

[13] A method for manufacturing a composition, which is a method for manufacturing a composition of any one of the compositions described in [1] to [7], comprising: a first step of obtaining a dispersion of the aforementioned quantum dot material; and a fourth step of adding the aforementioned olefin polymer to the aforementioned dispersion and dissolving the aforementioned olefin polymer in the aforementioned dispersion.

[0021]

[14] A method for manufacturing a thin film, which uses any one of the components described in [1] to [7] to manufacture the thin film, comprising: a fifth step of forming a component layer using the aforementioned components; and a sixth step of drying the aforementioned component layer.

[0022]

[15] The method for manufacturing a thin film as described in

[14] , wherein the aforementioned fifth step is a step of coating the aforementioned composition onto a substrate to form the aforementioned composition layer, using a die coater, a rotary gravure coater, a stencil coater, a doctor blade coater or an inkjet coater to coat the aforementioned composition.

[0023] According to the present invention, a composition comprising a quantum dot material having a perovskite-type crystalline structure and an atmospheric stability thereof, and a method thereof for manufacturing the same, as well as a thin film comprising the aforementioned composition and a method thereof for manufacturing the same, are provided. Simple Explanation of the Diagram

[0024] <Figure 1> Figure 1 is the X-ray diffraction pattern of FAPbBr3 obtained in Example 1. Implementation

[0025] The following describes embodiments and examples to illustrate the present invention in detail. However, the present invention is not limited to the embodiments and examples disclosed below, and may be implemented in any way without departing from the scope of the claims of this application and their equivalents.

[0026] In the following description, the term "solvent" refers not only to the medium in a solution but also to the dispersion medium in which solids are dispersed.

[0027] In the following description, the terms "plate," "layer," and "film" can refer to rigid components or flexible components, such as resin films, unless otherwise noted.

[0028] [1. Composition]

[0029] One embodiment of the present invention comprises: a quantum dot material having a perovskite-type crystalline structure and an olefin polymer.

[0030] According to the present invention, by combining the aforementioned specific quantum dot material with a specific polymer, a composition exhibiting good atmospheric stability of quantum dot material can be obtained. Furthermore, by using this composition, articles such as thin films exhibiting good atmospheric stability of quantum dot material can be obtained.

[0031] [1.1. Quantum dot materials]

[0032] Quantum dot materials are nanoscale semiconductor materials that exhibit quantum effects by trapping electrons within the quantum dots. Furthermore, quantum dot materials function as phosphors, absorbing light of a specific wavelength as excitation light and emitting fluorescence of another wavelength. In quantum dot materials, the following quantum effect occurs: excitons (electrons) generated by light absorption are trapped in a nanoscale region, restricting their movement and causing energy levels to become discrete. Moreover, the band gap varies depending on the particle size of the quantum dot material. Therefore, quantum dot materials possess the property of emitting fluorescence at wavelengths that vary with particle size.

[0033] The wavelength of the excitation light of the quantum dot material used in this embodiment is, for example, 300 nm or more and 800 nm or less. Furthermore, the wavelength of the fluorescence of the quantum dot material is, for example, in the visible light region (e.g., 400 nm or more and 750 nm or less).

[0034] The quantum dot material of this embodiment has a perovskite-type crystalline structure. The term "perovskite-type crystalline structure" refers to a crystalline structure identical to that of perovskite (CaTiO3). For example, if the positions of the crystalline structure are designated as A′, B′, and X′, the ideal structure of a perovskite-type crystalline structure is as follows: a cubic lattice, with A′ positioned at each vertex of the cubic crystal, B′ at the body center, and X′ positioned at the face centers of the cubic crystal with B′ as the center. This structure can be represented by the formula A′B′X′3.

[0035] For example, the material shown in the following experimental formula (1) is preferred as a quantum dot material with a perovskite-type crystalline structure. A (1 + a)B (1 + b)X (3 + c)(1) (In the aforementioned experimental formula (1), A is a monovalent cation, B is a divalent metal ion, X is a monovalent anion, a is -0.2≦a≦0.2, b is -0.2≦b≦0.2, and c is -0.5≦a≦0.5.)

[0036] In the aforementioned experimental formula (1), A is a monovalent cation. A is usually located at the A′ position in a perovskite-type crystal structure. Examples of A include: methylammonium (MA) ion, formamidinium (FA) ion, and cesium (Cs) ion.

[0037] In the aforementioned experimental formula (1), B is a divalent metal ion. B is usually located at the B′ site in a perovskite-type crystal structure. Examples of B include Pb.

[0038] In experimental formula (1), X is a monovalent anion. X is usually located at the X′ position in a perovskite-type crystal structure. Examples of X include Cl, Br, and I. In the quantum dot material shown by experimental formula (1), the color of the fluorescent light emitted by the quantum dot material can be adjusted by using the anion of X. Specifically, using Cl, a quantum dot material with blue fluorescence can be produced; using Br, a quantum dot material with green fluorescence can be produced; and using I, a quantum dot material with red fluorescence can be produced.

[0039] In the aforementioned experimental formula (1), a is typically -0.2 ≤ a ≤ 0.2, preferably -0.1 ≤ a ≤ 0.1, and ideally a = 0. Furthermore, b is typically -0.2 ≤ b ≤ 0.2, preferably -0.1 ≤ b ≤ 0.1, and ideally b = 0. And c is -0.5 ≤ c ≤ 0.5, preferably -0.3 ≤ c ≤ 0.3, and ideally c = 0. In this embodiment, it is preferable that a = b = c = 0 in the aforementioned experimental formula (I), that is, the quantum dot material has the composition shown in ABX 3.

[0040] More specific examples of quantum dot materials include FAPbBr3, which exhibits green fluorescence; CsPbCl3, MAPbCl3, and FAPbCl3, which exhibit blue fluorescence; and CsPbI3, MAPbI3, and FAPbI3, which exhibit red fluorescence.

[0041] Quantum dot materials possess a perovskite-type crystalline structure, which can be confirmed, for example, by using spectra obtained through powder X-ray diffraction (XRD). Specifically, the presence of peaks in the spectra of quantum dot materials with known perovskite-type crystalline structures confirms the existence of this structure. For instance, in the case of quantum dot materials containing FA, Pb, and Br, the presence of peaks at 2θ = 14.7°, 21.4°, 29.8°, 33.3°, 42.6°, and 45.4° in powder X-ray diffraction using CuKα lines can confirm the presence of a perovskite-type crystalline structure. The positions of each peak should be within an error range of, for example, ±0.5°.

[0042] The average particle size of quantum dot materials should be selected appropriately according to the desired fluorescence color, but it is better to be above 1 nm, better to be above 3 nm, better to be below 20 nm, and better to be below 10 nm.

[0043] The average particle size of quantum dot materials can be observed using a transmission electron microscope (TEM). Thirty sizes are randomly measured, and the result is calculated as the arithmetic mean of the measurement results.

