TW201710399A - Resin composition, film, wavelength conversion member and method for forming film - Google Patents

Abstract

The purpose of the present invention is to provide: a wavelength conversion member-forming composition that can suppress a reduction in fluorescence quantum yield of a semiconductor quantum dot following heat treatment; a cured film obtained from the wavelength conversion member-forming composition; a wavelength conversion member which uses the cured film; and a method for forming a cured film by using the wavelength conversion member-forming composition. This wavelength conversion member-forming composition contains a binder resin, semiconductor quantum dots and at least one type of compound selected from among the group consisting of a compound having a phenylphosphine structure, a compound having a cycloalkylphosphine structure, a compound having a thiobisphenol structure, a compound having a dialkylthiodipropionate structure and a compound having a benzothiazole structure.

Description

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

The present invention relates to a resin composition, a film, a wavelength converting member, and a method of forming a film.

In recent years, semiconductor quantum dots (Quantum Dot, hereinafter also referred to as "QD") obtained by forming a semiconductor such as cadmium sulfide (CdS) or cadmium telluride (CdTe) into a nanometer size have attracted attention. Such a QD exhibits a special optical characteristic, that is, exhibits broad light absorption and emits fluorescence having a narrow spectral width, etc., and various applications are currently being studied. For example, the QD is used in a display using an organic electroluminescence (EL) element or the like (refer to Japanese Laid-Open Patent Publication No. 2014-174406).

Specifically, the display is a semiconductor quantum dot that emits green fluorescence by exciting a blue light-emitting organic EL element by light from the blue light-emitting organic EL element (hereinafter also referred to as "G- QD") and semiconductor quantum dots (hereinafter also referred to as "R-QD") which emit red fluorescence by excitation from light of the blue light-emitting organic EL element. For example, a display including a film of G-QD (hereinafter also referred to as "G-QD layer") and a film containing R-QD (hereinafter also referred to as "R-QD layer") is formed on a substrate constituting the light-emitting unit. In the middle, 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 into red light. Such a display combines green fluorescence from the G-QD layer, red fluorescence from the R-QD layer, and unconverted blue light emitted from the blue light-emitting organic EL element, thereby reproducing light of various hue.

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

Further, the QD-containing film can be applied to, for example, a solar cell sealing sheet, an agricultural film, or a wavelength conversion film used as an illumination component, in addition to the display application. Such a film is obtained, for example, by applying a resin composition containing QD to a substrate, and then heat-treating the obtained coating film.

However, when QD is subjected to heat treatment (hereinafter also referred to as "post-baking") of the patterned coating film, free radicals may be generated by the influence of oxygen or the like in a heating environment. Free radicals cause a change in the crystal structure of QD, and the fluorescence quantum yield of QD decreases. In the display or the like including such a QD, the intensity of the green fluorescent light from the G-QD and the intensity of the red fluorescent light from the R-QD may be lowered with respect to the intensity of the blue light from the blue light-emitting organic EL element. Thereby, the color reproducibility of the display is lowered. Further, when QD is applied to heat treatment of a coating film applied to the substrate or during the step of manufacturing an electronic device using the obtained film, the fluorescence quantum yield may be similarly lowered in the same manner. The wavelength conversion efficiency of the sheet for sealing or the like is lowered. [Prior Art Document] [Patent Literature]

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

[Problem to be Solved by the Invention] The present invention has been made in view of the above circumstances, and an object thereof is to provide a resin composition capable of suppressing a decrease in fluorescence quantum yield of QD after heat treatment, and a resin composition obtained by the resin composition. A film, a wavelength converting member using the film, and a method of forming a film using the resin composition. [Means to solve the problem]

The invention to solve the above problems is a resin composition containing a binder resin (hereinafter also referred to as "[A] binder resin"); a semiconductor quantum dot (hereinafter also referred to as "[B]QD") 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, a compound having a dialkyl thiodipropionate structure, and having a benzothiazole structure At least one compound (hereinafter also referred to as "[C] compound") in the group consisting of the compounds.

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

Furthermore, the present invention includes a first method for forming a film, comprising: a step of forming a coating film on one surface side of the substrate by the resin composition, and a step of heating the coating film.

Further, the present invention includes a second method for forming a film, comprising: a step of forming a coating film on one surface side of the substrate by the resin composition, a step of irradiating at least a part of the coating film with radiation, and irradiating the radiation The subsequent step of developing the coating film and the step of heating the coating film after development. [Effects of the Invention]

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

<Resin Composition> The resin composition contains [A] binder resin, [B] QD and [C] compounds. The [C] compound is selected from the group consisting of 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 having a benzo compound. At least one of the groups consisting of the compounds of the thiazole structure is considered to function as an antioxidant as described later. Further, the resin composition may contain an antioxidant other than the [C] compound. Examples of the antioxidant other than the compound [C] include a peroxide decomposing agent (hereinafter also referred to as "[X] peroxide decomposing agent") which is not equivalent to the [C] compound, and a compound which is not equivalent to the [C] compound. A base scavenger (hereinafter also referred to as "[D] radical scavenger") or the like. Further, the resin composition may 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. (The following is also called "[G] solvent"). Further, the resin composition may contain two or more of the above components, respectively.

By having such a configuration, the resin composition can suppress a decrease in the fluorescence quantum yield of [B]QD after the heat treatment. The reason why the resin composition has the above-described configuration and exhibits the above-described effects is not necessarily clear, but is estimated, for example, as follows. In other words, the [C] compound used in the resin composition is, for example, a compound which is particularly excellent in a peroxide decomposition function, that is, a compound which decomposes a hydroperoxide (ROOH) formed in an oxidation reaction and becomes stable. Thereby, the chain initiation reaction is suppressed, so that generation of radicals which cause a decrease in the fluorescence quantum yield of [B]QD can be effectively suppressed. Therefore, it is considered that the peroxide which is a source of radical generation is decomposed by the [C] compound during the heat treatment in forming the film (wavelength conversion layer) by the resin composition, so that the heat treatment can be suppressed. The decrease in fluorescence quantum yield of [B]QD.

Further, when the QD is applied to a display using a blue light-emitting organic EL element, the conventional resin composition sometimes has red fluorescence from the R-QD due to radicals during heat treatment as described above. The intensity and the intensity of the green fluorescence from the G-QD are lowered with respect to the intensity of the blue light, and the color reproducibility is lowered. On the other hand, when the resin composition is used, it is considered that since the generation of radicals is effectively suppressed at the time of heat treatment as described above, it is possible to suppress [B]QD such as R-QD or G-QD. As a result of the decrease in the fluorescence quantum yield, the fluorescence intensity from [B]QD with respect to the intensity of blue light can be maintained, and high color reproducibility can be maintained.

Hereinafter, each component of the resin composition will be described in detail.

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

When the alicyclic structure is used as the [A] binder resin in the side chain, the deterioration of the fluorescence quantum yield of the [B]QD can be suppressed, which is preferable. The reason why the effect is exhibited by the use of the alicyclic structure in the side chain as the [A] binder resin is not necessarily clear, but is presumed as follows, for example. In other words, it is considered that due to the hydrophobicity of the alicyclic structure, moisture which may cause deterioration of the fluorescence quantum yield over time can be adhered to the surface of the [B]QD, so that the fluorescence quantum yield of [B]QD can be suppressed. The rate deteriorates over time.

The [A] binder resin having an alicyclic structure in a side chain can be obtained, for example, by polymerization using an unsaturated compound having an alicyclic structure as a monomer. The alicyclic structure may be a monocyclocycloalkane structure such as a cyclopropane structure, a cyclobutane structure, a cyclopentane structure, a cyclohexane structure, a cyclooctane structure or a cyclodecane structure; a cyclopentene structure; a monocyclic cycloolefin structure such as a cyclohexene structure or a cyclopentadiene structure; a polycyclic cycloalkane structure such as a norbornane structure, an adamantane structure, a tricyclodecane structure or a tetracyclododecane structure; norbornene A polycyclic cycloolefin structure such as a structure or a tricyclic terpene structure.

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

The [A] binder resin having an alicyclic structure in the side chain may, for example, be derived from a solvent selected from the group consisting of 3,4-epoxycyclohexyl methacrylate, a cyclic alkyl methacrylate, and an acrylic ring. a [a] resin or a cyclic olefin polymer of a structural unit of at least one compound selected from the group consisting of alkyl esters and N-cyclohexyl maleimine.

In the case where the resin composition is applied to a photosensitive resin composition which can be patterned by an alkaline developer, it is preferred to use [A'] alkali-soluble resin as exemplified below as [A] Adhesive resin.

