WO2017018392A1 - 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. Preferably, the wavelength conversion member-forming composition further contains a radical scavenger. Preferably, the wavelength conversion member-forming composition further contains a polymerizable compound. Preferably, the binder resin has an alicyclic structure in a side chain.

Description

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

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

In recent years, semiconductor quantum dots (hereinafter also referred to as “QD”) obtained by forming a semiconductor such as cadmium sulfide (CdS) or cadmium telluride (CdTe) in a nanometer size have attracted attention. Since such QD exhibits a broad optical absorption and a special optical characteristic of emitting fluorescence with a narrow spectral width, various applications are currently being studied. For example, the above-mentioned QD has been used for a display using an organic electroluminescence (EL) element or the like (see Japanese Patent Laid-Open No. 2014-174406).

Specifically, a blue light emitting organic EL element, a semiconductor quantum dot (hereinafter also referred to as “G-QD”) that emits green fluorescence when excited by light from the blue light emitting organic EL element, and a blue light emitting organic EL element A display combined with a semiconductor quantum dot (hereinafter also referred to as “R-QD”) that is excited by light from and emits red fluorescence attracts attention. For example, a display in which a film containing G-QD (hereinafter also referred to as “G-QD layer”) and a film containing R-QD (hereinafter also referred to as “R-QD layer”) are formed on a substrate constituting the light emitting unit. Then, 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. In such a display, various combinations of 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 are used. Reproduce the light of a simple hue.

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

Further, the film containing QD can be applied to a wavelength conversion film used as, for example, a solar cell sealing sheet, an agricultural film, a lighting part, etc., in addition to the above-described display use. Such a film can be obtained by, for example, applying a resin composition containing QD on a substrate and then heat-treating the obtained coating film.

However, QD generates free radicals due to the influence of oxygen or the like in the heating atmosphere during the heat treatment of the patterned coating film (hereinafter also referred to as “post-bake”). The structure may change and the QD fluorescence quantum yield may decrease. In such a display including QD, the intensity of green fluorescence from G-QD and the intensity of red fluorescence from R-QD are reduced with respect to the intensity of blue light from the blue light emitting organic EL element. This may reduce the color reproducibility of the display. QD also decreases the fluorescence quantum yield when heat treatment is applied to the coating film applied on the substrate or when heat is applied in the process of manufacturing an electronic device using the obtained film. And wavelength conversion efficiency, such as the above-mentioned sheet | seat for solar cell sealing, may fall.

JP 2014-174406 A

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

The invention made to solve the above problems has a binder resin (hereinafter also referred to as “[A] binder resin”), a semiconductor quantum dot (hereinafter also referred to as “[B] QD”), and a phenylphosphine structure. At least one compound selected from the group consisting of a compound, 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 (hereinafter referred to as “[C ] Is also referred to as a “compound”.

Moreover, this invention includes a wavelength conversion member provided with the film | membrane obtained with the above-mentioned resin composition, and the film | membrane formed with the above-mentioned resin composition.

Furthermore, this invention includes the 1st formation method of the film | membrane provided with the process of forming a coating film in the one surface side of a board | substrate with the above-mentioned resin composition, and the process of heating the said coating film.

Furthermore, this invention develops the said coating film after the process of forming a coating film in the one surface side of a board | substrate with the above-mentioned resin composition, the process of irradiating at least one part of the said coating film, and radiation. A second forming method of the film comprising a step and a step of heating the coating film after development.

According to the present invention, a resin composition capable of suppressing a decrease in the fluorescence quantum yield of QD after heat treatment, a film obtained from the resin composition, a wavelength conversion member comprising a film obtained from the resin composition, and the A method for forming a film can be provided.

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

<Resin composition>
The resin composition contains [A] a binder resin, [B] QD, and [C] compound. [C] The 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 dialkylthiodipropionate structure, and a compound having a benzothiazole structure. It is considered that it is at least one and functions as an antioxidant as described later. Moreover, the said resin composition may contain antioxidant other than a [C] compound. Examples of the antioxidant other than the [C] compound include a peroxide decomposer that does not correspond to the [C] compound (hereinafter, also referred to as “[X] peroxide decomposer”), and a radical that does not correspond to the [C] compound. Examples include scavengers (hereinafter also referred to as “[D] radical scavengers”). Further, the resin composition contains a polymerizable compound (hereinafter also referred to as “[E] polymerizable compound”), a radiation sensitive compound (hereinafter also referred to as “[F] radiation sensitive compound”) and / or a solvent ( Hereinafter, it may contain “[G] solvent”). In addition, the said resin composition may contain 2 or more types of the said component, respectively.

The said resin composition can suppress the fall of the fluorescence quantum yield of [B] QD after heat processing by having the said structure. The reason why the resin composition has the above-described configuration provides the above-mentioned effect is not necessarily clear, but is presumed as follows, for example. That is, the [C] compound used in the resin composition is, for example, a peroxide decomposition function that prevents the chain initiation reaction by decomposing hydroperoxide (ROOH) produced during the oxidation reaction into a stable compound. Therefore, it is considered that the generation of free radicals that cause a decrease in the fluorescence quantum yield of [B] QD can be effectively suppressed. Therefore, during the heat treatment for forming a film (wavelength conversion layer) with the resin composition, the peroxide that is a free radical generation source is decomposed by the [C] compound. It is considered that the decrease in the fluorescence quantum yield of QD can be suppressed.

In addition, when QD is applied to a display using a blue light-emitting organic EL element, in the conventional resin composition, red color from R-QD with respect to the intensity of blue light due to free radicals during the heat treatment as described above. The intensity of fluorescence and the intensity of green fluorescence from G-QD may decrease, and color reproducibility may decrease. On the other hand, when the resin composition is used, the generation of free radicals is effectively suppressed during the heat treatment as described above, and thus [B] QD fluorescence such as R-QD and G-QD is used. It is considered that the decrease in quantum yield can be suppressed, and as a result, 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 any resin may be used as long as it can serve as a base material for the film.

[A] Use of a binder resin having an alicyclic structure in the side chain is preferable because deterioration of the fluorescence quantum yield of [B] QD over time can be suppressed. [A] The reason why the above effect is achieved by using a binder resin having an alicyclic structure in the side chain is not necessarily clear, but is presumed as follows, for example. That is, the hydrophobicity of the alicyclic structure can suppress the adhesion of moisture that may cause deterioration of the fluorescence quantum yield over time to the surface of [B] QD. It is thought that deterioration over time can be suppressed.

