TWI698475B - Resin composition, film, wavelength conversion member, and film forming method - Google Patents

Abstract

The object of the present invention is to provide a resin composition capable of suppressing a decrease in the fluorescence quantum yield of semiconductor quantum dots after heat treatment, a film obtained from the resin composition, a wavelength conversion member using the film, and the resin The method of forming the film of the composition.

The resin composition of the present invention contains: a binder resin; semiconductor quantum dots; and a compound selected from the group consisting of a compound having a phenylphosphine structure, a compound having a cycloalkylphosphine structure, a compound having a thiobisphenol structure, and a compound having a thiodipropylene structure. At least one compound in the group consisting of a compound having an acid dialkyl ester structure and a compound having a benzothiazole structure.

Description

Resin composition, film, wavelength conversion member and film forming method law

The present invention relates to a resin composition, a film, a wavelength conversion member, and a method for forming the film.

In recent years, semiconductor quantum dots (Quantum Dot, also referred to as "QD" hereinafter) obtained by forming semiconductors such as cadmium sulfide (CdS) or cadmium telluride (CdTe) into nanometer sizes have attracted attention. Such QDs exhibit special optical characteristics, that is, they exhibit broad light absorption and emit fluorescence with a narrow spectral width. Therefore, various applications are currently being studied. For example, the QD is gradually used in displays using organic electroluminescence (EL) elements and the like (see Japanese Patent Laid-Open No. 2014-174406).

Specifically, the following displays are attracting attention. The displays are blue light-emitting organic EL elements, semiconductor quantum dots that emit green fluorescence by excitation of light from the blue light-emitting organic EL elements (hereinafter also referred to as "G- QD”), and a combination of semiconductor quantum dots (hereinafter also referred to as “R-QD”) that emit red fluorescence when excited by light from a blue light-emitting organic EL device. For example, a display in which a film containing G-QD (hereinafter also referred to as "G-QD layer") and a film containing R-QD (hereinafter also referred to as "R-QD layer") are formed on the substrate constituting the light-emitting unit Among them, the G-QD layer functions as a wavelength conversion layer that converts blue light into green light, and the R-QD layer functions as a wavelength conversion layer that converts blue light It functions as a wavelength conversion layer that converts to red light. This type of display combines the green fluorescent light from the G-QD layer, the red fluorescent light from the R-QD layer, and the unconverted blue light emitted by the blue light-emitting organic EL element, thereby reproducing light of various hues.

The QD-containing layers such as the G-QD layer and R-QD layer are formed by forming a coating film on one side of the substrate with a radiation-sensitive resin composition containing QD, and then patterning by a photolithography step, It is obtained by hardening the patterned coating film by heat treatment.

In addition, the QD-containing film can also be applied to, for example, a solar cell sealing sheet, an agricultural film, and a wavelength conversion film used as a lighting component, in addition to the display application. Such a film is obtained, for example, by applying a QD-containing resin composition on a substrate, and then heating the resulting coating film.

However, QD sometimes generates free radicals due to the influence of oxygen in the heating environment during the heat treatment of the patterned coating film (hereinafter also referred to as "post-baking"). Free radicals cause changes in the crystalline structure of QDs, and the fluorescence quantum yield of QDs decreases. For displays containing such QDs, the intensity of green fluorescence from G-QD and the intensity of red fluorescence from R-QD may decrease relative to the intensity of blue light from blue light-emitting organic EL elements. , Thereby reducing the color reproducibility of the display. In addition, when QD is applied to the heat treatment of the coating film applied on the substrate, or when heat is applied in the step of manufacturing an electronic device using the obtained film, the fluorescent quantum yield may decrease similarly, and the solar cell The wavelength conversion efficiency of the sealing sheet and the like is reduced.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2014-174406

The present invention is based on the above circumstances, and its object is to provide a resin composition capable of suppressing a decrease in QD fluorescence quantum yield after heat treatment, a film obtained from the resin composition, and wavelength conversion using the film A member and a method of forming a film using the resin composition.

The invention made to solve the above-mentioned problems is a resin composition containing: a binder resin (hereinafter also referred to as "[A] binder resin"); semiconductor quantum dots (hereinafter also referred to as "[B]QD" ); and selected from a compound having a phenylphosphine structure, a compound having a cycloalkylphosphine structure, a compound having a thiobisphenol structure, a compound having a dialkyl thiodipropionate structure, and a compound having a benzothiazole structure At least one compound in the group consisting of the compound (hereinafter also referred to as "[C] compound").

In addition, the present invention includes a film obtained from the resin composition and a wavelength conversion member including a film formed from the resin composition.

Furthermore, the present invention includes a first method of forming a film, which includes a step of forming a coating film on one side of a substrate from the resin composition, and a step of heating the coating film.

Furthermore, the present invention includes a second method of forming a film, which includes: The step of forming a coating film of the resin composition on one side of the substrate, the step of irradiating at least a part of the coating film with radiation, the step of developing the coating film after radiation exposure, and the step of developing the The coating film is heated.

According to the present invention, it is possible to provide a resin composition capable of suppressing a decrease in the fluorescence quantum yield of QD after heat treatment, a film obtained from the resin composition, a wavelength conversion member provided with a film obtained from the resin composition, And the method of forming the film.

11: Wavelength conversion substrate

12: The first substrate

13: Wavelength conversion layer

13a: The first wavelength conversion layer

13b: The second wavelength conversion layer

13c: third wavelength conversion layer

14: black matrix

15: Adhesive layer

16: The second substrate

17: light source

17a: first light source

17b: 2nd light source

17c: third light source

18: Light source substrate

100: Light-emitting display element

Fig. 1 is a cross-sectional view schematically showing a light-emitting display element according to an embodiment of the present invention.

<Resin composition>

This resin composition contains [A] binder resin, [B] QD and [C] compound. [C] The compound is selected from a compound having a phenylphosphine structure, a compound having a cycloalkylphosphine structure, a compound having a thiobisphenol structure, a compound having a dialkyl thiodipropionate structure, and a compound having a benzo At least one of the group consisting of the thiazole structure compound is considered to function as an antioxidant as described later. In addition, the resin composition may contain antioxidants other than the [C] compound. Examples of antioxidants other than [C] compounds include peroxide decomposers that are not equivalent to [C] compounds (hereinafter also referred to as "[X] peroxide decomposers"), and those that are not equivalent to [C] compounds. Base capture Agent (hereinafter also referred to as "[D] radical scavenger"), etc. Furthermore, the resin composition may also contain a polymerizable compound (hereinafter also referred to as "[E] polymerizable compound"), a radiation sensitive compound (hereinafter also referred to as "[F] radiation sensitive compound") and/or a solvent (Hereinafter also referred to as "[G] solvent"). Furthermore, the resin composition may contain two or more of these components, respectively.

By having the above-mentioned structure, the resin composition can suppress a decrease in the fluorescence quantum yield of [B]QD after heat treatment. The reason why the above-mentioned effect is exhibited by the resin composition having the above-mentioned structure is not necessarily clear, but it is estimated as follows, for example. That is, it is considered that the [C] compound used in the resin composition is, for example, a compound having a particularly excellent peroxide decomposition function, that is, it decomposes the hydroperoxide (ROOH) generated in the oxidation reaction to become a stable compound , Thereby inhibiting the chain initiation reaction, it can effectively inhibit the generation of free radicals that reduce the fluorescence quantum yield of [B]QD. Therefore, it is considered that during the heat treatment when the film (wavelength conversion layer) is formed from the resin composition, the peroxide, which is a source of radical generation, is decomposed by the [C] compound. The [B]QD's fluorescence quantum yield is reduced.

In addition, when QD is applied to a display using a blue light-emitting organic EL element, for the existing resin composition, as described above, the red fluorescence from R-QD may be caused by radicals during heat treatment. The intensity of G-QD and the intensity of green fluorescence from G-QD are lower than the intensity of blue light, and the color reproducibility is reduced. On the other hand, when the resin composition is used, it is considered that since the generation of free radicals is effectively suppressed during the heat treatment as described above, it is considered that [B]QD such as R-QD or G-QD can be suppressed The fluorescence quantum yield is reduced, and the result can be maintained relative to blue The intensity of the color light is the fluorescence intensity from [B]QD, which can maintain high color reproducibility.

Hereinafter, each component of this resin composition is demonstrated in detail.

[[A] Adhesive resin]

[A] The binder resin is not particularly limited, and any binder resin may be used as long as it can be the base material of the film.

If it is used as the [A] binder resin that has an alicyclic structure in the side chain, it is possible to suppress the degradation of the fluorescence quantum yield of [B]QD over time, which is preferable. Although the reason why the above-mentioned effect is exhibited by using a side chain having an alicyclic structure as [A] binder resin is not necessarily clear, it is estimated as follows, for example. That is, it is considered that due to the hydrophobicity of the alicyclic structure, it is possible to suppress the adhesion of moisture that may cause the temporal deterioration of the fluorescence quantum yield to the surface of the [B]QD, thereby suppressing the fluorescence quantum production of the [B]QD The rate of deterioration over time.

[A] The binder resin having an alicyclic structure in a side chain can be obtained by, for example, polymerizing an unsaturated compound having an alicyclic structure as a monomer. The alicyclic structure may include monocyclic cycloalkane structures such as cyclopropane structure, cyclobutane structure, cyclopentane structure, cyclohexane structure, cyclooctane structure, and cyclodecane structure; cyclopentene structure, Monocyclic cycloalkene structures such as cyclohexene structure and cyclopentadiene structure; polycyclic cycloalkane structures such as norbornene structure, adamantane structure, tricyclodecane structure, tetracyclododecane structure, etc.; norbornene structure Structures, polycyclic cycloolefin structures such as tricyclodecene structures, etc.

The alicyclic structure is preferably a cyclohexane structure, a cyclooctane structure, a cyclodecane structure and a tricyclodecane structure, and more preferably a cyclohexane structure and a tricyclodecane structure. borrow By using the specific structure as the alicyclic structure, the degradation of the fluorescence quantum yield of [B]QD with time can be further suppressed.

Examples of the [A] binder resin having an alicyclic structure in the side chain include those derived from 3,4-epoxycyclohexyl methacrylate, cyclic alkyl methacrylate, and acrylic ring as described later. [A] resin, or a cyclic olefin polymer, etc., as a structural unit of at least one compound in the group consisting of an alkyl ester and N-cyclohexylmaleimide.

In addition, when the resin composition is applied to a photosensitive resin composition that can be patterned by an alkaline developer, it is preferable to use [A'] alkali-soluble resin as exemplified below as [A] Binder resin.