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

[[a] Resin] [a] The resin has a structural unit containing a carboxyl group. Further, in order to improve the sensitivity, a structural unit containing a polymerizable group may be provided. The structural unit containing a polymerizable group is preferably a structural unit containing an epoxy group, a structural unit containing a (meth)acryl fluorenyl group, and a structural unit containing a vinyl group. By the resin having the specific polymerizable group-containing structural unit of [a], the resin composition which is excellent in surface hardenability and deep-hardenability at the time of forming a cured film can be obtained.

The carboxyl group-containing structural unit can be formed, for example, by using a carboxylic acid system such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid or a polycarboxylic acid mono[(meth)acryloxyalkylalkyl]ester. The unsaturated compound is used as a monomer, and is preferably subjected to radical polymerization together with other monomers.

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

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

The mono[(meth)acryloxyalkylalkyl] ester of the polyvalent carboxylic acid may, for example, be monosuccinic acid mono[2-(methyl)propenyloxyethyl]ester, phthalic acid mono[2- (Methyl) propylene methoxyethyl] ester and the like.

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

These carboxylic acid-based unsaturated compounds may be used singly or in combination of two or more.

The lower limit of the content ratio of the carboxyl group-containing structural unit in the [a] resin is preferably 1 mol% (% by mole), more preferably 5 mol%, and further preferably, relative to all the structural units constituting the [a] resin. 10 mol%. Further, the upper limit of the content ratio of the structural unit is preferably 80 mol%, more preferably 70 mol%, and still more preferably 60 mol%. When the content ratio of the structural unit containing a carboxyl group is in the above range, the solubility in the alkaline developing solution can be further improved.

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. The epoxy group-containing unsaturated compound may, for example, be an unsaturated compound containing an oxiranyl group (1,2-epoxy structure) or an oxetanyl group (1,3-epoxy structure).

Examples of the oxiranyl group-containing unsaturated compound include glycidyl methacrylate, 2-methyl glycidyl methacrylate, 3,4-butylene butyl methacrylate, and methacrylic acid 3. , 4-epoxycyclohexyl ester, o-vinylbenzyl glycidyl ether, and the like.

Examples of the oxetanyl group-containing unsaturated compound include 3-(methacryloxymethyl)oxetane and 3-(methacryloxymethyl)-2-methyl. Oxycyclobutane, 3-(methacryloxymethyl)-3-ethyloxetane, 3-(methacryloxymethyl)-2-phenyloxyheterocycle Butane, 3-(2-methylpropenyloxyethyl)oxetane, 3-(2-methylpropenyloxyethyl)-2-ethyloxetane, 3- A methacrylate such as (2-methacryloxyethyl)-3-ethyloxetane or the like.

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

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

In the case where the [a] resin has a structural unit containing an epoxy group, the lower limit of the content ratio of the structural unit is preferably 1 mol%, more preferably 5 mol%, based on all structural units constituting the resin of [a]. And then preferably 10 mol%. Further, 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 structural unit containing an epoxy group is in the above range, a film having higher hardness and more excellent solvent resistance can be formed.

The structural unit containing a (meth)acryl fluorenyl group can be formed, for example, by a method of reacting a polymer having an epoxy group with (meth)acrylic acid, a polymer having a carboxyl group, and having an epoxy group. Method for reacting a base (meth) acrylate, a method for reacting a polymer having a hydroxyl group with a (meth) acrylate having an isocyanate group, a method for reacting a polymer having an acid anhydride group with (meth)acrylic acid, and the like .

Examples of the monomer providing the other structural unit include a (meth)acrylic chain alkyl ester, a (meth)acrylic acid cyclic alkyl ester, an (meth)acrylic acid aryl ester, and an unsaturated dicarboxylic acid II. An ester, a maleimide compound, an unsaturated aromatic compound, a conjugated diene, an unsaturated compound having a tetrahydrofuran skeleton, a hydroxyl group-containing unsaturated compound, other unsaturated compounds, and the like.

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

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, and the like.

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

Examples of the maleimide compound include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and N-(4-hydroxyphenyl). ) Maleimide, N-(4-hydroxybenzyl) maleimide, 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 and the like.

Examples of the hydroxyl group-containing unsaturated compound include 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxyphenyl acrylate, 4-hydroxyphenyl methacrylate, and p-hydroxystyrene. Α-methyl-p-hydroxystyrene and the like.

Examples of the other unsaturated compound include acrylonitrile and the like.

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

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

In the case where the [a] resin has other structural units, the lower limit of the content ratio of the structural unit is preferably 1 mol%, more preferably 5 mol%, based on all the structural units constituting the resin of [a], and further preferably 10 mol%. Further, the upper limit of the content ratio is preferably 80 mol%, more preferably 70 mol%. When the content ratio is within the above range, for example, the molecular weight of [a] resin or the like can be adjusted without hindering the effect.

The lower limit of the weight average molecular weight (Mw) of the resin [a] is preferably 1,000, more preferably 2,000, 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 the [a] resin to the above range, storage stability and sensitivity can be further improved.

Further, the ratio of the number average molecular weight (Mn) of the Mw to the [a] resin, that is, the lower limit of the molecular weight distribution (Mw/Mn) is usually 1, preferably 1.2, 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 [a] resin to the above range, storage stability and sensitivity can be further improved.

Further, Mw and Mn in the present specification are values measured by Gel Permeation Chromatography (GPC).

([a] Method for Synthesizing Resin) [a] The method for synthesizing the resin is not particularly limited, and a known method can be employed. For example, it can be synthesized by subjecting the monomer to a polymerization reaction in the presence of a polymerization initiator in a solvent.

[Polyimide] The polyimine used in the resin composition is not particularly limited as long as it is a polymer compound having a quinone bond in a repeating unit, and from the viewpoint of alkali solubility, it is preferably A polyimine having a carboxyl group, a phenolic hydroxyl group, a sulfo group, a thiol group or a combination of such groups in the structural unit. The polyiminoimine can be provided with alkali-developability (alkali-soluble) by containing the alkali-soluble groups in the structural unit, and as a result, generation of scum in the exposed portion can be suppressed at the time of alkali development. The polyimine is synthesized by a method described in, for example, JP-A-2006-199945, JP-A-2008-163107, JP-A-2011-42701, and the like.

[Polyoxane] The polyoxyalkylene to be used in the resin composition is not particularly limited, and examples thereof include, for example, International Publication No. WO2009/028360, International Publication No. WO2011/155382, and Japanese Patent Laid-Open No. 2010-152302 Polyoxyalkylene described in the above.

[Novolak resin] The novolak resin to be used in the resin composition is not particularly limited, and examples thereof include a resin having a phenol novolak structure or a resin having a resol novolak structure. The novolak resin is obtained by reacting a phenol compound with an aldehyde compound. Specific examples of the novolac resin include those described in JP-A-2003-114531, JP-A-2012-137741, and JP-A-2013-127518.

[Alkali-soluble polyolefin] The alkali-soluble polyolefin used in the resin composition is not particularly limited, and from the viewpoint of alkali solubility, a cyclic olefin polymer having a protic polar group is preferred. Here, the protic polar group means 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 an alkali-soluble polyolefin described in JP-A-2012-211988.

[Resin having a Cardo skeleton] The resin having a cardo skeleton used in the resin composition is not particularly limited. The term "cardo skeleton" as used herein refers to a skeleton structure in which two other cyclic structures are bonded to a ring carbon atom constituting a cyclic structure, and for example, two carbon atoms at the 9-position of the anthracene ring are bonded to each other. The structure of an aromatic ring (for example, a benzene ring). Specific examples of the resin having a cardo skeleton include resins described in Japanese Patent No. 5,181,725 and Japanese Patent No. 5,327,345.

[[A]] [A] Adhesive Resin Other than Alkali-Soluble Resin] When the resin composition is not applied to a photosensitive resin composition which can be patterned by an alkaline developer, alkali insolubility can be used. [A] binder resin. The alkali-insoluble [A] binder resin may, for example, be an alkali-insoluble polyolefin.

[Alkali-insoluble polyolefin] The alkali-insoluble polyolefin used in the resin composition is not particularly limited, and is preferably a polyolefin having no protic polar group. Specific examples of the alkali-insoluble polyolefin include a polymer using a 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 a monomer. (cyclic olefin polymer) or the like. Examples of the olefin include ethylene, propylene, butylene, and the like. Examples of the cycloolefin include a monocyclic cycloolefin such as cyclopentene or cyclohexene, and a polycyclic cyclic olefin such as norbornane, tricyclodecene or tetracyclododecene. The substituent of the cycloolefin may, for example, be an alkyl group having 1 to 5 carbon atoms or a group in which the alkyl group is combined with at least one selected from the group consisting of -CO- and -O-. Preferred are methyl and methoxycarbonyl. The alkali-insoluble polyolefin is preferably a cyclic olefin polymer, more preferably a polymer having a substituted or unsubstituted cycloolefin as a monomer, and further preferably a norbornane and a substituted or unsubstituted four. Cyclododecene as a polymer of monomers. Specific examples of the alkali-insoluble polyolefin include an alkali-insoluble polyolefin described in JP-A-2015-127733.