The [A] binder resin having an alicyclic structure in the side chain can be obtained, for example, by polymerizing using an unsaturated compound having an alicyclic structure as a monomer. The alicyclic structure includes a monocyclic cycloalkane structure such as a cyclopropane structure, a cyclobutane structure, a cyclopentane structure, a cyclohexane structure, a cyclooctane structure, and a cyclodecane structure; a monocycle such as a cyclopentene structure, a cyclohexene structure, and a cyclopentadiene structure And a polycyclic cycloalkene structure such as a norbornane structure, an adamantane structure, a tricyclodecane structure, and a tetracyclododecane structure; a polycyclic cycloalkene structure such as a norbornene structure and a tricyclodecene structure.

As the alicyclic structure, a cyclohexane structure, a cyclooctane structure, a cyclodecane structure and a tricyclodecane structure are preferable, and a cyclohexane structure and a tricyclodecane structure are more preferable. By using the specific structure as the alicyclic structure, it is possible to further suppress deterioration with time of the fluorescence quantum yield of [B] QD.

The [A] binder resin having an alicyclic structure in the side chain is, for example, selected from the group consisting of 3,4-epoxycyclohexyl methacrylate, cyclic alkyl esters of methacrylic acid, cyclic alkyl esters of acrylic acid, and N-cyclohexylmaleimide described later. [A] resin having a structural unit derived from at least one kind of compound, cyclic olefin polymer, and the like.

Moreover, when applying the said resin composition to the photosensitive resin composition which can be patterned with an alkali developing solution, [A '] alkali-soluble resin which is illustrated below may be used as a [A] binder resin. preferable.

[[A '] alkali-soluble resin]
[A ′] The alkali-soluble resin is a resin that is soluble in an alkaline solution. [A ′] As the alkali-soluble resin, a resin obtained by radical polymerization using an unsaturated compound containing a carboxy group as a monomer (hereinafter also referred to as “[a] resin”), polyimide, polysiloxane, novolak resin , Alkali-soluble polyolefins, resins having a cardo skeleton, and combinations thereof are preferred. Hereinafter, each of [a] resin, polyimide, polysiloxane, 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 carboxy group. Moreover, you may have a structural unit containing a polymeric group for a sensitivity improvement. The structural unit containing a polymerizable group is preferably a structural unit containing an epoxy group, a structural unit containing a (meth) acryloyl group, or a structural unit containing a vinyl group. [A] When the resin has a structural unit containing the specific polymerizable group, a resin composition having excellent surface curability and deep part curability can be obtained when a cured film is formed.

The structural unit containing the carboxy group is, for example, an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, a carboxylic acid unsaturated compound such as a mono [(meth) acryloyloxyalkyl] ester of a polyvalent carboxylic acid, as a monomer, It can be formed by radical polymerization with other monomers as appropriate.

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

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

Examples of the mono [(meth) acryloyloxyalkyl] ester of the polyvalent carboxylic acid include mono [2- (meth) acryloyloxyethyl] succinate, mono [2- (meth) acryloyloxyethyl] phthalate and the like. It is done.

Of these carboxylic acid unsaturated compounds, acrylic acid, methacrylic acid and succinic acid mono [2- (meth) acryloyloxyethyl] are preferable from the viewpoint of polymerizability.

These carboxylic unsaturated compounds may be used alone or in combination of two or more.

[A] As a minimum of the content rate of the structural unit containing the carboxyl group in resin, 1 mol% is preferable with respect to all the structural units which comprise [a] resin, 5 mol% is more preferable, 10 mol% Is more preferable. Moreover, as an upper limit of the content rate of the said structural unit, 80 mol% is preferable, 70 mol% is more preferable, and 60 mol% is further more preferable. When the content ratio of the structural unit containing a carboxy group is within the above range, the solubility in an alkali developer can be further improved.

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

Examples of the unsaturated compound having an oxiranyl group include glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl methacrylate, 3,4-epoxycyclohexyl methacrylate, o-vinylbenzyl glycidyl ether, and the like. Is mentioned.

Examples of the unsaturated compound having an oxetanyl group include 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -2-methyloxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- ( Methacryloyloxymethyl) -2-phenyloxetane, 3- (2-methacryloyloxyethyl) oxetane, 3- (2-methacryloyloxyethyl) -2-ethyloxetane, 3- (2-methacryloyloxyethyl) -3-ethyloxetane And methacrylic acid esters.

Of these epoxy group-containing unsaturated compounds, glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate and 3- (methacryloyloxymethyl) -3-ethyloxetane are preferable from the viewpoint of polymerizability.

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

[A] When the resin has a structural unit containing an epoxy group, the lower limit of the content ratio of the structural unit is preferably 1 mol% with respect to all structural units constituting the resin [a], and 5 mol%. More preferred is 10 mol%. Moreover, as an upper limit of the said content rate, 80 mol% is preferable, 70 mol% is more preferable, and 60 mol% is further more preferable. When the content ratio of the structural unit containing an epoxy group is in the above range, a film having higher hardness and excellent solvent resistance can be formed.

The structural unit containing the (meth) acryloyl group is, for example, a method of reacting a polymer having an epoxy group with (meth) acrylic acid, a polymer having a carboxy group and a (meth) acrylic acid ester having an epoxy group. It can be formed by a method, a method of reacting a polymer having a hydroxyl group with a (meth) acrylic acid ester having an isocyanate group, a method of reacting a polymer having an acid anhydride group and (meth) acrylic acid, or the like.

Examples of the monomer that gives other structural units include (meth) acrylic acid chain alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated dicarboxylic acid diester, maleimide compound, unsaturated Aromatic compounds, conjugated dienes, unsaturated compounds having a tetrahydrofuran skeleton, hydroxyl group-containing unsaturated compounds, other unsaturated compounds, and the like can be mentioned.

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

Examples of the (meth) acrylic acid cyclic alkyl ester include cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclodecanyl methacrylate, isobornyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, and tricycloacrylate. [5.2.1.0 ^2,6 ] decan-8-yl, isobornyl acrylate, and the like.

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

Examples of the maleimide compound include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, 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.

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

Examples of the other unsaturated compounds include acrylonitrile.

Among the monomers giving the other structural units, from the viewpoint of polymerizability, styrene, methyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, t-butyl methacrylate, n-lauryl methacrylate, benzyl methacrylate, methacryl Preference is given to tricyclodecanyl acid, p-methoxystyrene, 2-methylcyclohexyl acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, tetrahydrofurfuryl methacrylate and 2-hydroxyethyl methacrylate.

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

[A] When the resin has other structural units, the lower limit of the content ratio of the structural units is preferably 1 mol%, more preferably 5 mol% with respect to all structural units constituting the resin [a]. 10 mol% is more preferable. Moreover, as an upper limit of the said content rate, 80 mol% is preferable and 70 mol% is more preferable. When the said content rate is in the said range, the molecular weight etc. of [a] resin can be adjusted, for example, without preventing the effect mentioned above.

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

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

In addition, Mw and Mn in this specification are values measured by gel permeation chromatography (GPC).