〔[A']Alkali-soluble resin〕

[A'] The alkali-soluble resin is a resin that is soluble in an alkaline solution. [A'] The alkali-soluble resin is preferably a resin obtained by radical polymerization using an unsaturated compound containing a carboxyl group as a monomer (hereinafter also referred to as "[a] resin"), polyimide, polysiloxane Alkanes, novolac resins, alkali-soluble polyolefins, resins having a cardo skeleton, and combinations of these resins. Hereinafter, [a] resin, polyimide, polysiloxane, novolak resin, alkali-soluble polyolefin, and resin having a cardo skeleton will be described in detail, respectively.

[[a] Resin]

[a] The resin has a structural unit containing a carboxyl group. In addition, in order to improve sensitivity, it may have a structural unit containing a polymerizable group. The structural unit containing a polymerizable group is preferably a structural unit containing an epoxy group, a structural unit containing a (meth)acrylic acid group, and a structural unit containing The structural unit of vinyl. [A] The resin having the above-mentioned specific polymerizable group-containing structural unit can be used as a resin composition having excellent surface curability and deep curability when forming a cured film.

The carboxyl-containing structural unit can be formed, for example, by using a carboxylic acid system such as unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, mono[(meth)acryloxyalkyl] ester of polycarboxylic acid, etc. As a monomer, the unsaturated compound is appropriately subjected to radical polymerization together with other monomers.

Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, and crotonic acid.

Examples of the unsaturated dicarboxylic acid include maleic acid and fumaric acid.

The mono[(meth)acryloyloxyalkyl] ester of the polycarboxylic acid includes, for example, succinic acid mono[2-(meth)acryloyloxyethyl] ester, phthalic acid mono[2- (Meth)acryloyloxyethyl]ester and the like.

Among these carboxylic acid-based unsaturated compounds, acrylic acid, methacrylic acid, and succinic acid mono[2-(meth)acryloxyethyl] ester are preferred from the viewpoint of polymerizability.

These carboxylic acid-based unsaturated compounds may be used alone, or two or more of them may be mixed and used.

With respect to all the structural units constituting the [a] resin, the lower limit of the content of the carboxyl group-containing structural unit in the [a] resin is preferably 1 mol% (mole percentage), more preferably 5 mol%, and still more preferably 10 mol% . In addition, the upper limit of the content of the structural unit is preferably 80 mol%, more preferably 70 mol%, and still more preferably 60 mol%. When the content ratio of the carboxyl group-containing structural unit is in the above range, it may be further Step to improve the solubility in alkaline developer.

The epoxy group-containing structural unit can be formed, for example, by using an epoxy group-containing unsaturated compound as a monomer, and performing radical polymerization together with other monomers as appropriate. Examples of the epoxy group-containing unsaturated compound include unsaturated compounds containing an oxirane group (1,2-epoxy structure) and oxetanyl group (1,3-epoxy structure).

Examples of the unsaturated compound containing an oxirane group include: glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl methacrylate, 3 ,4-Epoxycyclohexyl ester, o-vinylbenzyl glycidyl ether, etc.

Examples of the unsaturated compound containing oxetanyl group include: 3-(methacryloxymethyl)oxetane, 3-(methacryloxymethyl)-2-methyl Oxetane, 3-(methacryloxymethyl)-3-ethyloxetane, 3-(methacryloxymethyl)-2-phenyloxetane Butane, 3-(2-methacryloxyethyl)oxetane, 3-(2-methacryloxyethyl)-2-ethyloxetane, 3- (2-Methacryloyloxyethyl)-3-ethyloxetane and other methacrylates.

Among these epoxy-containing unsaturated compounds, from the viewpoint of polymerizability, glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, and 3-(methacrylic acid) are preferred. Oxymethyl)-3-ethyloxetane.

These epoxy group-containing unsaturated compounds may be used alone or in combination of two or more.

When [a] resin has a structural unit containing epoxy group, relative to For all the structural units constituting the resin [a], the lower limit of the content of the structural units is preferably 1 mol%, more preferably 5 mol%, and still more preferably 10 mol%. In addition, the upper limit of the content ratio is preferably 80 mol%, more preferably 70 mol%, and still more preferably 60 mol%. When the content ratio of the epoxy group-containing structural unit is in the above range, a film having higher hardness and better solvent resistance can be formed.

The structural unit containing the (meth)acryloyl group can be formed, for example, by the following method: a method of reacting a polymer having an epoxy group with (meth)acrylic acid, a method of reacting a polymer having a carboxyl group with an epoxy group Method of reacting (meth)acrylate esters of groups, method of reacting polymers having hydroxyl groups with (meth)acrylates having isocyanate groups, methods of reacting polymers having acid anhydride groups with (meth)acrylic acid, etc. .

The monomers that provide other structural units include, for example, chain alkyl (meth)acrylate, cyclic alkyl (meth)acrylate, aryl (meth)acrylate, unsaturated dicarboxylic acid Esters, maleimine compounds, unsaturated aromatic compounds, conjugated dienes, unsaturated compounds having a tetrahydrofuran skeleton, hydroxyl-containing unsaturated compounds, other unsaturated compounds, etc.

Examples of the (meth)acrylic acid chain alkyl ester include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, second butyl methacrylate, and third butyl methacrylate. , 2-ethylhexyl methacrylate, ethyl acrylate, n-butyl acrylate, second butyl acrylate, third butyl acrylate, 2-ethylhexyl acrylate, etc.

Examples of the cyclic alkyl (meth)acrylate include cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclodecyl methacrylate, isobornyl methacrylate, and acrylic acid. Cyclohexyl ester, 2-methylcyclohexyl acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl acrylate, isobornyl acrylate, etc.

Examples of the aryl (meth)acrylate include phenyl methacrylate, benzyl methacrylate, and benzyl acrylate.

The maleimide compound includes, for example, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-(4-hydroxyphenyl ) Maleimines, N-(4-hydroxybenzyl)maleimines and the like.

Examples of the unsaturated aromatic compound include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, and p-methoxystyrene.

Examples of the unsaturated compound having a tetrahydrofuran skeleton include tetrahydrofurfuryl methacrylate.

The hydroxyl-containing unsaturated compound may include: 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxyphenyl acrylate, 4-hydroxyphenyl methacrylate, p-hydroxystyrene, α-Methyl-p-hydroxystyrene, etc.

Examples of the other unsaturated compound include acrylonitrile.

Among the monomers forming other structural units, from the viewpoint of polymerizability, styrene, methyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, methyl Tertiary butyl acrylate, n-lauryl methacrylate, benzyl methacrylate, tricyclodecyl methacrylate, p-methoxystyrene, 2-methylcyclohexyl acrylate, N-phenyl maleate Imine, N-cyclohexylmaleimide, tetrahydrofurfuryl methacrylate and 2-hydroxyethyl methacrylate.

The monomers forming other structural units may be used alone or in combination of two or more.

When [a] resin has other structural units, the lower limit of the content ratio of the structural unit relative to all structural units constituting [a] resin is preferably 1 mol%, more preferably 5 mol%, and still more preferably 10 mol% . In addition, the upper limit of the content ratio is preferably 80 mol%, more preferably 70 mol%. When the content ratio is within the range, for example, the molecular weight of [a] resin can be adjusted without hindering the effect.

[a] The lower limit of the weight average molecular weight (Mw) of the resin is preferably 1,000, more preferably 2,000, and still more preferably 3,000. On the other hand, the upper limit of the Mw is preferably 30,000, more preferably 20,000, and still more preferably 15,000. By setting the Mw of [a] resin in the above range, storage stability and sensitivity can be further improved.

In addition, the ratio of the Mw to the number average molecular weight (Mn) of the resin [a], that is, the lower limit of the molecular weight distribution (Mw/Mn) is usually 1, preferably 1.2, and more preferably 1.5. The upper limit of the Mw/Mn is preferably 5, more preferably 4, and still more preferably 3. By setting the Mw/Mn of the resin [a] in the above range, storage stability and sensitivity can be further improved.

In addition, Mw and Mn in this specification are the values measured by Gel Permeation Chromatography (GPC).

([a] Synthesis method of resin)

[a] The synthesis method of the resin is not particularly limited, and a known method can be adopted. For example, the monomer can be polymerized in a solvent in the presence of a polymerization initiator And synthesis.

[Polyimide]

The polyimine used in the resin composition is not particularly limited as long as it is a polymer compound containing an imine bond in the repeating unit. From the standpoint of alkali solubility, it is preferable that the structural unit contains a carboxyl group, Polyimide of phenolic hydroxyl group, sulfo group, thiol group or a combination of these groups. The polyimide can have alkali developability (alkali solubility) by containing these alkali-soluble groups in the structural unit. As a result, it can suppress the generation of scum in the exposed portion during alkali development. The polyimide can be synthesized by, for example, methods described in Japanese Patent Laid-Open No. 2006-199945, Japanese Patent Laid-Open No. 2008-163107, Japanese Patent Laid-Open No. 2011-42701, and the like.

[Polysiloxane]

The polysiloxane used in the resin composition is not particularly limited. For example, the polysiloxane described in International Publication WO2009/028360, International Publication WO2011/155382, and Japanese Patent Laid-Open No. 2010-152302 can be cited. alkyl.

[Novolac resin]

The novolak resin used in the resin composition is not particularly limited, and examples thereof include resins having a phenol novolak structure, or resins having a resol novolak structure. The novolak resin is obtained by reacting a phenol compound with an aldehyde compound. Specific examples of the novolak resin include, for example, resins described in Japanese Patent Application Publication No. 2003-114531, Japanese Patent Application Publication No. 2012-137741, Japanese Patent Application Publication No. 2013-127518, and the like.

[Alkali-soluble polyolefin]

The alkali-soluble polyolefin used in the resin composition is not particularly limited, but from the viewpoint of alkali solubility, a cyclic olefin polymer having a protic polar group is preferred. The protic polar group here refers to a group in which a hydrogen atom is directly bonded to an atom belonging to group 15 or group 16 of the periodic table. The protic polar group is preferably a group in which a hydrogen atom is directly bonded to an oxygen atom, a group in which a hydrogen atom is directly bonded to a nitrogen atom, and a group in which a hydrogen atom is directly bonded to a sulfur atom. The group is more preferably a group in which a hydrogen atom is directly bonded to an oxygen atom. Specific examples of the alkali-soluble polyolefin include, for example, the alkali-soluble polyolefin described in JP 2012-211988 A.

[Resin with Cardo skeleton]

The resin having a cardo skeleton used in the resin composition is not particularly limited. The Cado skeleton here refers to a skeleton structure in which two other cyclic structures are bonded to the ring carbon atoms constituting the cyclic structure. For example, two cyclic structures are bonded to the 9-position carbon atom of the chrysanthemum ring. Structure of aromatic ring (for example, benzene ring), etc. Specific examples of resins having a cardo skeleton include resins described in Japanese Patent No. 5181725 and Japanese Patent No. 5327345.

