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

Abstract

To provide a method for producing an energy-responsive composition capable of disposing quantum dots at high density even when a polymer is used as a ligand.SOLUTION: There is provided a method for producing an energy-responsive composition which comprises: a step of preparing polymer-containing liquid containing a solvent having a relative dielectric constant having a predetermined value or less and an associative polymer which has a main chain containing a plurality of carbons and a polar group which is more polar than the main chain and self-associates in a solvent; a step of bringing the polymer-containing solution into contact with nanoparticles having energy responsiveness to prepare a mixed solution; and a step of extracting an energy-responsive composition containing a plurality of energy-responsive protective particles containing nanoparticles and an associative polymer from the mixed solution by reducing a content of the solvent.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present disclosure relates to a method for producing an energy responsive composition, and to an energy responsive composition. [Background technology]

[0002] Quantum dots with a perovskite crystal structure have a narrow full width at half maximum in the spectral sensitivity characteristics and exhibit high color purity, so they are known to be applied to organic electroluminescence materials, quantum dot luminescent materials, and solar cell materials. In addition, they have the advantage that it is easy to provide materials that respond to light in a wide wavelength range, because the absorption and emission wavelengths can be controlled by the halogen composition.

[0003] On the other hand, quantum dots with a perovskite crystal structure are known to have low stability against external stimuli such as light, heat, air, and moisture. In particular, when quantum dots exist in a high density in the solid phase, they tend to fuse together. When fusion occurs, the unique properties such as the quantum size effect are lost, and the desired physical properties are no longer expressed.

[0004] In Patent Document 1, the stability is improved by protecting the polymer from external stimuli using a ligand containing an organic acid salt and a polymer containing an acidic group. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent Publication No. 2021-91870 Summary of the Invention [Problem to be solved by the invention]

[0006] The quantum efficiency can be improved by using the technology described in Patent Document 1. However, when the quantum dots are protected using a polymer as in the technology described in Patent Document 1, the steric repulsion between the polymer chains makes it impossible to bring the quantum dots closer to each other. This leads to a decrease in the density of the quantum dots per unit volume, which causes a problem of a decrease in characteristics such as the amount of light emitted.

[0007] The present invention has been made in view of the above problems, and aims to provide a method for producing an energy responsive composition that can arrange quantum dots at a high density even when a polymer is used as a ligand, and also aims to provide an energy responsive composition that includes a polymer and has quantum dots arranged at a high density. [Means for solving the problem]

[0008] A method for producing an energy responsive composition according to an embodiment of the present invention includes the steps of: preparing a polymer-containing liquid containing a solvent exhibiting a relative dielectric constant of a predetermined value or less; and an associative polymer having a main chain containing a plurality of carbon atoms and a polar group having polarity relative to the main chain, and which self-associates in the solvent; A step of contacting energy responsive nanoparticles with a polymer-containing liquid (P) to prepare a mixed liquid, and extracting an energy responsive composition including a plurality of energy responsive protected particles including nanoparticles and an associative polymer from the mixed liquid R by reducing the content of the solvent.

[0009] In addition, the energy responsive composition according to an embodiment of the present invention includes energy responsive nanoparticles and and an associative polymer having a main chain containing a plurality of carbon atoms and a polar group having polarity greater than that of the main chain; Among the multiple energy responsive protected particles, a pair of adjacent energy responsive protected particles are in contact with each other as the associative polymers contained therein are in contact with each other, and the nanoparticles contained therein are spaced apart from each other. Effect of the Invention

[0010] According to the present invention, it is possible to provide a method for producing an energy responsive composition that can arrange quantum dots at a high density even when a polymer is used as a ligand. It is also possible to provide an energy responsive composition that includes a polymer and has quantum dots arranged at a high density. [Brief description of the drawings]

[0011] [Figure 1] FIG. 2 is a process diagram of a method for producing an energy responsive composition according to the first embodiment. [Diagram 2] FIG. 1 is a diagram showing schematic configurations of a polymer-containing liquid (a), a mixed liquid (b), and an energy responsive composition (c) according to a first embodiment. [Diagram 3] FIG. 13 is a diagram showing a form in which an energy responsive composition according to a second embodiment is extracted while being supported on a supporting substrate. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] Preferred embodiments of the present invention will be described in detail below with reference to the drawings. The dimensions, materials, shapes, relative positions, and so forth of the components described in these embodiments are not intended to limit the scope of the present invention.

[0013] <First embodiment> The method for producing an energy responsive composition according to the first embodiment will be described with reference to Figures 1 and 2. Figure 1 is a process diagram showing each step of the method for producing an energy responsive composition according to the first embodiment 1000. Figure 2 is a diagram showing the schematic configuration of the polymer-containing liquid (a), the mixed liquid (b), and the energy responsive composition (c) according to the first embodiment.

[0014] The method 1000 for producing an energy responsive composition includes steps S101 to S19 as shown in FIG.

[0015] (Step S103 of preparing polymer-containing liquid) Step S103 of adjusting the polymer-containing liquid includes a step of preparing a polymer-containing liquid (P) containing a solvent 10 exhibiting a relative dielectric constant equal to or less than a predetermined value, and an associative polymer 40 having a main chain 20 containing a plurality of carbons and a polar group 30 having polarity greater than that of the main chain 20, and which self-associates in the solvent.

[0016] (Step S105 of preparing a mixed solution) The step S105 of preparing a mixed liquid includes a step of contacting energy responsive nanoparticles (Q) with a polymer-containing liquid (P) to prepare a mixed liquid (R).

[0017] (Step S107 of extracting the energy responsive composition) Step S107 of extracting the energy-responsive composition includes a step of extracting an energy-responsive composition (S) including a plurality of energy-responsive protected particles including nanoparticles and an associative polymer from the mixed liquid R by reducing the solvent content.

[0018] (Consideration of effects) The detailed reasons why the above-mentioned effects are obtained in the manufacturing method 1000 for the energy responsive composition 100 according to this embodiment are not clear, but the present inventors believe it to be due to the following.