The lower limit of the content of the [A] binder resin in the resin composition is preferably 1% by mass, and more preferably 5% by mass. Further, the upper limit of the content is preferably 50% by mass, more preferably 40% by mass. By setting the content of the [A] binder resin to the lower limit or more, it is possible to form a film which further improves the sensitivity, has higher hardness, and is more excellent in solvent resistance. On the other hand, by setting the content to the upper limit or lower, the storage stability can be further improved.

[[B]QD] [B] QD is not particularly limited, and is preferably a semiconductor quantum dot containing a safety material which does not have Cd or Pb as a constituent element but, for example, In (indium) or Si (矽) and the like are constituted as constituent elements.

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

Examples of the element include Be (铍), Mg (magnesium), Ca (calcium), Sr (锶), Ba (钡), Cu (copper), Ag (silver), gold (Au), and zinc (Zn). ), B (boron), Al (aluminum), Ga (gallium), In (indium), Tl (铊), C (carbon), Si (矽), Ge (锗), Sn (tin), N (nitrogen) ), P (phosphorus), As (arsenic), Sb (锑), Bi (铋), O (oxygen), S (sulfur), Se (selenium), Te (碲), Po (钋), etc. From the viewpoint of fluorescent characteristics, In is preferred.

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

Further, [B]QD is also preferably a Si-based semiconductor quantum dot including a semiconductor quantum dot containing Si and a semiconductor quantum dot containing a compound of Si and another element.

Further, [B]QD is preferably a compound (A) having a fluorescence maximum in a wavelength range of green light of 500 nm or more and 600 nm or less, and/or red light of 600 nm or more and 700 nm or less. Compound (B) having a fluorescent maximum in the wavelength range. When the [B]QD contains the compound (A) and/or the compound (B) having the above-described fluorescent properties, the resin composition can be applied as a resin composition, that is, a light-emitting display for image display using visible light is formed. A resin composition of a wavelength conversion layer of the element.

[B] QD may be a homogeneous structural form comprising one compound or a core-shell structured form comprising two or more compounds.

The [B]QD of the core-shell structure type is formed by forming a core structure from one compound and covering the core structure with other kinds of compounds. For example, an exciton (electron-hole pair) generated by photoexcitation can be enclosed in a core by coating a semiconductor of a core with a semiconductor having a larger band gap. As a result, the probability of a non-radiative transition of the [B] QD surface is reduced, and the fluorescence quantum yield is improved.

From the viewpoint of improving the fluorescence characteristics, the [B]QD of the core-shell structure type is preferably a constituent element containing In as a core, 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 having InP as a core and ZnS as a shell. Other core-shell structured semiconductor quantum dots are also the same.

The lower limit of the average particle diameter of [B] QD is preferably 0.5 nm, more preferably 1.0 nm. Further, the upper limit of the average particle diameter is preferably 20 nm, more preferably 10 nm. When the average particle diameter is smaller 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 sealing effect may not be obtained, and the desired fluorescent characteristics may not be obtained.

Here, the average particle diameter of [B]QD is obtained by drying the sample and observing it using a transmission electron microscope, and the longest of each of the 10 [B]QDs contained in the field of view. The width is averaged.

Further, the wavelength range of the fluorescence of the [B]QD can be controlled by appropriately selecting the constituent material of [B]QD or the average particle diameter.

[B] The shape of the QD is not particularly limited, and may be, for example, a spherical shape, a rod shape, a disk shape, or the like. Information on the shape and dispersion state of [B]QD can be obtained by a transmission electron microscope.

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

Further, InP/ZnS, which is a core-shell structure type semiconductor quantum dot, can be synthesized, for example, by a method described in the journal "Journal of American Chemical Society. 2007, 129, 15432-15433". Further, CuInS ₂ /ZnS which is a core-shell structure type semiconductor quantum dot can also be referred to, for example, the method or technical document described in the "Journal of American Chemical Society. 2009, 131, 5691-5697". Synthesized by the method described in Chemistry of Materials. 2009, 21, 2422-2429.

Further, the Si-based semiconductor quantum dots can be synthesized, for example, by referring to the method described in the journal "Journal of American Chemical Society. 2010, 132, 248-253".

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, based on 100 parts by mass of the [A] binder resin. In addition, the upper limit of the content is preferably 150 parts by mass, more preferably 100 parts by mass, based on 100 parts by mass of the [A] binder resin. By setting the content of [B]QD to the above range, a film (wavelength conversion layer) having excellent fluorescent characteristics can be formed.

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

(Compound having a phenylphosphine structure) The compound having a phenylphosphine structure is a compound represented by the formula: P-(R ² ) ₃ . Here, R ² is a hydrogen atom or a monovalent organic group. The three R ^{2 's} may be the same or different. Wherein 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 three R ^{2 's} are substituted or unsubstituted phenyl groups.

Examples of the compound having a phenylphosphine structure include tri-o-tolylphosphine, tri-tolylphosphine, tri-p-tolylphosphine, tris-2,5-dimethylphenylphosphine, and tri-3,5-dimethylphenylphosphine. Triphenylphosphine, diphenyl (p-vinylphenyl) phosphine, tris(2,4,6-trimethylphenyl)phosphine, and the like.

From the viewpoint of more effectively suppressing the generation of radicals which cause a decrease in the fluorescence quantum yield of [B]QD, the compound having a phenylphosphine structure is preferably tri-o-tolylphosphine, tri-tolylphosphine, and tri-p-toluene. Further, phosphine, tris-2,5-dimethylphenylphosphine, diphenyl(p-vinylphenyl)phosphine, triphenylphosphine and tris(2,4,6-trimethylphenyl)phosphine, more preferably Tri-o-tolylphosphine, tri-tolylphosphine, tri-p-tolylphosphine, and tris(2,4,6-trimethylphenyl)phosphine.

(Compound having a cycloalkylphosphine structure) The compound having a cycloalkylphosphine structure is a compound represented by the formula: P-(R ³ ) ₃ . Here, R ³ is a hydrogen atom or a monovalent organic group. The three R ^{3 's} may be the same or different. Wherein at least one R ³ is a substituted or unsubstituted cycloalkyl group. Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group and the like. 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 's} are substituted or unsubstituted cycloalkyl groups.

The compound having a cycloalkylphosphine structure is preferably tricyclohexylphosphine.

(Compound having a thiobisphenol structure) The compound having a thiobisphenol structure is a compound represented by the formula: S-(R ⁴ ) ₂ . Here, R ⁴ is a substituted or unsubstituted hydroxyphenyl group. The two R ^{4 's} 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 has no more than two 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 having a dialkyl thiodipropionate structure) A compound having a dialkyl thiodipropionate structure of the formula: S-(CH ₂ -CH ₂ -COO-R ⁵ ) ₂ The compound represented. Here, R ⁵ is an alkyl group. The two R ^{5 's} 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.

Examples of the compound having a dialkyl thiodipropionate structure include dilauryl thiodipropionate, di-tridecyl thiodipropionate, dimyristyl thiodipropionate, and sulfur. Distearyl dipropionate and the like.

The compound having a dialkyl thiodipropionate structure is preferably dilauryl thiodipropionate from the viewpoint of more effectively suppressing the generation of a radical which causes a decrease in the fluorescence quantum yield of [B]QD. And distearyl thiodipropionate.

(Compound having a benzothiazole structure) The compound having a benzothiazole structure is a substituted or unsubstituted benzothiazole. The substituent of the benzothiazole may, for example, be an alkyl group having 1 to 10 carbon atoms, a hydroxyl group or a thioether group, and among these groups, a thioether group is preferred.

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

The [C] compound is preferably a compound having a phenylphosphine structure and a compound having a cycloalkylphosphine structure, 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 part by mass, more preferably 1 part by mass, even more preferably 2 parts by mass, based on 100 parts by mass of the [A] binder resin. The upper limit of the content is preferably 15 parts by mass, more preferably 10 parts by mass, even more preferably 8 parts by mass, based on 100 parts by mass of the [A] binder resin. By setting the content within the above range, generation of radicals which cause a decrease in the fluorescence quantum yield of [B]QD can be more effectively suppressed. Further, when the resin composition has curability, it is possible to suppress the curing reaction which hinders the resin composition.