[[A'] [A] Binder resin other than alkali-soluble resin]

When the resin composition is not applied to a photosensitive resin composition that can be patterned by an alkaline developer, an alkali-insoluble [A] binder resin can be used. Examples of the alkali-insoluble [A] binder resin include alkali-insoluble polyolefin.

[Alkali-insoluble polyolefin]

The alkali-insoluble polyolefin used in the resin composition is not particularly limited, but is preferably a polyolefin that does not have the protic polar group. Specific examples of the alkali-insoluble polyolefin include, for example, a polymer using an olefin having 1 to 10 carbon atoms as a monomer, and a polymer using a substituted or unsubstituted cycloolefin having 3 to 20 carbon atoms as the monomer. (Cyclic olefin polymer) and so on. Examples of the olefin include ethylene, propylene, butene and the like. Examples of the cycloolefin include monocyclic cycloolefins such as cyclopentene and cyclohexene, or polycyclic cycloolefins such as norbornene, tricyclodecene, and tetracyclododecene. Examples of the substituent of the cycloalkene include an alkyl group having 1 to 5 carbon atoms, or a combination of this alkyl group and at least one selected from the group consisting of -CO- and -O-, etc. , Preferably methyl and methoxycarbonyl. The alkali-insoluble polyolefin is preferably a cyclic olefin polymer, more preferably a polymer using a substituted or unsubstituted cyclic olefin as a monomer, and still more preferably a polymer composed of norbornene and a substituted or unsubstituted tetrafluoroethylene. Cyclododecene is a polymer of monomers. Specific examples of alkali-insoluble polyolefins include, for example, alkali-insoluble polyolefins described in JP 2015-127733 A and the like.

The lower limit of the content of the [A] binder resin in the resin composition is preferably 1% by mass, more preferably 5% by mass. In addition, the upper limit of the content is preferably 50% by mass, more preferably 40% by mass. By setting the content of the binder resin [A] to be greater than or equal to the above lower limit, a film with higher sensitivity, higher hardness, and better solvent resistance can be formed. On the other hand, by making the content less than or equal to the upper limit, storage stability can be further improved.

〔[B]QD〕

[B] QD is not particularly limited, preferably semiconductor quantum containing security materials In point, the security material does not use Cd or Pb as a constituent element, but is composed of, for example, In (indium) or Si (silicon) as a constituent element.

From the viewpoint of further improving the fluorescence characteristics such as the fluorescence quantum yield, [B]QD preferably contains elements selected from the group 2 elements, 11 elements, 12 elements, 13 elements, 14 elements, 15 elements and At least two elements in the group consisting of group 16 elements.

The elements include, for example, Be (beryllium), Mg (magnesium), Ca (calcium), Sr (strontium), Ba (barium), Cu (copper), Ag (silver), gold (Au), zinc (Zn) ), B (boron), Al (aluminum), Ga (gallium), In (indium), Tl (thallium), C (carbon), Si (silicon), Ge (germanium), Sn (tin), N (nitrogen) ), P (phosphorus), As (arsenic), Sb (antimony), Bi (bismuth), O (oxygen), S (sulfur), Se (selenium), Te (tellurium), Po (polonium), etc., increase From the viewpoint of fluorescence characteristics, In is preferred.

[B]QD containing In is preferably a core-shell structure type semiconductor quantum dot, a semiconductor quantum dot containing AgInS _{2 and} a semiconductor quantum dot containing Zn-doped AgInS ₂ described later.

In addition, [B]QD is also preferably Si-based semiconductor quantum dots such as semiconductor quantum dots containing Si and semiconductor quantum dots containing compounds of Si and other elements.

In addition, [B]QD preferably contains a compound (A) having a fluorescence maximum in the wavelength range of green light from 500 nm to 600 nm, and/or in the wavelength range of red light from 600 nm to 700 nm. Compound (B) with maximum fluorescence. Since [B] QD contains the compound (A) and/or compound (B) having the above-mentioned fluorescent properties, the resin composition can be used as the following resin composition, namely, A resin composition forming a wavelength conversion layer of a light-emitting display element that uses visible light for image display.

[B] QD may be a homogeneous structure type including one compound, or a core-shell structure type including two or more compounds.

Core-shell structure type [B]QD is composed of one compound forming a core structure, and other types of compounds covering the core structure. For example, by using a semiconductor with a larger band gap to cover the semiconductor of the core, excitons (electron-hole pairs) generated by light excitation can be enclosed in the core. As a result, the probability of non-radiative transition on the surface of [B]QD is reduced, and the fluorescence quantum yield is improved.

From the viewpoint of improving the fluorescence characteristics, the core-shell structure type [B]QD preferably contains In as a core constituent element, preferably InP/ZnS, InP/ZnSe, InP/ZnSe/ZnS, InP/ZnSSe , (InP/ZnSSe) solid solution/ZnS, CuInS ₂ /ZnS, and (ZnS/AgInS ₂ ) solid solution/ZnS. Furthermore, the InP/ZnS is a semiconductor quantum dot with InP as the core and ZnS as the shell. The same is true for other core-shell semiconductor quantum dots.

[B] The lower limit of the average particle diameter of QD is preferably 0.5 nm, more preferably 1.0 nm. In addition, the upper limit of the average particle diameter is preferably 20 nm, more preferably 10 nm. When the average particle size is less than the lower limit, the fluorescence characteristics of [B]QD may become unstable. On the other hand, when the average particle diameter of [B]QD exceeds the upper limit, the quantum confinement effect may not be obtained, and the desired fluorescent characteristics may not be obtained.

Here, the average particle size of [B]QD is obtained by the following method: After drying the sample, it is observed with a transmission electron microscope, and any content contained in the field of view The longest widths of each of the 10 [B]QDs are averaged.

Furthermore, the wavelength range of [B]QD fluorescence can be controlled by appropriately selecting the constituent materials or average particle size of [B]QD.

[B] The shape of the QD is not particularly limited, and may be, for example, a spherical shape, a rod shape, a disc shape, or other shapes. Information about the shape and dispersion state of [B]QD can be obtained with a transmission electron microscope.

As a method of obtaining [B]QD, for example, a known method of thermally decomposing an organometallic compound in a coordinating organic solvent can be used. In addition, the core-shell structure type [B]QD can be obtained, for example, by the following method: after a homogeneous core structure is formed by reaction, a precursor for forming a shell on the surface of the core is added to the reaction system to form a shell on the surface of the core. After the shell, the reaction is stopped and separated from the solvent. As a method of controlling the average particle diameter of [B]QD, for example, a method of adjusting the reaction temperature, reaction time, and the like can be cited. Furthermore, commercially available [B]QD can also be used.

In addition, InP/ZnS as a core-shell structure semiconductor quantum dot can be synthesized with reference to the method described in the technical document "Journal of American Chemical Society 2007, 129, 15432-15433", for example. In addition, CuInS ₂ /ZnS as a core-shell structure semiconductor quantum dot can also refer to the method or technical document described in the technical document "Journal of American Chemical Society. 2009, 131, 5691-5697". It was synthesized by the method described in "Chemistry of Materials. 2009, 21, 2422-2429".

In addition, regarding Si-based semiconductor quantum dots, for example, refer to technical literature It was synthesized by the method described in "Journal of American Chemical Society. 2010, 132, 248-253".

With respect to 100 parts by mass of [A] binder resin, the lower limit of the content of [B]QD in the resin composition is preferably 1 part by mass, and more preferably 10 parts by mass. In addition, with respect to 100 parts by mass of the binder resin of [A], the upper limit of the content is preferably 150 parts by mass, more preferably 100 parts by mass. By setting the content of [B]QD in the above range, a film (wavelength conversion layer) having excellent fluorescent characteristics can be formed.

[[C] Compound]

[C] The compound is selected from a compound having a phenylphosphine structure, a compound having a cycloalkylphosphine structure, a compound having a thiobisphenol structure, a compound having a dialkyl thiodipropionate structure, and a compound having a benzo At least one compound in the group consisting of thiazole structure compounds. It is considered that the [C] compound has, for example, an excellent peroxide decomposition function, that is, it decomposes the hydroperoxide (ROOH) generated in the oxidation reaction to become a stable compound, thereby inhibiting the chain initiation reaction, so it can Effectively suppress the generation of free radicals that reduce the fluorescence quantum yield of [B]QD. Therefore, it is considered that by containing the [C] compound, the resin composition can suppress the decrease in the fluorescence quantum yield of the QD after the heat treatment.

(Compounds with phenylphosphine structure)

The compound having a phenylphosphine structure is a compound represented by the general formula: P-(R ² ) ₃ . Here, R ² is a hydrogen atom or a monovalent organic group. The three R ² may be the same or different. Among them, at least one R ² is a substituted or unsubstituted phenyl group. Examples of the substituent of the phenyl group include an alkyl group having 1 to 5 carbon atoms and an alkenyl group having 2 to 5 carbon atoms. The compound having a phenylphosphine structure is preferably a compound having a triphenylphosphine structure in which all three R ² in the general formula are substituted or unsubstituted phenyl groups.

Examples of compounds having a phenylphosphine structure include tri-o-tolyl phosphine, tri-m-tolyl phosphine, tri-p-tolyl phosphine, tris-2,5-xylyl phosphine, tris-3,5-xylyl phosphine, Triphenylphosphine, diphenyl(p-vinylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, etc.

From the viewpoint of more effectively suppressing the generation of free radicals that reduce the fluorescence quantum yield of [B]QD, the compound having a phenylphosphine structure is preferably tri-o-tolyl phosphine, tri-m-tolyl phosphine, and tri-p-toluene Phosphine, tris-2,5-xylylphosphine, diphenyl(p-vinylphenyl)phosphine, triphenylphosphine and tris(2,4,6-trimethylphenyl)phosphine, more preferably Tri-o-tolyl phosphine, tri-m-tolyl phosphine, tri-p-tolyl phosphine and tris(2,4,6-trimethylphenyl) phosphine.

(Compounds with cycloalkylphosphine structure)

The compound having a cycloalkylphosphine structure is a compound represented by the general formula: P-(R ³ ) ₃ . Here, R ³ is a hydrogen atom or a monovalent organic group. The three R ³ may be the same or different. Among them, at least one R ³ is a substituted or unsubstituted cycloalkyl group. Examples of the cycloalkyl group include cyclopentyl and cyclohexyl. Examples of the substituent of the cycloalkyl group include an alkyl group having 1 to 5 carbon atoms and an alkenyl group having 2 to 5 carbon atoms. The compound having a cycloalkylphosphine structure is preferably a compound having a tricycloalkylphosphine structure in which three R ³ in the general formula are all substituted or unsubstituted cycloalkyl groups.

