Method for producing energy-responsive composition, and energy-responsive composition

Abstract

The method for producing the energy-responsive composition comprises: a step for preparing a polymer-containing solution containing a solvent having a relative dielectric constant of a prescribed value or less and an associative polymer that has a main chain containing a plurality of carbons and a polar group having a higher polarity than the main chain and that self-associates in the solvent; a step of bringing the polymer-containing solution into contact with the nanoparticles having energy responsiveness to prepare a mixed solution; and a step of extracting an energy-responsive composition including a plurality of energy-responsive protective particles including nanoparticles and an associative polymer from the mixed solution by reducing the content of the solvent.

Description

Technical Field

[0001] This disclosure relates to a method for manufacturing an energy-responsive composition and an energy-responsive composition. Background Technology

[0002] Quantum dots with a perovskite-type crystal structure are known to have narrow full width at half maximum (FWHM) in their spectral sensitivity characteristics and exhibit high color purity, thus making them suitable for applications in organic EL materials, quantum dot luminescent materials, and solar cell materials. Furthermore, since the absorption and emission wavelengths can be controlled by the halogen composition, quantum dots offer the advantage of readily providing materials with a wide wavelength range of light response.

[0003] Meanwhile, quantum dots with perovskite-type crystal structures are known to exhibit low stability to external stimuli such as light, heat, air, and moisture. In particular, when quantum dots exist at high density in a solid phase, they tend to fuse together. If fusion occurs, they lose unique properties such as quantum size effects and fail to exhibit the desired physical properties.

[0004] In Japanese Patent Application Publication No. 2021-91870, stability is improved by using ligands comprising organic acid salts and polymers comprising acidic groups to protect against external stimuli.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2021-91870 Summary of the Invention

[0008] The problem the invention aims to solve

[0009] Quantum efficiency can be improved by using the technology described in Japanese Patent Application Publication No. 2021-91870. However, when protected by using a polymer as described in Japanese Patent Application Publication No. 2021-91870, the distance between quantum dots cannot be reduced by the spatial repulsion between polymer chains. Therefore, the density of quantum dots per unit volume decreases, and there is a problem of reduced properties such as luminescence.

[0010] The present invention was made in view of the above-mentioned problems and aims to provide a method for manufacturing an energy-responsive composition that can be configured with quantum dots at a high density even when a polymer is used as a ligand. Furthermore, the present invention aims to provide an energy-responsive composition comprising a polymer and a high-density configured quantum dot.

[0011] Solution for solving the problem

[0012] A method for manufacturing an energy-responsive composition according to an embodiment of the present invention includes the steps of preparing a polymer-containing solution comprising a solvent having a relative permittivity below a predetermined value and an associating polymer comprising a backbone having a plurality of carbon atoms and polar groups having a polarity higher than that of the backbone and being self-associated in the solvent; preparing a mixture by contacting energy-responsive nanoparticles with the polymer-containing solution (P); and extracting an energy-responsive composition comprising a plurality of energy-responsive protective particles, each comprising nanoparticles and an associating polymer, from the mixture R by reducing the solvent content.

[0013] The energy-responsive composition according to an embodiment of the present invention comprises a plurality of energy-responsive protective particles, each comprising energy-responsive nanoparticles and an associative polymer having a main chain containing a plurality of carbon atoms and polar groups having a polarity higher than that of the main chain, wherein a pair of adjacent energy-responsive protective particles are in contact with each other through the contact of their associative polymers, and the nanoparticles of the adjacent energy-responsive protective particles are spaced apart from each other.

[0014] Advantages of the invention

[0015] According to the present invention, a method for manufacturing an energy-responsive composition is provided, which can be configured with quantum dots at high density even when a polymer is used as a ligand. Furthermore, an energy-responsive composition comprising a polymer and high-density configured quantum dots is provided. Attached Figure Description

[0016] [ Figure 1 [This is a flowchart of a method for manufacturing an energy-responsive composition according to the first embodiment.]

[0017] [ Figure 2A [Illustrated diagram of a polymer-containing solution according to a first embodiment.]

[0018] [ Figure 2B [Illustrated diagram] is a schematic diagram showing the structure of the mixture according to the first embodiment.

[0019] [ Figure 2C [Illustrated diagram showing the structure of the energy-responsive composition according to the first embodiment.]

[0020] [ Figure 3A [Illustration] is a diagram showing the form of the extracted energy-responsive composition according to the second embodiment in a state supported by a support substrate.

[0021] [ Figure 3B[Illustration] is a diagram showing the form of the extracted energy-responsive composition according to the second embodiment in a state supported by a support substrate.

[0022] [ Figure 3C [Illustration] is a diagram showing the form of the extracted energy-responsive composition according to the second embodiment in a state supported by a support substrate. Detailed Implementation

[0023] Preferred embodiments of the invention will now be described in detail with reference to the accompanying drawings. The dimensions, materials, shapes, and relative configurations of the components described in these embodiments are not intended to limit the scope of the invention.

[0024] <First Implementation Plan>

[0025] use Figure 1 and Figures 2A to 2C A method for manufacturing an energy-responsive composition according to a first embodiment is described. Figure 1 This is a flowchart illustrating the steps of a method 1000 for manufacturing an energy-responsive composition according to a first embodiment. Figures 2A to 2C This schematically illustrates a polymer-containing solution according to the first embodiment. Figure 2A ), mixture ( Figure 2B ) and energy-responsive compositions ( Figure 2C The diagram is composed of ).

[0026] The method for manufacturing the energy-responsive composition is carried out as follows: Figure 1 Each step from S101 to S19 in the process.

[0027] (Step S103: Preparing a polymer-containing solution)

[0028] Step S103 of preparing a polymer-containing solution includes the step of preparing a polymer-containing solution (P), which includes a solvent 10 having a relative permittivity below a specified value and an associative polymer 40, which comprises a main chain 20 having a plurality of carbon atoms and polar groups 30 having a polarity higher than that of the main chain 20 and is self-associated in the solvent.

[0029] (Step S105 for preparing the mixture)

[0030] Step S105 of preparing the mixture includes the step of preparing the mixture (R) by contacting the energy-responsive nanoparticles (Q) with a polymer-containing solution (P).

[0031] (Step S107 for extracting the energy-responsive composition)

[0032] Step S107 of extracting the energy-responsive composition includes the step of extracting an energy-responsive composition (S) comprising a plurality of energy-responsive protective particles, each containing nanoparticles and an associative polymer, from a mixture R by reducing the solvent content.

[0033] (Evaluation of effectiveness)

[0034] In the method 1000 for manufacturing the energy-responsive composition 100 according to this embodiment, although the detailed reasons for the above-mentioned effects are not clear, the inventors have considered the following.