([A] Resin synthesis method)
[A] The method for synthesizing the resin is not particularly limited, and a known method can be adopted. For example, it can be synthesized by polymerizing the above-described monomers in a solvent in the presence of a polymerization initiator.

[Polyimide]
The polyimide used in the resin composition is not particularly limited as long as it is a polymer compound containing an imide bond in the repeating unit, but from the viewpoint of alkali solubility, a carboxy group, a phenolic hydroxyl group, a sulfo group, a thiol group in the structural unit. Or a polyimide containing a combination thereof. The polyimide can be provided with alkali developability (alkali solubility) by including these alkali-soluble groups in the structural unit, and as a result, the occurrence of scum in the exposed portion can be suppressed during alkali development. The polyimide can be synthesized by a method described in, for example, JP-A-2006-199945, JP-A-2008-163107, JP-A-2011-42701, and the like.

[Polysiloxane]
The polysiloxane used in the resin composition is not particularly limited, and examples thereof include those described in International Publication WO2009 / 028360, International Publication WO2011 / 155382, and JP2010-152302A.

[Novolac resin]
The novolak resin used in the resin composition is not particularly limited, and examples thereof include a resin having a phenol novolac structure and a resin having a resole novolak structure. The novolac resin is obtained by reacting a phenol compound and an aldehyde compound. Specific examples of the novolak resin include those described in, for example, JP-A Nos. 2003-114531, 2012-137741, and 2013-127518.

[Alkali-soluble polyolefin]
The alkali-soluble polyolefin used in the resin composition is not particularly limited, but a cyclic olefin polymer having a protic polar group is preferable from the viewpoint of alkali solubility. 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. As the protic polar group, 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 are preferable, A group in which a hydrogen atom is directly bonded to an oxygen atom is more preferable. Specific examples of the alkali-soluble polyolefin include those described in JP2012-211988A.

[Resin having cardo skeleton]
The resin having a cardo skeleton used in the resin composition is not particularly limited. Here, the cardo skeleton refers to a skeleton structure in which another two cyclic structures are bonded to a ring carbon atom constituting the cyclic structure. For example, two aromatic rings (for example, a nine-position carbon atom of a fluorene ring) And a structure in which a benzene ring is bonded. Specific examples of the resin having a cardo skeleton include those described in Japanese Patent No. 5181725, Japanese Patent No. 5327345, and the like.

[[A '] Binder resin other than alkali-soluble resin]
When the resin composition is not applied to a photosensitive resin composition that can be patterned with an alkali developer, an alkali-insoluble [A] binder resin can be used. Examples of the alkali-insoluble [A] binder resin include alkali-insoluble polyolefin.

[Alkali insoluble polyolefin]
The alkali-insoluble polyolefin used in the resin composition is not particularly limited, but the polyolefin having no protic polar group is preferable. Specific examples of the alkali-insoluble polyolefin include, for example, a polymer using an alkene having 1 to 10 carbon atoms as a monomer, and a polymer using a substituted or unsubstituted cycloalkene having 3 to 20 carbon atoms as a monomer (cyclic olefin weight). For example). Examples of the alkene include ethylene, propylene, and butene. Examples of the cycloalkene include monocyclic cycloalkenes such as cyclopentene and cyclohexene, and polycyclic cycloalkenes such as norbornane, tricyclodecene, and tetracyclododecene. Examples of the substituent of the cycloalkene include, for example, an alkyl group having 1 to 5 carbon atoms, a group in which this alkyl group is combined with at least one selected from the group consisting of —CO— and —O—, and the like. A methyl group and a methoxycarbonyl group are preferred. The alkali-insoluble polyolefin is preferably a cyclic olefin polymer, more preferably a polymer having a substituted or unsubstituted cycloalkene as a monomer, and a polymer having norbornane and a substituted or unsubstituted tetracyclododecene as a monomer. Further preferred. Specific examples of the alkali-insoluble polyolefin include, for example, those described in JP-A-2015-127733.

The lower limit of the content of [A] binder resin in the resin composition is preferably 1% by mass, and more preferably 5% by mass. Moreover, as an upper limit of the said content, 50 mass% is preferable and 40 mass% is more preferable. [A] By setting the content of the binder resin to the above lower limit or more, it is possible to form a film having higher hardness and higher solvent resistance while improving sensitivity. On the other hand, storage stability can be improved more by making the said content below into the said upper limit.

[[B] QD]
[B] The QD is not particularly limited, but a semiconductor quantum dot made of a safe material composed of, for example, In (indium) or Si (silicon) without using Cd or Pb as a constituent element is preferable.

[B] QD is a group consisting of a group 2 element, a group 11 element, a group 12 element, a group 13 element, a group 14 element, a group 15 element and a group 16 element from the viewpoint of improving fluorescence characteristics such as a fluorescence quantum yield. Those containing at least two kinds of elements selected from are preferred.

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

The containing In [B] QD, semiconductor quantum dots having a core-shell structure type to be described later, the semiconductor quantum dots of AgInS _2, and semiconductor quantum dots of Zn-doped AgInS ₂ is preferred.

[B] QD is also preferably a Si-based semiconductor quantum dot such as a semiconductor quantum dot made of Si or a semiconductor quantum dot made of a compound of Si and another element.

[B] A compound (A) having a fluorescence maximum in a wavelength range of green light of 500 nm to 600 nm and / or a compound (B) having a fluorescence maximum in a wavelength range of red light of 600 nm to 700 nm. It is preferable to contain. [B] As a resin composition for forming a wavelength conversion layer of a light-emitting display element that displays an image using visible light, when QD includes the compound (A) and / or the compound (B) having the above-described fluorescence characteristics The resin composition can be applied.

[B] QD may be a homogeneous structure type composed of one kind of compound or a core-shell structure type composed of two or more kinds of compounds.

[B] QD of the core-shell structure type is formed by forming a core structure with one type of compound and coating the core structure with another type of compound. For example, by covering the core semiconductor with a semiconductor having a larger band gap, excitons (electron-hole pairs) generated by photoexcitation are confined in the core. As a result, the probability of non-radiative transition on the [B] QD surface is reduced, and the fluorescence quantum yield is improved.

The core-shell structure type [B] QD is preferably one containing In as a core constituent element from the viewpoint of improving fluorescence characteristics. InP / ZnS, InP / ZnSe, InP / ZnSe / ZnS, InP / ZnSSe, (InP / ZnSSe) solid solution / ZnS, CuInS ₂ / ZnS, and (ZnS / AgInS ₂ ) solid solution / ZnS are preferred. The InP / ZnS is a semiconductor quantum dot having InP as a core and ZnS as a shell. The same applies to other core-shell structure type semiconductor quantum dots.