The compound having a cycloalkylphosphine structure is preferably tricyclohexylphosphine.

(Compounds with thiobisphenol structure)

The compound having a thiobisphenol structure is a compound represented by the general formula: S-(R ⁴ ) ₂ . Here, R ⁴ is a substituted or unsubstituted hydroxyphenyl group. Two R ⁴ may be the same or different. Examples of the substituent of the hydroxyphenyl group include an alkyl group having 1 to 5 carbon atoms. The substituted hydroxyphenyl group preferably does not have two or more alkyl groups having 3 or more carbon atoms.

The compound having a thiobisphenol structure is preferably 4,4-thiobis(3-methyl-6-tert-butylphenol).

(Compound with dialkyl thiodipropionate structure)

The compound having a dialkyl thiodipropionate structure is a compound represented by the general formula: S-(CH ₂ -CH ₂ -COO-R ⁵ ) ₂ . Here, R ⁵ is an alkyl group. Two R ⁵ may be the same or different. The alkyl group is preferably a linear alkyl group having 10 or more and 20 or less carbon atoms.

The compound having a dialkyl thiodipropionate structure includes, for example, dilauryl thiodipropionate, ditridecyl thiodipropionate, dimyristyl thiodipropionate, and sulfur Distearyl dipropionate, etc.

From the viewpoint of more effectively suppressing the generation of free radicals that cause a decrease in the fluorescence quantum yield of [B]QD, the compound having a dialkyl thiodipropionate structure is preferably dilauryl thiodipropionate And distearyl thiodipropionate.

(Compounds with benzothiazole structure)

The so-called compound having a benzothiazole structure refers to substituted or unsubstituted benzothiazole. Examples of the substituent of the benzothiazole include an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, and a thioether group. Among these groups, a thioether group is preferred.

Examples of the compound having a benzothiazole structure include benzothiazole and 2-mercaptobenzothiazole. Among these compounds, 2-mercaptobenzothiazole is preferred.

[C] The compound is preferably a compound having a phenylphosphine structure and a compound having a cycloalkylphosphine structure, and more preferably a compound having a phenylphosphine structure.

The lower limit of the content of the [C] compound in the resin composition is preferably 0.1 parts by mass, more preferably 1 part by mass, and still more preferably 2 parts by mass relative to 100 parts by mass of the binder resin [A]. With respect to [A] 100 parts by mass of the binder resin, the upper limit of the content is preferably 15 parts by mass, more preferably 10 parts by mass, and still more preferably 8 parts by mass. By setting the content within the above range, it is possible to more effectively suppress the generation of radicals that reduce the fluorescence quantum yield of [B]QD. In addition, when the resin composition has curability, it is possible to suppress hindering the curing reaction of the resin composition.

〔[X]Peroxide Decomposer〕

[X] The peroxide decomposer is an antioxidant that is not equivalent to the [C] compound and has a peroxide decomposition function. [X] The peroxide decomposer includes, for example, phosphorus compounds, sulfur compounds, compounds containing phosphorus atoms and sulfur atoms, and specific examples include: compounds having a phosphite structure, compounds having a sulfide structure (wherein, will have Except for compounds having a thiobisphenol structure and compounds having a dialkyl thiodipropionate structure), compounds having a benzotriazole structure, compounds having a phosphorothioate structure, and the like.

(Compounds with phosphite structure)

The compound having a phosphite structure includes, for example, tris(nonylphenyl) phosphite, tris(p-third octylphenyl) phosphite, and tris[2,4,6-tris(α) phosphite -Phenyl ethyl Yl)) ester, tris(p-2-butenylphenyl) phosphite, bis(p-nonylphenyl)cyclohexyl phosphite, tris(2,4-di-tert-butylbenzene) phosphite Base) ester, 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, triphenyl phosphite, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]10 One gas and so on.

Commercial products of compounds having a phosphite structure include, for example, Japanese Patent Laid-Open No. 2003-26715, Japanese Patent Laid-Open No. 2009-97010, Japanese Patent Laid-Open No. 2012-211975, and Japanese Patent Laid-Open 2014 -126811, JP 2014-134763 A, etc.

(Compounds with thioether structure)

Examples of compounds having a thioether structure include: pentaerythritol tetrakis (3-lauryl thiopropionate), pentaerythritol tetrakis (3-octadecyl thiopropionate), and pentaerythritol tetrakis (3-myristyl thiopropionate). Propionate), pentaerythritol tetrakis (3-stearyl thiopropionate) and the like.

Commercial products of the compound having a thioether structure include, for example, the compounds described in JP 2014-48428 A, JP 2014-134763 and the like.

(Compounds with benzotriazole structure)

Examples of compounds having a benzotriazole structure include: 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-[2'-hydroxy-5'-(meth)acryloyloxy Methylphenyl]-2H-benzotriazole, 2-[2'-hydroxy-3'-tertiary butyl-5'-(meth)acryloyloxyethylphenyl]-2H-benzo Triazole and so on.

Commercial products of compounds having a benzotriazole structure include, for example, Japan Compounds described in Japanese Patent Application Publication No. 2003-26715, Japanese Patent Application Publication No. 2009-97010, Japanese Patent Application Publication No. 2012-211975, and the like.

(Compounds with phosphorothioate structure)

Examples of the compound having a thiophosphite structure include trilauryl trithiophosphite, tributyl trithiophosphite, and triphenyl trithiophosphite.

〔[D]Free radical scavenger〕

The resin composition may further contain [D] a radical scavenger. [D] The free radical scavenger is an antioxidant that is not equivalent to the [C] compound, and has the effect of capturing high-activity chain propagators (ROO. and R.) to stop the chain reaction, thereby preventing oxidation. When a film (wavelength conversion layer) is formed from the resin composition during heat treatment, or when excessive heat is applied to the film in the manufacturing process of an electronic device, radicals may be generated in the film. If free radicals are generated in the film in this way, since the free radicals are chemically unstable, they are likely to react with other compounds to further form new free radicals and degrade QD in a chain manner, which is a cause of inducing a reduction in the function of the film. If the resin composition contains the [D] radical scavenger, even if the free radicals are generated, the [D] radical scavenger will capture the free radicals, so that the [B]QD after heat treatment can be further suppressed Reduction of fluorescence quantum yield. Furthermore, [D] radical scavengers also include compounds having a function of decomposing peroxides. In addition, in this specification, a compound having a function of decomposing peroxides and a function of capturing radicals is regarded as [D] a radical scavenger.

[D] The free radical scavenger is not particularly limited as long as it can capture free radicals and deactivate free radicals. For example, phenols and aromatic amines can be used, and it is preferable to have a receptor Compounds with hindered phenol structure and compounds with hindered amine structure. By using the specific compound as the [D] radical scavenger, free radicals can be captured more reliably.

[Compounds with hindered phenol structure]

The hindered phenol structure includes, for example, a structure having a hydroxyphenyl group substituted with two or more monovalent organic groups having 3 or more and 10 or less carbon atoms. Examples of compounds having a hindered phenol structure include: pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2'-thiodiethylene bis [3-(3,5-Di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionate, tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3, 5-Di-tert-butyl-4-hydroxybenzyl)benzene, 3,9-bis[1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5- Methylphenyl)propionyloxy]ethyl]2,4,8,10-tetraoxaspiro[5,5]-undecane and polymers of these compounds.

Commercially available products of the compound having a hindered phenol structure include, for example, the compounds described in Japanese Patent Application Publication No. 2011-227106, Japanese Patent Application Publication No. 2013-164471, and the like.

[Compounds with hindered amine structure]

Examples of compounds having a hindered amine structure include: bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(2,2,6,6-tetramethyl) succinate 4-piperidinyl) ester, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, bis(N-octyloxy-2, 2,6,6-Tetramethyl-4-piperidinyl) ester, bis(N-benzyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, N ,N',N",N'''-Tetra-[4,6-bis-[butyl-(N-methyl-2,2,6,6-tetramethylpiperidin-4-yl)amine Yl]-triazin-2-yl]-4,7-diazadecane-1,10-diamine and other low molecular compounds, A polymer in which a plurality of piperidine rings are bonded via a triazine skeleton and a polymer in which a plurality of piperidine rings are bonded via an ester bond.

Commercial products of the compound having a hindered amine structure include, for example, the compounds described in Japanese Patent Application Publication No. 2011-112823, Japanese Patent Application Publication No. 2014-134763, and the like.

From the viewpoint of capturing free radicals more reliably, the [D] radical scavenger is preferably a compound having a hindered phenol structure, and more preferably 2,2'-thiodiethylenebis[3-(3, 5-di-tert-butyl-4-hydroxyphenyl) propionate], and 3,9-bis[1,1-dimethyl-2-[β-(3-tert-butyl-4- Hydroxy-5-methylphenyl)propionyloxy]ethyl]2,4,8,10-tetraoxaspiro[5,5]-undecane.

When the resin composition contains [D] radical scavenger, the lower limit of the content of [D] radical scavenger is preferably 0.1 parts by mass, more preferably, relative to 100 parts by mass of [A] binder resin 1 part by mass, more preferably 2 parts by mass. With respect to [A] 100 parts by mass of the binder resin, the upper limit of the content is preferably 10 parts by mass, more preferably 5 parts by mass. By setting the content within the above range, radicals can be captured more reliably. In addition, when the resin composition has curability, it is possible to suppress hindering the curing reaction of the resin composition.

[[E] Polymeric compound]

The resin composition may further contain [E] a polymerizable compound. When the resin composition contains [E] a polymerizable compound, the curing reaction of the resin composition can be promoted. [E] The polymerizable compound is not particularly limited as long as it is a compound that is polymerized by radiation irradiation or heating. From the viewpoint of improving sensitivity, it is preferable to have (former The compound of the acryloyl group, epoxy group, vinyl group or a combination of these groups is more preferably a compound having two or more (meth)acryloyl groups in the molecule.

[E] polymerizable compounds having two or more (meth)acrylic acid groups in the molecule include, for example, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, and diethylene glycol diacrylate. Ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylol Propane dimethacrylate, trimethylolpropane trimethacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, neopentyl glycol diacrylate , 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol dimethacrylate, 1 , 10-decanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, di-trimethylolpropane tetra Acrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol heptaacrylate, tripentaerythritol octaacrylate, pentaerythritol nona acrylate, pentaerythritol deca acrylate, pentaerythritol undecanoate Acrylate, pentaerythritol dodecaacrylate, tripentaerythritol heptamethacrylate, tripentaerythritol octamethacrylate, pentaerythritol nonamethacrylate, pentaerythritol decamethacrylate, pentaerythritol undecamethacrylate , Pentapentaerythritol dodecamethacrylate, dimethylol-tricyclodecane diacrylate, ethoxylated bisphenol A diacrylate, 9,9-bis[4-(2-propylene oxyethyl) Oxy) phenyl] 茀, 9,9-bis[4-(2-methacryloxyethoxy) phenyl] 茀, 9,9-bis[4-(2-methylpropene (Oxyoxyethoxy)-3-methylphenyl]茀, (2-propenoxypropoxy)-3-methylphenyl]茀, 9,9-bis[4-(2-propylene (Oxyoxyethoxy)-3,5-dimethylphenyl]茀, 9,9-bis[4-(2-methacryloxyethoxy)-3,5-dimethylbenzene Ji] Fu et al.