[0035] An associative polymer 40 comprising a main chain 20 having multiple carbon atoms and polar groups 30 with higher polarity than the main chain 20, and which self-associates in solvent 10, takes the form of so-called unimolecular micelles, in which polar groups 30 associate with each other within a polymer molecule under specific conditions. Figure 2A Monomolecular micelles have a small size of about a few nanometers (the average particle size of the micelles is about 2 nm to 10 nm), and the polar groups 30 are hidden inside. Therefore, even when monomolecular micelles are mixed with energy-responsive nanoparticles 60, coordination is difficult. Figure 2B When the content of solvent 10 in the mixture (R) decreases, firstly, the distance between nanoparticles 60 decreases with increasing concentration. Secondly, associative dissolution occurs, and coordination takes place while maintaining a short distance between nanoparticles 60. In this case, since coordination partially occurs, causing the particles to crosslink with each other, it becomes even more difficult to increase the distance between nanoparticles 60. Figure 2C ).

[0036] (Self-association)

[0037] In this embodiment, self-association means intramolecular association through electrostatic interactions of at least a portion of the polar groups 30 in a solvent 10 with a relative permittivity below a specified value. The polar groups 30 do not necessarily have to interact directly with each other, and trace amounts of polar materials such as water may be present. Furthermore, self-association is considered even when different types of polar groups associate with each other through electrostatic interactions.

[0038] (Nanoparticles)

[0039] In this embodiment, the energy-responsive nanoparticle Q is preferably a nanoparticle comprising a perovskite-type crystal structure having nanocrystals as allotropes, wherein the A-site (monovalent cation), B-site (divalent cation), and X-site (monovalent anion containing a halide anion) are structural components. The perovskite-type crystal structure is further described as a perovskite-type structure, an ABX3-type crystal structure, or an ABX3-type structure. Furthermore, a double perovskite-type crystal structure represented by A2B1B2X6 is also included in the perovskite-type crystal structure. In this specification, the energy-responsive nanoparticle Q can be further described as a nanoparticle, a luminescent nanoparticle, a luminescent nanocrystal, a photoresponsive nanocrystal, or a quantum dot.

[0040] The average particle size of the nanoparticles is preferably 1 nm or more and 30 nm or less, and more preferably 2 nm or more and 25 nm or less. If the average particle size is less than 1 nm, the stability may be insufficient. If the average particle size is greater than 30 nm, the dispersibility in the medium may be insufficient.

[0041] [A site of perovskite structure]

[0042] A monovalent cation is used as the A-site. Examples of monovalent cations used for the A-site include nitrogen-containing organic compound cations, such as ammonium cations (NH4+). + Alkylammonium cations with 6 or fewer carbon atoms, and formamidinium cations (HC(NH2)2) + ), guanidinium cation (C(NH2)3) + Imidazolium cations, pyridinium cations, and pyrrolidineium cations, and include alkali metal cations such as lithium cations (Li). + ), sodium cation (Na) + ), potassium cation (K) + ), rubidium cations (Rb + ) and cesium cations (Cs + ).

[0043] The monovalent cations used in the A site have small ionic diameters and are large enough to be embedded in the lattice, so the perovskite compound can form a stable three-dimensional crystal.

[0044] Preferred examples of alkylammonium cations having 6 or fewer carbon atoms include methylammonium cations (CH3NH3). + ), ethylammonium cation (C2H5NH3) + ) and propylammonium cation (C3H7NH3) + ).

[0045] From the viewpoint of obtaining high luminescence efficiency, it is preferable to use at least any one of methylammonium cation, formamidinium cation, and cesium cation as the A-site, and from the viewpoint of suppressing color changes, the A-site is more preferably a cesium cation. These monovalent cations can be used at the A-site in combinations of two or more.

[0046] When the A-site is a cesium cation, cesium salts are used as the starting material for synthesizing nanoparticles. Suitable cesium salts include cesium chloride, cesium bromide, cesium iodide, cesium hydroxide, cesium carbonate, cesium bicarbonate, cesium bicarbonate, cesium formate, cesium acetate, cesium propionate, cesium neopentanoate, or cesium oxalate. The appropriate cesium salt from these candidates can be used depending on the synthetic method.

[0047] When the A site is another alkali metal cation, for example, a salt obtained by replacing the cesium element of the above-mentioned cesium compound with another alkali metal cation element can be used as a raw material.

[0048] When the A site is a nitrogen-containing cation such as a methylammonium cation, a neutral compound other than a salt, such as methylamine, can be used as a raw material. These raw materials can be used in combination of two or more.

[0049] [Perovskite-type crystal structure B-site]

[0050] For the B site of the perovskite-type crystal structure, a divalent transition metal cation or a divalent cation containing a typical divalent metal cation is used.

[0051] Scandium cations (Sc) are used as divalent transition metal cations. 2+ ), titanium cations (Ti 2+ ), Vanadium cation (V) 2+ ), chromium cations (Cr 2+ ), manganese cations (Mn 2+ ), iron cations (Fe) 2+ ), cobalt cations (Co) 2+ ), nickel cations (Ni 2+ ), copper cations (Cu 2+ ), palladium cation (Pd) 2+ europium cations (Eu) 2+ ) or ytterbium cation (Yb 2+ ).

[0052] Magnesium cations (Mg) can be used as typical divalent metal cations. 2+ ), calcium cations (Ca 2+ ), Strontium cation (Sr) 2+ ), barium cations (Ba 2+ ), zinc cations (Zn) 2+ ), cadmium cations (Cd) 2+ ), germanium cation (Ge2+ ), tin cation (Sn) 2 + ) or lead cations (Pb 2+ ).

[0053] Among these divalent cations, typical divalent metal cations are preferred for stabilizing the growth of three-dimensional crystals, with tin or lead cations being more preferred, and lead cations being particularly preferred from the viewpoint of obtaining high luminescence intensity. These divalent cations can be used in combinations of two or more, and the perovskite crystal structure can be a so-called double perovskite type.

[0054] When the B-site is a lead cation, lead compounds are used as raw materials for synthesizing nanoparticles. Appropriate lead compounds can be used depending on the synthesis method. Examples of lead compounds include lead chloride, lead bromide, lead iodide, lead oxide, lead hydroxide, lead sulfide, lead carbonate, lead formate, lead acetate, lead 2-ethylhexanoate, lead oleate, lead stearate, lead naphthenate, lead citrate, lead maleate, or lead acetylacetone. When the B-site is another divalent metal cation, salts obtained by replacing the lead element in the above-mentioned lead compounds with other divalent metal cations can be used as raw materials. These raw materials can be used in combinations of two or more.

[0055] [X-position of perovskite crystal structure]

[0056] X, representing a perovskite-type crystal structure, employs a monovalent anion containing a halide anion. Examples of halide anions include fluoride anions (F...). - ), chloride anion (Cl - ), bromide anion (Br) - ) and iodide anion (I - In particular, from the viewpoint of forming stable three-dimensional crystals and exhibiting strong luminescence in the visible light region, chloride anions, bromide anions, and iodide anions are preferred. The luminescence color is blue when chloride anions are used, green when bromide anions are used, and red when iodide anions are used.

[0057] Two or more types of halide anions can be used. In particular, when chloride anions, bromide anions, and iodide anions are used in combination, the emission wavelength of the nanoparticles can be tuned to the desired wavelength according to the content ratio of the anion species. That is, in particular, the combination of chloride anions, bromide anions, and iodide anions is preferred because an emission spectrum covering almost the entire visible light spectrum from blue to red can be obtained according to the content ratio of the anion species, while maintaining a narrow full width at half maximum (FWHM).