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

Here, the average particle diameter of [B] QD is determined by observing with a transmission electron microscope after drying the sample, and averaging the longest width of each of the arbitrary 10 [B] QDs included in the field of view. Is required.

In addition, the wavelength region of the fluorescence of [B] QD can be controlled by appropriately selecting the constituent material and average particle diameter of [B] QD.

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

[B] As a method of obtaining QD, for example, a known method of thermally decomposing an organometallic compound in a coordinating organic solvent can be used. The core-shell structure type [B] QD, for example, forms a homogeneous core structure by reaction, and then adds a precursor for forming a shell on the core surface in the reaction system to form a shell on the core surface. The reaction is then stopped and separated from the solvent. [B] As a method of controlling the average particle diameter of QD, for example, a method of adjusting the reaction temperature, reaction time and the like can be mentioned. A commercially available product can also be used.

InP / ZnS, which is a core-shell structure semiconductor quantum dot, can also be synthesized by referring to a method described in, for example, a technical document “Journal of American Chemical Society. 2007, 129, 15432-15433”. Further, CuInS ₂ / ZnS, which is a core-shell structure type semiconductor quantum dot, can be obtained by a method described in, for example, a technical document “Journal of American Chemical Society. 2009, 131, 5691-5697” or a technical document “Chemistry of Materials 9. , 21, 2422-2429 ”can also be synthesized.

Further, the Si-based semiconductor quantum dots can be synthesized with reference to a method described in the technical document “Journal of American Chemical Society. 2010, 132, 248-253”, for example.

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 with respect to 100 parts by mass of [A] binder resin. Moreover, as an upper limit of the said content, 150 mass parts is preferable with respect to 100 mass parts of [A] binder resin, and 100 mass parts is more preferable. [B] By setting the QD content in the above range, a film (wavelength conversion layer) having excellent fluorescence characteristics can be formed.

[[C] Compound]
[C] The 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 dialkylthiodipropionate structure, and a compound having a benzothiazole structure. At least one compound. The compound [C] has an excellent peroxide decomposition function that prevents the chain initiation reaction by, for example, decomposing hydroperoxide (ROOH) produced during the oxidation reaction into a stable compound. It is considered that the generation of free radicals that cause a decrease in the fluorescence quantum yield of QD can be effectively suppressed. Therefore, it is thought that the said resin composition can suppress the fall of the fluorescence quantum yield of QD after heat processing by containing a [C] compound.

(Compound having a phenylphosphine structure)
The compound having a phenylphosphine structure is a compound represented by the general formula: P- (R ² ) ₃ . Here, R ² is a hydrogen atom or a monovalent organic group. Three R ² may be the same or different. However, 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. As the compound having a phenylphosphine structure, a compound having a triphenylphosphine structure in which all three R ² in the above general formula is a substituted or unsubstituted phenyl group is preferable.

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

Examples of the compound having a phenylphosphine structure include tri-o-tolylphosphine and tri-m-tolyl from the viewpoint of more effectively suppressing the generation of free radicals that cause a decrease in the fluorescence quantum yield of [B] QD. Preferred are phosphine, tri-p-tolylphosphine, tri-2,5-xylylphosphine, diphenyl (p-vinylphenyl) phosphine, triphenylphosphine and tris (2,4,6-trimethylphenyl) phosphine. -Tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine and tris (2,4,6-trimethylphenyl) phosphine are more preferred.

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

The compound having a cycloalkylphosphine structure is preferably tricyclohexylphosphine.

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

As the compound having a thiobisphenol structure, 4,4-thiobis (3-methyl-6-t-butylphenol) is preferable.

(Compound having a dialkylthiodipropionate structure)
The compound having a dialkylthiodipropionate structure is a compound represented by the general formula: S— (CH ₂ —CH ₂ —COO—R ⁵ ) ₂ . Here, R ⁵ is an alkyl group. Two R ⁵ may be the same or different. The alkyl group is preferably a linear alkyl group having 10 to 20 carbon atoms.

Examples of the compound having a dialkylthiodipropionate structure include dilauryl thiodipropionate, ditridecyl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate.

As the compound having a dialkylthiodipropionate structure, dilaurylthiodipropionate and distearyl are used from the viewpoint of more effectively suppressing the generation of free radicals that cause a decrease in the fluorescence quantum yield of [B] QD. Thiodipropionate is preferred.

(Compound having benzothiazole structure)
The compound having a benzothiazole structure is a substituted or unsubstituted benzothiazole. Examples of the substituent of benzothiazole include an alkyl group having 1 to 10 carbon atoms, a hydroxy group, a thioether group, and the like, and among these, a thioether group is preferable.

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

As the [C] compound, a compound having a phenylphosphine structure and a compound having a cycloalkylphosphine structure are preferable, and a compound having a phenylphosphine structure is more preferable.

As a minimum of content of the [C] compound in the said resin composition, 0.1 mass part is preferable with respect to 100 mass parts of [A] binder resin, 1 mass part is more preferable, and 2 mass parts is further more preferable. . The upper limit of the content is preferably 15 parts by mass, more preferably 10 parts by mass, and still more preferably 8 parts by mass with respect to 100 parts by mass of [A] binder resin. By setting the content within the above range, it is possible to more effectively suppress the generation of free radicals that cause a decrease in the fluorescence quantum yield of [B] QD. Moreover, when the said resin composition has sclerosis | hardenability, it can suppress inhibiting the hardening reaction of the said resin composition.

[[X] peroxide decomposer]
[X] A peroxide decomposer is an antioxidant that does not fall under the [C] compound and has a peroxide decomposition function. [X] A peroxide decomposer is an antioxidant that does not fall under the [C] compound and has a peroxide decomposition function. [X] Examples of the peroxide decomposer include phosphorus compounds, sulfur compounds, compounds containing phosphorus atoms and sulfur atoms, and the like. Specifically, compounds having a phosphite structure, compounds having a thioether structure ( However, a compound having a thiobisphenol structure and a compound having a dialkylthiodipropionate structure are excluded), a compound having a benzotriazole structure, a compound having a thiophosphite structure, and the like.

(Compound having phosphite structure)
Examples of the compound having a phosphite structure include tris (nonylphenyl) phosphite, tris (pt-octylphenyl) phosphite, tris [2,4,6-tris (α-phenylethyl)] phosphite, Tris (p-2-butenylphenyl) phosphite, bis (p-nonylphenyl) cyclohexyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, 3,9-bis (octadecyloxy)- 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, triphenyl phosphite, 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2 4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane and the like.

Examples of commercially available compounds having a phosphite structure include, for example, JP-A No. 2003-26715, JP-A No. 2009-97010, JP-A No. 2012-211975, JP-A No. 2014-126811, and JP-A No. 2014-134763. And the like, and the like.