[0019] An associative polymer 40 that has a main chain 20 containing multiple carbons and a polar group 30 that is more polar than the main chain 20 and self-associates in a solvent 10 takes a form called a unimer micelle in which the polar groups 30 associate with each other within one polymer molecule under certain conditions (Figure 2a). The unimer micelle is small, about a few nanometers in size (average particle size of the micelle is about 2 nm to 10 nm), and the polar groups 30 are hidden inside, so coordination is difficult to proceed even when mixed with energy-responsive nanoparticles 60 (Figure 2b). When the content of the solvent 10 in the mixed liquid (R) is reduced, the distance between the nanoparticles 60 first approaches as the concentration increases. Next, the association is dissolved, and coordination proceeds while maintaining the distance between the nanoparticles 60 close to each other. At that time, coordination proceeds in such a way that some of the particles bridge each other, making it even more difficult for the distance between the nanoparticles 60 to increase. (Figure 2c)

[0020] (self-meeting) In this embodiment, self-association means that at least some of the polar groups 30 are associated with each other intramolecularly by electrostatic interaction in a solvent 10 exhibiting a specific dielectric constant or less. The polar groups 30 do not necessarily have to interact with each other directly, and a small amount of polar substance such as water may be present between them. In addition, when different types of polar groups are associated with each other by electrostatic interaction, it is also considered that self-association occurs.

[0021] (Nanoparticles) The energy-responsive nanoparticles Q in this embodiment are preferably nanoparticles containing nanocrystals having a perovskite crystal structure, the constituents of which are an A site (monovalent cation), a B site (divalent cation), and an X site (monovalent anion including a halide anion), as allotropes. The perovskite crystal structure is alternatively referred to as a perovskite structure, an ABX3 crystal structure, or an ABX3 structure. The double perovskite crystal structure represented by A2B1B2X6 is also included in the perovskite crystal structure. In this specification, the energy-responsive nanoparticles Q may be alternatively referred to as nanoparticles, luminescent nanoparticles, luminescent nanocrystals, photoresponsive nanocrystals, or quantum dots.

[0022] The average particle size of the nanoparticles is preferably 1 nm or more and 30 nm or less, 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 more than 30 nm, the dispersibility in the medium may be insufficient.

[0023] [A site of perovskite structure] A monovalent cation is used at the A site. The monovalent cation used at the A site is the ammonium cation (NH4 + ), and alkylammonium cations with carbon atoms of 6 or less, formamidinium cations (HC(NH2)2 + ), guanidinium cation (C(NH2)3 +), imidazolium cation, pyridinium cation, pyrrolidinium cation, and other nitrogen-containing organic compound cations; and lithium cation (Li + ), sodium cation (Na + ), potassium cation (K + ), rubidium cation (Rb + ), and the cesium cation (Cs + ) and other alkali metal cations.

[0024] These monovalent cations employed in the A site have a small ionic diameter and are small enough to fit into the crystal lattice, enabling the perovskite compound to form stable three-dimensional crystals.

[0025] A preferred example of an alkylammonium cation having 6 or less carbon atoms is a methylammonium cation (CH3NH3 + ), ethylammonium cation (C2H5NH3 + ), propylammonium cation (C3H7NH3 + ) etc.

[0026] From the viewpoint of obtaining high luminous efficiency, it is preferable to use at least one of methylammonium cation, formamidinium cation, and cesium cation as the A site, and from the viewpoint of suppressing color change, it is more preferable to use cesium cation as the A site. Two or more kinds of these monovalent cations employed as the A site may be used in combination.

[0027] When the A site is a cesium cation, the raw material for nanoparticle synthesis may be a cesium salt. As the cesium salt, cesium chloride, cesium bromide, cesium iodide, cesium hydroxide, cesium carbonate, cesium hydrogen carbonate, cesium bicarbonate, cesium formate, cesium acetate, cesium propionate, cesium pivalate, or cesium oxalate may be appropriately used. Among these cesium salt candidates, an appropriate one may be used depending on the synthesis method.

[0028] When the A site is another alkali metal cation, a salt in which the cesium element of the above-mentioned cesium compound is replaced with another alkali metal cation element can be used as the raw material.

[0029] When the A site is a nitrogen-containing organic compound cation such as a methylammonium cation, for example, a neutral compound other than a salt such as methylamine can be used as a raw material. Two or more of these raw materials may be used in combination.

[0030] [Perovskite-type crystal structure B site] The B site of the perovskite crystal structure employs a divalent cation including a divalent transition metal cation or a divalent typical metal cation.

[0031] The divalent transition metal cation is the scandium cation (Sc 2+ ), titanium cation (Ti 2 +), vanadium cation (V 2+ ), chromium cation (Cr 2+ ), manganese cation (Mn 2+ ), iron cation (Fe 2+ ), cobalt cation (Co 2+ ), nickel cation (Ni 2+ ), copper cation (Cu 2+ ), palladium cation (Pd 2+ ), europium cation (Eu 2+ ), ytterbium cation (Yb 2+ ) will be adopted.

[0032] The divalent typical metal cation is the magnesium cation (Mg 2+ ), calcium cation (Ca 2+ ), strontium cation (Sr 2+ ), barium cation (Ba 2+ ), zinc cation (Zn 2+ ), cadmium cation (Cd 2+ ), germanium cation (Ge 2+ ), tin cation (Sn 2+ ), lead cation (Pb2+ ) may be adopted.

[0033] Among these divalent cations, divalent typical metal cations are preferred from the viewpoint of growing stable three-dimensional crystals, tin cations or lead cations are more preferred, and lead cations are particularly preferred from the viewpoint of obtaining high luminescence intensity. Two or more of these divalent cations may be used in combination, and the perovskite crystal structure may be a so-called double perovskite structure.

[0034] When the B site is a lead cation, the raw material for nanoparticle synthesis includes lead compounds, and an appropriate one can be used depending on the synthesis method. As the lead compound, 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, and lead acetylacetonate are adopted. When the B site is another divalent metal cation, a salt in which the lead element of the above-mentioned lead compound is replaced with another divalent metal cation element can be used as the raw material. Two or more of these raw materials may be used in combination.

[0035] [X site of perovskite crystal structure] X in the perovskite crystal structure is a monovalent anion including a halide anion. The halide anion is a fluoride anion (F - ), chloride anion (Cl - ), bromide anion (Br - ), iodide anion (I - Among them, chloride anion, bromide anion, or iodide anion are preferred because they form stable three-dimensional crystals and emit strong light in the visible light range. The color of the emitted light is blue when chloride anion is used, green when bromide anion is used, and red when iodide anion is used.

[0036] Two or more kinds of halide anions may be used in combination. In particular, when chloride anions, bromide anions, and iodide anions are used in combination, the emission wavelength of the nanoparticles can be set to a desired wavelength depending on the content ratio of the anion species. That is, in particular, when chloride anions, bromide anions, and iodide anions are used in combination, it is preferable because it is possible to obtain an emission spectrum that covers almost the entire range of visible light from blue to red while maintaining a narrow full width at half maximum depending on the content ratio of the anion species.