Among them, from the viewpoint of improving sensitivity, a polymerizable compound having 3 or more (meth)acrylic groups is preferable, and a polymerizable compound having 4 or more (meth)acrylic groups is more preferable. Further preferred are pentaerythritol tetraacrylate, di-trimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol heptaacrylate, and tripentaerythritol octaacrylate.

When the resin composition contains [E] polymerizable compound, the lower limit of the content of [E] polymerizable compound is preferably 1 part by mass, more preferably 10 parts by mass relative to 100 parts by mass of [A] binder resin Parts, more preferably 20 parts by mass. In addition, the upper limit of the content is preferably 200 parts by mass, more preferably 150 parts by mass, and still more preferably 120 parts by mass. By setting the content within the above range, it is possible to form a film with higher storage stability and sensitivity, higher hardness, and better solvent resistance.

〔[F]Radiation-sensitive compound〕

The resin composition may further contain [F] a radiation-sensitive compound. In this case, radiation sensitivity can be imparted to the resin composition. [F] The radiation-sensitive compound may be used alone or in combination of two or more.

[F] The radiation-sensitive compound includes, for example, a radiation-sensitive radical polymerization initiator, a quinonediazide compound, and a combination of these compounds.

[Radiation-sensitive radical polymerization initiator]

For example, when using a radical polymerizable compound as [E] polymerizable compound In case, the radiation-sensitive linear radical polymerization initiator can further promote the curing reaction of the resin composition caused by radiation.

The radiation-sensitive radical polymerization initiator includes, for example, exposure to radiation such as visible light, ultraviolet light, extreme ultraviolet light, electron beam, X-ray, etc., which can initiate a radical polymerization reaction of the [E] polymerizable compound The active species of compounds, etc.

Specific examples of the radiation-sensitive radical polymerization initiator include, for example, ethyl ketone, 1-[9-ethyl-6-(2-methyl-5-tetrahydrofurylbenzyl)-9H-carb Azol-3-yl]-,1-(O-acetyloxime), ethyl ketone, 1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1 ,3-Dioxolane) methoxybenzyl}-9H-carbazol-3-yl]-, 1-(O-acetyloxime), ethyl ketone, 1-[9- Ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxybenzyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), 1,2- Octanedione-1-[4-(phenylthio)-2-(O-benzyl oxime)], ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl oxime) )-9H-carbazol-3-yl]-, 1-(O-acetyloxime) and other O-acetoxy oxime compounds; 2-benzyl-2-dimethylamino-1-(4-? (Alkolinylphenyl)-butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butane -1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one and other α-amino ketone compounds; 1-phenyl-2-hydroxy-2 -Methylpropane-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenyl ketone and other α-hydroxy ketone compounds; two Phenyl (2,4,6-trimethylbenzyl)phosphine oxide, bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide and other phenylphosphine oxide compounds Wait.

From the viewpoint of further accelerating the curing reaction caused by radiation, the radiation-sensitive radical polymerization initiator is preferably ethyl ketone, 1-[9-ethyl-6-(2-methylbenzamide) Yl)-9H-carbazol-3-yl]-,1-(O-acetyloxime), 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzene Methyl oxime)), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, diphenyl(2,4,6-trimethylbenzyl) Phosphine oxide and bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide.

[Quinone Diazide Compound]

The quinonediazide compound is suitable for a radiation-sensitive compound when the resin composition is used as a positive-type radiation-sensitive composition. As the quinonediazide compound, a 1,2-quinonediazide compound that generates a carboxylic acid by irradiation with radiation can be used. As the 1,2-quinonediazide compound, a condensate of a phenolic compound or an alcoholic compound and a 1,2-naphthoquinonediazide sulfonate halide can be used.

Examples of the quinone diazide compound include: 1,2-naphthoquinone diazide sulfonic acid such as 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone azide-4-sulfonate Esters; 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylene]bisphenol-1,2-naphthoquinonediazide -4-sulfonate, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylene]bisphenol-1,2- Naphthoquinonediazide-5-sulfonate, bis(2,5-dimethyl-4-hydroxyphenyl)-2-hydroxyphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid 1,2-naphthoquinone diazide sulfonate of (polyhydroxyphenyl) alkanes such as esters. Specific examples of the quinonediazide compound include, for example, the compounds described in Japanese Patent No. 5453321, Japanese Patent No. 5630068, Japanese Patent No. 5592064, and the like.

From the viewpoint of improving the radiation sensitivity of the resin composition, the quinonediazide compound is preferably 1,2-naphthoquinonediazide sulfonate of (polyhydroxyphenyl)alkane, more preferably 4, 4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylene]bisphenol-1,2-naphthoquinonediazide-5-sulfon Acid ester.

When the resin composition contains [F] the radiation-sensitive compound, the lower limit of the content of [F] the radiation-sensitive compound is preferably 1 part by mass, more preferably, relative to 100 parts by mass of the [A] binder resin 10 parts by mass. In addition, with respect to 100 parts by mass of the binder resin of [A], the upper limit of the content is preferably 150 parts by mass, more preferably 100 parts by mass. By setting the content in the above range, the radiation sensitivity of the resin composition can be further improved.

〔[G]Solvent〕

This resin composition may further contain [G] solvent. If the resin composition contains the [G] solvent, its coatability is improved. [G] The solvent is not particularly limited as long as it can dissolve or disperse the respective components, and examples thereof include solvents used in the synthesis of resins such as the [a] resin. In addition, the [G] solvent may be used alone or in combination of two or more kinds.

〔[H]Other ingredients〕

In addition to the above-mentioned components, the resin composition may contain other components such as [H] such as a thermal polymerization initiator, a storage stabilizer, and an adhesive agent within a range that does not impair the effects of the present invention. [H] The other components may be used alone or in combination of two or more. When the resin composition contains [H] other components, the upper limit of the content is preferably 10 parts by mass, more preferably 1 part by mass relative to 100 parts by mass of the [A] binder resin.

The resin composition can be prepared by an appropriate method, for example, by [G] It is prepared by mixing [A] binder resin, [B] QD, [C] compound and optional components in a solvent. The lower limit of the concentration of the solid content in the composition during mixing is preferably 5% by mass, more preferably 10% by mass. In addition, the upper limit of the concentration is preferably 80% by mass, more preferably 70% by mass. By setting the concentration of the solid content in the above range, coating properties can be improved. In addition, the "solid content" refers to the remaining content obtained by drying the sample on a hot plate at 175°C for 1 hour to remove volatile substances.

<film>

The film is obtained from the resin composition. Since the film is obtained from the resin composition, the decrease in the QD fluorescence quantum yield after the heat treatment is suppressed, and for example, a film as a wavelength conversion layer with high color reproducibility can be provided. The film may be patterned or unpatterned. If the film is patterned, it can be applied to a wavelength conversion layer useful as a sub-pixel. The film is usually heated to remove volatile components or promote various chemical reactions, so that it can be preferably used as a wavelength conversion layer. The film may be a film using a crosslinked resin as a base material (hereinafter also referred to as a "cured film"), or a film using a non-crosslinked resin as a base material. The cured film can be obtained, for example, by using the resin composition having curability. The method of imparting curability to the resin composition includes, for example, a method of using a curable resin such as a thermosetting resin as the [A] binder resin, or a method of containing [E] a polymerizable compound or other crosslinking agent, etc. .

<Wavelength conversion member>

This film is suitable as a wavelength conversion layer provided in wavelength conversion members such as light-emitting display elements and wavelength conversion films. Hereinafter, as a preferred embodiment of the wavelength conversion member provided with the film, a wavelength conversion film and a light-emitting display element will be described as examples.

〔Wavelength conversion film〕

The wavelength conversion film as one embodiment of the wavelength conversion member is suitable as a wavelength conversion member used in a solar cell sealing sheet, an agricultural film, a lighting component, and the like. The average thickness of the wavelength conversion layer in the wavelength conversion film can be set to, for example, 1 μm or more and 1,000 μm or less. In addition, the wavelength conversion film may be a single-layer film composed of only the film (wavelength conversion layer), or a multilayer film further provided with other layers.

[Light-emitting display element]

FIG. 1 is a cross-sectional view schematically showing a light-emitting display device 100 according to an embodiment. The light-emitting display element 100 has: a wavelength conversion substrate 11, which is configured by providing a wavelength conversion layer 13 (13a, 13b, 13c) and a black matrix 14 on a first base material 12; and a light source substrate 18, which is formed through an adhesive layer 15 and bonded to the wavelength conversion substrate 11.

The first substrate 12 is composed of glass, quartz, transparent resin, or the like. Examples of the transparent resin include transparent polyimide, polyethylene naphthalate, polyethylene terephthalate, and cyclic olefin resin.

The wavelength conversion layer 13 of the wavelength conversion substrate 11 is formed by patterning using the resin composition. Since the wavelength conversion layer 13 is formed using this resin composition, it is possible to suppress the decrease in the fluorescence quantum yield of the QD after the heat treatment.

The wavelength conversion substrate 11 wavelength-converts the excitation light from the light source 17 of the light source substrate 18 by the QD contained in each of the wavelength conversion layers 13 to emit fluorescence of a desired wavelength. In the wavelength conversion substrate 11, the first wavelength conversion layer 13a, the second wavelength conversion layer 13b, and the third wavelength conversion layer 13c are composed of different QDs. It can emit different fluorescence. For example, the wavelength conversion substrate 11 can be configured as follows: the first wavelength conversion layer 13a converts the excitation light into red light, the second wavelength conversion layer 13b converts the excitation light into green light, and the third wavelength conversion layer 13c converts the excitation light into Blue light.

In this case, the QDs contained in each of the wavelength conversion layer 13a, the wavelength conversion layer 13b, and the wavelength conversion layer 13c are selected so that each has a desired fluorescent characteristic. Therefore, when the wavelength conversion layer 13a, the wavelength conversion layer 13b, and the wavelength conversion layer 13c of the wavelength conversion substrate 11 are formed, for example, three types of resin compositions containing QDs with different light emission characteristics are prepared.