[[X] Peroxide Decomposing Agent] [X] The peroxide decomposing agent is an antioxidant not equivalent to the [C] compound, and has a peroxide decomposition function. The [X] peroxide decomposing agent is an antioxidant not equivalent to the [C] compound, and has a peroxide decomposition function. Examples of the [X] peroxide decomposing agent include a phosphorus compound, a sulfur compound, a compound containing a phosphorus atom and a sulfur atom, and the like, and specific examples thereof include a compound having a phosphite structure and a compound having a thioether structure (wherein A compound having a thiobisphenol structure and a compound having a dialkyl thiodipropionate structure, a compound having a benzotriazole structure, a compound having a thiophosphite structure, and the like.

(Compound having a phosphite structure) Examples of the compound having a phosphite structure include tris(nonylphenyl)phosphite, tris(p-trioctylphenyl)phosphite, and triphosphite [ 2,4,6-tris(α-phenylethyl)]ester, tris(p-butenylphenyl) phosphite, bis(p-nonylphenyl)cyclohexyl phosphite, phosphorous acid Tris(2,4-di-t-butylphenyl)ester, 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphorane [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]undecane and the like.

A commercially available product having a phosphite structure, 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 Publication No. 2014 A compound or the like described in JP-A-2014-134763, and the like.

(Compound having a thioether structure) Examples of the compound having a thioether structure include pentaerythritol tetrakis(3-laurylthiopropionate), pentaerythritol tetrakis(3-octadecylthiopropionate), and pentaerythritol IV. (3-myristylthiopropionate), pentaerythritol tetrakis(3-stearylthiopropionate), and the like.

The commercially available product of the compound having a thioether structure, for example, a compound described in JP-A-2014-48428, JP-A-2014-134763, and the like.

(Compound having a benzotriazole structure) A compound having a benzotriazole structure may, for example, be 2-(2-hydroxy-5-methylphenyl)benzotriazole or 2-[2'-hydroxy-5. '-(Methyl)acryloxymethylphenyl]-2H-benzotriazole, 2-[2'-hydroxy-3'-tert-butyl-5'-(methyl)propenyloxy Ethylphenyl]-2H-benzotriazole and the like.

The commercially available product of the benzotriazole-containing compound, for example, a compound described in JP-A-2003-172715, JP-A-2009-97010, JP-A-2012-211975, and the like. .

(Compound having a thiophosphite structure) Examples of the compound having a thiophosphite structure include trilauryl trithiophosphite, tributyl trithiophosphate, triphenyl trithiophosphate, and the like. .

[[D] Radical Scavenger] The resin composition may further contain a [D] radical scavenger. The [D] radical scavenger is an antioxidant which is not equivalent to the [C] compound, and has an action of capturing a chain-transporting agent (ROO· and R·) having high activity and stopping the chain reaction, thereby preventing oxidation. In the case of heat treatment at the time of forming a film (wavelength conversion layer) by the resin composition or when excessive heat is applied to the film in the manufacturing process of an electronic device, radicals may be generated in the film. When radicals are generated in the film as described above, since the radicals are chemically unstable, it is easy to react with other compounds to further form new radicals and to degrade the QD in a chain manner, which causes a decrease in the function of the induced membrane. When the resin composition contains a [D] radical scavenger, even if the radical is generated, the radical is trapped by the [D] radical scavenger, so that the [B]QD after the heat treatment can be further suppressed. A decrease in the fluorescence quantum yield. Further, the [D] radical scavenger also includes a compound having a function of decomposing a peroxide. Further, in the present specification, a compound having a function of decomposing a peroxide and having a function of trapping a radical is regarded as a [D] radical scavenger.

The [D] radical scavenger is not particularly limited as long as it can capture a radical and deactivate the radical. For example, a phenol or an aromatic amine, preferably a compound having a hindered phenol structure and a hindered amine structure can be used. compound of. By using the specific compound as the [D] radical scavenger, free radicals can be captured more reliably.

[Compound having a hindered phenol structure] The hindered phenol structure is, 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 the compound having a hindered phenol structure include pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2'-thiodiethylidene double [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) Propionate, tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3, 5-di-t-butyl-4-hydroxybenzyl)benzene, 3,9-bis[1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-) Methylphenyl)propenyloxy]ethyl]2,4,8,10-tetraoxaspiro[5,5]-undecane and polymers of such compounds and the like.

The commercially available product of the compound having a hindered phenol structure is, for example, a compound described in JP-A-2011-227106, JP-A-2013-164471, and the like.

[Compound having a hindered amine structure] A compound having a hindered amine structure may, for example, be bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate or bis(2, succinate). 2,6,6-tetramethyl-4-piperidinyl), bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, azelaic acid bis ( N-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl), azelaic acid bis(N-benzyloxy-2,2,6,6-tetramethyl-4 -piperidinyl)ester, N,N',N'',N'''-tetra-[4,6-bis-[butyl-(N-methyl-2,2,6,6-tetramethyl) Low molecular compound such as cypiperidin-4-yl)amino]-triazin-2-yl]-4,7-diazadecane-1,10-diamine, multiple piperidine rings via triazine skeleton A polymer obtained by bonding a polymer and a plurality of piperidine rings via an ester bond.

The commercially available product of the compound having a hindered amine structure, for example, a compound described in JP-A-2011-112823, JP-A-2014-134763, and the like.

From the viewpoint of more reliably capturing free radicals, the [D] radical scavenger is preferably a compound having a hindered phenol structure, more preferably 2,2'-thiodiethylidene [3-(3, 5-di-t-butyl-4-hydroxyphenyl)propionate], and 3,9-bis[1,1-dimethyl-2-[β-(3-tert-butyl-4- Hydroxy-5-methylphenyl)propanoxy]ethyl]2,4,8,10-tetraoxaspiro[5,5]-undecane.

When the resin composition contains a [D] radical scavenger, the lower limit of the content of the [D] radical scavenger is preferably 0.1 part by mass, more preferably 100 parts by mass of the [A] binder resin. 1 part by mass, and more preferably 2 parts by mass. The upper limit of the content is preferably 10 parts by mass, more preferably 5 parts by mass, based on 100 parts by mass of the [A] binder resin. By setting the content within the above range, radicals can be more reliably captured. Further, when the resin composition has curability, it is possible to suppress the curing reaction which hinders the resin composition.

[[E] Polymerizable Compound] The resin composition may further contain [E] a polymerizable compound. When the resin composition contains the [E] 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 which is polymerized by radiation irradiation or heating, and is preferably a (meth)acryl fluorenyl group or an epoxy group from the viewpoint of improving sensitivity. A compound having a vinyl group or a combination of such groups is more preferably a compound having two or more (meth) acrylonitrile groups in the molecule.

Examples of the [E] polymerizable compound having two or more (meth) acrylonitrile groups in the molecule include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, and Ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trishydroxyl Propane dimethacrylate, trimethylolpropane trimethacrylate, 1,3-butanediol diacrylate, 1,3-butylene glycol 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 four Acrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, Pentaerythritol heptaacrylate, tripentaerythritol octaacrylate, pentaerythritol nona acrylate, pentaerythritol decaacrylate, pentaerythritol eleven acrylate, pentaerythritol dodecyl acrylate, tripentaerythritol heptamethacrylate, tripentaerythritol octamethyl Acrylate, pentaerythritol nonyl methacrylate, pentaerythritol decamethacrylate, pentaerythritol eleven methacrylate, pentaerythritol dodecyl methacrylate, dimethylol-tricyclodecane diacrylate, Ethoxylated bisphenol A diacrylate, 9,9-bis[4-(2-propenyloxyethoxy)phenyl]anthracene, 9,9-bis[4-(2-methylpropene oxime) Oxyethoxy)phenyl]anthracene, 9,9-bis[4-(2-methylpropenyloxyethoxy)-3-methylphenyl]anthracene, (2-propenyloxypropane) Oxy)-3-methylphenyl]anthracene, 9,9-bis[4-(2-propenyloxyethoxy)-3,5-dimethylphenyl]anthracene, 9,9-double [4-(2-Methylacryloxyethoxyethoxy)-3,5-dimethylphenyl]anthracene.

Among them, from the viewpoint of improving the sensitivity, a polymerizable compound having three or more (meth)acryl fluorenyl groups is preferable, and a polymerizable compound having four or more (meth) acryl fluorenyl 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 the [E] polymerizable compound, the lower limit of the content of the [E] polymerizable compound is preferably 1 part by mass, more preferably 10 mass, per 100 parts by mass of the [A] binder resin. It is preferably 20 parts by mass. Further, 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 which further improves storage stability and sensitivity, and has higher hardness and more excellent solvent resistance.