[0044] The weight ratio of quantum dot material contained in the composition should be appropriately selected according to the intended use of the composition. However, it is preferable to have 0.05 parts by weight or more, 0.5 parts by weight or more, 1 part by weight or more, and preferably 50 parts by weight or less, 40 parts by weight or less, and 30 parts by weight or less, relative to 100 parts by weight of the olefin polymer. This is because by maintaining the aforementioned weight ratio of quantum dot material, the quantum dot material can be well dispersed in the composition.

[0045] [1.2. Olefin Polymers]

[0046] Olefin polymers are polymers or their hydrides obtained by polymerizing olefin monomers. Furthermore, olefin polymers can be homopolymers, copolymers, or hydrides of copolymers. Examples of olefin polymers include: chain olefin polymers containing chain olefin units, and cyclic olefin polymers containing cyclic olefin monomer units. Among these, cyclic olefin polymers are preferred because they exhibit high heat resistance and excellent moisture absorption.

[0047] Cycloolefin polymers are those that possess a cyclic structure within their molecules. Typically, cycloolefin polymers have alicyclic structures in their repeating units. Cycloolefin polymers can be polymers with alicyclic structures in the main chain, polymers with alicyclic structures in the side chains, polymers with alicyclic structures in both the main chain and side chains, and mixtures of two or more of these in any ratio. From the viewpoint of mechanical strength and heat resistance, polymers containing alicyclic structures in the main chain are preferred.

[0048] Examples of alicyclic structures include saturated alicyclic hydrocarbons (cycloalkanes) and unsaturated alicyclic hydrocarbons (cycloalkenes, cycloalkynes). From the perspective of mechanical strength and heat resistance, cycloalkanes and cycloalkenes are preferred, with cycloalkanes being particularly advantageous.

[0049] The number of carbon atoms constituting the alicyclic structure is preferably 4 or more, more preferably 5 or more, and preferably 30 or less, more preferably 20 or less, and especially preferably 15 or less. When it is within the aforementioned range, a high balance can be achieved between mechanical strength, heat resistance and the formability of the substrate layer.

[0050] In cyclic olefin polymers, the proportion of alicyclic structural units relative to all structural units should be appropriately selected according to the intended use. A proportion of 55% by weight or more is preferred, 70% by weight or more is preferable, and 90% by weight or more is even better. If the proportion of alicyclic structural units relative to all structural units falls within this range, it is preferable from the viewpoint of the substrate layer's transparency and heat resistance.

[0051] Examples of cyclic olefin polymers include: [list of examples would be inserted here] Alkene polymers; monocyclic cyclic olefin polymers, cyclic conjugated diene polymers, ethylene alicyclic hydrocarbon polymers and their hydrides; and hydrides of ethylene aromatic hydrocarbon polymers. Among these, those with good transparency are preferred for free fall-off. It is preferred to have one or more of the following groups: olefin polymers; ethylene alicyclic hydrocarbon polymers and their hydrides; and ethylene aromatic hydrocarbon polymers.

[0052] As a reduction Examples of olefin polymers include those with reducing... Ring-opening polymers of monomers with olefin structures and their hydrides, as well as those with degrading properties Addition polymers of monomers with an olefinic structure and their hydrides. Furthermore, as a polymer with degrading properties... Examples of ring-opening polymers of monomers with olefin structures can be listed as follows: those with degrading properties... Ring-opening homopolymers of one monomer with an olefin structure, possessing degrading properties Ring-opening copolymers of two or more monomers with an olefinic structure, and those with degrading properties Monomers with an olefinic structure and ring-opening copolymers of any monomers thereof. Furthermore, as a [material / method / product] with [a certain characteristic / effect]... Examples of addition polymers of monomers with olefin structures can be listed as follows: those with reducing... An addition homopolymer of a monomer with an olefin structure, possessing degrading properties Addition copolymers of two or more monomers with an olefinic structure, and those with reducing properties Monomers with an olefinic structure and addition copolymers of any monomers thereof. Among these, those with reducing... Hydroxides of ring-opening polymers of monomers with olefin structures, possessing degrading properties Addition copolymers of monomers with olefin structures and α-olefins and those with degrading properties Hydrogenates of addition copolymers of olefinic monomers and α-olefins are preferred, as they have degrading properties. Hydrogenates of ring-opening copolymers of two or more monomers with an olefin structure, possessing degrading properties Addition copolymers of monomers with olefin structures and α-olefins and those with degrading properties Hydrogenates of addition copolymers of olefinic monomers and α-olefins are preferred.

[0053] As a product with reduction Monomers with an alkene structure can be listed as, for example: bicyclic [2.2.1]hept-2-ene (common name: thiohepten-2-ene). This includes compounds such as benzo[4.3.0.1 2,5]dec-3,7-diene (common name: dicyclopentadiene), 7,8-benzotricyclo[4.3.0.1 2,5]dec-3-ene (common name: methyl-bridged tetrahydrobenzene), tetracyclo[4.4.0.1 2,5.1 7,10]dodecyl-3-ene (common name: tetracyclododecene), and derivatives of these compounds (e.g., those with substituents on the ring). Examples of substituents include alkyl groups, alkyl groups, and polar groups. Multiple identical or different substituents may be bonded to the ring. This has a degrading effect. A single monomer of an olefin structure can be used alone, or two or more monomers can be combined in any ratio.

[0054] Examples of polar groups include heteroatoms or groups containing heteroatoms. Examples of heteroatoms include oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, and halogen atoms. Specific examples of polar groups include carboxyl groups, carbonyloxycarbonyl groups, epoxy groups, hydroxyl groups, oxygen groups, ester groups, silyl groups, silyl groups, amino groups, nitrile groups, and sulfonic acid groups.

[0055] As capable of reducing Monomers that undergo ring-opening copolymerization of olefinic monomers include, for example: monocyclic alkenes such as cyclohexene, cycloheptene, and cyclooctene, and their derivatives; cyclic conjugated dienes such as cyclohexadiene and cycloheptadiene, and their derivatives; etc. They can react with monomers that have a degrading effect. The monomers in the ring-opening copolymerization of olefinic monomers can be used alone or in any ratio of two or more.

[0056] With reduction Ring-opening polymers of monomers with an olefinic structure, for example, can be manufactured by polymerizing or copolymerizing the monomers in the presence of a ring-opening polymerization catalyst.

[0057] With a decrease In addition copolymers of monomers with olefin structures and α-olefins, examples of α-olefins include ethylene, propylene, 1-butene, and other α-olefins with 2 to 20 carbon atoms, as well as their derivatives. Among these, ethylene is preferred. An α-olefin can be used alone or in any combination of two or more.

[0058] With reduction Addition polymers of monomers with an olefinic structure, for example, can be manufactured by polymerizing or copolymerizing the monomers in the presence of an addition polymerization catalyst.

[0059] For example, the hydrides of the aforementioned ring-opening polymers and addition polymers can be manufactured by hydrogenating more than 90% of the carbon-carbon unsaturated bonds in a solution of the ring-opening polymers and addition polymers in the presence of a hydrogenation catalyst containing transition metals such as nickel and palladium.