The lower limit of the average thickness of the wavelength conversion layer 13 of the wavelength conversion substrate 11 is preferably 100 nm, more preferably 1 μm. In addition, the upper limit of the average thickness is preferably 100 μm. If the average thickness is less than the lower limit, the excitation light cannot be absorbed sufficiently, and the light conversion efficiency is reduced. Therefore, problems such as insufficient brightness of the light-emitting display element may not be ensured.

A black matrix 14 is arranged between the wavelength conversion layers 13 on the first substrate 12. The black matrix 14 can be formed by patterning using a known light-shielding material in accordance with a known method. In addition, the black matrix 14 is not an essential component of the wavelength conversion substrate 11, and the wavelength conversion substrate 11 may also be set to a configuration in which the black matrix 14 is not provided.

The adhesive layer 15 is formed using a known adhesive that transmits ultraviolet light or blue light, which will be described later. Furthermore, the adhesive layer 15 does not need to be provided in such a manner that the entire surface of each wavelength conversion layer 13 is covered on the first substrate 12 as shown in FIG. Placed on the outer edge of the wavelength conversion substrate 11.

The light source substrate 18 includes a second base material 16 and a light source 17 arranged on the wavelength conversion substrate 11 side of the second base material 16. The light source 17 respectively emits ultraviolet light or blue light as excitation light.

The light source 17 (17a, 17b, 17c) is not particularly limited, and ultraviolet light-emitting organic EL elements, blue light-emitting organic EL elements, etc., having a known structure can be used, and can be produced by a known manufacturing method. Here, the ultraviolet light preferably has a main emission peak of 360 nm or more and 435 nm or less, and the blue light preferably has a main emission peak of over 435 nm and 480 nm or less. The light source 17 preferably has directivity in such a way that the respective emitted light irradiates the opposing wavelength conversion layer 13.

The light-emitting display element 100 performs wavelength conversion of the excitation light from the first light source 17 a by QD of the first wavelength conversion layer 13 a of the wavelength conversion substrate 11. Similarly, the QD of the second wavelength conversion layer 13b of the wavelength conversion substrate 11 performs wavelength conversion of the excitation light from the second light source 17b, and the QD of the third wavelength conversion layer 13c of the wavelength conversion substrate 11 performs the wavelength conversion of the excitation light from the third wavelength conversion layer 13c. The excitation light of the light source 17c undergoes wavelength conversion. In this way, the excitation light from each light source 17 is converted into visible light of a desired wavelength and used for display.

In the light-emitting display element 100, the portion where the first wavelength conversion layer 13a is provided constitutes a sub-pixel that performs red display. That is, the first wavelength conversion layer 13a of the wavelength conversion substrate 11 converts the excitation light from the opposing first light source 17a of the light source substrate 18 into red light. In addition, the portion where the second wavelength conversion layer 13b is provided constitutes a sub-pixel that performs green display. That is, the second wavelength conversion layer 13b absorbs the phase from the light source substrate 18 The exciting light from the second light source 17b is converted into green light. In addition, the portion where the third wavelength conversion layer 13c is provided constitutes a sub-pixel that performs blue display. For example, when ultraviolet light is used as the excitation light, the third wavelength conversion layer 13c converts the ultraviolet light from the opposing third light source 17c of the light source substrate 18 into blue light.

Furthermore, in the light-emitting display element 100, the excitation light from the third light source 17c may be used as blue light. In this case, the wavelength conversion substrate 11 may use a light scattering layer formed by dispersing light scattering particles in resin instead of the third wavelength conversion layer 13c. If set in this way, it is possible to use the original wavelength characteristics of the blue light as the excitation light without performing wavelength conversion.

The light-emitting display element 100 is composed of three sub-pixels including a sub-pixel with a first wavelength conversion layer 13a, a sub-pixel with a second wavelength conversion layer 13b, and a sub-pixel with a third wavelength conversion layer 13c to form one pixel. , This one pixel becomes the smallest unit that constitutes an image.

The light-emitting display element 100 having the above-mentioned configuration controls the red, green, or sub-pixels of the sub-pixels having the first wavelength conversion layer 13a, the sub-pixels having the second wavelength conversion layer 13b, and the sub-pixels having the third wavelength conversion layer 13c, respectively. The blue light emits light and displays in full color.

Furthermore, in the light-emitting display element 100, a color filter may be provided between the wavelength conversion layer 13 and the first substrate 12. That is, a red color filter can be provided between the first wavelength conversion layer 13a and the first substrate 12, and a green color filter can be provided between the second wavelength conversion layer 13b and the first substrate 12, and A blue color filter is provided between the third wavelength conversion layer 13c and the first base material 12. In this way, the display color can be improved The purity. Here, as for the color filter, a color filter known as a liquid crystal display element or the like can be formed and used by a known method.

<First Formation Method of Film>

The first method of forming the film can preferably form an unpatterned film such as a wavelength conversion layer used as a wavelength conversion film. The first method of forming the film includes a step of forming a coating film on one side of the substrate (hereinafter also referred to as "coating film formation step"), and a step of heating the coating film (hereinafter also referred to as "heating Step") to form the coating film from the resin composition.

According to the first method of forming the film, since the above-mentioned resin composition is used, it is possible to easily and reliably form a film in which the decrease in the fluorescence quantum yield of the QD after the heat treatment is suppressed. The "coating film" used here refers to a film-like member that has not been sufficiently heated. Hereinafter, each step will be described separately.

[Coating film formation step]

In the coating film forming step, the coating film is formed by, for example, coating the resin composition on the substrate. In the coating film forming step, after coating the resin composition, the coating surface may be heated by an appropriate heating device such as a hot plate and an oven to remove the solvent and the like. Regarding the heating conditions, for example, a heating temperature of 70°C or more and 130°C or less, and a heating time of 1 minute or more and 10 minutes or less may be used.

The substrate on which the coating film is formed can use the same substrate or the like as the substrate described in the second method of forming the film hereinafter.

The coating method of the resin composition is not particularly limited. For example, spray method, roll coating method, spin coating method (spin coating method), slot die coating method, bar coating can be used. Law and other methods.

[Heating step]

In the heating step, the coating film is heated by an appropriate heating device such as a hot plate and an oven. Thereby, various chemical reactions such as volatile components contained in the coating film can be removed, and various chemical reactions such as imidization can be promoted. As a result, the characteristics of the formed film can be adjusted. In the heating step, for example, the heating temperature may be 150°C or higher and 250°C or lower, and the heating time may be 5 minutes or more and 180 minutes or less.

By the heating step, a film laminated on the substrate can be obtained, so the laminate of the substrate and the film can be used as a wavelength conversion film or the like. In addition, when the resin composition having curability is used in this method, a crosslinking reaction occurs in the resin composition by the heating, thereby obtaining a cured film.

<Second Formation Method of Film>

The second method of forming the film can preferably form a patterned film. The second method of forming the film includes: a step of forming a coating film on one side of a substrate (hereinafter also referred to as a "coating film forming step"), and a step of irradiating at least a part of the coating film with radiation (exposure) (hereinafter Also referred to as "radiation irradiation step"), the step of developing the coating film after radiation exposure (hereinafter also referred to as the "development step"), and the step of heating the coating film (hereinafter also referred to as the "heating step") , And the coating film is formed by the resin composition containing the radiation-sensitive compound. In addition, the second method of forming the film may also include a step of exposing the developed pattern between the development step and the heating step (hereinafter also referred to as "post-exposure step").

According to the second forming method of the film, because the resin group described above is used As a result, it is possible to easily and reliably form a film in which the decrease in the fluorescence quantum yield of the QD after the heat treatment is suppressed. In addition, the film obtained by this second film formation method is usually a cured film. Hereinafter, each step will be described separately.

[Coating film formation step]

In the coating film forming step, the coating film is formed by, for example, coating the resin composition on the substrate. After the resin composition is applied, the applied surface may be heated (pre-baked) to remove the solvent and the like.

The material of the substrate on which the coating film is formed is not particularly limited, and examples thereof include glass, quartz, silicon, and resin. Specific examples of the resin include, for example, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyether sulfide, polycarbonate, polyimide, cyclic Addition polymers of cyclic olefins, ring-opening polymers of cyclic olefins, and hydrogenated products thereof. In addition, for these substrates, pretreatments such as chemical treatment using a silane coupling agent, plasma treatment, ion plating, sputtering, and vacuum deposition may be performed as needed.

The coating method of the resin composition is not particularly limited. For example, methods such as spray method, roll coating method, spin coating method (spin coating method), slot die coating method, and bar coating method can be used. Among these coating methods, the spin coating method and the slot die coating method are preferred. The conditions for heating (pre-baking) also differ depending on the types of components, blending ratios, and the like. For example, it may be set to a temperature of 70°C or more and 130°C or less, and a heating time of 1 minute or more and 10 minutes or less.

[Radiation irradiation step]

In the radiation irradiation step, at least a part of the coating film formed on the substrate Expose radiation. When only a part of the coating film is irradiated with radiation, for example, the radiation may be irradiated through a mask having a pattern of a desired shape. By using this photomask, part of the irradiated radiation passes through the photomask, and this part of the radiation is irradiated to the coating film.

Examples of radiation used for irradiation include visible rays, ultraviolet rays, extreme ultraviolet rays, electron beams, and X-rays. Among these radiations, radiation having a wavelength in the range of 190 nm or more and 450 nm or less is preferable, and radiation including ultraviolet rays having a wavelength of 365 nm is more preferable.

Accumulated irradiation amount (exposure amount) of the lower limit of the irradiation step is preferably 100J / m ^2, more preferably 200J / m ^2. In addition, the upper limit of the cumulative irradiation amount is preferably 2,000 J/m ² , and more preferably 1,000 J/m ² . Furthermore, the "cumulative exposure" in this manual refers to the intensity of radiation at the wavelength of 365nm using an illuminance meter (for example, "OAI model (OAI model) 356" of OAI Optical Associates Inc.) The cumulative value of the measured values.

[Development step]

In the development step, the coating film irradiated with radiation is developed to remove unnecessary parts.

The developer used for development can be used, for example: sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, tetramethylammonium hydroxide, tetraethylammonium hydroxide, etc. An aqueous solution of at least one compound. In the aqueous solution of the basic compound, an appropriate amount of water-soluble organic solvents such as methanol and ethanol may also be added and used.

Examples of developing methods include liquid filling, dipping, shaking dipping, spraying Fog method, etc. The development time varies depending on the composition of the resin composition, and the lower limit of the development time is preferably 5 seconds, more preferably 10 seconds. In addition, the upper limit of the development time is preferably 300 seconds, more preferably 80 seconds. After the development process, for example, running water cleaning is performed for 30 seconds or more and 90 seconds or less, and then compressed air or compressed nitrogen is used for drying, thereby obtaining a desired pattern.