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

Examples of the [F] radiation sensitive compound include a radiation sensitive radical polymerization initiator, a quinonediazide compound, a combination of these compounds, and the like.

[Inductive Radical Radical Polymerization Starter] For example, when a radically polymerizable compound is used as the [E] polymerizable compound, the radiation-sensitive radical polymerization initiator can further promote the resin composition. Hardening reaction caused by radiation.

The radiation-sensitive radical polymerization initiator may, for example, be a radical polymerization reaction capable of inducing [E] a polymerizable compound by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, or X-ray. Active species of compounds, etc.

Specific examples of the radiation-sensitive radical polymerization initiator are, for example, ethyl ketone, 1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzylidene)-9H-oxime Zyrid-3-yl]-, 1-(O-ethylindenyl), ethyl ketone, 1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1 ,3-dioxolyl)methoxybenzylidene}-9H-indazol-3-yl]-,1-(O-ethylindenyl), ethyl ketone, 1-[9- Ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzylidene)-9H-indazol-3-yl]-, 1-(O-ethylindenyl), 1,2- Octanone-1-[4-(phenylthio)-2-(O-benzylidenehydrazide)], ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl) O-indenyl hydrazine compound such as -9H-carbazol-3-yl]-, 1-(O-ethenyl fluorene); 2-benzyl-2-dimethylamino-1-(4-? Phenylphenyl)-butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butane Α-amino ketone compound such as 1-ketone or 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropan-1-one; 1-phenyl-2-hydroxy-2 An α-hydroxyketone compound such as methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl) ketone or 1-hydroxycyclohexyl phenyl ketone; Phenyl (2,4,6-trimethylbenzhydryl) Oxide, bis (2,4,6-trimethyl benzoyl-yl) - phenyl phosphine oxide acyl phosphine oxide compound.

The radiation-sensitive radical polymerization initiator is preferably ethyl ketone, 1-[9-ethyl-6-(2-methylbenzamide), from the viewpoint of further promoting the hardening reaction by radiation. -9H-carbazol-3-yl]-, 1-(O-ethylindenyl), 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzene Methyl hydrazide)], 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropan-1-one, diphenyl (2,4,6-trimethylbenzene) Amidino)phosphine oxide and bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide.

[Orynium azide compound] The quinonediazide compound is suitable as a radiation sensitive compound in the case where the resin composition is used as a positive type radiation sensitive composition. As the quinonediazide compound, a 1,2-quinonediazide compound which 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 1,2-naphthoquinonediazidesulfonium halide can be used.

Examples of the quinonediazide compound include 1,2-naphthoquinonediazidesulfonic acid such as 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone azide-4-sulfonate. Ester; 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol-1,2-naphthoquinonediazide 4-sulfonate, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol-1,2- Naphthoquinonediazide-5-sulfonate, bis(2,5-dimethyl-4-hydroxyphenyl)-2-hydroxyphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid 1,2-naphthoquinonediazide sulfonate such as ester (polyhydroxyphenyl) alkane. Specific examples of the quinonediazide compound include compounds described in, for example, Japanese Patent No. 5,545,321, Japanese Patent No. 5,630,068, and Japanese Patent No. 5,592,064.

The quinonediazide compound is preferably a 1,2-naphthoquinonediazide sulfonate of a (polyhydroxyphenyl)alkane, more preferably 4, from the viewpoint of improving the radiation sensitivity of the resin composition. 4'-[1-[4-[1-[4-Hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol-1,2-naphthoquinonediazide-5-sulfonate Acid ester.

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

[[G] Solvent] The resin composition may further contain a [G] solvent. When the resin composition contains a [G] solvent, the coatability thereof is improved. The [G] solvent is not particularly limited as long as it can dissolve or disperse the respective components, and examples thereof include a solvent used for synthesizing the resin such as the [a] resin. Further, the [G] solvent may be used singly or in combination of two or more.

[[H] other components] The resin composition may contain a thermal polymerization initiator, a storage stabilizer, a binder, etc., in addition to the above components, insofar as the effects of the present invention are not impaired [H] other ingredient. [H] Other components may be used singly or in combination of two or more. When the resin composition contains [H] other components, the upper limit of the content of the [A] binder resin is preferably 10 parts by mass, more preferably 1 part by mass, based on 100 parts by mass of the [A] binder resin.

The resin composition can be produced by a suitable method, for example, by mixing [A] binder resin, [B]QD, [C] compound and optionally any component in a [G] solvent. The lower limit of the concentration of the solid content in the composition at the time of mixing is preferably 5% by mass, and more preferably 10% by mass. Further, the upper limit of the concentration is preferably 80% by mass, more preferably 70% by mass. By setting the concentration of the solid component to the above range, the coatability can be improved. In addition, the "solid content" means the remaining component obtained by drying a sample by a hot plate of 175 ° C for 1 hour to remove volatile matter.

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

<Wavelength Conversion Member> This film is suitable as a wavelength conversion layer provided in a wavelength conversion member such as a light-emitting display element or a wavelength conversion film. Hereinafter, as a preferred embodiment of the wavelength conversion member including the film, a wavelength conversion film and a light-emitting display element will be described as an example.

[Wavelength Conversion Film] The wavelength conversion film which is one embodiment of the wavelength conversion member is suitable as a wavelength conversion member used for a solar cell sealing sheet, an agricultural film, an illumination component, or the like. The average thickness of the wavelength conversion layer in the wavelength conversion film can be, for example, 1 μm or more and 1,000 μm or less. Further, the wavelength conversion film may be a single layer film composed only of the film (wavelength conversion layer), or may be a multilayer film having other layers.

[Light-emitting display element] Fig. 1 is a cross-sectional view schematically showing a light-emitting display element 100 according to an embodiment. The light-emitting display element 100 includes a wavelength conversion substrate 11 including a wavelength conversion layer 13 (13a, 13b, 13c) and a black matrix 14 on the first substrate 12, and a light source substrate 18 via an adhesive layer. 15 is attached to the wavelength conversion substrate 11.

The first base material 12 is made of glass, quartz, a transparent resin or the like. Examples of the transparent resin include transparent polyimine, 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 the resin composition, it is possible to suppress a 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 included in each of the wavelength conversion layers 13, and emits 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 formed by containing different QDs, and can emit different fluorescence. For example, the wavelength conversion substrate 11 can be configured such that 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, each of the wavelength conversion layer 13a, the wavelength conversion layer 13b, and the wavelength conversion layer 13c selects the QD contained so as to have a desired fluorescence 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 kinds of resin compositions containing QDs having different light-emitting 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. Further, the upper limit of the average thickness is preferably 100 μm. When the average thickness is less than the lower limit, the excitation light is not sufficiently absorbed, and the light conversion efficiency is lowered. Therefore, there is a possibility that the brightness of the light-emitting display element cannot be sufficiently ensured.

A black matrix 14 is disposed between the respective 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. Further, the black matrix 14 is not an essential component in the wavelength conversion substrate 11, and the wavelength conversion substrate 11 may be configured such that the black matrix 14 is not provided.

The subsequent agent layer 15 is formed using a known adhesive that transmits ultraviolet light or blue light, which will be described later. Further, the adhesive layer 15 is not required to be provided on the first base material 12 so as to cover the entire surface of each of the wavelength conversion layers 13 as shown in FIG. 1, and may be provided only 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 disposed on the wavelength conversion substrate 11 side of the second base material 16 . Ultraviolet light or blue light is emitted from the light source 17 as excitation light, respectively.

The light source 17 (17a, 17b, 17c) is not particularly limited, and an ultraviolet light-emitting organic EL element or a blue light-emitting organic EL element having a known structure can be used, and can be produced by a known production method. Here, the ultraviolet light preferably has a main luminescence peak of 360 nm or more and 435 nm or less, and the blue light preferably has a main luminescence peak exceeding 435 nm and is 480 nm or less. The light source 17 preferably has directivity so that the respective outgoing light beams illuminate the opposite wavelength conversion layers 13.

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

In the light-emitting display element 100, a portion in which the first wavelength conversion layer 13a is provided constitutes a sub-pixel that is displayed in red. In other words, the first wavelength conversion layer 13a of the wavelength conversion substrate 11 converts the excitation light from the first light source 17a facing the light source substrate 18 into red light. Further, the portion in which the second wavelength conversion layer 13b is provided constitutes a sub-pixel that performs green display. In other words, the second wavelength conversion layer 13b converts the excitation light from the opposing second light source 17b of the light source substrate 18 into green light. Further, the portion in which 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.