[0060] As a reduction Trade names for olefin polymers include, for example: "ZEONOR" and "ZEONEX" manufactured by Zeon Corporation of Japan; "ARTON" manufactured by JSR Corporation; "APEL" manufactured by Mitsui Chemicals Co., Ltd.; etc.

[0061] Examples of ethylene alicyclic hydrocarbon polymers include polymers of ethylene alicyclic hydrocarbon monomers such as vinylcyclohexene and vinylcyclohexane, and their hydrides; hydrides of the aromatic ring portion of polymers of ethylene aromatic monomers; etc. Furthermore, copolymers of ethylene alicyclic hydrocarbon monomers or ethylene aromatic monomers and other monomers capable of copolymerizing with these monomers are also possible. Examples of such copolymers include: random copolymers, block copolymers, etc. Examples of block copolymers include: diblock copolymers, triblock copolymers, or multiblock copolymers of more than one type, or tilted block copolymers, etc., and are not particularly limited.

[0062] As an ethylene alicyclic hydrocarbon polymer, the hydride of an ethylene aromatic polymer is preferred. An ethylene aromatic polymer means a polymer containing repeating units[I] derived from aromatic ethylene compounds. The repeating unit derived from aromatic ethylene compounds means a repeating unit having a structure obtained by polymerizing aromatic ethylene compounds. However, the polymer and its structural units are not limited by its manufacturing method.

[0063] Examples of aromatic ethylene compounds corresponding to the repeating unit [I] include: styrene; styrene compounds having alkyl groups having 1 to 6 carbon atoms as substituents, such as α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 4-tributylstyrene, and 5-tributyl-2-methylstyrene; styrene compounds having halogen atoms as substituents, such as 4-chlorostyrene, dichlorostyrene, and 4-monofluorostyrene; styrene compounds having alkoxy groups having 1 to 6 carbon atoms as substituents, such as 4-methoxystyrene; styrene compounds having aryl groups as substituents, such as 4-phenylstyrene; ethylene naphthalene compounds such as 1-vinylina and 2-vinylina; etc. Each of these can be used alone or in any combination of two or more. Among these, styrene and aromatic ethylene compounds without polar groups, such as styrene and styrene compounds having alkyl groups having 1 to 6 carbon atoms as substituents, are preferred in terms of reducing hygroscopicity; styrene is particularly preferred in terms of industrial availability.

[0064] Polymers containing repeating units [I] derived from aromatic ethylene compounds are preferably specific block copolymers [D]. Block copolymer [D] is a block copolymer composed of "polymer block [A]" and "polymer block [B] or polymer block [C]". Polymer block [A] is a polymer block whose main component is a repeating unit [I] derived from aromatic ethylene compounds. Polymer block [B] is a polymer block whose main components are a repeating unit [I] derived from aromatic ethylene compounds and a repeating unit [II] derived from chain-like conjugated diene compounds. Polymer block [C] is a polymer block whose main component is a repeating unit [II] derived from chain-like conjugated diene compounds. Here, "main component" refers to a component that accounts for 50% by weight or more in the polymer block. The proportion of the main component in the polymer block is preferably 80% by weight or more, more preferably 90% by weight or more, and more preferably 100% by weight. The term "repeating unit derived from chain-like conjugated diene compounds" refers to a repeating unit with a structure obtained by polymerizing chain-like conjugated diene compounds.

[0065] Examples of chain-like conjugated diene compounds corresponding to the repeating unit [II] include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and 1,3-pentadiene. One of these compounds may be used alone, or two or more may be used in any ratio. The chain-like conjugated diene compounds may be linear or branched.

[0066] The hydride of the ethylene aromatic polymer is a hydride of a polymer comprising repeating units [I] derived from aromatic ethylene compounds. A specific block copolymer hydride [E] is preferred as a hydride of the polymer comprising repeating units [I] derived from aromatic ethylene compounds. The block copolymer hydride [E] is a hydride of the aforementioned block copolymer [D].

[0067] Hydrogenates of ethylene aromatic polymers are substances obtained by hydrogenating the unsaturated bonds of ethylene aromatic polymers. Here, the unsaturated bonds of the hydrogenated ethylene aromatic polymer include both carbon-carbon unsaturated bonds in the polymer's main chain and side chains, as well as carbon-carbon unsaturated bonds in the aromatic ring.

[0068] Hydrates, for example, can be manufactured by hydrogenating more than 90% of the unsaturated bonds of an ethylene aromatic polymer in the presence of a hydrogenation catalyst containing transition metals such as nickel and palladium in a solution of the polymer.

[0069] As a further example of using polymers as cyclic olefin polymers, polymers containing silicon-containing polar groups can be cited. Such polymers include modified hydrides of the aforementioned ethylene aromatic polymers resulting from silicon-containing polar groups. By using polymers containing silicon-containing polar groups as olefin polymers, the adhesion between components of the composition and other components (e.g., substrates) can be improved.

[0070] The polymer used in the reaction to obtain the aforementioned modified product will be referred to as the "pre-reaction polymer". The aforementioned modified product, for example, may have a structure obtained by graft polymerization of the pre-reaction polymer with a compound having a silicon-containing polar group as a monomer. However, the modified product is not limited by its manufacturing method. Alkoxysilicon groups are preferred as silicon-containing polar groups.

[0071] Examples of compounds containing silicon-containing polar groups that can be used as monomers for graft polymerization include, for instance, compounds containing alkoxysilane groups: vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, p-styryltrimethoxysilane, p-styryltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-propenyloxypropyltrimethoxysilane, 3-propenyloxypropyltriethoxysilane, and 2-... Ethylene-5-yltrimethoxysilane and other vinyl unsaturated silane compounds with alkoxysilyl groups.

[0072] By reacting a polymer prior to the reaction with a compound containing a silicon-atom polar group, a silicon-atom polar group can be introduced into the polymer prior to the reaction, resulting in a modified product containing a silicon-atom polar group. When an alkoxysilicon group is introduced as the silicon-atom polar group, the amount of alkoxysilicon group introduced relative to 100 parts by weight of the polymer prior to the reaction is preferably 0.1 parts by weight or more, more preferably 0.2 parts by weight or more, more preferably 0.3 parts by weight or more, and preferably 10 parts by weight or less, more preferably 5 parts by weight or less, and more preferably 3 parts by weight or less. When the amount of alkoxysilicon group introduced falls within the aforementioned range, the degree of crosslinking between alkoxysilicon groups that decompose due to moisture can be suppressed from becoming excessively high, thus maintaining a high degree of bonding. Examples of substances containing alkoxysilicon groups and modification methods for introducing alkoxysilicon groups can be cited in International Patent Publication No. 2015 / 099079.

[0073] The amount of polar group introduced can be measured by 1H-NMR spectroscopy. Furthermore, when measuring the amount of polar group introduced, if the amount introduced is small, the number of accumulation times can be increased.