[Post Exposure Step]

For example, when a quinonediazide compound is used as the [F] radiation-sensitive compound, the non-exposed part is red, so by post-exposing the developed non-exposed part in this step, the coating film can be made colorless . The post-exposure conditions at this time may be, for example, the same conditions as the exposure step.

[Heating step]

In the heating step, the coating film is heated (post-baking) by an appropriate heating device such as a hot plate and an oven. Thus, a film is formed on the substrate.

The lower limit of the heating temperature is preferably 150°C. In addition, the upper limit of the heating temperature is preferably 250°C. In the case of heating using a hot plate, the lower limit of the heating time is preferably 5 minutes, and the upper limit is preferably 30 minutes. In addition, in the case of heating in an oven, the lower limit of the heating time is preferably 10 minutes, and the upper limit is preferably 180 minutes.

When the method is applied to the case of forming the wavelength conversion layer of the light-emitting display element 100, it is only necessary to use three kinds of resin compositions respectively, and repeat the method of forming the wavelength conversion layer including the steps to form the first wavelength conversion layer. The layer 13a, the second wavelength conversion layer 13b, and the third wavelength conversion layer 13c may be sufficient.

<Other embodiments>

Above, the preferred embodiments of the present invention have been described, but the present invention is not limited to these embodiments. For example, in the preferred embodiment, an example in which the resin composition of the present invention is applied to the sub-pixels of a light-emitting display element has been described, but the present invention is not limited to this, and can also be applied to a backlight unit of a liquid crystal display. Wait. For example, in the case of using a blue light-emitting diode as the light source of the backlight unit, by combining with the film obtained from the resin composition of the present invention containing G-QD and R-QD, it is possible to reproduce white with high purity Light. In addition, in the preferred embodiment, as the first forming method of the film, the method of forming the film laminated on the substrate has been described, but the film may be formed by, for example, other film forming methods such as a casting method. When formed, in this case, for example, the film can be obtained in the form of a single-layer film.

[Example]

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples.

[Weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw/Mn)]

Mw and Mn were measured by gel permeation chromatography (GPC) under the following conditions. In addition, the molecular weight distribution (Mw/Mn) is calculated from the obtained Mw and Mn.

Installation: "GPC-101" of Showa Denko Corporation

Pillar: Connect Showa Denko's "GPC-KF-801", "GPC-KF-802", "GPC-KF-803" and "GPC-KF-804"

Mobile phase: Tetrahydrofuran

Column temperature: 40℃

Flow rate: 1.0mL/min

Sample concentration: 1.0% by mass

Sample injection volume: 100μL

Detector: Differential refractometer

Standard material: monodisperse polystyrene

<Synthesis of binder resin ([a] resin)>

[Synthesis example 1] Synthesis of resin (A-1)

In a beaker equipped with a condenser and a stirrer, 150 parts by mass of propylene glycol monomethyl ether acetate was added and replaced with nitrogen. It was heated to 80°C, and 50 parts by mass of propylene glycol monomethyl ether acetate, 10 parts by mass of methacrylic acid, 30 parts by mass of cyclohexyl methacrylate, and 10 parts by mass of benzene were added dropwise over 2 hours at this temperature. Ethylene, 20 parts by mass of mono[2-methacryloxyethyl] succinate, 3 parts by mass of 2-hydroxyethyl methacrylate, 15 parts by mass of 2-ethylhexyl methacrylate, A mixed solution of 12 parts by mass of N-phenylmaleimide and 6 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) was polymerized at this temperature for 1 hour. After that, the temperature of the reaction solution was increased to 90° C., and polymerization was further performed for 1 hour to obtain a propylene glycol monomethyl ether acetate solution of resin (A-1) (solid content concentration: 33% by mass). The obtained resin had Mw=10,800, Mn=5,900, and Mw/Mn=1.83.

[Synthesis example 2] Synthesis of resin (A-2)

In a beaker equipped with a condenser and a stirrer, 150 parts by mass of propylene glycol monomethyl ether acetate was added and replaced with nitrogen. Heat to 80°C, and add 50 parts by mass of propylene glycol monomethyl ether acetate and 5 parts by mass of methacrylic acid dropwise over 2 hours at this temperature Acid, 25 parts by mass of tricyclodecyl methacrylate, 10 parts by mass of styrene, 20 parts by mass of succinic acid mono[2-methacryloxyethyl] ester, 18 parts by mass of methacrylic acid 2 -Ethylhexyl ester, 12 parts by mass of N-phenylmaleimide, 10 parts by mass of 3-(methacryloxymethyl)-3-ethyloxetane and 6 parts by mass A mixed solution of 2,2'-azobis(2,4-dimethylvaleronitrile) was maintained at this temperature for polymerization for 1 hour. After that, the temperature of the reaction solution was increased to 90° C., and polymerization was further performed for 1 hour to obtain a propylene glycol monomethyl ether acetate solution (solid content concentration: 33% by mass) of resin (A-2). The obtained resin had Mw=11,100, Mn=6,000, and Mw/Mn=1.85.

[Synthesis example 3] Synthesis of resin (A-3)

In a reaction vessel purged with nitrogen was charged with 430 parts by mass of 8-methyl-8-methoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, and bicyclo [2.2 .1] 80 mol of hept-2-ene: a mixture of 20 mol and 750 parts by mass of toluene, heated to 60°C. 0.62 parts by mass of triethylaluminum (1.5 mol/L) in toluene solution, 3.7 parts by mass of tert-butanol/methanol modified (tert-C ₄ H ₉ OH/CH ₃ OH/W= 0.35 mol/0.3 mol/1 mol) tungsten chloride (WCl ₆ ) solution (concentration 0.05 mol/L), heated and stirred at 80°C for 3 hours to obtain a resin (A- 3). The polymerization conversion rate of this polymerization reaction was 95%, and the weight average molecular weight of the resin (A-3) was 21,000.

<Preparation of resin composition, film formation and physical property evaluation>

The components used to prepare each resin composition are shown below.

[[A] Adhesive resin]

A-1: Resin (A-1)

A-2: Resin (A-2)

A-3: Resin (A-3)

[[B]QD]

B-1: InP/ZnS as a core-shell structure semiconductor quantum dot (average particle size: 4nm)

B-2: CdSe/ZnS-TOPO as a core-shell structure semiconductor quantum dot (average particle size: 4nm, the quantum dot used in Example 4 in International Publication WO2006/103908)

Furthermore, the average particle size of [B]QD is obtained by the following method: Observe using a transmission electron microscope (H-7650 from Hitachi High-Tech Fielding), The longest widths of any 10 [B]QDs included in the field of view are averaged.

[[C] Compound]

C-1: Triphenylphosphine

C-2: Tri-o-tolyl phosphine

C-3: Trim-tolyl phosphine

C-4: Tri-p-tolyl phosphine

C-5: Tris(2,4,6-trimethylphenyl)phosphine

C-6: Tris-2,5-xylylphosphine

C-7: Diphenyl (p-vinylphenyl) phosphine

C-8: Tricyclohexylphosphine

C-9: 4,4-thiobis(3-methyl-6-tertiary butylphenol)

C-10: Dilauryl thiodipropionate

C-11: Distearyl thiodipropionate

C-12: 2-Mercaptobenzothiazole

[[X] Peroxide Decomposer]

X-1: pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]

X-2: 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane

X-3: bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate

X-4: pentaerythritol tetrakis (3-mercaptobutyrate)

[[D] Free radical scavenger]

D-1: 2,2'-thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (BASF's "Yan IRGANOX (registered trademark) 1035'')

[[E]Polymerizable compound]

E-1: Dipentaerythritol hexaacrylate

E-2: Di-trimethylolpropane tetraacrylate

[[F]Radiation-sensitive compound]

F-1: Diphenyl (2,4,6-trimethylbenzyl) phosphine oxide ("LUCIRIN (registered trademark) TPO" of BASF)

F-2: Bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide ("IRGACURE (registered trademark) 819" of BASF)

F-3: 2-Methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one ("IRGACURE" (registered trademark) 907 of BASF ")

F-4: Ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9.H.-carbazol-3-yl]-, 1-(O-acetyl Oxime) (BASF's "IRGACURE (registered trademark) OXE02"

F-5: 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylene]bisphenol-1,2-naphthoquinone Azide-5-sulfonate

F-6: 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzyloxime)] (BASF's "IRGACURE" ( Registered trademark) OXE01'')

[[G] Solvent]

G-1: Propylene glycol monomethyl ether acetate

[Example 1]

In 90 parts by mass of the synthetic resin (A-1), a propylene glycol monomethyl ether acetate solution (containing 30 parts by mass of (A-1) as [A] binder resin, and 60 parts by mass as [G] solvent (G-1)), add 10 parts by mass of (B-1) as [B]QD, 2 parts by mass of (C-1) as [C] compound, and 30 parts by mass As [E] (E-1) as a polymerizable compound, and 5 parts by mass of (F-1) as [F] a radiation-sensitive compound, the resin composition of Example 1 was prepared.

[Example 2 to Example 18 and 1 to Comparative Example 8]

Each resin composition was prepared in the same manner as in Example 1, except that the type and the amount of each compounding component were set as described in Table 1 below. Furthermore, the "-" in Table 1 indicates that the corresponding ingredients are not used.

The obtained resin compositions of Example 1 to Example 18 and Comparative Example 1 to Comparative Example 8 were evaluated according to the following method. The evaluation results are shown in Table 1.

[Patternability]

Regarding the patternability, the QD-containing patterned film obtained by the following forming method was observed with an optical microscope. If there is no development residue and the linear portion of the pattern is formed into a straight line, it is judged as A (good) and development The case of the residue and/or the case where the linear portion of the pattern was not formed in a linear shape was judged as B (defect).

(Method for forming QD-containing pattern film of Example 1)

After the resin composition of Example 1 was coated on an alkali-free glass substrate by a spinner, it was prebaked on a hot plate at 90° C. for 2 minutes to form a coating film. Then, radiation of each wavelength including 365 nm, 405 nm, and 436 nm was irradiated with a high-pressure mercury lamp with a cumulative irradiation amount of 700 J/m ² through a photomask with a predetermined pattern. Then, development was performed with a 0.04% by mass potassium hydroxide aqueous solution under conditions of 25° C. for 90 seconds to form a QD-containing pattern film with an average thickness of 5 μm.