Further, in the light-emitting display element 100, the excitation light from the third light source 17c may be used as the blue light. In this case, the wavelength conversion substrate 11 may be replaced by a light scattering layer formed by dispersing light scattering particles in a resin instead of the third wavelength conversion layer 13c. By setting it as such, it is possible to use the blue light as the excitation light for wavelength conversion and to use the original wavelength characteristic.

The light-emitting display element 100 constitutes one pixel by the sub-pixel including the first wavelength conversion layer 13a, the sub-pixel including the second wavelength conversion layer 13b, and the sub-pixels including the sub-pixels of the third wavelength conversion layer 13c. The one pixel becomes the smallest unit constituting the image.

The light-emitting display element 100 having the above configuration controls the sub-pixel including the first wavelength conversion layer 13a, the sub-pixel including the second wavelength conversion layer 13b, and the sub-pixel including the third wavelength conversion layer 13c to control red, green, or The blue light is illuminated for full color display.

Further, in the light-emitting display element 100, a color filter may be provided between the wavelength conversion layer 13 and the first substrate 12. In other words, a red color filter can be disposed between the first wavelength conversion layer 13a and the first substrate 12, and a green color filter can be disposed between the second wavelength conversion layer 13b and the first substrate 12. A blue color filter is provided between the third wavelength conversion layer 13c and the first base material 12. Thereby, the purity of the display color can be improved. Here, the color filter can be used by forming a color filter known as a liquid crystal display element or the like by a known method.

<First Formation Method of Film> The first formation method of the film can preferably form an unpatterned film which is used as a wavelength conversion layer of a wavelength conversion film or the like. The first method for forming the film includes a step of forming a coating film on one surface side of the substrate (hereinafter also referred to as "coating film forming step"), and a step of heating the coating film (hereinafter also referred to as "heating" Step"), the coating film is formed by the resin composition.

According to the first formation method of the film, since the resin composition described above 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 term "coating film" as used herein refers to a film-like member that is not subjected to sufficient heat treatment. Hereinafter, each step will be described separately.

[Coating Film Forming Step] In the coating film forming step, for example, a coating film is formed by applying the resin composition onto a substrate. In the coating film forming step, after applying the resin composition, the coated surface may be heated by a suitable heating means such as a hot plate or an oven to remove the solvent or the like. The heating conditions may be, for example, a heating temperature of 70° C. or higher and 130° C. or lower, and a heating time of 1 minute or longer and 10 minutes or shorter.

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

The method of applying the resin composition is not particularly limited, and examples thereof include a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, and a bar coating method.

[Heating Step] In the heating step, the coating film is heated by a suitable heating means such as a hot plate or an oven. Thereby, the volatile components contained in the coating film or various chemical reactions such as ruthenium imidization can be removed, and as a result, the properties of the formed film can be adjusted. In the heating step, for example, a heating temperature of 150° C. or higher and 250° C. or lower, and a heating time of 5 minutes or longer and 180 minutes or shorter may be used.

Since the film laminated on the substrate can be obtained by the heating step, the laminate of the substrate and the film can be used as a wavelength conversion film or the like. In the case where the resin composition having curability is used in the method, a crosslinking reaction occurs in the resin composition by the heating, whereby a cured film can be obtained.

<Second Forming Method of Film> The second forming method of the film can preferably form a patterned film. The second method for forming the film includes a step of forming a coating film on one surface side of the substrate (hereinafter also referred to as "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"), a step of developing a coating film after radiation irradiation (hereinafter also referred to as "development step"), and a step of heating the coating film (hereinafter also referred to as "heating step") And the coating film is formed by the resin composition containing a radiation sensitive compound. Further, the second forming method of the film may include a step of exposing the developed pattern (hereinafter also referred to as "post exposure step") between the developing step and the heating step.

According to the second formation method of the film, since the resin composition described above 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. Further, the film obtained by the second formation method of the film is usually a cured film. Hereinafter, each step will be described separately.

[Coating Film Forming Step] In the coating film forming step, for example, a coating film is formed by applying the resin composition onto a substrate. After the resin composition is applied, the coated surface may be heated (prebaked) to remove the solvent or the like.

The material of the substrate on which the coating film is formed is not particularly limited, and examples thereof include glass, quartz, rhodium, and resin. Specific examples of the resin include polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyether oxime, polycarbonate, polyimine, and a ring. An addition polymer of an olefin, a ring-opening polymer of a cyclic olefin, a hydride thereof, or the like. Further, for these substrates, pretreatment such as chemical treatment, plasma treatment, ion plating, sputtering, or vacuum vapor deposition using a decane coupling agent or the like may be performed.

The method of applying the resin composition is not particularly limited, and examples thereof include a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, and a bar coating method. Among these coating methods, a spin coating method and a slit die coating method are preferred. The conditions of the heating (pre-baking) may vary depending on the type of each component, the mixing ratio, and the like. For example, the heating time may be 70° C. or higher and 130° C. or lower, and the heating time may be 1 minute or longer and 10 minutes or shorter.

[Radiation Radiation Step] In the radiation irradiation step, at least a part of the coating film formed on the substrate is irradiated with 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 the photomask, a part of the irradiated radiation passes through the photomask, and the part of the radiation is irradiated onto the coating film.

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

The lower limit of the cumulative irradiation amount (exposure amount) in the radiation irradiation step is preferably 100 J/m ² , more preferably 200 J/m ² . Further, the upper limit of the cumulative irradiation amount is preferably 2,000 J/m ² , more preferably 1,000 J/m ² . In addition, the term "cumulative irradiation amount" as used in the present specification means an illuminometer (for example, "OAI model (OAI model) 356" by OAI Optical Associates Inc.) at a wavelength of 365 nm. The cumulative value of the value obtained by measuring the intensity.

[Developing Step] In the developing step, the coating film after the radiation irradiation is developed to remove unnecessary portions.

The developer for development may be, for example, an alkaline solution in which sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, ammonia, tetramethylammonium hydroxide or tetraethylammonium hydroxide are dissolved. An aqueous solution of at least one of the compounds. To the aqueous solution of the basic compound, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol may be added and used.

Examples of the developing method include a liquid-filling method, a dipping method, a shaking dipping method, and a spray method. 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. Further, the upper limit of the development time is preferably 300 seconds, more preferably 80 seconds. After the development treatment, for example, the water is washed with a time of 30 seconds or more and 90 seconds or less, and then dried by compressed air or compressed nitrogen gas, whereby a desired pattern can be obtained.

[Post Exposure Step] For example, when a quinonediazide compound is used as the [F] sensitizing compound, the non-exposed portion is red, so that the post-exposure of the non-exposed portion after development can be performed in this step. The coating film is made colorless. The post-exposure conditions at this time may be, for example, the same conditions as those of the exposure step.

[Heating Step] In the heating step, the coating film is heated (post-baking) by a suitable heating means such as a hot plate or an oven. Thereby a film is formed on the substrate.

The lower limit of the heating temperature is preferably 150 °C. Further, the upper limit of the heating temperature is preferably 250 °C. In the case of heating by a hot plate, the lower limit of the heating time is preferably 5 minutes, and the upper limit is preferably 30 minutes. Further, 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.

In the case where the method is applied to the formation of the wavelength conversion layer of the light-emitting display element 100, the formation method of the wavelength conversion layer including the above steps is repeated as long as three resin compositions are respectively used, and the first wavelength conversion is respectively formed. The layer 13a, the second wavelength conversion layer 13b, and the third wavelength conversion layer 13c may be used.

<Other Embodiments> Although the preferred embodiments of the present invention have been described above, the present invention is not limited to the embodiments. For example, in the preferred embodiment, an example in which the resin composition of the present invention is applied to a sub-pixel of a light-emitting display element has been described. However, the present invention is not limited thereto and can be applied to a backlight unit of a liquid crystal display. Wait. For example, when a blue light-emitting diode is used as a light source of a backlight unit, a white having a high purity can be reproduced by combining with a film obtained from the resin composition of the present invention containing G-QD and R-QD. Light. Further, in the preferred embodiment, a method of forming a film laminated on a substrate has been described as a first method of forming the film. However, the film may be formed by, for example, another film forming method such as a casting method. Forming, in this case, for example, a film of a single layer film shape can be obtained. [Examples]

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to the 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. Further, the molecular weight distribution (Mw/Mn) was calculated from the obtained Mw and Mn.