[0058] The X position can contain monovalent anions other than halide anions. Examples of monovalent anions other than halide anions include pseudohalide anions, such as cyanide anions (CN). - ), thiocyanate anion (SCN) - ) and isothiocyanate anion (CNS) - The raw materials for the synthesis of nanoparticles can be appropriately selected from salts having counter cations at the A and B sites, such as cesium chloride and lead bromide, as well as salts having cations other than those mentioned above, depending on the synthesis method.

[0059] The nanoparticles Q in this embodiment can be manufactured by the following processes. For example, a hot injection method can be used to generate microparticles by mixing a raw material liquid at high temperature and then rapidly cooling it to obtain a stable product, or a ligand-assisted redeposition method can be used to obtain microparticles by utilizing the difference in miscibility between the product and the solvent for redeposition.

[0060] In addition, a room-temperature synthesis method is also proposed, in which a mixture of a non-halide derivative (excluding the component for the X-site), i.e., a raw material for the A-site and a raw material for the B-site, is mixed with a separately prepared raw material solution for the X-site under mild conditions at around room temperature to obtain microparticles. Furthermore, a mechanochemical method is proposed, in which product microparticles are obtained by mechanically mixing solid raw materials through reactions such as grinding or ultrasonic treatment, and in-situ synthesis methods are proposed, in which reaction products are obtained by coating a raw material solution onto a substrate and then performing direct crystal growth.

[0061] The ligands, described later, coordinate with the surface of nanoparticle Q by coexisting during the fabrication of nanoparticle Q and can stabilize the dispersion. If necessary, residual ligands can be removed by centrifugation or the like.

[0062] (solvent)

[0063] As a solvent, a solvent with a relative permittivity of 6.0 or less can be used, and more preferably 4.5 or less.

[0064] Specifically, examples include aromatic hydrocarbons such as xylene (relative permittivity: 2.3) and toluene (relative permittivity: 2.4); hydrocarbons such as hexane (relative permittivity: 1.9); alicyclic hydrocarbons such as cyclohexane (relative permittivity: 2.0); esters such as ethyl acetate (relative permittivity: 6.0) and butyl acetate (relative permittivity: 5.0); haloalkyl compounds such as chloroform (relative permittivity: 4.9); and ethers such as diethyl ether (relative permittivity: 4.3). These solvents can also be used as mixtures as needed. In such cases, the relative permittivity is a weighted average of all solvents. Furthermore, polymerizable compounds, described later, can also be used as solvents.

[0065] (ligand)

[0066] In this embodiment, the ligand 30 is preferably at least one compound or ion selected from the group consisting of weak acids such as carboxylic acids, weak bases such as amines, their salts, and ions.

[0067] Examples of acids include branched or straight-chain fatty acids having 1 to 30 carbon atoms. The alkyl chain can be saturated or unsaturated. In particular, straight-chain fatty acids are preferred from the viewpoint of solubility and stability in solvents, and oleic acid is further preferred.

[0068] Examples of bases include branched or straight-chain organic bases having 1 to 30 carbon atoms. The alkyl chain may be saturated or unsaturated. In particular, straight-chain organic bases are preferred from the viewpoint of solubility and stability in solvents, and oleylamines are further preferred.

[0069] Ligands can consist of a single ligand or a combination of two or more ligands.

[0070] (Amount of ligand relative to nanoparticle Q)

[0071] When the amount of nanoparticle Q is 100, the amount of ligand is preferably 10 or more and 500 or less, more preferably 20 or more and 400 or less, and even more preferably 30 or more and 300 or less. When the amount of ligand is less than 10 or greater than 300, the dispersion stability of nanoparticle Q may be insufficient.

[0072] (Associative polymers)

[0073] In this embodiment, the associative polymer 40 comprises a main chain 20 having a plurality of carbon atoms and polar groups 30 having a polarity higher than that of the main chain 20, and is a self-associative associative polymer contained in solvent 10.

[0074] The main chain 20 is the longest series of covalently bonded atoms and may contain side chains. Side chains are linear, branched, or cyclic alkyl groups, linear, branched, or cyclic heteroalkyl groups, aryl groups, heteroaryl groups, aralkyl groups, or heteroaralkyl groups. These compounds may be further partially substituted.

[0075] The polar group 30 is selected from at least one of the following groups: strong acids such as sulfonic acid and phosphonic acid, strong bases such as quaternary ammonium cations, zwitterionic groups such as sulfobetaine, phosphate betaine and carboxybetaine, and their salts or ions.

[0076] As an associative polymer, copolymers obtained by polymerizing at least two types of monomers (described later) can be used.

[0077] (Amount of associative polymer relative to nanoparticles Q)

[0078] When the nanoparticle Q is 100, the amount of associating polymer is preferably 1 or more and 1000 or less, more preferably 10 or more and 800 or less, and even more preferably 30 or more and 600 or less. When the amount of associating polymer is less than 10, sufficient fusion effect may not be achieved. When the amount of associating polymer is greater than 600, monomolecular micelles may not form well in the solvent.

[0079] (Number of millimoles of polar groups per 1g of nanoparticle Q)

[0080] The millimolecular number of polar groups per 1g of nanoparticles Q is preferably 0.01 to 10, more preferably 0.03 to 8, and even more preferably 0.1 to 6. When the millimolecular number of polar groups per 1g of nanoparticles Q is within the above range, it is easy to obtain an effect that prevents fusion. When the millimolecular number is less than 0.01, it may not be able to effectively prevent fusion. When the millimolecular number is greater than 10, monomolecular micelles may not form well in low-polarity solvents. The millimolecular number corresponds to the content of polar groups contained in 1g of nanoparticles Q, and is corresponding to ×10 -3 The unit is mol.

[0081] <Method for manufacturing energy-responsive compositions>

[0082] The method for manufacturing the nanoparticles of the present invention will be described in detail below.

[0083] The manufacturing method of the present invention includes the following steps:

[0084] - The step of preparing a polymer-containing solution (P) comprising a solvent 10 having a relative permittivity below a specified value and an associative polymer 40 comprising a main chain having a plurality of carbon atoms and polar groups 30 having a polarity higher than that of the main chain and being self-associated in the solvent 10.

[0085] - The step of preparing a mixture (C) by contacting energy-responsive nanoparticles (Q) with a polymer-containing solution (P); and

[0086] - The step of extracting an energy-responsive composition (S) comprising multiple energy-responsive protective particles, each containing nanoparticles Q and associative polymer 40, from the mixture C by reducing the content of solvent 10.

[0087] (Steps for preparing mixture (C))

[0088] The nanoparticles Q manufactured by the above method are brought into contact with a polymer-containing solution P obtained by dispersing the associative polymer 40 manufactured by the following method in solvent 10. The contact method can be any known method. For example, a method of mixing the dispersion of nanoparticles Q with the liquid phase of the polymer-containing solution P, or a method of adding the polymer-containing solution P to the solid phase of nanoparticles Q for redispersibility and mixing. Another contact method can be a method of applying the polymer-containing solution P to the solid phase of nanoparticles Q on a support while rotating the support (spin coating). When nanoparticles Q are dispersed in a liquid, the dispersion solvent can be the same as or different from the solvent of the polymer-containing solution P. The dispersion solvent of nanoparticles Q preferably has a relative permittivity of less than a specified value. The specified value is preferably 6.0 or less, and more preferably 4.5 or less.