[0074] Introducing alkoxysilane groups as polar groups into the pre-reaction polymer is called silane modification. During silane modification, the alkoxysilane groups can be directly bonded to the pre-reaction polymer, or they can be bonded through intermediaries such as divalent organic groups like alkyl groups. The polymer obtained through silane modification of the pre-reaction polymer will also be referred to as a "silane-modified polymer."

[0075] As a silane-modified polymer, a polymer selected from one or more of the following: silane-modified styrene-butadiene block copolymers, silane-modified styrene-butadiene-styrene block copolymers, silane-modified styrene-isoprene block copolymers, and silane-modified styrene-isoprene-styrene block copolymers.

[0076] Good examples of olefin polymers other than cyclic olefin polymers include polymers comprising repeating units derived from chain conjugated diene compounds and copolymers comprising repeating units derived from chain conjugated diene compounds and other repeating units. More specific examples include the block copolymers [D] mentioned above, which comprise repeating units [I] derived from aromatic ethylene compounds.

[0077] The weight-average molecular weight (Mw) of olefin polymers is preferably above 10,000, more preferably above 15,000, especially above 20,000, and preferably below 100,000, more preferably below 80,000, and especially preferably below 50,000. When the weight-average molecular weight is within this range, a high balance can be achieved between the mechanical strength and formability of the olefin polymer.

[0078] The molecular weight distribution (Mw / Mn) of the olefin polymer is preferably 1.2 or higher, more preferably 1.5 or higher, especially 1.8 or higher, and preferably 3.5 or lower, more preferably 3.0 or lower, and especially preferably 2.7 or lower. Here, Mn represents the number average molecular weight. By making the molecular weight distribution above or below the lower limit of the aforementioned range, the productivity of the olefin polymer can be improved and manufacturing costs can be reduced. Furthermore, by making it below the upper limit, the amount of low molecular weight components will be reduced. As a result, relaxation of the layer of the composition during high-temperature exposure can be suppressed, and the stability of the layer can be improved.

[0079] The aforementioned weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be measured using gel permeation chromatography (GPC). Examples of solvents used in GPC include cyclohexane, toluene, and tetrahydrofuran. When using GPC, the weight-average molecular weight can be measured, for example, as a relative molecular weight converted from polyisoprene or polystyrene.

[0080] The weight percentage (content) of the olefin polymer in the composition should be appropriately selected according to the intended use of the composition, but it is preferred to be 5% by weight or more, 10% by weight or more, 50% by weight or less, and 40% by weight or less.

[0081] [1.3. Any component]

[0082] In addition to the quantum dot materials and olefin polymers described above, the components of this embodiment may also include any other components. Examples of such arbitrary components include, for instance, solvents.

[0083] The solvent included in the composition is preferably a non-polar solvent. Examples of non-polar solvents include xylene, toluene, hexane, cyclohexane, ethylcyclohexane, and decahydronaphthalene. Only one of these solvents may be used, or two or more may be mixed.

[0084] The weight ratio (content) of the solvent in the composition should be appropriately selected according to the intended use of the composition.

[0085] 〔2.Film〕

[0086] One embodiment of the present invention relates to a thin film comprising the aforementioned components. However, the thin film typically does not contain solvent, or, if it does contain solvent, to a degree that is unavoidable in the thin film manufacturing process.

[0087] According to the present invention, since the thin film contains the aforementioned components, it is possible to produce a thin film with good atmospheric stability of quantum dot materials. Furthermore, this suppresses the reduction of the functionality imparted to the thin film by the quantum dot materials.

[0088] The thickness of the film can be appropriately selected according to its application and is not particularly limited, but is, for example, above 10 μm and below 1000 μm.

[0089] The thin film related to this embodiment may be a structure having only a thin film layer containing the aforementioned components, or it may be a structure in which a thin film layer containing the aforementioned components is disposed on a substrate serving as a support. Examples of materials that can be used as the substrate include: resin and glass.

[0090] Furthermore, in addition to the thin film layer containing the aforementioned components, the thin film of this embodiment may also have any layer such as a shielding layer or a light scattering layer.

[0091] [3. Light-emitting device]

[0092] One embodiment of the present invention is a light-emitting device that uses the aforementioned thin film as a light conversion element.

[0093] According to the present invention, by using the aforementioned thin film as a light conversion element, a light-emitting device with good luminous efficiency and the ability to suppress the historical decrease in luminous efficiency can be made.

[0094] Light-emitting devices typically have a light source and a light conversion element, which converts the wavelength by allowing a portion of the light from the light source to pass through the light conversion element.

[0095] As a light source, any light source that emits light of a wavelength suitable for excitation by quantum dot materials is acceptable. Examples include well-known light sources such as light-emitting diodes (LEDs) and lasers. Among these, LEDs are preferred, with blue LEDs and ultraviolet LEDs being even more desirable.

[0096] For example, when using a blue light-emitting diode (LED) as a light source, it is preferable to use quantum dot materials that emit red and green fluorescence as the quantum dot materials contained in the thin film. By converting a portion of the blue light from the blue LED into red and green light, a light-emitting device that emits white light can be made.

[0097] [4. Power generation device]

[0098] One embodiment of the present invention is a power generation device that uses the aforementioned thin film as a power generation element. This power generation device utilizes quantum dot materials with a perovskite-type crystalline structure as semiconductors, and is also called a perovskite-type solar cell. Furthermore, the power generation element is also called an active layer.

[0099] According to the present invention, by using the aforementioned thin film as a power generation element, the atmospheric stability of the quantum dot material in the thin film is optimized, thus enabling the fabrication of a power generation device that can suppress the historical degradation of the power generation element.

[0100] A power generation device typically comprises, in sequence, a first electrode, an electron transport layer, an active layer serving as a power generation element, a hole transport layer, and a second electrode. When light is irradiated onto the active layer, electrons flow to the first electrode, and holes flow to the second electrode, thereby generating an electromotive force. In such a power generation device, the aforementioned thin film is usually used as the active layer. The first electrode, electron transport layer, hole transport layer, and second electrode used in the power generation device can be made identical to those used in well-known power generation devices.

[0101] [5. Monitor]

[0102] One embodiment of the present invention is a display that uses the aforementioned thin film as a light conversion element.

[0103] According to the present invention, by using the aforementioned thin film as a light conversion element, the display image can be displayed vividly, and a display that can suppress the degradation of display quality over time can be made.

[0104] A display typically includes a light source, a display panel, and a light conversion element. In the case of a self-emissive display panel, the display panel can also serve as the light source. Examples of display panels include: a liquid crystal panel for a display used in a liquid crystal display device, and an organic EL panel for a display used in an organic electroluminescent display device (hereinafter referred to as "organic EL display device").