(Method for forming QD-containing pattern film of Example 2 to Example 18 and Comparative Example 1 to Comparative Example 8)

Regarding the QD-containing patterned film of Example 2, in the method for forming the QD-containing patterned film of Example 1, the resin composition of Example 2 was used, and the cumulative irradiation amount was set to 1,000 J/m ² , Otherwise, the same method was used to form a patterned film containing QD. In addition, with regard to the QD-containing patterned films of Example 14, Example 17, and Example 18, and Comparative Examples 6 to 7, in the method of forming a QD-containing patterned film of Example 1, the examples were used. 14. Except for the resin compositions of Example 17 and Example 18 and Comparative Examples 6 to 7, and the cumulative irradiation dose was set to 800 J/m ² , the same method was used to form a QD-containing pattern film. In addition, regarding the QD-containing patterned film of Example 13, in the method of forming the QD-containing patterned film of Example 1, the resin composition of Example 13 was used, and the cumulative irradiation amount was set to 2,000 J/m ² Furthermore, a high-pressure mercury lamp was used to irradiate the developed pattern with ultraviolet rays at a cumulative irradiation amount of 10,000 J/m ² , and other than that, the same method was used to form a QD-containing pattern film. Furthermore, with regard to the QD-containing patterned film of Example 3 to Example 12, Example 15 and Example 16, and Comparative Example 1 to Comparative Example 5 and Comparative Example 8, the QD-containing patterned film of Example 1 In the forming method of, the resin compositions of Examples 3 to 12, Example 15 and Example 16, and Comparative Example 1 to Comparative Example 5 and Comparative Example 8 were used, and the cumulative irradiation amount was set to 1,500 J/m ² , Otherwise, the same method was used to form a patterned film containing QD.

[Shrink resistance]

For the QD-containing patterned film formed by the same method as in the case of the patternability evaluation described above, a high-pressure mercury lamp was further used to irradiate ultraviolet rays with a cumulative irradiation dose of 10,000 J/m ^{2 and} a stylus-type film thickness measuring machine ( The "Alpha-Step IQ" of KLA-Tencor Company measured the average thickness of the QD-containing pattern film before and after the ultraviolet irradiation. Then, the residual film rate was calculated by the following formula, and the case where the residual film rate was 99% or more was judged as A (good shrinkage resistance), and the case of less than 99% was judged as B (poor shrinkage resistance) .

Residual film rate (%)=(average thickness after treatment/average thickness before treatment)×100

[Lightfastness]

For the QD-containing patterned film formed by the same method as in the case of the patternability evaluation, an ultraviolet irradiation device ("UVX-02516S1JS01" of Ushio) was further used to irradiate 800,000J with an illuminance of 130mW. /m ² of ultraviolet rays, using a stylus-type film thickness measuring machine ("Alpha-Step IQ" from KLA-Tencor), the pattern film containing QD before and after the ultraviolet irradiation The average thickness is measured. Then, the amount of film thinning was calculated by the following formula, and the case where the amount of film thinning was 2% or less was judged as A (good light resistance), and the case of more than 2% was judged as B (bad light resistance) .

Film thinning (%)={(Average thickness before treatment-Average thickness after treatment)/Average thickness before treatment}×100

[Fluorescence Quantum Yield]

Regarding the fluorescence quantum yield, for the QD-containing patterned film formed by the same method as in the case of the patternability evaluation, the absolute PL fluorescence quantum yield measuring device (Hamamatsu Photonics Co., Ltd. "C11347 -01”), the measurement is performed at 25°C. The wavelength of the excitation light is set to 450 nm. In addition, the QD-containing patterned film formed by the same method as in the patterning evaluation described above was heat treated (post-baked) at 180°C for 20 minutes in a clean oven to form a cured film. The fluorescence quantum yield was measured using the same method as described above. Table 1 shows the fluorescence quantum yield of the former as "untreated" and the fluorescence quantum yield of the latter as "after heat treatment".

[Change rate of fluorescence quantum yield]

The rate of change of the fluorescence quantum yield is calculated by the following equation by setting the untreated fluorescence quantum yield as Φ ₁ and the fluorescence quantum yield after the heating treatment as Φ ₂ . The smaller the rate of change in the fluorescence quantum yield, the more it can be evaluated that the decrease in the fluorescence quantum yield of [B]QD after the heat treatment (after post-baking) is suppressed.

Change rate of fluorescent quantum yield (%)={(Φ ₁ -Φ ₂ )/Φ ₁ }×100

[Wavelength Conversion Evaluation]

Regarding the evaluation of the wavelength conversion, the QD-containing patterned film after heat treatment (after post-baking) formed by the same method as the patterning evaluation described above was measured using an absolute PL fluorescent quantum yield measuring device (Hamamatsu The measurement was carried out at 25°C (“C11347-01” from Hamamatsu Photonics). Specifically, the evaluation is performed by reading the value of the maximum fluorescence wavelength measured simultaneously with the quantum yield. The wavelength of the excitation light is set to 450 nm. This fluorescence maximum wavelength (nm) is regarded as the wavelength conversion evaluation (nm). The evaluation of the wavelength conversion shows that the closer to 630 nm, the better the wavelength can be converted to the desired wavelength after the heat treatment.

[Fluorescence half-value width]

Regarding the fluorescence half-value width, an absolute PL fluorescence quantum yield measuring device was used for the QD-containing patterned film after heat treatment (after post-baking) formed by the same method as the patterning evaluation. (Hamamatsu Photonics "C11347-01"), the measurement was performed at 25°C. Specifically, the evaluation is performed by reading the value of the fluorescence half-value width measured at the same time as the quantum yield. The wavelength of the excitation light is set to 450 nm. Fluorescence half-value width (nm) display, the smaller the value is, the more the wavelength can be converted into fluorescence with high color purity after heat treatment, so it is better.

As shown by the results in Table 1, Examples 1 to 18 using the resin composition containing the [C] compound have good patterning properties, shrinkage resistance, and light resistance, and are comparable to those of Comparative Example 1 to Comparative Example 8. In comparison, the rate of change of fluorescence quantum yield, wavelength conversion evaluation and fluorescence half-value width are smaller. In addition, in Example 1 to Example 18, a compound having a phenylphosphine structure or a compound having a cycloalkylphosphine structure was used as the [C] compound of Example 1 to Example 8, Example 13, and Example 15 to Compared with other examples, Example 18 has smaller fluorescence quantum yield change rate and fluorescence half-value width. Furthermore, in Examples 1 to 18, the fluorescence quantum yields of Examples 2 to 5, Example 16 and Example 18 using (C-2) to (C-5) as [C] compounds The rate of change and the fluorescence half-value width are extremely small.

[Example 19 to Example 22 and Comparative Example 9]

Each resin composition was prepared in the same manner as in Example 1, except that the type and the amount of each compounding component were set as described in Table 2 below. Furthermore, the "-" in Table 2 means that the corresponding ingredients are not used.

The obtained resin compositions of Examples 19 to 22 and Comparative Example 9 were evaluated according to the following methods. The evaluation results are shown in Table 2.

(Methods of forming QD-containing films of Example 19 to Example 22 and Comparative Example 9)

After coating the resin compositions of Examples 19 to 22 and Comparative Example 9 on an alkali-free glass substrate with a spinner, they were heated on a hot plate at 90° C. for 2 minutes to form a coating film. Then, the substrate on which the coating film was formed was heat-treated (baked) on a hot plate at 200°C for 30 minutes to form an average thickness of 5μm. QD film.

The QD-containing film was used instead of the QD-containing patterned film. Other than that, the same operation as in Example 1 to Example 18 and Comparative Example 1 to Comparative Example 8 was performed. The shrinkage resistance, light resistance, fluorescent quantum yield, and The rate of change of the fluorescence quantum yield, wavelength conversion evaluation, and fluorescence half-value width were evaluated.

As shown by the results in Table 2, the shrinkage resistance of Examples 19 to 22 is good, and compared with Comparative Example 9, the fluorescence quantum yield and its rate of change, wavelength conversion evaluation, and fluorescence half-value width evaluation The project is better. In addition, in Example 19, Example 21, and Example 22 in which the content of the [C] compound with respect to 100 parts by mass of the [A] binder resin is 2 parts by mass or more, the light resistance is also good.

[Industrial availability]

According to the present invention, it is possible to provide a resin composition capable of suppressing a decrease in the fluorescence quantum yield of QD after heat treatment, a film obtained from the resin composition, a wavelength conversion member using the film, and the resin composition The film formation method.

11: Wavelength conversion substrate

12: The first substrate

13: Wavelength conversion layer

13a: The first wavelength conversion layer

13b: The second wavelength conversion layer

13c: third wavelength conversion layer

14: black matrix

15: Adhesive layer

16: The second substrate

17: light source

17a: first light source

17b: 2nd light source

17c: third light source

18: Light source substrate

100: Light-emitting display element

Claims (15)

A resin composition comprising: a binder resin; semiconductor quantum dots; and a compound selected from a compound having a phenylphosphine structure, a compound having a cycloalkylphosphine structure, a compound having a thiobisphenol structure, and a compound having a thiodipropionic acid At least one compound in the group consisting of a compound with a dialkyl ester structure and a compound with a benzothiazole structure. The resin composition described in item 1 of the scope of patent application further contains a radical scavenger. The resin composition described in item 1 or item 2 of the scope of patent application further contains a polymerizable compound. The resin composition according to item 1 or item 2 of the scope of patent application, wherein the binder resin has an alicyclic structure in the side chain. The resin composition according to item 1 or item 2 of the scope of patent application, wherein the binder resin is an alkali-soluble resin. The resin composition according to item 5 of the patent application, wherein the alkali-soluble resin has a carboxyl group in a side chain. The resin composition according to item 1 or item 2 of the scope of the patent application, wherein the semiconductor quantum dots contain elements selected from group 2 elements, 11 elements, 12 elements, 13 elements, 14 elements, and 15 elements And at least two elements in the group consisting of group 16 elements. The resin composition according to item 7 of the scope of patent application, wherein the semiconductor quantum dot contains In. The resin composition according to item 8 of the scope of patent application, wherein the semiconductor quantum dot has a core-shell structure containing In as a core constituent element. The resin composition according to item 1 or item 2 of the scope of patent application, wherein the semiconductor quantum dot contains Si. The resin composition described in item 1 or item 2 of the scope of patent application further contains a radiation-sensitive compound. A film formed by the resin composition as described in any one of items 1 to 11 in the scope of the patent application. A wavelength conversion member is provided with a film formed of the resin composition described in any one of items 1 to 11 in the scope of patent application. A method for forming a film includes: a step of forming a coating film on one side of a substrate, and a step of heating the coating film, and as described in any one of items 1 to 11 The resin composition described above forms the coating film. A method of forming a film includes: forming a coating film on one side of a substrate, irradiating at least a part of the coating film with radiation, developing the coating film after radiation exposure, and developing After the coating film is heated, and The coating film is formed by the resin composition described in item 11 of the scope of patent application.

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