[0089] The preferred temperature for preparing mixture C is above -80°C and below 50°C, and more preferably above -30°C and below 40°C. When the temperature is below -80°C, contact between the nanoparticles and the solution containing the associative polymer cannot proceed adequately. When the temperature is above 50°C, the associative polymer undergoes associative dissolution and coordination may occur.

[0090] (Steps for extracting the energy-responsive composition (S))

[0091] An energy-responsive composition (S) comprising multiple energy-responsive protective particles, each containing nanoparticles Q and an associative polymer 40, extracted from a mixture C by reducing the solvent content. The method for reducing the solvent content is preferably by evaporating the solvent at atmospheric pressure or by evaporating the solvent under reduced pressure. In such cases, the mixture C is preferably applied to a support.

[0092] The temperature at which the solvent evaporates is preferably above -80°C and below 50°C, and more preferably above -30°C and below 40°C. When the temperature is below -80°C, solvent evaporation may not occur effectively. When the temperature is above 50°C, associative dissolution of the associative polymer occurs, and coordination may take place.

[0093] In the step of extracting the energy-responsive composition, it is preferred that a pair of adjacent energy-responsive protective particles of a plurality of energy-responsive protective particles are in contact with each other through the contact of their associative polymer 40, and the nanoparticles of the adjacent energy-responsive protective particles are spaced apart from each other.

[0094] The step of extracting the energy-responsive composition preferably includes the step of removing solvent 10.

[0095] After the step of extracting the energy-responsive composition, a step of coordinating the associative polymer with the nanoparticles by heating may be performed, if necessary.

[0096] (Methods for manufacturing associative polymers)

[0097] The following describes in detail a method for manufacturing a high molecular weight compound that can be used as an associative polymer 40. There are no particular limitations on the method for manufacturing the polymer compound, as long as the above-described structure is obtained; however, the polymer compound can be manufactured by, for example, the following methods (i) or (ii).

[0098] That is, examples of methods for manufacturing polymer compounds (i) include manufacturing methods by producing monomers having structural units containing polar groups and then polymerizing the monomers. Examples of methods for manufacturing polymer compounds (ii) include methods by synthesizing a polymer backbone and then incorporating polar groups into the polymer backbone.

[0099] From the viewpoint of monomer availability and control over the amount of functional groups, preparation by method (i) is preferred. The following describes in detail a method for synthesizing polymers containing zwitterionic groups as polar groups, using method (i).

[0100] As monomers for introducing polar groups into polymers, vinyl ether derivatives, acrylate derivatives, methacrylate derivatives, α-olefin derivatives, or aromatic vinyl derivatives can be used. From the viewpoint of ease of monomer manufacture, it is preferred to use acrylate derivatives or methacrylate derivatives as monomers.

[0101] The corresponding acrylate derivatives or methacrylate derivatives can be manufactured by methods described, for example, in the following literature: K. Ishihara et al., "Polymer Journal", (Japan), The Society of Polymer Science, 1990, Vol. 22, pp. 355-360.

[0102] Examples of methods for polymerizing the aforementioned monomers include free radical polymerization and ionic polymerization, and living polymerization for purposes of molecular weight distribution control and structure control can also be used. Industrially, free radical polymerization is preferred.

[0103] Free radical polymerization can be carried out through the use of free radical polymerization initiators, light irradiation such as radiation and lasers, a combination of photopolymerization initiators and light irradiation, or heating. Free radical polymerization initiators can be initiators that can generate free radicals and initiate polymerization, and are selected from compounds that generate free radicals through the action of heat, light, radiation, and redox reactions.

[0104] Examples of compounds include azo compounds, organic peroxides, inorganic peroxides, organometallic compounds, and photopolymerization initiators.

[0105] More specific examples include azo compounds such as 2,2'-azobisisobutyronitrile (AIBN) and 2,2'-azobis(2,4-dimethylpentanonitrile); organic peroxides such as benzoyl peroxide (BPO), tert-butyl peroxypentanoate, and tert-butyl peroxyisopropyl carbonate; inorganic peroxides such as potassium persulfate and ammonium persulfate; and redox initiators such as hydrogen peroxide-iron(II) salts, BPO-dimethylanilines, and cerium(IV) salts-alcohols. Examples of photopolymerization initiators include acetophenones, benzoin ethers, and ketals. These free radical polymerization initiators can be used in combinations of two or more.

[0106] The preferred range of polymerization temperature for vinyl monomers varies depending on the type of polymerization initiator used, and polymerization is generally carried out at temperatures from -30°C to 150°C, with a more preferred temperature range of 40°C to 120°C.

[0107] In this case, the amount of polymerization initiator used is more than 0.1 parts by mass and less than 20 parts by mass per 100 parts by mass of monomer, and is preferably adjusted to obtain a polymer compound with a target molecular weight distribution.

[0108] The polymerization method can be any of solution polymerization, suspension polymerization, emulsion polymerization, dispersion polymerization, precipitation polymerization and bulk polymerization, and is not particularly limited thereto.

[0109] The obtained polymeric compounds can be purified as needed. There are no particular limitations on the manufacturing method, and methods such as reprecipitation, dialysis, and column chromatography can be used.

[0110] Various analytical instruments can be used to identify the structure of manufactured polymer compounds. These instruments include nuclear magnetic resonance (NMR), gel permeation chromatography (GPC), and inductively coupled plasma atomic emission spectrometry (ICP-AES).

[0111] (polymeric compounds)

[0112] The polymerization of polymerizable compounds is promoted by receiving energy such as light and heat, and the compound becomes the component that imparts viscosity to the photoresponsive composition and causes it to solidify. Free radical polymerizable compounds or cationic polymerizable compounds can be used as polymerizable compounds. These compounds can be used alone or in combination of two or more. Optionally, photopolymerizable compounds or thermal polymerizable compounds can also be used. In this specification, the form in which the viscosity increases through the polymerization of the polymerizable compound can be described as a polymer.

[0113] As free radical polymerizable compounds, for example, monofunctional (meth)acrylate compounds, difunctional (meth)acrylate compounds, trifunctional or higher (meth)acrylate compounds, hydroxyl-containing (meth)acrylate compounds, carboxyl-containing (meth)acrylate compounds, or ethylene compounds can be used.

[0114] As monofunctional (meth)acrylates, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, benzyl (meth)acrylate, 3,3,5-trimethylcyclohexyl acrylate, tetrahydrofurfuryl (meth)acrylate, phenoxyethyl (meth)acrylate, methoxyethyl (meth)acrylate, ethyl carbitol (meth)acrylate, isobornyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolane-4-yl)methyl (meth)acrylate, (3-ethyloxetane-3-yl)methyl (meth)acrylate, or cyclic trimethylolpropane methyl acetal (meth)acrylate can be used.