[0037] The X site may contain a monovalent anion other than a halide anion. Such a monovalent anion other than a halide anion may be a cyanide anion (CN - ), thiocyanate anion (SCN - ), isothiocyanate anion (CNS - As for the raw materials for nanoparticle synthesis, salts with counter cations at the A and B sites, such as cesium chloride and lead bromide, and salts with other cations can be selected appropriately according to the synthesis method.

[0038] The nanoparticles Q in this embodiment can be produced by the following process: For example, the hot injection method, in which raw material liquids are mixed at high temperature and then rapidly cooled after the generation of fine particles to obtain a stable product, and the ligand-assisted reprecipitation method, in which fine particles are obtained by reprecipitation utilizing the difference in miscibility of the product with the solvent, are adopted.

[0039] Also, a room temperature synthesis method is used in which a mixture of A-site raw materials and B-site raw materials, which are non-halogenated and do not contain X-site components, is mixed with a separately prepared X-site raw material liquid under mild conditions at around room temperature to obtain fine particles.Furthermore, this method is used in a mechanochemical method in which solid raw materials are reacted by mechanical mixing such as milling or ultrasonic treatment to obtain product fine particles, and an in situ synthesis method in which a raw material liquid is applied to a substrate and then directly crystallized to obtain a reaction product.

[0040] By allowing the ligand described below to coexist during the production of nanoparticle Q, the ligand can be coordinated to the surface of nanoparticle Q, thereby stabilizing the dispersion. If necessary, excess ligand can be removed by centrifugation or the like.

[0041] (solvent) The solvent may be one that exhibits a relative dielectric constant of a predetermined value or less, preferably 6.0 or less, and more preferably 4.5 or less.

[0042] Specifically, aromatic hydrocarbons such as xylene (dielectric constant 2.3) and toluene (dielectric constant 2.4); hydrocarbons such as hexane (dielectric constant 1.9); alicyclic hydrocarbons such as cyclohexane (dielectric constant 2.0); esters such as ethyl acetate (dielectric constant 6.0) and butyl acetate (dielectric constant 5.0); alkyl halides such as chloroform (dielectric constant 4.9); and ethers such as diethyl ether (dielectric constant 4.3). If necessary, these solvents can be mixed and used. In that case, the weighted average of the dielectric constant of each solvent is used. In addition, a polymerizable compound described later can also be used as a solvent.

[0043] (ligand) In this embodiment, the ligand 30 is preferably selected from at least one compound or ion selected from the group consisting of weak acids such as carboxylic acids, weak bases such as amines, and salts or ions thereof.

[0044] The acid may be, for example, a branched or straight chain fatty acid having 1 to 30 carbon atoms. The alkyl chain may be either saturated or unsaturated. Among them, from the viewpoint of solubility in a solvent and stability, a straight chain fatty acid is preferred, and oleic acid is more preferred.

[0045] The base may be, for example, a branched or linear organic base having 1 to 30 carbon atoms. The alkyl chain may be either saturated or unsaturated. Among them, from the viewpoint of solubility in a solvent and stability, a linear organic base is preferred, and oleylamine is more preferred.

[0046] The ligands may be used alone or in combination of two or more.

[0047] (Amount of ligand relative to nanoparticle Q) The amount of the ligand, when the nanoparticle Q is taken as 100, is preferably from 10 to 500, more preferably from 20 to 400, and even more preferably from 30 to 300. If the amount of the ligand is less than 10 or more than 300, the dispersion stability of the nanoparticle Q may be insufficient.

[0048] (Associative Polymer) In this embodiment, the associative polymer 40 comprises an associative polymer having a main chain 20 containing multiple carbons and a polar group 30 that is more polar than the main chain 20, and which self-associates in a solvent 10.

[0049] The main chain 20 is the longest series of covalently bonded atoms and may have side chains. The side chains may be linear, branched or cyclic alkyl groups, linear, branched or cyclic heteroalkyl groups, aryl groups, heteroaryl groups, aralkyl groups or heteroaralkyl groups. Some of these groups may further have a substituent.

[0050] As the polar group 30, at least one selected from the group consisting of strong acids such as sulfonic acid and phosphonic acid, strong bases such as quaternary ammonium cations, zwitterionic groups such as sulfobetaine, phosphobetaine, and carboxybetaine, and salts or ions thereof is used.

[0051] As the associative polymer, a copolymer (described later) obtained by polymerizing at least two types of monomers can be used.

[0052] (Amount of associative polymer relative to nanoparticle Q) When the nanoparticle Q is 100, the amount of the associative polymer is preferably 1 to 1000, more preferably 10 to 800, and even more preferably 30 to 600. If the amount of the associative polymer is less than 10, the effect of fusion may not be sufficient. If the amount of the associative polymer is more than 600, the unimer micelle may not be formed well in the solvent.

[0053] (mmol of polar groups per 1g of nanoparticles Q) The number of mmol of polar groups per 1 g of nanoparticles Q is preferably 0.01 to 10, more preferably 0.03 to 8, and more preferably 0.1 to 6. When the number of mmol of polar groups per 1 g of nanoparticles Q is within the above range, the effect of preventing fusion is easily obtained. When it is less than 0.01, fusion may not be effectively prevented. When it is more than 10, unimer micelles may not be formed well in a low-polarity medium. The number of mmol corresponds to the content of polar groups contained in 1 g of nanoparticles Q, and is expressed as x 10 -3 This is the unit equivalent to mol.

[0054] <Method of producing energy responsive composition> The method for producing nanoparticles of the present invention will be described in detail below.

[0055] The manufacturing method of the present invention includes the following steps. A step of preparing a polymer-containing liquid (P) containing a solvent 10 exhibiting a relative dielectric constant equal to or less than a predetermined value, and an associative polymer 40 having a main chain containing a plurality of carbon atoms and a polar group 30 having polarity relative to the main chain, and which self-associates in the solvent 10. A step of contacting energy-responsive nanoparticles (Q) with a polymer-containing liquid (P) to prepare a mixture (C). A step of extracting an energy-responsive composition (S) including a plurality of energy-responsive protected particles including nanoparticles Q and an associative polymer 40 from the mixture C by reducing the content of the solvent 10.