(Compound having thioether structure)
Examples of the compound having a thioether structure include pentaerythritol tetrakis (3-lauryl thiopropionate), pentaerythritol tetrakis (3-octadecyl thiopropionate), pentaerythritol tetrakis (3-myristyl thiopropionate), pentaerythritol. And tetrakis (3-stearyl thiopropionate).

Examples of commercially available compounds having a thioether structure include compounds described in JP2014-44828A, JP2014-134763A, and the like.

(Compound having benzotriazole structure)
Examples of the compound having a benzotriazole structure include 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- [2′-hydroxy-5 ′-(meth) acryloyloxymethylphenyl] -2H-benzotriazole 2- [2′-hydroxy-3′-tert-butyl-5 ′-(meth) acryloyloxyethylphenyl] -2H-benzotriazole, and the like.

Examples of commercially available compounds having a benzotriazole structure include compounds described in JP2003-26715A, JP2009-97010A, JP2012-211975A, and the like.

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

[[D] radical scavenger]
The resin composition may further contain a [D] radical scavenger. [D] The radical scavenger is an antioxidant that does not correspond to the [C] compound, and acts to prevent oxidation by trapping highly active chain propagators (ROO. And R.) and stopping the chain reaction. To do. Free radicals are generated in the film during heat treatment when forming a film (wavelength conversion layer) with the resin composition, or when excessive heat is applied to the film in the manufacturing process of the electronic device. There is. In this way, when free radicals are generated in the film, these free radicals are chemically unstable, so that they can easily react with other compounds to create new free radicals and further degrade QD in a chained manner. , Causing a decrease in membrane function. When the resin composition contains a [D] radical scavenger, the free radicals are captured by the [D] radical scavenger even when the above-mentioned free radicals are generated, and thus [B] QD fluorescence after heat treatment The decrease in quantum yield can be further suppressed. [D] The radical scavenger includes those having a function of decomposing peroxide. Moreover, in this specification, what has a function which decomposes | disassembles a peroxide, and has a function which capture | acquires a free radical is made into a [D] radical scavenger.

[D] The radical scavenger is not particularly limited as long as it can scavenge free radicals and deactivate radicals. For example, phenols and aromatic amines can be used, and a hindered phenol structure can be used. And compounds having a hindered amine structure are preferred. [D] By using the specific compound as a radical scavenger, free radicals can be trapped more reliably.

[Compound having a hindered phenol structure]
Examples of the hindered phenol structure include a structure having a hydroxyphenyl group substituted with 2 or more monovalent organic groups having 3 to 10 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′-thiodiethylenebis [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-methylfienyl) propionyloxy] ethyl] 2,4,8,10-te Raokisasupiro [5,5] - polymer and the like of undecane and their compounds.

Examples of commercially available compounds having a hindered phenol structure include compounds described in JP 2011-227106 A, JP 2013-164471 A, and the like.

[Compound having a hindered amine structure]
Examples of the compound having a hindered amine structure include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis ( 1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (N-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-benzyloxy-2, 2,6,6-tetramethyl-4-piperidyl) sebacate, N, N ′, N ″, N ″ ′-tetrakis- [4,6-bis- [butyl- (N-methyl-2,2, 6,6-tetramethylpiperidin-4-yl) amino] -triazin-2-yl] -4,7-diazadecane-1,10-diamine and other low molecular compounds, and the piperidine ring is bonded via a triazine skeleton. Bound polymer and piperidine ring polymer in which a plurality of linked via an ester bond.

Examples of commercially available compounds having a hindered amine structure include compounds described in JP2011-112823A, JP2014-134763A, and the like.

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

When the resin composition contains a [D] radical scavenger, the lower limit of the content of the [D] radical scavenger is preferably 0.1 parts by mass with respect to 100 parts by mass of the [A] binder resin, 1 part by mass is more preferable, and 2 parts by mass is more preferable. As an upper limit of said content, 10 mass parts is preferable with respect to 100 mass parts of [A] binder resin, and 5 mass parts is more preferable. By setting the content within the above range, free radicals can be captured more reliably. Moreover, when the said resin composition has sclerosis | hardenability, it can suppress inhibiting the hardening reaction of the said resin composition.

[[E] polymerizable compound]
The resin composition may further contain [E] a polymerizable compound. When the resin composition contains [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 that is polymerized by irradiation or heating, but a compound having a (meth) acryloyl group, an epoxy group, a vinyl group, or a combination thereof is preferable from the viewpoint of improving sensitivity. A compound having two or more (meth) acryloyl groups in the molecule is more preferable.

Examples of the [E] polymerizable compound having two or more (meth) acryloyl groups in the molecule include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, Tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, neopentyl Glycol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate 1,6-hexanediol diacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetra Acrylate, ditrimethylolpropane tetraacrylate pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol heptaacrylate, tripentaerythritol octaacrylate, tetrapentaerythritol nonaacrylate, tetrapentaerythritol decaacrylate, pentapenta Erisritorun Acrylate, pentapentaerythritol dodecaacrylate, tripentaerythritol hepta methacrylate, tripentaerythritol octamethacrylate, tetrapentaerythritol nonamethacrylate, tetrapentaerythritol decamethacrylate, pentapentaerythritol undecamethacrylate, pentapentaerythritol dodecamethacrylate, dimethylol-tricyclo Decane diacrylate, ethoxylated bisphenol A diacrylate, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, 9,9-bis [4- (2-methacryloyloxyethoxy) phenyl] fluorene, 9 , 9-bis [4- (2-methacryloyloxyethoxy) -3-methylphenyl] fluore (2-acryloyloxypropoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2-acryloyloxyethoxy) -3,5-dimethylphenyl] fluorene, 9,9-bis [4- (2-methacryloyloxyethoxy) -3,5-dimethylphenyl] fluorene and the like.

Among these, from the viewpoint of improving sensitivity, a polymerizable compound having three or more (meth) acryloyl groups is preferable, and a polymerizable compound having four or more (meth) acryloyl groups is more preferable, pentaerythritol tetraacrylate, ditrimethylol. More preferred are propanetetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol heptaacrylate and tripentaerythritol octaacrylate.

When the said resin composition contains a [E] polymeric compound, as a minimum of content of [E] polymeric compound with respect to 100 mass parts of [A] binder resin, 1 mass part is preferable and 10 mass parts is more. 20 parts by mass is preferable. Moreover, as an upper limit of the said content, 200 mass parts is preferable, 150 mass parts is more preferable, and 120 mass parts is further more preferable. By setting the content within the above range, it is possible to form a film having higher hardness and higher solvent resistance while further improving storage stability and sensitivity.

[[F] radiation sensitive compound]
The resin composition may further contain a [F] radiation sensitive compound. In this case, radiation sensitivity can be imparted to the resin composition. [F] A radiation sensitive compound may be used independently and may be used in combination of 2 or more type.