[0115] As bifunctional (meth)acrylate compounds, for example, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol 200 di(meth)acrylate, polyethylene glycol 300 di(meth)acrylate, polyethylene glycol 400 di(meth)acrylate, etc., can be used. Ethylene glycol 600 di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, polypropylene glycol 400 di(meth)acrylate, polypropylene glycol 700 di(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentyl glycol PO modified di(meth)acrylate, EO modified bisphenol A di(meth)acrylate, PO modified bisphenol A di(meth)acrylate, or hydroxypentanoic acid neopentyl glycol di(meth)acrylate.

[0116] As a trifunctional or higher (meth)acrylate compound, for example, trimethylolpropane tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, glycerol propoxytri(meth)acrylate, pentaerythritol tri(meth)acrylate, tri(acryloyloxyethyl)isocyanurate, or EO-modified pentaerythritol tetraacrylate can be used.

[0117] As an ethylene compound, for example, vinyl acetate, vinyl benzoate, vinyl pentanoate, vinyl butyrate, vinyl methacrylate, or N-vinylpyrrolidone can be used.

[0118] As cationic polymerizable compounds, photopolymerizable or thermally polymerizable compounds can be used. These compounds can be used alone or in combination of two or more. Representative examples of cationic polymerizable compounds include epoxides, oxetanes, and vinyl ethers.

[0119] The amount of polymerizable compounds used, such as free radical polymerizable compounds and cationic polymerizable compounds, is preferably 1 to 99 parts by mass, more preferably 3 to 90 parts by mass, and even more preferably 5 to 80 parts by mass, based on the total mass of the photoresponsive composition.

[0120] (Polymerization initiator)

[0121] In polymerization reactions, polymerization initiators and polymerizable compounds are typically used together. A polymerization initiator is a compound that generates active species that initiate polymerization reactions via irradiation with active energy rays or heat, and known polymerization initiators can be used. Major examples of active species that initiate polymerization reactions include radical polymerization initiators that generate free radicals and cationic polymerization initiators that generate acids, and they can be used in combination. Examples of photoradiative polymerization initiators that generate free radicals via active energy rays include acetophenones, such as diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylprop-1-one, benzyl methyl ketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinoprop-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane, oligomeric [2-hydroxy-2- Methyl-1-[4-(1-methylvinyl)phenyl]acetone] and 2-hydroxy-1-[4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl]-2-methylprop-1-one; benzoin derivatives, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; phosphine derivatives, such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; and other examples, such as methyl phenylglyoxylate.

[0122] Among photoradical polymerization initiators, acetophenones (represented by aminoketones), phosphine compounds, and oxime esters are preferred. They can be used alone or in combination, depending on the desired properties of the cured product. The amount of free radical polymerization initiator used is preferably 0.01 to 100 parts by mass based on 100 parts by mass of the total solid content in the composition, and more preferably 0.1 to 50 parts by mass.

[0123] (Other additives)

[0124] In this embodiment, the energy-responsive composition can be used as needed by mixing with scavengers, antioxidants, scattering agents such as titanium dioxide, surfactants, antifungals, light stabilizers, other additives that impart various properties, and diluents.

[0125] <Second Implementation Plan>

[0126] use Figures 3A to 3C Describes an energy-responsive composition 100 according to a second embodiment.

[0127] Figures 3A to 3C Each is shown in the form of an extracted energy-responsive composition 200 according to this embodiment, which is supported by a substrate 90 having a support surface 90S. Figure 3B and Figure 3C These are two views showing the supported state of the energy-responsive composition 200 as observed from a macroscopic perspective. Figure 3A yes Figure 3B A magnified partial view.

[0128] The energy-responsive composition 100 comprises a plurality of energy-responsive protective particles 150. Each energy-responsive protective particle 150 comprises energy-responsive nanoparticles 110 and an associative polymer 140, the associative polymer 140 comprising a backbone 120 having a plurality of carbon atoms and polar groups 130 having a polarity higher than that of the backbone 120 and being coordinated with the nanoparticles 110.

[0129] A pair of adjacent energy-responsive protective particles (150, 150') in a plurality of energy-responsive protective particles are in contact with each other through the contact of their associative polymer (140, 140'), and the nanoparticles (110, 110') of the adjacent energy-responsive protective particles are spaced apart from each other.

[0130] (Nanoparticles)

[0131] In this embodiment, the nanoparticles 110 are preferably nanoparticles comprising a perovskite-type crystal structure having nanocrystals as allotropes, wherein the A-site (monovalent cation), B-site (divalent cation), and X-site (monovalent anion containing a halide anion) are structural components. The same components as those used in the nanoparticles Q described in the first embodiment can be used as structural components.

[0132] (Associative polymers)

[0133] In this embodiment, the associative polymer 140 comprises a main chain 120 having a plurality of carbon atoms and polar groups 130 having a higher polarity than the main chain 120. Furthermore, at least a portion of the associative polymer 140 is preferably coordinated with the nanoparticles 110 to protect each nanoparticle Q.

[0134] The main chain 120 is the longest series of covalently bonded atoms and may contain side chains. Side chains are linear, branched, or cyclic alkyl groups, linear, branched, or cyclic heteroalkyl groups, aryl groups, heteroaryl groups, aralkyl groups, or heteroaralkyl groups. These compounds may be further partially substituted.

[0135] The polar group 130 is selected from at least one of the following groups: strong acids such as sulfonic acids and phosphonic acids, strong bases such as quaternary ammonium cations, zwitterionic groups such as sulfobetaine, phosphate betaine and carboxybetaine, and their salts or ions.

[0136] As the associative polymer 140, a copolymer obtained by polymerizing at least two types of monomers can be used. As the associative polymer 140, the same polymer as those associative polymers 40 shown in the first embodiment can be used.

[0137] <Third Implementation Plan>

[0138] The energy-responsive composition of the present invention can be applied to quantum dot wavelength conversion wafers (QD wafers), quantum dot wavelength conversion layers (QD-CC), and quantum dot electroluminescence (QD-EL) devices.

[0139] Here, a QD-EL device employing the energy-responsive composition according to the present invention is described.

[0140] The QD-EL device of the present invention includes, for example, electrodes (cathode and anode), an electron injection / transport layer, a light-emitting layer, and a hole injection / transport layer. A surface treatment layer may be disposed on any surface of the light-emitting layer.

[0141] (electrode)

[0142] There are no particular limitations on the material of the electrode. For example, materials used in organic electroluminescent (EL) devices, etc., can be suitably used, and examples include transparent conductive oxides such as indium tin oxide (ITO), metals such as Al, alloys of Ag, Pd and Cu (APC electrode), alloys of Mg and Ag, and laminates in which metal layers and transparent conductive oxide layers such as ITO are stacked (laminated electrode). In both the anode and cathode, the electrode on the side from which light is extracted from the light-emitting layer is preferably transparent.

[0143] There are no particular limitations on the thickness of the anode, and it can be, for example, 10 nm or more, 30 nm or more, or 50 nm or more but less than 1000 nm, less than 500 nm, or less than 200 nm. There are no particular limitations on the thickness of the cathode, and it can be, for example, 10 nm or more, 30 nm or more, or 50 nm or more but less than 1000 nm, less than 500 nm, or less than 200 nm.