[0056] (Step of preparing mixture (C)) The nanoparticles Q produced by the above-mentioned method are brought into contact with the polymer-containing liquid P in which the associative polymer 40 produced by the below-mentioned method is dispersed in a solvent 10. A known method is applied as the contact method. As the contact method, a method of mixing the liquid in which the nanoparticles Q are dispersed with the polymer-containing liquid P in liquid phase, a method of adding the polymer-containing liquid P to the solid-phase nanoparticles Q and redispersing them, and the like are adopted. In addition, as another contact method, a method of applying the polymer-containing liquid P while rotating the nanoparticles Q existing as a solid phase on a support (spin coating) can be adopted. When the nanoparticles Q are dispersed in a liquid, the dispersion solvent may be the same as or different from the solvent of the polymer-containing liquid P. The dispersion solvent of the nanoparticles Q preferably exhibits a specific dielectric constant of a predetermined value or less. The predetermined value is preferably 6.0 or less, more preferably 4.5 or less.

[0057] The temperature at which mixture C is prepared is preferably from -80°C to 50°C, and more preferably from -30°C to 40°C. If the temperature is less than -80°C, the nanoparticles may not come into contact with the associative polymer-containing liquid. If the temperature is higher than 50°C, the association of the associative polymer may dissolve, and coordination may proceed.

[0058] (Step of extracting the energy responsive composition (S)) By reducing the content of the solvent, an energy responsive composition (S) containing a plurality of energy responsive protected particles containing nanoparticles Q and an associative polymer 40 is extracted from the mixture C. As a method for reducing the content of the solvent, a method of volatilizing the solvent under atmospheric pressure or a method of volatilizing the solvent under reduced pressure is preferable. In this case, it is preferable to apply the mixture C onto a support.

[0059] The temperature at which the solvent is evaporated is preferably from -80°C to 50°C, and more preferably from -30°C to 40°C. If the temperature is less than -80°C, the solvent may not evaporate efficiently. If the temperature is higher than 50°C, the association of the associative polymer may be dissolved, and coordination may proceed.

[0060] In the process of extracting the energy responsive composition, it is preferable that adjacent pairs of energy responsive protected particles among the multiple energy responsive protected particles are in contact with each other by contacting the associative polymers 40 that they possess, and that the nanoparticles that they possess are spaced apart.

[0061] The step of extracting the energy responsive composition preferably includes removing the solvent 10 .

[0062] After the step of extracting the energy responsive composition, a step of promoting coordination of the associative polymer with the nanoparticles by heating may be included, if necessary.

[0063] (Method of Producing Associative Polymer) A detailed description is given below of a method for producing a polymer compound that can be used as the associative polymer 40. The method for producing the polymer compound is not particularly limited as long as it can produce the above-mentioned structure, but it can be produced, for example, by the following method (i) or (ii).

[0064] That is, the method (i) for producing a polymer compound includes a method of producing a monomer having a structural unit containing a polar group, and then polymerizing the monomer to produce the polymer compound. Furthermore, the method (ii) for producing a polymer compound includes a method of synthesizing a polymer main chain, and then bonding a polar group to the polymer main chain.

[0065] From the viewpoints of easy availability of monomers and control of the amount of functional groups, the method shown in (i) is preferable. Hereinafter, a method for synthesizing a polymer compound containing a zwitterionic group as a polar group using the method shown in (i) will be described in detail.

[0066] As a monomer for introducing a polar group into a polymer compound, a vinyl ether derivative, an acrylate derivative, a methacrylate derivative, an α-olefin derivative, an aromatic vinyl derivative, etc. From the viewpoint of ease of production of the monomer, it is preferable to use an acrylate derivative or a methacrylate derivative as such a monomer.

[0067] The corresponding acrylate or methacrylate derivatives can be prepared by the methods described in the following documents. K. Ishihara and 2 others, "Polymer Journal" (Japan), The Society of Polymer Science, 1990, Vol. 22, p.355-360

[0068] The above monomers can be polymerized by radical polymerization or ionic polymerization, and living polymerization can also be used for the purpose of controlling the molecular weight distribution or structure. From an industrial perspective, it is preferable to use radical polymerization.

[0069] Radical polymerization can be carried out by using a radical polymerization initiator, irradiating with light such as radiation or laser light, using a photopolymerization initiator in combination with light irradiation, heating, etc. The radical polymerization initiator may be any that can generate radicals and initiate a polymerization reaction, and is selected from compounds that generate radicals by the action of heat, light, radiation, oxidation-reduction reactions, etc.

[0070] For example, azo compounds, organic peroxides, inorganic peroxides, organometallic compounds, photopolymerization initiators, etc. may be mentioned.

[0071] More specifically, examples of the initiator include azo compounds such as 2,2'-azobisisobutyronitrile (AIBN) and 2,2'-azobis(2,4-dimethylvaleronitrile), organic peroxides such as benzoyl peroxide (BPO), tert-butyl peroxypivalate, and tert-butylperoxyisopropyl carbonate, inorganic peroxides such as potassium persulfate and ammonium persulfate, and redox initiators such as hydrogen peroxide-iron(II) salt, BPO-dimethylaniline, and cerium(IV) salt-alcohol. Photopolymerization initiators include acetophenone, benzoin ether, and ketal. Two or more of these radical polymerization initiators may be used in combination.

[0072] The polymerization temperature of the vinyl monomer is not particularly limited and the preferred temperature range varies depending on the type of polymerization initiator used, but polymerization is generally carried out at a temperature of -30°C to 150°C, and a more preferred temperature range is 40°C to 120°C.

[0073] The amount of the polymerization initiator used in this case is preferably 0.1 to 20 parts by mass per 100 parts by mass of the monomer, and the amount used is preferably adjusted so as to obtain a polymer compound having a target molecular weight distribution.

[0074] The polymerization method is not particularly limited and may be any method such as solution polymerization, suspension polymerization, emulsion polymerization, dispersion polymerization, precipitation polymerization, and bulk polymerization.

[0075] The resulting polymer compound may be subjected to a purification treatment as necessary. There are no particular limitations on the production method, and methods such as reprecipitation, dialysis, and column chromatography may be used.

[0076] The structure of the produced polymer compound can be identified by various instrumental analyses, such as nuclear magnetic resonance (NMR), gel permeation chromatography (GPC), and inductively coupled plasma atomic emission spectrometry (ICP-AES).

[0077] (polymerizable compound) The polymerizable compound is a component that is accelerated in polymerization upon receiving energy such as light or heat, and imparts viscosity to the photoresponsive composition and hardens it. The polymerizable compound may be a radically polymerizable compound or a cationic polymerizable compound. These may be used alone or in combination of two or more. In addition, either a photopolymerizable compound or a thermally polymerizable compound may be used. In the present specification, the form in which the polymerizable compound is polymerized to increase the viscosity may be referred to as a polymer.