[F] Examples of the radiation sensitive compound include a radiation sensitive radical polymerization initiator, a quinonediazide compound, and combinations thereof.

[Radiation sensitive radical polymerization initiator]
For example, when a radical polymerizable compound is used as the [E] polymerizable compound, the radiation sensitive radical polymerization initiator can further accelerate the curing reaction of the resin composition by radiation.

As the radiation-sensitive radical polymerization initiator, for example, active species capable of initiating a radical polymerization reaction of the [E] polymerizable compound are generated by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. And the like.

Specific examples of the radiation-sensitive radical polymerization initiator include, for example,
Ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl -6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), 1,2-octanedione-1- [4 -(Phenylthio) -2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- O- acetyloxime) and the like O- acyl oxime compound;
2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) Α-aminoketone compounds such as 2-butan-1-one and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one;
Α-hydroxy ketones such as 1-phenyl-2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone Compound;
And acylphosphine oxide compounds such as diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.

As the radiation-sensitive radical polymerization initiator, etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, from the viewpoint of further promoting the curing reaction by radiation, 1- (O-acetyloxime), 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)], 2-methyl-1- (4-methylthiophenyl) -2- Morpholinopropan-1-one, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide are preferred.

[Quinonediazide compound]
The quinonediazide compound is suitable for a radiation-sensitive compound when the resin composition is used as a positive radiation-sensitive composition. As the quinonediazide compound, a 1,2-quinonediazide compound that generates a carboxylic acid upon 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-naphthoquinonediazidesulfonic acid halide can be used.

Examples of the quinonediazide compound include:
1,2-naphthoquinone diazide sulfonic acid ester such as 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone azido-4-sulfonic acid ester;
4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-4-sulfonic acid ester, 4,4′- [1- [4- [1- [4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis (2,5-dimethyl-4- And 1,2-naphthoquinone diazide sulfonic acid esters of (polyhydroxyphenyl) alkanes such as hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinone diazide-5-sulfonic acid ester. Specific examples of the quinonediazide compound include those described in Japanese Patent No. 5454321, Japanese Patent No. 5630068, Japanese Patent No. 559604, and the like.

The quinonediazide compound is preferably 1,2-naphthoquinonediazidesulfonic acid ester of (polyhydroxyphenyl) alkane, from the viewpoint of increasing the radiation sensitivity of the resin composition, and 4,4 ′-[1- [4- [1 -[4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonic acid ester is more preferred.

When the said resin composition contains a [F] radiation sensitive compound, as a minimum of content of a [F] radiation sensitive compound, 1 mass part is preferable with respect to 100 mass parts of [A] binder resin, 10 Part by mass is more preferable. Moreover, as an upper limit of the said content, 150 mass parts is preferable with respect to 100 mass parts of [A] binder resin, and 100 mass parts is more preferable. The radiation sensitivity of the said resin composition can be raised more by making the said content into the said range.

[[G] solvent]
The resin composition may further contain a [G] solvent. When the said resin composition contains a [G] solvent, the applicability | paintability will improve. [G] The solvent is not particularly limited as long as the above-described components can be dissolved or dispersed, and examples thereof include a solvent used when synthesizing the resin such as the above-described [a] resin. In addition, a [G] solvent may be used independently and may be used in combination of 2 or more type.

[[H] Other ingredients]
In addition to the components described above, the resin composition may contain [H] other components such as a thermal polymerization initiator, a storage stabilizer, and an adhesion assistant as long as the effects of the present invention are not impaired. [H] Other components may be used alone or in combination of two or more. When the said resin composition contains [H] other components, as an upper limit of the content, 10 mass parts is preferable with respect to 100 mass parts of [A] binder resin, and 1 mass part is more preferable.

The resin composition can be prepared by an appropriate method. For example, in the [G] solvent, the [A] binder resin, the [B] QD, the [C] compound, and optional components as necessary. It can be prepared by mixing. As a minimum of the concentration of solid content in the composition at the time of mixing, 5 mass% is preferred and 10 mass% is more preferred. Moreover, as an upper limit of the said density | concentration, 80 mass% is preferable and 70 mass% is more preferable. By making the concentration of the solid content in the above range, the coating property can be improved. The “solid content” means a residue obtained by drying a sample on a hot plate at 175 ° C. for 1 hour to remove volatile substances.

<Membrane>
The film is obtained from the resin composition. Since the said film | membrane is obtained with the said resin composition, the fall of the fluorescence quantum yield of QD after heat processing is suppressed, For example, the film | membrane as a wavelength conversion layer which has high color reproducibility can be provided. The film may or may not be patterned. However, if the film is patterned, the film can be applied to a wavelength conversion layer useful as a subpixel. The film is usually subjected to heat treatment to remove volatile components and promote various chemical reactions so that the film can be suitably used as a wavelength conversion layer. The film may be a film using a crosslinked resin as a base material (hereinafter also referred to as “cured film”) or a film using a non-crosslinked resin as a base material. The cured film can be obtained, for example, by using the resin composition having curability. Examples of a method for imparting curability to the resin composition include [A] a method using a curable resin such as a thermosetting resin as a binder resin, and [E] a polymerizable compound or other crosslinking agent. The method etc. are mentioned.

<Wavelength conversion member>
The said film | membrane is suitable as a wavelength conversion layer with which wavelength conversion members, such as a light emitting display element and a wavelength conversion film, are equipped. 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 examples.

[Wavelength conversion film]
The wavelength conversion film which is one Embodiment of the said wavelength conversion member is suitable as a wavelength conversion member used for the sheet | seat for solar cell sealing, the film for agriculture, an illumination component, etc. The average thickness of the wavelength conversion layer in the wavelength conversion film may be, for example, 1 μm or more and 1,000 μm or less. In addition, the said wavelength conversion film may be a single layer film comprised only by the said film | membrane (wavelength conversion layer), and may be a multilayer film further provided with another layer.

(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 configured by providing a wavelength conversion layer 13 (13a, 13b, 13c) and a black matrix 14 on a first base material 12, and an adhesive layer 15 on the wavelength conversion substrate 11. And the light source substrate 18 bonded together.

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

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

The wavelength conversion substrate 11 converts the wavelength of the excitation light from the light source 17 of the light source substrate 18 by the QD contained in each of the wavelength conversion layers 13, and emits fluorescence having 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 configured to include different QDs, and can emit different fluorescence. For example, in the wavelength conversion substrate 11, 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 becomes the excitation light. Can be configured to convert blue light into blue light.

In that case, the QDs to be contained are selected so that each of the wavelength conversion layers 13a, 13b, and 13c has a desired fluorescence characteristic. Therefore, in the formation of the wavelength conversion layers 13a, 13b, and 13c of the wavelength conversion substrate 11, for example, three types of resin compositions containing QDs having different light emission characteristics are prepared.