[0144] (Hollow injection / delivery layer)

[0145] As materials for the hole injection / delivery layer, materials used in organic EL devices can be appropriately used, for example. Examples of organic materials include polyvinylcarbazole (PVK), poly(9,9-dioctylfluorene-co-N-(4-butylphenyl)-diphenylamine) (TFB), poly(bis(4-phenyl)(2,4,6-trimethylphenyl)amine) (PTAA), poly[N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)-benzidine] (poly-TPD), and poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS). Examples of inorganic materials include NiO, TiO2, and MoO. x These materials can be used alone or in combination of two or more.

[0146] The hole injection / transport layer can have a single-layer structure or a multilayer structure. The multilayer structure can include a hole injection layer disposed on the anode side and a hole transport layer disposed on the light-emitting layer side.

[0147] Considering the impact on hole injection and transport properties as well as optical characteristics, the thickness of the hole injection / transport layer in the monolayer structure can be appropriately adjusted. For example, the lower limits of the thickness of the hole injection layer and the hole transport layer can be 10 nm and 20 nm, respectively, and the upper limits of the thickness of the hole injection layer and the hole transport layer can be 1000 nm and 500 nm, respectively.

[0148] (Emitting layer)

[0149] The energy-responsive composition according to the present invention can be used as a light-emitting layer.

[0150] There are no particular restrictions on the thickness of the light-emitting layer, and it can be, for example, 10nm or more, 50nm or more, or 75nm or more and 1000nm or less, 500nm or less, or 250nm or less.

[0151] (Electron injection / delivery layer)

[0152] As materials for the electron injection / transport layer, materials used in organic EL devices can be appropriately used, for example. Examples of organic materials include LiF, 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene (TPBi), N,N'-di-1-naphthyl-N,N'-diphenylbenzidine (NPD), 4,4'-bis(N-carbazolyl)-1,1'-biphenyl (CBP), and 4,6-bis(3,5-di(pyridin-3-yl)phenyl)-2-methylpyrimidine (B3PyMPM). Examples of inorganic materials include α-ZSO (amorphous zinc silicate; Zn-Si-O), ZnO, and SnO. These materials can be used alone or in combination of two or more.

[0153] The electron injection / transport layer can have a single-layer structure or a multilayer structure. The multilayer structure can include an electron injection layer disposed on the cathode side and an electron transport layer disposed on the light-emitting layer side.

[0154] The thickness of the electron injection / transport layer in the monolayer structure is not particularly limited and is appropriately adjusted to take into account its impact on electron injection and transport properties, as well as optical characteristics. For example, the lower limits for the thickness of the electron injection layer and the electron transport layer are 1 nm and 10 nm, respectively. The upper limits for the thickness of the electron injection layer and the electron transport layer are below 1000 nm and below 500 nm, respectively.

[0155] The above description primarily focuses on a bottom-emitting type of light-emitting device that extracts light from the anode side (substrate side), but the light-emitting device is not limited to this. For example, the light-emitting device can be a top-emitting type that extracts light from the cathode side (opposite side of the substrate).

[0156] ((Measurement Method))

[0157] Various physical properties can be measured as follows.

[0158] ((Configuration Density))

[0159] The packing density of an energy-responsive composition can be measured using a transmission electron microscope (TEM) or a scanning electron microscope (SEM) when it can be observed vertically, and can be measured using cross-sectional SEM images when it cannot be observed vertically relative to the energy-responsive composition. Packing density can be evaluated using, for example, the average inter-surface distance of the particles and the particle occupancy rate per unit area in the image. The average inter-surface distance of the particles can be determined by selecting, for example, 100 particles using image processing software, measuring the shortest distance between each particle, and averaging them.

[0160] Alternatively, the relative configuration density can be calculated from the amount of light absorbed or emitted per unit volume of the film. Since the amount of light emitted varies with the photoluminescence quantum yield (PLQY), the configuration density is preferably calculated from the amount of light absorbed.

[0161] ((Stability Evaluation))

[0162] The stability of energy-responsive compositions can be evaluated, for example, by assessing PLQY or by observing the fusion rate between nanoparticles using TEM.

[0163] (Measurement of molecular weight distribution)

[0164] The molecular weight distribution of the associative polymer can be calculated from monodisperse polymethyl methacrylate using gel permeation chromatography (GPC). Molecular weight measurement by GPC can be performed, for example, as follows.

[0165] The sample was added to the eluent as described below to a concentration of 1% by mass. The mixture was allowed to stand at room temperature for 24 hours to prepare a solution. The solution was then filtered through a solvent-resistant membrane filter with a pore size of 0.45 μm to obtain the sample solution, which was then measured under the following conditions:

[0166] Equipment: Agilent 1260 Infinity system (manufactured by Agilent Technologies, Inc.);

[0167] Column: PFG analysis linear M column (manufactured by Precision System Science Co., Ltd.);

[0168] Elution buffer: 2,2,2-trifluoroethanol;

[0169] Flow rate: 0.2 mL / min;

[0170] Oven temperature: 40℃; and

[0171] Sample injection volume: 20 μL.

[0172] In the calculation of the molecular weight distribution of the samples, a molecular weight calibration curve was used, which was prepared by using standard polymethyl methacrylate resin (manufactured by Agilent Technologies, Inc., EasiVial PM Polymer Standard Kit).

[0173] (Structural Analysis of Associative Polymers)

[0174] Structural analysis of associated polymers can be performed using nuclear magnetic resonance (NMR). For example, measurements were taken using an ECA-600 (600 MHz) manufactured by JEOL Ltd. 1 H-NMR and 13 C-NMR spectra were obtained. Measurements were performed at 25°C in a deuterated solvent containing tetramethylsilane as an internal standard. The ppm shift value (δ value) with the tetramethylsilane internal standard set to 0 was read as the chemical shift value.

[0175] (Verification method for coordination between associative polymers and nanoparticles)

[0176] Nuclear magnetic resonance (NMR) can be used to verify whether the associative polymer 40 is coordinated with the nanoparticle Q. For example, measurements were performed using an ECA-600 (600 MHz) manufactured by JEOL Ltd. 1 H-NMR. Coordination can be achieved through the structure of betaine. 1 The δ value of the H signal is determined by the offset of the individual δ value of the associated polymer or the change in the half-value width.

[0177] (Analysis of the association state of associative polymers)

[0178] The association state of associative polymers can be analyzed using NMR or dynamic light scattering (DLS). When using NMR, for example, an ECA-600 (600 MHz) manufactured by JEOL Ltd can be used for measurement. 1 ¹H-NMR. When polymers associate, the chemical shift values ​​of the polar group signals change compared to the unassociated state. Furthermore, when polymers associate, a broader spectrum is observed overall due to the confinement of molecular motion. The association state can also be analyzed in more detail by relaxation time measurements if needed. When using DLS, the association state can be analyzed from the particle size. When associating polymers intramolecularly, particle sizes of approximately several nanometers are observed.