[0105] LCD panels typically include liquid crystal cells that contain liquid crystal and electrodes to which a voltage can be applied. Liquid crystal cells can use any of the following modes: In-Plane Switching (IPS) mode, Vertical Alignment (VA) mode, Multi-Area Vertical Alignment (MVA) mode, Continuous Firework Alignment (CPA) mode, Hybrid Alignment Nematic (HAN) mode, Twisted Nematic (TN) mode, Super Twisted Nematic (STN) mode, Optically Compensated Bending (OCB) mode, etc.

[0106] In the case of a display panel that is an LCD panel, there is usually a light source, and the display panel consists of a light source, a thin film as a light conversion element, and an LCD panel in sequence.

[0107] Organic EL panels typically comprise organic EL elements that "usually sequentially include a transparent electrode layer, a light-emitting layer, and an electrode layer." In this organic EL element, light is generated by applying a voltage to the transparent electrode layer and the electrode layer. Examples of materials constituting the organic light-emitting layer include: polyethylene terephthalate (PET), polyvinyl chloride (PVC), and polyvinylcarbazole (PCLC) materials. Furthermore, the light-emitting layer may also be a stack of multiple layers with different emission colors or a mixed layer in which different pigments are doped into a single pigment layer. Moreover, organic EL elements may also include functional layers such as a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, an equipotential surface formation layer, and a charge generation layer. In the case of an organic EL panel, a thin film serving as a light conversion element is disposed on the viewing side of the organic EL panel.

[0108] [6. Method for manufacturing the components]

[0109] The manufacturing method of the aforementioned components is not particularly limited, but for example, the following manufacturing method is preferred, which includes: a first step of obtaining a dispersion of quantum dot material; a second step of obtaining a solution of olefin polymer; and a third step of mixing the dispersion of quantum dot material with the solution of olefin polymer.

[0110] Furthermore, as a method for manufacturing the aforementioned components, the following manufacturing method is preferred, for example, the manufacturing method comprising: a first step of obtaining a dispersion of quantum dot material; and a fourth step of adding the aforementioned olefin polymer to the dispersion and dissolving the aforementioned polymer in the dispersion.

[0111] The following describes a manufacturing method having steps 1 to 3 as a first embodiment, and a manufacturing method having steps 1 and 4 as a second embodiment. The components related to this embodiment may include solvent as an arbitrary component; however, the components obtained by the manufacturing methods of the first and second embodiments generally include solvent unless it is removed.

[0112] [6.1. Manufacturing method of the first embodiment]

[0113] The method for manufacturing the composition related to the first embodiment includes: a first step of obtaining a dispersion of quantum dot material; a second step of obtaining a solution of olefin polymer; and a third step of mixing the dispersion of quantum dot material with the solution of olefin polymer.

[0114] According to the first embodiment, by separately preparing a dispersion of quantum dot material and a solution of olefin polymer and then mixing them, the quantum dot material can be well dispersed in the mixture, thereby optimizing the dispersibility of quantum dots in the composition.

[0115] [6.1.1. First Process]

[0116] The first step in the first implementation type is the step of obtaining a dispersion of quantum dot material.

[0117] Dispersions typically contain quantum dot materials and a solvent as the dispersion medium. For quantum dot materials, the same applies as described in the section [1. Composition] above.

[0118] For example, a non-polar solvent is preferred as the solvent. The description of the non-polar solvent is the same as that already provided in the section [1. Composition] above. As the solvent in the first step, a solvent that can dissolve the olefin polymer used in the second step described below is preferred.

[0119] The concentration of the quantum dot material in the dispersion medium is, for example, 1 kg / m³ (mg / mL) or more, preferably 2 kg / m³ or more, and for example, 20 kg / m³ or less, preferably 10 kg / m³ or less. This is because by having the weight ratio of the quantum dot material within the aforementioned range, the quantum dot material can be well dispersed in the dispersion medium.

[0120] In the first step, for example, a dispersion can be obtained by adding quantum dot material to the dispersion medium and stirring it using a well-known stirring method.

[0121] [6.1.2. Second Process]

[0122] The second step in the first implementation type is the step of obtaining a solution of olefin polymer.

[0123] The solution typically contains an olefin polymer and a solvent. The olefin polymer and solvent should be formulated to be identical to those described in the section [1. Composition] above.

[0124] The weight percentage of the olefin polymer in the solution is preferably 5% by weight or more, preferably 15% by weight or more, and preferably 50% by weight or less, and preferably 45% by weight or less, depending on the molecular weight and composition of the olefin polymer.

[0125] In the second step, for example, a solution can be obtained by adding quantum dot material to the dispersion medium and stirring it using a well-known stirring method.

[0126] [6.1.3. Third Process]

[0127] The third step in the first implementation type is the process of mixing the dispersion of quantum dot material with the solution of olefin polymer.

[0128] The mixing amounts of the quantum dot material dispersion and the olefin polymer solution should be appropriately selected according to the intended use of the composition. However, for example, it is preferable to mix the dispersion and solution in a manner where the weight ratio of the quantum dot material to the olefin polymer is the desired ratio. The preferred range for the weight ratio of the quantum dot material to the olefin polymer can be the same as that described in the section [1. Composition] above.

[0129] [6.2. Manufacturing method of the second embodiment]

[0130] The method for manufacturing the composition related to the second embodiment includes: a first step of obtaining a dispersion of quantum dot material; and a fourth step of adding an olefin polymer to the dispersion and dissolving the polymer in the dispersion.

[0131] According to the second embodiment, an olefin polymer is directly added to and dissolved in a dispersion of quantum dot material, thus enabling the manufacture of the composition with fewer steps.

[0132] The solvent used as a dispersion medium in the first step of the second embodiment is a solvent that can disperse quantum dot materials and dissolve olefin polymers. As such a solvent, it may be appropriately selected from the solvents described in the [1. Composition] section above, depending on whether it is a quantum dot material or an olefin polymer. The first step of the second embodiment may be made identical to the first step of the first embodiment described above.

[0133] The fourth step in the second embodiment involves adding an olefin polymer to the dispersion of the quantum dot material and dissolving the olefin polymer in the dispersion. In the third step of the first embodiment, a solution in which the olefin polymer has been dissolved in a solvent is prepared beforehand, and then the dispersion of the quantum dot material and the solution of the olefin polymer are dispersed. However, in the fourth step, the quantum dot material and the olefin polymer are mixed by adding an olefin polymer to the dispersion of the quantum dot material and dissolving the olefin polymer in the dispersion medium (solvent). In the fourth step, for example, it is preferable to add the olefin polymer to the dispersion of the quantum dot material and then promote the dissolution of the olefin polymer by stirring.

[0134] [7. Thin film manufacturing method]

[0135] As for the aforementioned method of manufacturing the thin film, it is not particularly limited as long as the desired thin film can be obtained. However, for example, the following manufacturing method is preferred, which includes: a fifth step of forming a composition layer using the composition; and a sixth step of drying the aforementioned composition layer.

[0136] [7.1. Step 5]

[0137] Step 5 is the process of using components to form a component layer.