[0078] Examples of the radically polymerizable compound that can be used include monofunctional (meth)acrylate compounds, bifunctional (meth)acrylate compounds, trifunctional or higher (meth)acrylate compounds, hydroxyl group-containing (meth)acrylate compounds, carboxy group-containing (meth)acrylate compounds, and vinyl compounds.

[0079] Examples of monofunctional (meth)acrylates include 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, and 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-dioxolan-4-yl)methyl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate, and cyclic trimethylolpropane formal (meth)acrylate can be used.

[0080] Examples of bifunctional (meth)acrylate compounds include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol 200 di(meth)acrylate, polyethylene glycol 300 di(meth)acrylate, polyethylene glycol 400 di(meth)acrylate, and polyethylene glycol 600. Di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, polypropylene glycol 400 di(meth)acrylate, polypropylene glycol 700 di(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentyl glycol PO-modified di(meth)acrylate, EO-modified bisphenol A di(meth)acrylate, PO-modified bisphenol A di(meth)acrylate, and hydroxypivalic acid neopentyl glycol di(meth)acrylate can be used.

[0081] Examples of trifunctional or higher (meth)acrylate compounds that can be used include trimethylolpropane tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, glycerin propoxy tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tris(acryloxyethyl)isocyanurate, and EO-modified pentaerythritol tetraacrylate.

[0082] Examples of the vinyl-based compound that can be used include vinyl acetate, vinyl benzoate, vinyl pivalate, vinyl butyrate, vinyl methacrylate, and N-vinylpyrrolidone.

[0083] The cationic polymerizable compound may be either a photopolymerizable or a thermally polymerizable compound. These may be used alone or in combination of two or more. Representative cationic polymerizable compounds include, for example, epoxy compounds, oxacene compounds, and vinyl ether compounds.

[0084] The amount of the polymerizable compound including the above radical polymerizable compound and cationic polymerizable compound used 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, relative to the total parts by mass of the photoresponsive composition.

[0085] (Polymerization initiator) In a polymerization reaction, a polymerization initiator and a polymerizable compound are generally used in combination. The polymerization initiator is a compound that generates an active species that initiates a polymerization reaction by irradiation with active energy rays or heat, and a known polymerization initiator can be used. The main active species that initiate a polymerization reaction include a radical polymerization initiator that generates a radical and a cationic polymerization initiator that generates an acid, and these may be used in combination. Examples of photoradical polymerization initiators that generate radicals by active energy rays include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl methyl ketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane, oligo[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]butane, and oligo[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]butane. acetophenones such as 2-hydroxy-1-[4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl]-2-methylpropan-1-one; benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; phosphines such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; and other phenyl glyoxylic methyl esters.

[0086] Among the photoradical polymerization initiators, acetophenones such as aminoketones, phosphines, and oxime ester compounds are preferred. These can be used alone or in combination depending on the properties required for the cured product. When using a radical polymerization initiator, the amount used is preferably 0.01 to 100 parts by mass, more preferably 0.1 to 50 parts by mass, based on 100 parts by mass of the total solid content in the composition.

[0087] (Other additives) In this embodiment, the energy responsive composition may be mixed with an oxygen remover, an antioxidant, a scattering agent such as titanium oxide, a surfactant, an anti-mold agent, a light stabilizer, or other additives that impart various properties, a diluting solvent, etc., as necessary.

[0088] <Second embodiment> An energy responsive composition 100 according to a second embodiment will be described with reference to FIG.

[0089] Fig. 3 shows the form of the energy-responsive composition 200 according to this embodiment, which is extracted while being supported on a substrate 90 having a support surface 90S. Fig. 3(b) and (c) are two-sided views showing the supported form of the energy-responsive composition 200 viewed macroscopically. Fig. 3(a) is a partially enlarged view microscopically enlarged from Fig. 3(b).

[0090] The energy responsive composition 100 includes a plurality of energy responsive protected particles 150. Each of the energy responsive protected particles 150 includes a nanoparticle 110 having energy responsiveness, and an associative polymer 140 having a main chain 120 including a plurality of carbons and a polar group 130 that is more polar than the main chain 120 and that is coordinated to the nanoparticle 110.

[0091] Among the multiple energy-responsive protected particles, a pair of adjacent energy-responsive protected particles (150, 150') are in contact with each other by the associative polymers (140, 140') that they possess being in contact with each other, and the nanoparticles (110, 110') that they possess are spaced apart from each other.

[0092] (Nanoparticles) The nanoparticles 110 in this embodiment are preferably nanoparticles containing nanocrystals having a perovskite crystal structure as allotropes, the nanocrystals having A site (monovalent cation), B site (divalent cation), and X site (monovalent anion including halide anion) as constituents. Each of the constituents may be the same as that of the nanoparticles Q shown in the first embodiment.

[0093] (Associative Polymer) In this embodiment, the associative polymer 140 has a main chain 120 containing multiple carbon atoms and a polar group 130 that is more polar than the main chain. In addition, at least a portion of the associative polymer 140 is preferably coordinated to the nanoparticles 110 so that the nanoparticles Q are protected on a particle-by-particle basis.

[0094] The main chain 120 is the longest series of covalently bonded atoms and may have side chains. The side chains may be linear, branched or cyclic alkyl groups, linear, branched or cyclic heteroalkyl groups, aryl groups, heteroaryl groups, aralkyl groups or heteroaralkyl groups. Some of these groups may further have a substituent.

[0095] As the polar group 130, at least one selected from the group consisting of strong acids such as sulfonic acid and phosphonic acid, strong bases such as quaternary ammonium cations, zwitterionic groups such as sulfobetaine, phosphobetaine, and carboxybetaine, and salts or ions thereof is used.

[0096] A copolymer obtained by polymerizing at least two types of monomers can be used as the associative polymer 140. As the associative polymer 140, one similar to the associative polymer 40 shown in the first embodiment can be used.

[0097] <Third embodiment> The energy responsive composition of the present invention can be applied to a quantum dot-containing wavelength conversion sheet (QD sheet), a quantum dot-containing wavelength conversion layer (QD-CC), and a quantum dot-containing electroluminescence (QD-EL) device.

[0098] Here, a QD-EL device to which the energy responsive composition according to the present invention is applied will be described.

[0099] The QD-EL device of the present invention comprises, for example, electrodes (cathode and anode), an electron injection / transport layer, an emission layer, and a hole injection / transport layer. A surface treatment layer may be provided on any surface of the emission layer.