[0179] (Analysis of the crystal structure (crystalline phase) of nanoparticles)

[0180] X-ray diffraction (XRD) can be used for crystal structure (crystalline phase) and composition analysis of nanoparticles. For example, the crystal structure and composition can be analyzed by measuring the X-ray diffraction pattern using a RINT 2100 (manufactured by Rigaku Corporation) and comparing it with diffraction patterns in a database. Depending on the morphology and size of the sample being analyzed, electron beam diffraction (ED) with a cross-sectional TEM can be used.

[0181] (Compositional analysis of nanoparticles)

[0182] The composition of nanoparticles can also be analyzed using XPS and ICP emission spectroscopy. The molar ratio of A to B can be measured by the signal intensity of XPS, and the concentration of X can be measured by the luminescence intensity in ICP emission spectroscopy (e.g., a CIROS CCD (manufactured by SPECTRO GmbH)).

[0183] ((Amount of ligands and associating polymers relative to nanoparticles))

[0184] The amounts of ligands and associating polymers relative to nanoparticles can be determined using TG-DTA and NMR measurements. For example, the amount of nanoparticles in an energy-responsive composition can be measured using TG-DTA. Subsequently, the amounts of ligands and associating polymers in the energy-responsive composition are determined separately using NMR measurements, thereby determining the amounts of ligands and associating polymers relative to nanoparticles.

[0185] (Amount of polar groups in associative polymers)

[0186] The amount of polar groups in associative polymers can be determined by NMR measurements. For example, an ECA-600 (600 MHz) NMR spectrometer manufactured by JEOL Ltd can be used for measurement. 1 H-NMR. The amount of polar groups in an associative polymer is calculated by comparing the signal intensity originating from polar groups with the signal intensity originating from parts other than polar groups.

[0187] ((millimoles of polar groups per 1g of nanoparticles))

[0188] The number of millimoles of polar groups per 1g of nanoparticles can be calculated from the amount of nanoparticles, the amount of associative polymer, and the amount of polar groups in the associative polymer determined by the above method.

[0189] Example

[0190] The present disclosure is described in more detail below through embodiments, but the present disclosure is not limited thereto.

[0191] [Preparation of Associative Polymer A]

[0192] A reaction vessel equipped with a condenser, stirrer, thermometer, and nitrogen inlet pipe is provided. 3-[[2-(methacryloyloxy)ethyl]dimethylammonio]propane-1-sulfonate (5.9 parts), hexyl methacrylate (48.0 parts), azobisisobutyronitrile (3.9 parts), and 2,2,2-trifluoroethanol (900 parts) are charged into the reaction vessel. The reaction vessel is further bubbled with nitrogen for 30 minutes. The resulting reaction mixture is heated at 65°C for 8 hours under a nitrogen atmosphere to complete the polymerization reaction. The reaction solution is cooled to room temperature, and then water (300 parts) is added to precipitate the product. After centrifugation, the supernatant is removed. The solvent is distilled off under reduced pressure, and then dried at 50°C under reduced pressure below 0.1 kPa to obtain associative polymer a. NMR measurements confirmed that the structure included polar groups, comprising 7 mol% of the total monomer units. The weight-average molecular weight (Mw) determined by GPC analysis was 13200.

[0193] [Preparation of Associative Polymer B]

[0194] Except that the amounts of 3-[[2-(methacryloyloxy)ethyl]dimethylammonium]propane-1-sulfonate and hexyl methacrylate are changed from 5.9 parts to 15.2 parts and from 48.0 parts to 42.3 parts, respectively, in the manufacture of associative polymer a, associative polymer b is manufactured in the same manner as in the manufacture of associative polymer a.

[0195] Table 1 shows the structure, composition, and molecular weight of the manufactured associative polymers a and b.

[0196] [Table 1]

[0197]

[0198] [Preparation of solutions containing associative polymers]

[0199] (Association solution a of associative polymer a in toluene)

[0200] Associating polymer a (0.8 parts) and toluene (99.2 parts) were charged into a reaction vessel equipped with a stirrer, thermometer, and reflux condenser, and the temperature was raised to 80°C and maintained for 5 minutes. After confirming that associating polymer a was completely dissolved, the solution was rapidly cooled to room temperature to obtain an associating liquid a of associating polymer a in toluene. DLS measurements confirmed the formation of monomolecular micelles with a particle size of 5 nm.

[0201] (Association solution b-1 of associative polymer b in toluene)

[0202] Except for using associating polymer b instead of associating polymer a, associating polymer b in toluene was prepared as associating polymer a in toluene as associating polymer a in toluene. DLS measurements confirmed the formation of monomolecular micelles with a particle size of 4 nm.

[0203] (Association solution b-2 of associative polymer b in chloroform)

[0204] Associating polymer b (0.8 parts) and chloroform (99.2 parts) were charged into a reaction vessel equipped with a stirrer, thermometer, and reflux condenser, and the temperature was raised to 60°C and maintained for 5 minutes. The mixture was then rapidly cooled to room temperature to obtain associating polymer b in chloroform, solution b-2.

[0205] [Manufacturing of Q-1 Nanoparticles]

[0206] Cesium carbonate (10 parts), oleic acid (27 parts), and 1-octadecene (385 parts) were placed in a flask, and the solution temperature was raised to 120°C, followed by degassing using a vacuum pump for 30 minutes. Further, the solution temperature was raised to 150°C under a dry nitrogen stream and maintained for 30 minutes to obtain a cationic feed solution.

[0207] Separately, lead(II) bromide (10 parts) and 1-octadecene (494 parts) were placed in a flask, and the solution temperature was raised to 120°C, followed by degassing with a vacuum pump for 1 hour. Oleic acid (89 parts) and oleylamine (31 parts) were added, and the solution was further degassed with a vacuum pump for 30 minutes. Then, instead of a nitrogen flow, the solution temperature was set to 185°C.

[0208] A cationic feedstock solution (40 parts) was added, and the mixture was cooled on ice after 5 seconds. Ethyl acetate (2000 parts) was added, centrifuged, and the supernatant was removed. The resulting residue was dispersed in toluene, and the solids concentration was adjusted to 1 wt% to obtain a dispersion of nanoparticles Q-1 with a perovskite-type crystal structure of CsPbBr3. The proportion of nanoparticles Q in the solids composition, as measured by TG-DTA, was 53 wt%.

[0209] [Manufacturing of Q-2 Nanoparticles]

[0210] A dispersion of nanoparticles Q-2 with a perovskite-type crystal structure of CsPb(Br / I)3 was obtained, except that lead(II) bromide (3.2 parts) and lead(II) iodide (9.3 parts) were used instead of lead(II) bromide (10 parts), as in the luminescent nanocrystal dispersion a. The proportion of nanoparticles Q in the solid composition was 52 wt%, as measured by TG-DTA.

[0211] (Example 1)

[0212] A dispersion a (100 parts) of nanoparticles Q-1 was placed in a container, and the solvent was distilled off under reduced pressure. An associative polymer a in toluene (100 parts) was added to the dispersion for redispersibility. The dispersion was spin-coated at 1000 rpm for 20 seconds on a 2 cm × 2 cm glass substrate washed with UV-O3 to obtain the energy-responsive composition 100-1.