The lower limit of the average thickness of the wavelength conversion layer 13 of the wavelength conversion substrate 11 is preferably 100 nm, and more preferably 1 μm. Moreover, as an upper limit of the said average thickness, 100 micrometers is preferable. If the average thickness is less than the lower limit, excitation light cannot be sufficiently absorbed, and light conversion efficiency is lowered, so that there is a possibility that the luminance of the light emitting display element cannot be sufficiently secured.

A black matrix 14 is disposed between the wavelength conversion layers 13 on the first substrate 12. The black matrix 14 can be formed by using a known light-shielding material and patterning it according to a known method. Note that the black matrix 14 is not an essential component in the wavelength conversion substrate 11, and the wavelength conversion substrate 11 may be configured without the black matrix 14.

The adhesive layer 15 is formed using a known adhesive that transmits ultraviolet light or blue light described later. As shown in FIG. 1, the adhesive layer 15 does not have to be provided on the first base 12 so as to cover the entire surface of each wavelength conversion layer 13, and may be provided only on the outer edge of the wavelength conversion substrate 11. Is possible.

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. From the light source 17, ultraviolet light or blue light is emitted as excitation light, respectively.

The light source 17 (17a, 17b, 17c) is not particularly limited, and an ultraviolet light emitting organic EL element, a blue light emitting organic EL element, or the like having a known structure can be used, and is manufactured by a known manufacturing method. It is possible. Here, as the ultraviolet light, the main emission peak is preferably 360 nm or more and 435 nm or less, and as the blue light, the main emission peak is preferably more than 435 nm and not more than 480 nm. It is preferable that the light source 17 has directivity so that each emitted light irradiates the wavelength conversion layer 13 which opposes.

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

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

In the light emitting display element 100, blue light can be used as excitation light from the third light source 17c. In this case, the wavelength conversion substrate 11 may use a light scattering layer configured by dispersing light scattering particles in a resin instead of the third wavelength conversion layer 13c. In this way, the blue light that is the excitation light can be used as it is without converting the wavelength.

The light emitting display element 100 includes an image formed by three types of sub-pixels: a sub-pixel including the first wavelength conversion layer 13a, a sub-pixel including the second wavelength conversion layer 13b, and a sub-pixel including the third wavelength conversion layer 13c. One pixel that is the minimum unit that constitutes.

The light-emitting display element 100 having the above configuration has a red color for each 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. The emission of green or blue light is controlled, and a full color display is performed.

In the light emitting display element 100, a color filter can be provided between the wavelength conversion layer 13 and the first substrate 12. That is, a red color filter is provided between the first wavelength conversion layer 13a and the first substrate 12, a green color filter is provided between the second wavelength conversion layer 13b and the first substrate 12, and the third A blue color filter can be provided between the wavelength conversion layer 13 c and the first substrate 12. Thereby, the purity of the display color can be increased. Here, as a color filter, what is known for liquid crystal display elements etc. can be formed and used by a well-known method.

<First Forming Method of Film>
The 1st formation method of the said film | membrane can form suitably the film | membrane which is not patterned used as a wavelength conversion layer etc. of a wavelength conversion film. The first forming method of the film includes a step of forming a coating film on one surface side of the substrate (hereinafter, also referred to as “coating layer forming step”) and a step of heating the coating film (hereinafter referred to as “heating step”). And the coating film is formed from the resin composition.

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

[Coating film forming process]
In the coating film forming step, for example, the coating film is formed by applying the resin composition on a substrate. In the coating film forming step, after applying the resin composition, the solvent or the like may be removed by heating the coated surface with a suitable heating device such as a hot plate or oven. As heating conditions, for example, a heating time of 70 to 130 ° C. and a heating time of 1 to 10 minutes may be used.

As the substrate on which the coating film is formed, the same substrate as that described later in the second method for forming the film can be used.

The application method of the resin composition is not particularly limited, and for example, a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, or the like can be employed.

[Heating process]
In the heating step, the coating film is heated by a suitable heating device such as a hot plate or an oven. Thereby, removal of the volatile component contained in the said coating film, promotion of various chemical reactions, such as imidation, etc. can be performed, As a result, the characteristic of the film | membrane etc. which are formed can be adjusted. In the heating step, for example, a heating time of 150 to 250 ° C. and a heating time of 5 to 180 minutes may be used.

Since the film laminated on the substrate is obtained by the heating process, the laminate of the substrate and the film can be used as a wavelength conversion film or the like. Moreover, when the said resin composition which has sclerosis | hardenability is used in this method, a cured film is obtained because a crosslinking reaction arises with the said resin composition by the said heating.

<Second Forming Method of Film>
The second method for forming the film can favorably form a patterned film. The second forming method of 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 irradiating at least a part of the coating film (exposure). A process (hereinafter also referred to as “radiation irradiation process”), a process of developing the coating film after radiation irradiation (hereinafter also referred to as “development process”), and a process of heating the coating film (hereinafter referred to as “heating process”). Said coating film is formed with the said resin composition containing a radiation sensitive compound. Further, the second method for forming the film may include a step of exposing the pattern after development (hereinafter also referred to as “post-exposure step”) between the development step and the heating step.

According to the second method for forming the film, since the resin composition described above is used, it is possible to easily and reliably form a film in which a decrease in the fluorescence quantum yield of QD after heat treatment is suppressed. it can. In addition, the film | membrane obtained with the 2nd formation method of the said film | membrane is a cured film normally. Hereinafter, each step will be described.

[Coating film forming process]
In the coating film forming step, for example, the coating film is formed by applying the resin composition on a substrate. After application of the resin composition, the solvent or the like may be removed by heating (pre-baking) the application surface.

The material of the substrate on which the coating film is formed is not particularly limited, and examples thereof include glass, quartz, silicon, and resin. Specific examples of the resin include, for example, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide, cyclic olefin addition polymer, cyclic olefin ring-opening polymer, and hydrogenated product thereof. It is done. In addition, these substrates may be subjected to pretreatment such as chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, vacuum deposition, or the like, if desired.

The application method of the resin composition is not particularly limited, and for example, a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, or the like can be employed. Among these coating methods, spin coating and slit die coating are preferable. The heating (pre-baking) conditions vary depending on the type of each component, the blending ratio, and the like. For example, the heating time may be 1 to 10 minutes at a temperature of 70 to 130 ° C.

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

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

The lower limit of the integrated irradiation amount (exposure amount) in the radiation irradiation step is preferably 100 J / m ^{2 and} more preferably 200 J / m ² . Moreover, as an upper limit of the said integrated irradiation amount, 2,000 J / m < ² > is preferable and 1,000 J / m < ² > is more preferable. In this specification, the “integrated dose” refers to an integrated value of values obtained by measuring the intensity of radiation at a wavelength of 365 nm with an illuminometer (for example, “OAI model 356” manufactured by OAI Optical Associates Inc.).