[0100] (electrode) The material of the electrodes is not particularly limited, and those used in organic electroluminescence (EL) elements can be suitably used. Examples include transparent conductive oxides such as indium tin oxide (ITO), metals such as Al, alloys of Ag, Pd and Cu (APC electrodes), alloys of Mg and Ag, and laminates (laminate electrodes) in which a metal layer and a transparent conductive oxide layer such as ITO are laminated. Of the anode and cathode, the electrode on the side where light emitted from the light-emitting layer is extracted is preferably transparent.

[0101] The thickness of the anode is not particularly limited and may be, for example, 10 nm or more, 30 nm or more, or 50 nm or more, and may be 1000 nm or less, 500 nm or less, or 200 nm or less. The thickness of the cathode is not particularly limited and may be, for example, 10 nm or more, 30 nm or more, or 50 nm or more, and may be 1000 nm or less, 500 nm or less, or 200 nm or less.

[0102] (Hole injection / transport layer) As the material of the hole injection / transport layer, for example, those used in organic EL can be suitably used. As the organic material, for example, 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), poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), etc. can be mentioned. In addition, as the inorganic material, for example, NiO, TiO2, MoOx, etc. can be mentioned. These may be used alone or in combination of two or more kinds.

[0103] The hole injection / transport layer may have a single layer structure or a laminated structure. In the case of a laminated structure, it may include a hole injection layer disposed on the anode side and a hole transport layer disposed on the light emitting layer side.

[0104] In the case of a single-layer structure, the thickness of the hole injection / transport layer is appropriately adjusted in consideration of the effects on the hole injection property, transport property, and optical properties. For example, the lower limit of the thickness of the hole injection layer and the hole transport layer may be 10 nm and 20 nm, respectively, and the upper limit of the thickness of the hole injection layer and the hole transport layer may be 1000 nm and 500 nm, respectively.

[0105] (Light Emitting Layer) The energy responsive composition according to the present invention can be used as a light emitting layer.

[0106] The thickness of the light-emitting layer is not particularly limited and may be, for example, 10 nm or more, 50 nm or more, or 75 nm or more, and may be 1000 nm or less, 500 nm or less, or 250 nm or less.

[0107] (electron injection / transport layer) As the material of the electron injection / transport layer, for example, those used in organic EL can be suitably used. As the organic material, for example, 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), 4,6-bis(3,5-di(pyridin-3-yl)phenyl)-2-methylpyrimidine (B3PyMPM), etc. can be mentioned. In addition, as the inorganic material, for example, a-ZSO (amorphous zinc silicate; Zn-Si-O), ZnO, SnO, etc. can be mentioned. These may be used alone or in combination of two or more kinds.

[0108] The electron injection / transport layer may have a single layer structure or a laminated structure. In the case of a laminated structure, it may include an electron injection layer disposed on the cathode side and an electron transport layer disposed on the light emitting layer side.

[0109] In the case of a single-layer structure, the thickness of the electron injection / transport layer is not particularly limited, and is appropriately adjusted in consideration of the effects on the electron injection property, transport property, and optical properties. For example, the lower limit of the thickness of the electron injection layer and the electron transport layer is 1 nm and 10 nm, respectively. The upper limit of the thickness of the electron injection layer and the electron transport layer is 1000 nm or less and 500 nm or less.

[0110] In the above description, the light-emitting element is mainly a bottom-emission type that extracts light from the anode side (substrate side), but is not limited to this. For example, the light-emitting element may be a top-emission type that extracts light from the cathode side (opposite substrate side).

[0111] ((Measurement method)) The various physical property measurements can be carried out as follows.

[0112] ((placement density)) The arrangement density of the energy-responsive composition can be measured by a transmission electron microscope (TEM) or a scanning electron microscope (SEM) when observation from a vertical direction is possible. When observation from a vertical direction is not possible, it can be measured using a cross-sectional SEM. The arrangement density can be evaluated, for example, using the average inter-surface distance of particles, the particle occupancy rate per unit area in an image, etc. The average inter-surface distance of particles can be obtained by selecting, for example, 100 particles using image processing software, measuring the shortest distance between each particle, and averaging the results.

[0113] The relative arrangement density can also be calculated from the amount of light absorbed or emitted per unit volume of the film. Since the amount of light emitted varies depending on the luminescence quantum yield (PLQY), it is preferable to calculate from the amount of absorption.

[0114] ((Stability Evaluation)) The stability of the energy responsive composition can be evaluated, for example, by PLQY evaluation and evaluation of the fusion rate between nanoparticles by TEM observation.

[0115] ((Molecular weight distribution measurement)) The molecular weight distribution of the associative polymer can be calculated in terms of monodisperse poly(methyl methacrylate) by gel permeation chromatography (GPC). Measurement of the molecular weight by GPC can be carried out, for example, as follows.

[0116] The sample is added to the eluent below so that the sample concentration becomes 1% by mass, and the solution is left to stand at room temperature for 24 hours to dissolve. The solution is then filtered through a solvent-resistant membrane filter with a pore size of 0.45 μm to obtain the sample solution, which is then measured under the following conditions. Apparatus: Agilent 1260 infinity system (Agilent Technologies) Column: PFG analytical linear M columns (PSS) Eluent: 2,2,2-trifluoroethanol Flow rate: 0.2ml / min Oven temperature: 40℃ Sample injection volume: 20 μL

[0117] In calculating the molecular weight distribution of the sample, a molecular weight calibration curve prepared using a standard polymethyl methacrylate resin (EasiVial PM Polymer Standard Kit manufactured by Agilent Technologies) is used.

[0118] (Structural Analysis of Associative Polymers) The structure of the associative polymer can be analyzed by nuclear magnetic resonance (NMR). For example, the structure of the associative polymer can be analyzed by using ECA-600 (600 MHz) manufactured by JEOL Ltd. 1 H-NMR and 13 The C-NMR spectrum is measured. The measurement is performed at 25°C in a deuterated solvent containing tetramethylsilane as an internal standard. The chemical shift value is read as a ppm shift value (δ value) with the internal standard tetramethylsilane set as 0.

[0119] ((Method for confirming that associative polymers are coordinated to nanoparticles)) Whether or not the associative polymer 40 is coordinated to the nanoparticle Q can be confirmed by using nuclear magnetic resonance (NMR). For example, using ECA-600 (600 MHz) manufactured by JEOL Ltd., 1 H-NMR measurement is performed. 1 Coordination can be confirmed by the fact that the δ value of the H signal shifts from the δ value for the associative polymer alone and the half-value width changes.