Device: "GPC-101" from Showa Denko Co., Ltd.: "GPC-KF-801", "GPC-KF-802", "GPC-KF-803" and "GPC-KF-804" from Showa Denko Co., Ltd. Linked mobile phase: tetrahydrofuran column temperature: 40 ° C Flow rate: 1.0 mL / min Sample concentration: 1.0 mass % Sample injection amount: 100 μL Detector: differential refractometer standard material: monodisperse polystyrene

<Synthesis of a 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 carried out. Nitrogen replacement. Heating to 80 ° C, at this temperature, 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. Ethylene, 20 parts by mass of succinic acid mono [2-methylpropenyloxyethyl] ester, 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 maintained at this temperature for 1 hour. Thereafter, the temperature of the reaction solution was raised to 90 ° C, and further polymerization was carried out for 1 hour to obtain a propylene glycol monomethyl ether acetate solution (solid content concentration: 33% by mass) of the resin (A-1). The obtained resin was 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. The mixture was heated to 80 ° C, and 50 parts by mass of propylene glycol monomethyl ether acetate, 5 parts by mass of methacrylic acid, 25 parts by mass of tricyclodecyl methacrylate, and 10 parts by mass were added dropwise at this temperature for 2 hours. Styrene, 20 parts by mass of succinic acid mono [2-methylpropenyloxyethyl] ester, 18 parts by mass of 2-ethylhexyl methacrylate, and 12 parts by mass of N-phenyl malayan Amine, 10 parts by mass of 3-(methacryloxymethyl)-3-ethyloxetane and 6 parts by mass of 2,2'-azobis(2,4-dimethylpentane) A mixed solution of nitrile) was maintained at this temperature for 1 hour. Thereafter, the temperature of the reaction solution was raised to 90 ° C, and further polymerization was carried out for 1 hour, whereby a propylene glycol monomethyl ether acetate solution (solid content concentration: 33% by mass) of the resin (A-2) was obtained. The obtained resin had Mw = 11,100, Mn = 6,000, and Mw / Mn = 1.85.

8-methyl [Synthesis Example 3] Synthesis of Resin (A-3) in the reaction vessel was purged with nitrogen, was added 430 parts by mass of 8-methoxy-carbonyl tetracyclo [4.4.0.1 ^2,5 .1 ⁷ 80 mol of ¹⁰ ]-3-dodecene and bicyclo[2.2.1]hept-2-ene: 20 mol of the mixture, and 750 parts by mass of toluene, heated to 60 °C. 0.62 parts by mass of a toluene solution of triethylaluminum (1.5 mol/L) and 3.7 parts by mass of a third butanol/methanol modified (tert-C ₄ H ₉ OH/CH ₃ OH/W=) were added thereto. 0.35 mol/0.3 mol/1 mol) tungsten chloride (WCl ₆ ) solution (concentration: 0.05 mol/L), and heating and stirring at 80 ° C for 3 hours to obtain a resin as a hydrolyzed polymer (A- 3). The polymerization conversion ratio of the 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> Each component for preparing each resin composition is shown below.

[[A] Binder Resin] A-1: Resin (A-1) A-2: Resin (A-2) A-3: Resin (A-3)

[[B]QD] B-1: InP/ZnS (average particle size: 4 nm) as a core-shell structured semiconductor quantum dot B-2: CdSe/ZnS-TOPO as a core-shell structured semiconductor quantum dot (average Particle size: 4 nm, the quantum dot used in Example 4 of WO2006/103908

Further, the average particle diameter of [B]QD was obtained by observing using a transmission electron microscope (Hitachi High-Tech Fielding "H-7650"). The longest width of each of the 10 [B]QDs contained in the field of view is averaged.

[[C] compound] C-1: triphenylphosphine C-2: tri-o-tolylphosphine C-3: tri-tolylphosphine C-4: tri-p-tolylphosphine C-5: three (2, 4, 6-trimethylphenyl)phosphine C-6: tris-2,5-dimethylphenylphosphine C-7: diphenyl(p-vinylphenyl)phosphine C-8:tricyclohexylphosphine C-9: 4,4-Thiobis(3-methyl-6-tert-butylphenol) C-10: Dilauryl thiodipropionate C-11: Distearyl thiodipropionate C-12: 2-mercaptobenzothiazole

[[X] peroxide decomposer] X-1: pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] X-2:3,9-double (octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane X-3: sebacic acid bis(2,2,6,6 -tetramethyl-4-piperidinyl)ester X-4: pentaerythritol tetrakis(3-mercaptobutyrate)

[[D] radical scavenger] D-1: 2,2'-thiodiethyl bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (IRGANOX (registered trademark) 1035" by BASF

[[E] polymerizable compound] E-1: dipentaerythritol hexaacrylate E-2: di-trimethylolpropane tetraacrylate

[[F]Radiosensitive compound] F-1: Diphenyl (2,4,6-trimethylbenzylidene)phosphine oxide (BACI) LUCIRIN (registered trademark) )TPO") F-2: bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide (IRGACURE (registered trademark) 819 by BASF) F-3: 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropan-1-one (IRGACURE (BANK), BASF Corporation (registered trademark) 907") F-4: ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9.H.-carbazol-3-yl]-, 1-(O-乙醯基肟) (IRGACURE (registered trademark) OXE02 by BASF) F-5: 4,4'-[1-[4-[1-[4-hydroxyphenyl] -1-methylethyl]phenyl]ethylidene]bisphenol-1,2-naphthoquinonediazide-5-sulfonate F-6: 1,2-octanedione-1-[4- (phenylthio)-2-(O-benzhydrylhydrazine)] (IRGACURE (registered trademark) OXE01 by BASF)

[[G] solvent] G-1: propylene glycol monomethyl ether acetate

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

[Examples 2 to 18 and 1 to Comparative Example 8] Each of the resin compositions was prepared in the same manner as in Example 1 except that the types and the amounts of the respective components were adjusted as described in the following Table 1. Furthermore, the "-" in Table 1 indicates that the corresponding component is not used.

The resin compositions of the obtained Examples 1 to 18 and Comparative Examples 1 to 8 were evaluated in accordance with the methods described below. The evaluation results are shown in Table 1.

[Patternability] The QD-containing pattern film obtained by the following formation method was observed by an optical microscope, and the linear portion where no development residue or pattern was formed was linearly determined as A (good). In the case where the development residue is present and/or the straight portion of the pattern is not formed into a straight line, it is determined as B (bad).

(Method for Forming QD-Containing Pattern Film of Example 1) The resin composition of Example 1 was applied onto an alkali-free glass substrate by a spinner, and then prebaked on a hot plate at 90 ° C for 2 minutes. Thereby, a coating film is formed. Then, radiation including respective wavelengths of 365 nm, 405 nm, and 436 nm was irradiated with a total irradiation amount of 700 J/m ² through a photomask having a predetermined pattern using a high pressure mercury lamp. Then, development was carried out by using a 0.04% by mass aqueous potassium hydroxide solution at 25 ° C for 90 seconds to form a QD-containing pattern film having 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) The QD-containing pattern film of Example 2 was subjected to the QD-containing pattern film of Example 1 In the formation method, a pattern film containing QD was formed by the same method except that the resin composition of Example 2 was used and the total irradiation amount was set to 1,000 J/m ² . Further, the QD-containing pattern films of Example 14, Example 17, and Example 18 and Comparative Example 6 to Comparative Example 7 were respectively used in the method of forming the QD-containing pattern film of Example 1 14, Example 17 and Example 18 and Comparative Examples 6 to the resin composition of Comparative Example 7, and the total irradiation amount is set to 800 J / m ^2, except that, by the same method of forming a film containing a pattern of QD . Further, in the QD-containing pattern film of Example 13, in the method of forming the QD-containing pattern film of the first embodiment, the resin composition of Example 13 was used, and the total irradiation amount was set to 2,000 J/m ^{2 .} Further, a pattern film containing QD was formed by the same method except that the developed pattern was irradiated with ultraviolet rays at a cumulative irradiation amount of 10,000 J/m ² using a high-pressure mercury lamp. Further, the QD-containing pattern films of Examples 3 to 12, 15 and 16, and Comparative Examples 1 to 5 and Comparative Example 8 were used for the QD-containing pattern film of Example 1. In the formation method, the resin compositions of Examples 3 to 12, Example 15 and Example 16, and Comparative Examples 1 to 5 and Comparative Example 8 were used, and the total irradiation amount was 1,500 J/m ² . Except for this, a pattern film containing QD was formed by the same method.