[0138] As for the method of forming the composition layer, it is not particularly limited as long as a composition layer with the desired thickness can be obtained. Examples include: a method of coating the composition on a substrate or a method of forming the composition layer by filling the composition in a mold, but the former is preferred.

[0139] Methods for coating compositions onto substrates include, for example, using a die coater, a rotary gravure coater, a stencil coater, a doctor blade coater, or an inkjet coater.

[0140] The thickness of the constituent layer can be adjusted appropriately according to the concentration of solid components in the constituent and the desired film thickness.

[0141] [7.2. Step 6]

[0142] The sixth step is to dry the constituent layers.

[0143] As a method for drying the constituent layers, the solvent in the solvent layer must be removed.

[0144] The drying method can be chosen according to the boiling point of the solvent used. Examples of drying methods include: natural drying, heat drying, vacuum drying, and vacuum heating drying.

[0145] Example

[0146] The following embodiments are disclosed to specifically illustrate the present invention. However, the present invention is not limited to the embodiments disclosed below, and may be implemented in any way without departing from the scope of the claims and their equivalents.

[0147] In the following description, the terms "%" and "parts" are by weight unless otherwise noted. Furthermore, the operations described below are performed at room temperature and pressure unless otherwise noted.

[0148] [Evaluation Method]

[0149] [Weight-average molecular weight (Mw) and number-average molecular weight (Mw / Mn)]

[0150] The molecular weights of the block copolymers and block copolymer hydrides were measured at 38°C using a GPC with THF as the solvent, in the form of standard polystyrene conversion values. The measuring apparatus was a Tosoh HLC8020 GPC.

[0151] [Hydrogenation rate]

[0152] The hydrogenation rate of the block copolymer hydride was calculated by measuring the 1H-NMR spectra of the block copolymer and the block copolymer hydride.

[0153] [Methods for measuring powder X-ray diffraction]

[0154] Powder X-ray diffraction (XRD) measurements were performed on the FAPbBr3 obtained in Example 1 using CuKα rays. During the measurements, the sample was placed in a glass bath and X-ray diffraction was performed using a MiniFlexII device (manufactured by Rigaku Co., Ltd.) under the following conditions: measurement temperature: room temperature (25°C); voltage: 45 kV (CuKα radiation); current: 200 mA; sample width: 0.01°; scan speed: 0.025° / s; and the range of measured diffraction angles (2θ): 10°–50°.

[0155] [Thickness Measurement Method]

[0156] The thickness of the produced film layer was measured 5 times using a thickness gauge (manufactured by Mitoyo Co., Ltd., product name "ABS digital thickness gauge (547-401)"), and the average value was defined as the thickness of each film.

[0157] [Atmospheric stability]

[0158] The fabricated thin film (sample) was stored at 25°C and 50%RH for at least 30 days. The change in luminescence intensity at 530 nm when the sample was irradiated with excitation light at a wavelength of 365 nm was calculated as the ratio of the luminescence intensity during the storage period to the luminescence intensity before storage (initial stage) (luminescence intensity ratio). Furthermore, the presence or absence of peak position shift was measured. Measurements were performed using a spectrophotometer, FP-8050 series, manufactured by Nippon Spectrophotometer Co., Ltd. The results were evaluated using the following indicators. A: The peak displacement from the initial peak position has not been confirmed, and the period during which the aforementioned luminescence intensity ratio is above 90% is more than 30 days. B: The peak displacement from the initial peak position was not confirmed, and the period during which the aforementioned luminescence intensity ratio was above 90% was more than 20 days but less than 30 days. C: A peak shift towards the lower wavelength side was confirmed from the initial peak position. Furthermore, the period during which the aforementioned luminescence intensity ratio was above 90% did not reach 20 days, or the aforementioned luminescence intensity ratio did not reach 90% throughout the entire storage period.

[0159] [Dispersion]

[0160] For a polymer solution in which the polymer has been dissolved in an organic solvent, a quantum dot material dispersion was added at a ratio of 5, 10, 15, 20, 25, and 30 parts (cumulative amount) relative to 100 parts of the polymer dispersion (0.05, 0.11, 0.16, 0.21, 0.26, and 0.32 parts (cumulative amount) relative to 100 parts of the polymer dispersion). After stirring the mixture, it was allowed to stand for 24 hours, and the presence or absence of precipitate was observed. The polymer solution and the quantum dot material dispersion were prepared in the same manner as those used in the various examples and comparative examples. The results were evaluated using the following indicators. A: Even with the addition of more than 30 parts of quantum dot material, no precipitate was observed. B: Adding 20 to 30 parts of quantum dot material resulted in the observation of precipitates. C: Adding 15 parts or more but less than 20 parts of quantum dot material resulted in the observation of precipitates. D: When less than 15 parts of quantum dot material were added, precipitates were observed.

[0161] [Luminous efficiency (luminescent quantum yield)]

[0162] The luminescence quantum yield of the quantum dot material was measured using a spectrophotometer, the "FP-8050 series," manufactured by Nippon Spectrophotometer Co., Ltd. A higher luminescence quantum yield indicates higher luminescence efficiency.

[0163] First, toluene for spectrophotometry was placed in a quartz cell (transparent on all four sides), and the baseline value was measured using the aforementioned spectrophotometer. Next, a dispersion of the quantum dot material (described later) was placed in the spectrophotometer-toluene in the quartz cell with the sample absorbance at 50%, and the sample value was measured using the aforementioned spectrophotometer. Based on the obtained baseline and sample values, the luminescent quantum yield (PLQY) was measured using the quantum yield calculation software of the aforementioned spectrophotometer. The results were evaluated using the following indicators. A: The luminescent quantum yield is over 70%. B: Luminescent quantum yield did not reach 70%.

[0164] [Seamless]

[0165] A thin film layer is formed on a glass substrate using the same method as the sample preparation method used for evaluation. The obtained thin film layer is then subjected to a cross-cutting test as specified in JIS K5600-5-6.

[0166] Cut notches at 1 mm intervals in a 10 mm × 10 mm area on the obtained thin film layer to create 100 squares of 1 mm each. Apply Cyrovan tape to the surface of this coating and then peel it off. Measure the number of squares of the thin film layer remaining on the glass substrate without being peeled off. Evaluate the results using the following metrics. A: No peeling was observed in more than 90% of the film layer. B: No peeling was observed in more than 80% but less than 90% of the film layer. C: No peeling was observed in 50% to 80% of the film layer. D: No peeling was observed when the film layer was less than 50% complete.

[0167] [Manufacturing Example 1: Manufacturing of Olefin Polymer (SIS)]

[0168] The following block copolymer [D1] is manufactured as an olefin polymer using the following procedure.

[0169] 400 parts of dehydrated cyclohexane, 10 parts of dehydrated styrene, and 0.475 parts of dibutyl ether were placed in a reactor equipped with a stirrer and fully purged with nitrogen. While stirring all contents at 60°C, 0.88 parts of n-butyllithium (15% cyclohexane solution) were added to initiate polymerization. Next, while stirring all contents at 60°C, 15 parts of dehydrated styrene were continuously added to the reactor for 40 minutes to carry out the polymerization reaction. After the addition was completed, all contents were stirred at 60°C for an additional 20 minutes. Gas chromatography (GC) analysis of the reaction mixture showed a polymerization conversion of 99.5% at this point.