[0120] ((Analysis of the association state of associative polymers)) The state of association of the associative polymer can be analyzed by NMR or dynamic light scattering (DLS). When NMR is used, for example, ECA-600 (600 MHz) manufactured by JEOL Ltd. is used. 1 H-NMR is measured. When the polymer is associated, the chemical shift value of the polar group signal changes from the value when the polymer is not associated. When the polymer is associated, the movement of the molecules is restricted, so the spectrum is observed to be broadened overall. If necessary, relaxation time measurements can be performed to analyze the association state in more detail. When DLS is used, the association state can be analyzed from the particle size. When the associative polymer is associated intramolecularly, a particle size of about several nm is observed.

[0121] ((Crystal structure (crystal phase) analysis of nanoparticles)) The crystal structure (crystal phase) and composition of nanoparticles can be analyzed using X-ray diffraction (XRD). For example, the X-ray diffraction pattern can be measured using a RINT 2100 (Rigaku) ​​and compared with a diffraction pattern in a database to analyze the crystal structure and composition. Depending on the shape and size of the sample, electron diffraction (ED) accompanying a cross-sectional TEM may be used.

[0122] ((Nanoparticle Composition Analysis)) The composition of the nanoparticles can also be analyzed by XPS and ICP emission spectroscopy. The molar ratio of A and B can be measured from the signal intensity of XPS, and the concentration of X can be measured from the emission intensity of ICP emission spectroscopy (for example, CIROS CCD (SPECTRO)).

[0123] ((Amount of ligand and associative polymer relative to nanoparticles)) The amount of the ligand and the associative polymer relative to the amount of nanoparticles can be determined by TG-DTA measurement and NMR measurement. For example, the amount of nanoparticles in the energy-responsive composition is measured by TG-DTA measurement. Next, the amount of the ligand and the amount of the associative polymer in the energy-responsive composition are determined by NMR measurement, so that the amount of the ligand and the associative polymer relative to the nanoparticles can be determined.

[0124] ((Amount of polar groups in the associative polymer)) The amount of polar groups in the associative polymer can be determined by NMR measurement. For example, 1H-NMR is measured using ECA-600 (600 MHz) manufactured by JEOL Ltd. The amount of polar groups in the associative polymer is calculated by comparing the signal intensity derived from the polar groups with the signal intensity derived from other parts.

[0125] ((mmol of polar groups per gram of nanoparticles)) The number of mmoles of polar groups per 1 g of nanoparticles can be calculated from the amount of nanoparticles determined by the above method, the amount of associative polymer, and the amount of polar groups in the associative polymer. EXAMPLES

[0126] The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited thereto.

[0127] [Preparation of associative polymer a] A reaction vessel equipped with a cooling tube, a stirrer, a thermometer, and a nitrogen inlet tube was prepared. 5.9 parts of 3-[[2-(methacryloyloxy)ethyl]dimethylammonio]propane-1-sulfonic acid, 48.0 parts of hexyl methacrylate, 3.9 parts of azobisisobutyronitrile, and 900 parts of 2,2,2-trifluoroethanol were charged into the reaction vessel. Nitrogen bubbling was then performed for 30 minutes into the reaction vessel. The resulting reaction mixture was heated at 65°C for 8 hours under a nitrogen atmosphere to complete the polymerization reaction. After cooling the reaction liquid to room temperature, 300 parts of water were added to precipitate the product. After centrifugation, the supernatant was removed. After distilling off the solvent under reduced pressure, the product was dried under reduced pressure at 50°C and 0.1 kPa or less to obtain an associative polymer a. It was confirmed by NMR measurement that the structural unit having a polar group was contained in 7 mol% of the total monomer units. In addition, GPC analysis revealed that the weight average molecular weight (Mw) was 13,200.

[0128] [Preparation of associative polymer b] Associative polymer b was produced in the same manner as associative polymer a, except that in the production of associative polymer a, the amount of 3-[[2-(methacryloyloxy)ethyl]dimethylammonio]propane-1-sulfonic acid was changed from 5.9 parts to 15.2 parts, and the amount of hexyl methacrylate was changed from 48.0 parts to 42.3 parts.

[0129] The structures, compositions and molecular weights of the produced associative polymers a to b are shown in Table 1.

[0130] [Table 1]

[0131] [Preparation of associative polymer-containing liquid] (Association solution a of associative polymer a in toluene) In a reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser, 0.8 parts of associative polymer a and 99.2 parts of toluene were charged, and the temperature was raised to 80°C and heated for 5 minutes. After confirming that associative polymer a was completely dissolved, the mixture was rapidly cooled to room temperature to obtain an association solution a of associative polymer a in toluene. DLS measurement confirmed that unimer micelles with a particle size of 5 nm were formed.

[0132] (Association solution b-1 of associative polymer b in toluene) Except for using associative polymer b instead of associative polymer a, associative polymer b-1 in toluene was prepared in the same manner as associative polymer a in toluene. DLS measurement confirmed that unimer micelles with a particle size of 4 nm were formed.

[0133] (Association solution b-2 of associative polymer b in chloroform) In a reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser, 0.8 parts of associative polymer b and 99.2 parts of chloroform were charged, heated to 60°C, and heated for 5 minutes. The mixture was then rapidly cooled to room temperature to obtain an association liquid b-2 of associative polymer b in chloroform.

[0134] [Production of nanoparticles Q-1] 10 parts of cesium carbonate, 27 parts of oleic acid, and 385 parts of 1-octadecene were placed in a flask, heated to 120°C, and degassed with a vacuum pump for 30 minutes. The mixture was further heated to 150°C under a dry nitrogen stream and held for 30 minutes to obtain a cation raw material liquid.

[0135] Separately, 10 parts of lead(II) bromide and 494 parts of 1-octadecene were placed in a flask, heated to 120°C, and degassed with a vacuum pump for 1 hour. 89 parts of oleic acid and 31 parts of oleylamine were added, and the mixture was degassed with a vacuum pump for 30 minutes. The nitrogen flow was then replaced and the liquid temperature was raised to 185°C.

[0136] 40 parts of the cation source liquid was added, and after 5 seconds, the mixture was cooled on ice. 2000 parts of ethyl acetate was added, and the mixture was centrifuged to remove the supernatant. The resulting residue was dispersed in toluene to adjust the solid concentration to 1% by weight, and a dispersion of nanoparticles Q-1 with a perovskite crystal structure of CsPbBr3 was obtained. The ratio of nanoparticles Q in the solid content measured by TG-DTA was 53 wt%.