[Shrinkage Resistance] The QD-containing pattern film formed by the same method as the patterning evaluation was further irradiated with ultraviolet rays having a cumulative irradiation amount of 10,000 J/m ² using a high-pressure mercury lamp, using a stylus type. A film thickness measuring machine ("Alpha-Step IQ" of KLA-Tencor Co., Ltd.) measures the average thickness of the QD-containing pattern film before and after the ultraviolet irradiation. Then, the residual film ratio was calculated by the following formula, and the case where the residual film ratio was 99% or more was judged as A (good shrinkage resistance), and when it was less than 99%, it was judged as B (poor shrinkage resistance) . Residual film rate (%) = (average thickness after treatment / average thickness before treatment) × 100

[Light resistance] Further, an ultraviolet irradiation device ("UVX-02516S1JS01" of Ushio Co., Ltd.) was used at 130 mW for the QD-containing pattern film formed by the same method as the patterning evaluation. The illuminance is irradiated with ultraviolet rays of 800,000 J/m ² , and the thixo-type film thickness measuring machine (KLA-Tencor's "Alpha-Step IQ") is used to contain the ultraviolet rays before and after the irradiation. The average thickness of the QD pattern film was measured. Then, the film thinning amount is calculated by the following formula, and it is judged that A (light resistance is good) when the film thinning amount is 2% or less, and B (light resistance poorness) when it exceeds 2%. . Film thinning amount (%) = {(average thickness before treatment - average thickness after treatment) / average thickness before treatment} × 100

[Fluorescence quantum yield] With respect to the fluorescence quantum yield, an absolute PL fluorescence quantum yield measuring device (Hamamatsu) was used for the QD-containing pattern film formed by the same method as the patterning evaluation. Photonics) "C11347-01") was measured at 25 °C. The wavelength of the excitation light is set to 450 nm. Further, the QD-containing pattern film formed by the same method as the patterning evaluation was subjected to a heat treatment (post-baking) at 180 ° C for 20 minutes by using a clean oven, thereby forming a cured film. The fluorescence quantum yield was determined by the same method as described. Table 1 shows the fluorescence quantum yield of the former as "untreated" and the latter fluorescence quantum yield as "after heat treatment".

[Change rate of fluorescence quantum yield] The rate of change of the fluorescence quantum yield is such that the untreated fluorescence quantum yield is Φ ₁ and the heat-treated fluorescence quantum yield is set to Φ ₂ by Calculated by the formula. The smaller the rate of change of the fluorescence quantum yield, the more the decrease in the fluorescence quantum yield of the [B]QD after heat treatment (after post-baking) can be evaluated. Rate of change of fluorescence quantum yield (%) = {(Φ _{1 -} Φ ₂ ) / Φ ₁ } × 100

[Evaluation of Wavelength Conversion] Regarding the wavelength conversion evaluation, the absolute PL fluorescence quantum is used for the QD-containing pattern film after the heat treatment (after post-baking) formed by the same method as the patterning evaluation. The rate measuring device ("C11347-01" of Hamamatsu Photonics Co., Ltd.) was measured at 25 °C. Specifically, the evaluation was performed by reading the value of the maximum wavelength of fluorescence measured simultaneously with the quantum yield. The wavelength of the excitation light is set to 450 nm. The maximum wavelength (nm) of the fluorescence was evaluated as a wavelength conversion (nm). The wavelength conversion evaluation shows that the closer to 630 nm, the better the conversion to the desired wavelength after the heat treatment is performed.

[Fluorescence half value width] Regarding the half value of the fluorescence, the QD-containing pattern film after the heat treatment (post-baking) formed by the same method as the patterning evaluation is used. The PL fluorescence quantum yield measuring device ("C11347-01" of Hamamatsu Photonics Co., Ltd.) was measured at 25 °C. Specifically, the evaluation was performed by reading the value of the half value of the fluorescence measured simultaneously with the quantum yield. The wavelength of the excitation light is set to 450 nm. The fluorescence half-value width (nm) shows that the smaller the value, the better the wavelength can be converted into the fluorescence with high color purity after the heat treatment.

[Table 1]

As shown by the results of Table 1, each of Examples 1 to 18 using the resin composition containing the [C] compound was excellent in patterning property, shrinkage resistance, and light resistance, and Comparative Examples 1 to 8 In contrast, the rate of change in fluorescence quantum yield, wavelength conversion evaluation, and fluorescence half-value width are smaller. Further, in Examples 1 to 18, Examples 1 to 8, Examples 13 and 15 to which the compound having a phenylphosphine structure or a compound having a cycloalkylphosphine structure was used as the [C] compound were used. In Example 18, the rate of change in fluorescence quantum yield and the half value width of the fluorescence were smaller as compared with the other examples. Further, 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 the [C] compound were used. The rate of change and the half value of the fluorescence are particularly small.

[Examples 19 to 22 and Comparative Example 9] Each of the resin compositions was prepared in the same manner as in Example 1 except that the types and the amounts of the respective components were adjusted as described in the following Table 2. Furthermore, the "-" in Table 2 indicates that the corresponding component is not used.

The obtained resin compositions of Examples 19 to 22 and Comparative Example 9 were evaluated in accordance with the methods described below. The evaluation results are shown in Table 2. (Methods for Forming QD-Containing Films of Examples 19 to 22 and Comparative Example 9) After applying the resin compositions of Examples 19 to 22 and Comparative Example 9 to an alkali-free glass substrate by a spinner It was 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 subjected to heat treatment (baking) on a hot plate at 200 ° C for 30 minutes, thereby forming a film containing QD having an average thickness of 5 μm.

The film containing QD was used in the same manner as in Examples 1 to 18 and Comparative Examples 1 to 8 except that the film containing QD was used instead of the pattern film containing QD, and the shrinkage resistance, light resistance, fluorescence quantum yield, and The rate of change of the fluorescence quantum yield, the wavelength conversion evaluation, and the fluorescence half-value width were evaluated.

[Table 2]

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

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

11‧‧‧wavelength conversion substrate
12‧‧‧1st substrate
13‧‧‧wavelength conversion layer
13a‧‧‧1st wavelength conversion layer
13b‧‧‧2nd wavelength conversion layer
13c‧‧‧3rd wavelength conversion layer
14‧‧‧Black matrix
15‧‧‧ adhesive layer
16‧‧‧2nd substrate
17‧‧‧Light source
17a‧‧‧1st light source
17b‧‧‧2nd light source
17c‧‧‧3rd light source
18‧‧‧Light source substrate
100‧‧‧Lighting display elements

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

11‧‧‧wavelength conversion substrate

12‧‧‧1st substrate

13‧‧‧wavelength conversion layer

13a‧‧‧1st wavelength conversion layer

13b‧‧‧2nd wavelength conversion layer

13c‧‧‧3rd wavelength conversion layer

14‧‧‧Black matrix

15‧‧‧ adhesive layer

16‧‧‧2nd substrate

17‧‧‧Light source

17a‧‧‧1st light source

17b‧‧‧2nd light source

17c‧‧‧3rd light source

18‧‧‧Light source substrate

100‧‧‧Lighting display elements

Claims (15)

A resin composition comprising: a binder resin; a semiconductor quantum dot; 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 thiodipropionic acid At least one compound of the group consisting of a compound of a dialkyl ester structure and a compound having a benzothiazole structure. The resin composition as described in claim 1 further contains a radical scavenger. The resin composition as described in claim 1 or 2 further contains a polymerizable compound. The resin composition according to the first, second or third aspect of the invention, wherein the binder resin has an alicyclic structure in a side chain. The resin composition according to any one of claims 1 to 4, wherein the binder resin is an alkali-soluble resin. The resin composition according to claim 5, wherein the alkali-soluble resin has a carboxyl group in a side chain. The resin composition according to any one of claims 1 to 6, wherein the semiconductor quantum dot contains an element selected from the group consisting of a group 2 element, a group 11 element, a group 12 element, a group 13 element, and a group 14 element. At least two of the group consisting of a group 15 element and a group 16 element. The resin composition according to claim 7, wherein the semiconductor quantum dot contains In. The resin composition according to claim 8, wherein the semiconductor quantum dot has a core-shell structure containing In as a constituent element of a core. The resin composition according to any one of claims 1 to 6, wherein the semiconductor quantum dot contains Si. The resin composition according to any one of claims 1 to 10, further comprising a radiation sensitive compound. A film formed by the resin composition according to any one of claims 1 to 11. A wavelength conversion member comprising a film formed by the resin composition according to any one of claims 1 to 11. A method of forming a film, comprising: a step of forming a coating film on one surface side of a substrate, and a step of heating the coating film, and by any one of items 1 to 11 of the patent application scope The resin composition described to form the coating film. A method for forming a film, comprising: a step of forming a coating film on one surface side of a substrate, a step of irradiating at least a part of the coating film with radiation, a step of developing the coating film after radiation irradiation, and a developing method The subsequent coating film is subjected to a heating step, and the coating film is formed by the resin composition as described in claim 11.