[0170] Next, 50.0 parts of dehydrated isoprene were continuously added to the reaction solution over a period of 130 minutes, followed by continuous stirring for 30 minutes after the addition was completed. At this point, GC analysis of the reaction solution showed a polymerization conversion rate of 99.5%.

[0171] Subsequently, 25.0 parts of dehydrated styrene were continuously added to the reaction solution over a period of 70 minutes, followed by stirring for another 60 minutes after the addition was completed. At this point, GC analysis of the reaction solution showed that the polymerization conversion rate was almost 100%.

[0172] Herein, the reaction was terminated by adding 0.5 parts of isopropanol to obtain a polymer solution containing a [A]-[B]-[A] type block copolymer [D1]. This block copolymer [D1] is a ternary block copolymer composed of blocks (St) containing repeating units derived from styrene and blocks (Ip) containing repeating units derived from isoprene, with a weight ratio of St:Ip:St = 1:2:1. The weight average molecular weight (Mw) of the block copolymer [D1] is 40,000, and the molecular weight distribution (Mw / Mn) is 1.5.

[0173] [Manufacturing Example 2: Manufacturing of Olefin Polymer (HSIS)]

[0174] The following process is used to manufacture hydrogenated block copolymer [E1], which is a hydride of block copolymer [D1], as an olefin polymer.

[0175] The polymer solution obtained in Manufacturing Example 1 was transferred to a pressure reactor equipped with a stirring device. 4.0 parts of diatomaceous earth-supported nickel catalyst (product name "E22U", nickel loading 60%, manufactured by Nichibukai Catalyst Chemical Co., Ltd.) and 30 parts of dehydrated cyclohexane were added and mixed. The reactor was purged with hydrogen, and hydrogen was supplied while the solution was stirred. The hydrogenation reaction was carried out for 6 hours at a temperature of 190°C and a pressure of 4.5 MPa.

[0176] The block copolymer hydride [E1] contained in the reaction solution obtained by hydrogenation has a weight average molecular weight (Mw) of 49,000 and a molecular weight distribution (Mw / Mn) of 1.36.

[0177] After the hydrogenation reaction is completed, the reaction solution is filtered to remove the hydrogenation catalyst. Then, 2.0 parts of xylene solution containing 0.1 parts of neopentyl ester {3-[3,5-bis(tert-butyl)-4-hydroxyphenyl]propionic acid (product name "Songnox (registered trademark) 1010", manufactured by Matsubara Sangyo Co., Ltd.), a phenolic antioxidant, are added and dissolved.

[0178] Subsequently, cyclohexane, xylene, and other volatile components were removed from the above solution using a cylindrical concentrator (product name "KONTRO", manufactured by Hitachi, Ltd.) at a temperature of 260°C and a pressure of 0.001 MPa or less. The molten polymer was extruded from a die into strands, cooled, and then granulated using a granulator to produce 95 parts of block copolymer hydride [E1] granules.

[0179] The obtained hydrogenated block copolymer [E1] has a weight-average molecular weight (Mw) of 47,500 and a molecular weight distribution (Mw / Mn) of 1.3. Furthermore, the hydrogenation rate is 99.8%.

[0180] [Manufacturing Example 3: Manufacturing of Olefin Polymer (Si-HSIS)]

[0181] The following process is used to manufacture an alkoxysilyl modified product [S1] of hydrogenated block copolymer [E1] as an olefin polymer.

[0182] Relative to 100 parts of the block copolymer hydride [E1] particles obtained above, 2 parts by weight of vinyltrimethoxysilane (KBM-1003; manufactured by Shin-Etsu Silicon Power Co., Ltd.) and 0.1 parts by weight of 2,5-dimethyl-2,5-di(tertiary butylperoxy)hexane (product name "PERHEXA (registered trademark) 25B", manufactured by Nippon Oil Co., Ltd.) were stirred and externally lubricated in a Henchel mixer (Super mixer SMV; manufactured by KAWATA MFG. Co., Ltd.). The externally lubricated block copolymer hydride [D] was placed into the metering funnel of a biaxial mixer (TEM-37B; manufactured by Shibaura Machinery Co., Ltd.) and melt-mixed at a screw barrel temperature of 220°C, a screw speed of 150 rpm, and a residence time of 90 seconds. While the extruded strands were cooled in a water tank, they were granulated using a granulator (FAN-CUTTER; manufactured by HOSHI PLASTIC Co., Ltd.) to prepare alkoxysilane-modified compound [S1] (silane-modified SIS block copolymer hydride).

[0183] The obtained alkoxysilyl modified product [S1] was subjected to 1H-NMR spectroscopy, which confirmed that vinyltrimethoxysilane had bonded to the polymer.

[0184] In the FT-IR spectrum of the alkoxysilyl modified [S1], a new absorption band derived from the Si-OCH3 group was observed at 1090 cm⁻¹, and new absorption bands derived from the Si-CH2 group were observed at 825 cm⁻¹ and 739 cm⁻¹, respectively, which are different from the absorption bands of vinyltrimethoxysilane derived from the Si-OCH3 group and Si-CH group.

[0185] Furthermore, the 1H-NMR spectrum of the alkoxysilyl modified compound [S1] (in deuterated chloroform) was measured, and a peak originating from the methoxy group was observed at 3.6 ppm.

[0186] [Example 1]

[0187] (Manufacturing of the components)

[0188] The following procedure was used to prepare a dispersion of perovskite quantum dot material.

[0189] FAPbBr3, a quantum dot material with a perovskite-type crystalline structure, was prepared using the well-known ligand-assisted redeposition method (LARP). Specifically, NHCH2Br, PbBr2, oleic acid, and octylamine were dissolved in N-methylpyrrolidone (NMP) to obtain a precursor solution. The obtained precursor solution was added dropwise to toluene for extended separation, thereby collecting the FAPbBr3 generated in the lower layer. XRD measurements of the collected FAPbBr3 were performed, and the results are shown in Figure 1, confirming the spectral peaks originating from the perovskite-type crystalline structure.

[0190] The obtained FAPbBr3 was dispersed in toluene to obtain a dispersion of quantum dot material with a concentration of 2 mg / mL (2 kg / m3).

[0191] Next, the olefin polymer (HSIS) produced in Manufacturing Example 2 is dissolved in cyclohexane as an organic solvent to prepare a solution (polymer solution). The concentration of the olefin polymer in the polymer solution is set to 25%.

[0192] The dispersion of the aforementioned quantum dot material was mixed with the polymer solution in such a manner that 0.26 parts of quantum dot material were included for every 100 parts of olefin polymer to obtain the composition.