[0137] [Production of nanoparticles Q-2] A dispersion of nanoparticles Q-2 having a perovskite crystal structure of CsPb(Br / I)3 was obtained in the same manner as in the luminescent nanocrystal dispersion a, except that 3.2 parts of lead(II) bromide and 9.3 parts of lead(II) iodide were used instead of 10 parts of lead(II) bromide. The ratio of nanoparticles Q in the solid content measured by TG-DTA was 52 wt%.

[0138] Example 1 100 parts of the dispersion liquid a of nanoparticle Q-1 was placed in a container, and the solvent was distilled off under reduced pressure. 100 parts of the association liquid a of the associative polymer a in toluene was added and redispersed. The mixture was spin-coated at 1000 rpm for 20 seconds on a 2 cm x 2 cm glass substrate that had been cleaned with UV-O3, to obtain an energy-responsive composition 100-1.

[0139] (Examples 2 to 4, Comparative Example 2) Energy responsive compositions 100-2 to 100-4 and 100-6 were obtained in the same manner as in Example 1, except that the types of nanoparticles Q, associative polymer, and associative liquid were changed as shown in Table 2.

[0140] Comparative Example 1 100 parts of the dispersion liquid a of nanoparticle Q-1 was placed in a container, and the solvent was distilled off under reduced pressure. 100 parts of the association liquid a of the associative polymer a in toluene was added and redispersed, and then heated at 50°C for 20 minutes to complete the coordination. The mixture was spin-coated at 1000 rpm for 20 seconds on a 2 cm x 2 cm glass substrate that had been cleaned with UV-O3, to obtain an energy-responsive composition 100-5.

[0141] [Table 2]

[0142] [evaluation] [Nanoparticle density evaluation 1] The density of the nanoparticles was evaluated based on the amount of light absorbed by the energy responsive compositions 100-1 to 100-6.

[0143] The measurement conditions and evaluation criteria are shown below. <Measurement conditions> Measurement equipment: Absolute PL quantum yield measurement equipment C9920-03 (Hamamatsu Photonics) Excitation light wavelength: 460 nm Excitation light integration range: Excitation light wavelength ±10nm <Evaluation criteria> A: The absorbance is 6 x 10 6 End B: The absorbance is 4×10 6 That's it, 6 x 10 6 less than C: The absorbance is 4×10 6 less than

[0144] The evaluation results are shown in Table 3.

[0145] [Stability rating 1] After each sample was allowed to stand in air for 7 days, the PLQY was measured and the stability was evaluated.

[0146] The measurement conditions and evaluation criteria are shown below. <Measurement conditions> Measurement equipment: Absolute PL quantum yield measurement equipment C9920-03 (Hamamatsu Photonics) Excitation light wavelength: 460 nm Excitation light integration range: Excitation light wavelength ±10nm Emission integral range: (excitation light wavelength + 20) nm to 770 nm <Evaluation criteria> A: PLQY is 70% or more B: PLQY is 50% or more and lower than 70% C: PLQY is 50% or less

[0147] The evaluation results are shown in Table 3.

[0148] [Nanoparticle density evaluation 2] Each of the energy-responsive compositions 100-1 to 100-6 was diluted 20 times and 3 μL was applied onto a support film (high-resolution carbon HRC-C10). The solvent was evaporated at room temperature, and TEM observation was performed using Technai F30 (manufactured by FEI). The average surface distance of 100 particles was calculated from the TEM image, and the density of the nanoparticles was evaluated according to the following criteria. A: Average surface distance is 5 nm or less B: Average surface distance is greater than 5 nm and less than 15 nm C: Average surface distance is greater than 15 nm

[0149] The evaluation results are shown in Table 3.

[0150] [Stability rating 2] In the above TEM image, 100 particles were selected, and the stability of the nanoparticles was evaluated according to the following criteria. A: 5 or fewer particles are fused B: More than 5 particles and up to 10 particles fused together C: 10 or more particles are fused together

[0151] The evaluation results are shown in Table 3.

[0152] [Table 3]

[0153] According to Table 3, the energy responsive compositions 100-1 to 100-4 according to Examples 1 to 4 have high nanoparticle density and high stability. On the other hand, the energy responsive composition 100-5 according to Comparative Example 1 has high stability but low nanoparticle density. Moreover, the energy responsive composition 100-6 according to Comparative Example 2 has high nanoparticle density but low stability.

[0154] These results indicate that the associative polymer forms unimer micelles in low-polarity solvents, and coordination does not occur in the dispersion state, but rather occurs after the nanoparticles are densely arranged during film formation. [Explanation of symbols]

[0155] 100, S Energy responsive composition 1000 Method for producing energy responsive composition 10 Solvents 20 Main Chain 30 polar group 40 Associative Polymers 50, P Polymer-containing liquid 60, Q Nanoparticles 70, R mixed solution 80 Energy-Responsive Protective Particles

Claims

1. A step of preparing a polymer-containing liquid comprising a solvent exhibiting a dielectric constant below a predetermined value, and an associative polymer having a main chain containing multiple carbon atoms and polar groups that are more polar than the main chain, and that self-associate in the solvent, The process includes a step of preparing a mixture by contacting nanoparticles having energy responsiveness and a perovskite-type crystal structure with a polymer-containing liquid, A method for producing an energy-responsive composition, comprising the step of extracting an energy-responsive composition containing multiple energy-responsive protective particles, each containing nanoparticles and an associated polymer, from a mixture by reducing the solvent content.

2. A method for producing an energy-responsive composition according to claim 1, wherein the step of extracting the energy-responsive composition is such that, among a plurality of energy-responsive protective particles, a pair of adjacent energy-responsive protective particles come into contact with each other through contact between the associative polymers they each possess, and the nanoparticles they each possess are separated from each other.

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

4. Energy-responsive nanoparticles, The present invention comprises multiple energy-responsive protective particles, each having a main chain containing multiple carbon atoms and an associative polymer having polar groups that are more polar than the main chain and coordinate to the nanoparticles. An energy-responsive composition in which, among multiple energy-responsive protective particles, adjacent pairs of energy-responsive protective particles come into contact with each other through contact between their respective associative polymers, while the nanoparticles they each possess are separated from each other.

5. The energy-responsive composition according to claim 4, wherein the nanoparticles include a perovskite-type crystal structure.

6. The energy-responsive composition according to claim 4 or 5, wherein the ligand is coordinated to the nanoparticles such that each nanoparticle is protected.

7. The energy-responsive composition according to claim 4 or 5, wherein a plurality of energy-responsive protective particles are supported on a substrate having a support surface.

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