[0213] (Examples 2 to 4 and Comparative Example 2)

[0214] Except by changing the types of nanoparticles Q, associative polymers, and associative liquids to those shown in Table 2, energy-responsive compositions 100-2 to 100-4 and 100-6 were obtained as in Example 1.

[0215] (Comparative Example 1)

[0216] A dispersion a (100 parts) of nanoparticles Q-1 was placed in a container, and the solvent was distilled off under reduced pressure. An associative polymer a in toluene (100 parts) was added to the dispersion for redispersibility, and the dispersion was heated at 50°C for 20 minutes to complete coordination. The dispersion was spin-coated at 1000 rpm for 20 seconds on a 2 cm × 2 cm glass substrate washed with UV-O3 to obtain the energy-responsive composition 100-5.

[0217] [Table 2]

[0218]

[0219] [evaluate]

[0220] [Density Evaluation of Nanoparticles 1]

[0221] The density of nanoparticles was evaluated by the absorbance of energy-responsive compositions 100⁻¹ to 100⁻⁶.

[0222] The measurement conditions and evaluation criteria are as follows.

[0223] <Measurement Conditions>

[0224] Measurement equipment: Absolute PL quantum yield measurement instrument C9920-03 (manufactured by Hamamatsu Photonics KK);

[0225] Excitation wavelength: 460nm; and

[0226] Excitation light integration range: excitation light wavelength ±10nm.

[0227] <Evaluation Criteria>

[0228] A: Absorbance is 6×10 6 above;

[0229] B: Absorbance is 4×10 6 Above and less than 6×10 6 ;and

[0230] C: Absorbance less than 4 × 10 6 .

[0231] Table 3 shows the evaluation results.

[0232] [Stability Evaluation 1]

[0233] Each sample was left to stand in air for 7 days, and then PLQY was measured to evaluate stability.

[0234] The measurement conditions and evaluation criteria are as follows.

[0235] <Measurement Conditions>

[0236] Measurement equipment: Absolute PL quantum yield measurement instrument C9920-03 (manufactured by Hamamatsu Photonics KK);

[0237] Excitation wavelength: 460nm;

[0238] Excitation light integration range: excitation light wavelength ±10 nm; and

[0239] Luminescence integral range: (excitation wavelength + 20) nm to 770 nm.

[0240] <Evaluation Criteria>

[0241] A: PLQY is over 70%;

[0242] B: PLQY is above 50% and less than 70%; and

[0243] C: PLQY is below 50%.

[0244] Table 3 shows the evaluation results.

[0245] [Density Evaluation of Nanoparticles 2]

[0246] Each of the energy-responsive compositions 100⁻¹ to 100⁻⁶ was diluted 20-fold, and 3 μL of each was added to a support film (high-resolution carbon HRC-C10). The solvents were allowed to evaporate at room temperature, and TEM observation was performed using a Technai F30 (manufactured by FEI Company). The average intersurface distance of the particles was calculated for 100 particles selected from the TEM images, and the density of the nanoparticles was evaluated according to the following criteria.

[0247] A: The average inter-surface distance is less than 5 nm;

[0248] B: Average inter-surface distance greater than 5nm and less than 15nm; and

[0249] C: Average inter-surface distance is greater than 15nm.

[0250] Table 3 shows the evaluation results.

[0251] [Stability Evaluation 2]

[0252] In the TEM images above, 100 particles were selected, and the stability of the nanoparticles was evaluated according to the following criteria.

[0253] A: Fusion was observed in fewer than 5 particles;

[0254] B: Fusion was observed in particles larger than 5 but less than 10; and

[0255] C: Fusion was observed in more than 10 particles.

[0256] Table 3 shows the evaluation results.

[0257] [Table 3]

[0258]

[0259] According to Table 3, the energy-responsive compositions 100-1 to 100-4 of Examples 1 to 4 exhibit high nanoparticle density and high stability. In contrast, the energy-responsive composition 100-5 of Comparative Example 1 exhibits high stability but low nanoparticle density. The energy-responsive composition 100-6 of Comparative Example 2 exhibits high nanoparticle density but low stability.

[0260] These results indicate that associative polymers form monomolecular micelles in low-polarity solvents, thus remaining uncoordinated in the dispersed state, while the nanoparticles are densely configured during film formation and then coordinated.

[0261] This invention is not limited to the above-described embodiments, and various modifications and variations can be made without departing from the spirit and scope of the invention. Therefore, the claims are appended to inform the scope of the invention.

[0262] This application claims the benefit of Japanese Patent Application No. 2023-083371, filed on May 19, 2023, the entire contents of which are incorporated herein by reference.

[0263] Explanation of reference numerals in the attached figures

[0264] 100, S energy-responsive composition

[0265] Method for manufacturing a 1000 energy-responsive composition

[0266] 10 Solvents

[0267] 20 main chains

[0268] 30 polar groups

[0269] 40 Associative Polymers

[0270] 50. P is a solution containing polymers.

[0271] 60. Q nanoparticles

[0272] 70, R mixture

[0273] 80 Energy-responsive protective particles

Claims

1. A method of manufacturing an energy-responsive composition, comprising: a step of preparing a polymer-containing solution including a solvent having a relative dielectric constant of a prescribed value or less and an associating polymer having a main chain including a plurality of carbon atoms and a polar group having a polarity higher than the main chain and self-associating in the solvent; a step of preparing a mixed solution by bringing an energy-responsive nanoparticle into contact with the polymer-containing solution; and a step of extracting an energy-responsive composition including a plurality of energy-responsive protective particles each including the nanoparticle and the associating polymer from the mixed solution by reducing a content of the solvent.

2. The method of manufacturing an energy-responsive composition according to claim 1, wherein in the step of extracting an energy-responsive composition, a pair of adjacent energy-responsive protective particles of the plurality of energy-responsive protective particles are in contact with each other through contact of their associating polymers, and the nanoparticles of the adjacent energy-responsive protective particles are spaced apart from each other.

3. The method of manufacturing an energy-responsive composition according to claim 1 or 2, wherein the step of extracting an energy-responsive composition includes a step of removing the solvent.

4. The method of manufacturing an energy-responsive composition according to claim 1 or 2, wherein the nanoparticle has a perovskite-type crystal structure.

5. An energy-responsive composition, comprising: a plurality of energy-responsive protective particles each including: an energy-responsive nanoparticle; and an associating polymer including a main chain having a plurality of carbon atoms and a polar group having a polarity higher than the main chain and coordinated with the nanoparticle, wherein a pair of adjacent energy-responsive protective particles of the plurality of energy-responsive protective particles are in contact with each other through contact of their associating polymers, and the nanoparticles of the adjacent energy-responsive protective particles are spaced apart from each other.

6. The energy-responsive composition according to claim 5, wherein the nanoparticle has a perovskite-type crystal structure.

7. The energy-responsive composition according to claim 5 or 6, wherein a ligand is coordinated with the nanoparticle to protect each nanoparticle.

8. The energy-responsive composition according to claim 5 or 6, wherein the plurality of energy-responsive protective particles are supported by a substrate having a support surface.

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