[0193] (Thin film manufacturing)

[0194] The obtained composition was coated onto a glass substrate using a spin coating method to form a composition layer. Subsequently, the obtained composition layer was left to stand in a dark room at room temperature (approximately 20°C) for 24 hours to remove the solvent and dispersion medium, thereby producing a film (thin film) of approximately 600 μm.

[0195] [Example 2]

[0196] Except that the olefin polymer (SIS) manufactured in Manufacturing Example 1 was used instead of the olefin polymer (HSIS) manufactured in Manufacturing Example 2, the composition and film were manufactured in accordance with Example 1.

[0197] [Example 3]

[0198] Except that the olefin polymer (Si-HSIS) manufactured in Manufacturing Example 3 was used instead of the olefin polymer (HSIS) manufactured in Manufacturing Example 2, the composition and film were manufactured in accordance with Example 1.

[0199] [Example 4]

[0200] In addition to using a type of cyclic olefin polymer, An olefin polymer (manufactured by Zeon Corporation, Japan, glass transition temperature: 140°C) was used instead of the olefin polymer (SIS) manufactured in Example 1. Except that the concentration of the olefin polymer in the polymer solution was set to 10%, and the amount of quantum dot material mixed with 100 parts of the olefin polymer was set to 0.11 parts, the composition and film were prepared in accordance with Example 1.

[0201] [Comparative Example 1]

[0202] Except that an acrylic polymer (polymethyl methacrylate polymer: PMMA) (manufactured by TOYOPOLYMER Co., Ltd., "RUBYLON P") was used instead of the olefin polymer (SIS) manufactured in Example 1, the composition and film were manufactured in accordance with Example 1.

[0203] [Comparative Example 2]

[0204] The following procedure was used to prepare a dispersion of core-shell quantum dot materials.

[0205] A dispersion of Sigma-Aldrich core-shell quantum dot material (CdSe / Zn) was prepared in toluene to obtain a concentration of 2 mg / mL (2 kg / m3) of quantum dot material.

[0206] Except that the dispersion of the quantum dot material described above was used instead of the dispersion of the quantum dot material obtained in Example 1, the composition and film were prepared in accordance with Example 1.

[0207] [Comparative Example 3]

[0208] Except that the dispersion of the quantum dot material described above was used instead of the dispersion of the quantum dot material obtained in Example 1, the composition and film were prepared in accordance with Example 4.

[0209] The compositions and films obtained through Examples 1-4 and Comparative Examples 1-3 were evaluated using the evaluation methods described above. The results are shown in Table 1.

[0210] The abbreviations in the table have the following meanings. "SIS": Cycloolefin polymer manufactured through manufacturing example 1 "HSIS": Cycloolefin polymers manufactured through manufacturing example 2 "Si-HSIS": Cycloolefin polymers manufactured through manufacturing example 3 "COP": Descend olefin polymers "PMMA": Acrylic polymer (polymethyl methacrylate polymer) Blending amount (parts): The proportion relative to 100 parts of the polymer quantum dot material.

[0211] Table 1 Table 1 composition evaluate polymer Quantum dot materials Blending amount (parts) atmosphere stability Dispersion Light efficiency tightness Example 1 HSIS Perovskite type QD material (FAPBr 3) 0.26 A A A C Example 2 SIS Perovskite type QD material (FAPBr 3) 0.26 B A A C Example 3 Si-HSIS Perovskite type QD material (FAPBr 3) 0.26 A A A A Example 4 COP Perovskite type QD material (FAPBr 3) 0.11 A B A C Comparative Example 1 PMMA Perovskite type QD material (FAPBr 3) 0.26 C A A B Comparative Example 2 HSIS Core-shell QD Materials (CdSe / ZnS) 0.26 B A C C Comparative Example 3 COP Core-shell QD Materials (CdSe / ZnS) 0.11 B C C C

[0212] In Examples 1-4, it was confirmed that the atmospheric stability of the perovskite quantum dot material could be optimized. On the other hand, when the acrylic polymer was used in combination with the perovskite quantum dot material as shown in Comparative Example 1, sufficient atmospheric stability could not be obtained.

[0213] Furthermore, when the olefin polymer and core-shell quantum dot material were used as shown in Comparative Examples 2 and 3, it was confirmed that the luminous efficiency and atmospheric stability were lower compared to Examples 1 and 4.

[0214] none

Claims

1. A composition comprising: a quantum dot material having a perovskite-type crystalline structure and an olefin polymer, wherein the olefin polymer comprises a cyclic olefin polymer, the cyclic olefin polymer comprises a deuterene polymer, and the deuterene polymer comprises a hydride of a ring-opening polymer of a monomer having a deuterene structure.

2. A composition comprising: a quantum dot material having a perovskite-type crystalline structure and an olefin polymer, wherein the olefin polymer comprises a block copolymer hydride [E], the block copolymer hydride [E] being a hydride of a block copolymer [D], said block copolymer [D] being formed of a polymer block [A] whose main component is a repeating unit [I] derived from an aromatic ethylene compound and a polymer block [B] whose main components are a repeating unit [I] derived from an aromatic ethylene compound and a repeating unit [II] derived from a chain conjugated diene compound, or a polymer block [C] whose main component is a repeating unit [II] derived from a chain conjugated diene compound.

3. The composition as claimed in claim 2, wherein the aforementioned olefin polymer comprises an alkoxysilane group.

4. The composition as claimed in claim 1 or 2, wherein the quantum dot material contained in the aforementioned composition is 0.05 parts by weight or more and 50 parts by weight or less relative to 100 parts by weight of the aforementioned olefin polymer.

5. A thin film comprising the composition as described in any one of claims 1 to 4.

6. A light-emitting device that uses the thin film as described in claim 5 as a light conversion element.

7. A power generation device that uses the thin film as a power generation element as claimed in claim 5.

8. A display that uses a thin film as a light conversion element as described in claim 5.

9. A method for manufacturing a composition comprising: a method for manufacturing a composition of any one of claims 1 to 4, comprising: a first step of obtaining a dispersion of the aforementioned quantum dot material; a second step of obtaining a solution of the aforementioned olefin polymer; and a third step of mixing the dispersion of the aforementioned quantum dot material with the solution of the aforementioned olefin polymer.

10. A method for manufacturing a composition comprising a composition of any one of claims 1 to 4, comprising: a first step of obtaining a dispersion of the aforementioned quantum dot material; and a fourth step of adding the aforementioned olefin polymer to the aforementioned dispersion and dissolving the aforementioned olefin polymer in the aforementioned dispersion.

11. A method for manufacturing a thin film, comprising: a fifth step of forming a composition layer using the aforementioned composition; and a sixth step of drying the aforementioned composition layer.

12. The method for manufacturing a thin film as claimed in claim 11, wherein the aforementioned fifth step is a step of coating the aforementioned composition onto a substrate to form the aforementioned composition layer, and the aforementioned composition is coated using a die coater, a rotary gravure coater, a stencil coater, a doctor blade coater, or an inkjet coater.

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