[Development process]
In the development step, the coating after irradiation is developed to remove unnecessary portions.

Examples of the developer used for development include at least one alkaline compound such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and the like. An aqueous solution in which is dissolved can be used. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol can be added to the aqueous solution of the alkaline compound described above.

Examples of the developing method include a liquid filling method, a dipping method, a rocking dipping method, and a spray method. The development time varies depending on the composition of the resin composition, but the lower limit of the development time is preferably 5 seconds and more preferably 10 seconds. Further, the upper limit of the development time is preferably 300 seconds, and more preferably 180 seconds. Following the development process, for example, washing with running water is performed for 30 seconds to 90 seconds, and then drying with compressed air or compressed nitrogen provides a desired pattern.

[Post exposure process]
For example, when a quinonediazide compound is used as the [F] radiation-sensitive compound, the non-exposed portion exhibits a red color, and thus the unexposed portion after development in this step can be post-exposed to make the coating colorless. it can. As post-exposure conditions at this time, for example, the same conditions as those in the above-described exposure process may be used.

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

The lower limit of the heating temperature is preferably 150 ° C. Moreover, as an upper limit of heating temperature, 250 degreeC is preferable. When heating is performed with a hot plate, the lower limit of the heating time is preferably 5 minutes, and the upper limit is preferably 30 minutes. When heating is performed in an oven, the lower limit of the heating time is preferably 10 minutes, and the upper limit is preferably 180 minutes.

When the above method is applied to the formation of the wavelength conversion layer of the light emitting display element 100 described above, the wavelength conversion layer forming method including the above-described steps is repeated using each of the three resin compositions, and the first wavelength. The conversion layer 13a, the second wavelength conversion layer 13b, and the third wavelength conversion layer 13c may be formed.

<Other embodiments>
The preferred embodiments of the present invention have been described above, but the present invention is not limited to these embodiments. For example, in the above 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 to this and is also applied to a backlight unit of a liquid crystal display. be able to. For example, when a blue light emitting diode is used as the light source of the backlight unit, white light with 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 described above. In the preferred embodiment, the method for forming a film laminated on the substrate has been described as the first method for forming the film. However, the film can also be formed by other film forming methods such as a casting method. In this case, for example, the film in the form of a single layer film can be obtained.

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

[Weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw / Mn)]
Mw and Mn were measured by gel permeation chromatography (GPC) under the following conditions. The molecular weight distribution (Mw / Mn) was calculated from the obtained Mw and Mn.

Equipment: “GPC-101” from Showa Denko
Column: Concatenated “GPC-KF-801”, “GPC-KF-802”, “GPC-KF-803” and “GPC-KF-804” from Showa Denko KK Mobile phase: Tetrahydrofuran Column temperature: 40 ° C.
Flow rate: 1.0 mL / min Sample concentration: 1.0% by mass
Sample injection volume: 100 μL
Detector: Differential refractometer Standard material: Monodisperse polystyrene

<Synthesis of binder resin ([a] resin)>
[Synthesis Example 1] Synthesis of Resin (A-1) A flask equipped with a condenser and a stirrer was charged with 150 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. Heat to 80 ° C., and at the same 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, 10 parts by mass of styrene, 20 parts by mass of mono [2-methacryloyloxyethyl] succinate Part mixed solution of 3 parts by weight of 2-hydroxyethyl methacrylate, 15 parts by weight of 2-ethylhexyl methacrylate, 12 parts by weight of N-phenylmaleimide and 6 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) Was added dropwise over 2 hours, and polymerization was carried out for 1 hour while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 90 ° C., and further polymerized for 1 hour to obtain a propylene glycol monomethyl ether acetate solution of resin (A-1) (solid content concentration: 33% by mass). The obtained resin was Mw = 10,800, Mn = 5,900, and Mw / Mn = 1.83.

[Synthesis Example 2] Synthesis of Resin (A-2) A flask equipped with a condenser and a stirrer was charged with 150 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. Heat to 80 ° C., and at the same temperature, 50 parts by mass of propylene glycol monomethyl ether acetate, 5 parts by mass of methacrylic acid, 25 parts by mass of tricyclodecanyl methacrylate, 10 parts by mass of styrene, mono [2-methacryloyloxyethyl succinate 20 parts by mass, 18 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide, 10 parts by mass of 3- (methacryloyloxymethyl) -3-ethyloxetane and 2,2′-azobis (2,4-dimethyl) A mixed solution of 6 parts by weight of valeronitrile) was dropped over 2 hours, and polymerization was performed for 1 hour while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 90 ° C., and further polymerized for 1 hour to obtain a propylene glycol monomethyl ether acetate solution of resin (A-2) (solid content concentration: 33% by mass). The obtained resin was Mw = 11,100, Mn = 6,000, Mw / Mn = 1.85.

[Synthesis Example 3] Synthesis of Resin (A-3) Into a nitrogen-substituted reaction vessel, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1, ¹⁰ ] -3-dodecene and bicyclo [2.2.1] hept-2-ene 80 mol: 430 parts by mass of a mixture of 20 mol and 750 parts by mass of toluene were charged and heated to 60 ° C. . To this, 0.62 parts by mass of a toluene solution of triethylaluminum (1.5 mol / L) and modified with tert-C ₄ H ₅ OH / CH ₃ OH (tert-C ₄ H ₉ OH / CH ₃ OH / W) = 0.35 mol / 0.3 mol / 1 mol) WCl ₆ solution (concentration 0.05 mol / L) 3.7 parts by mass was added and heated and stirred at 80 ° C. for 3 hours. A resin (A-3) was obtained. The polymerization conversion in this polymerization reaction was 95%, and the weight average molecular weight of the resin (A-3) was 21,000.

<Preparation of resin composition, formation of film, and evaluation of physical properties>
Each component used for preparation of 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) which is a core-shell structure type semiconductor quantum dot
B-2: CdSe / ZnS-TOPO which is a core-shell structure type semiconductor quantum dot (average particle diameter: 4 nm, quantum dots used in Example 4 in International Publication WO2006 / 103908)

The average particle size of [B] QD was observed using a transmission electron microscope (“H-7650” manufactured by Hitachi High-Tech Fielding Co., Ltd.), and each of 10 arbitrary [B] QDs contained in the field of view was observed. It was obtained by averaging the longest width of.

[[C] Compound]
C-1: Triphenylphosphine C-2: Tri-o-tolylphosphine C-3: Tri-m-tolylphosphine C-4: Tri-p-tolylphosphine C-5: Tris (2,4,6-trimethyl Phenyl) phosphine C-6: Tri-2,5-xylylphosphine C-7: Diphenyl (p-vinylphenyl) phosphine C-8: Tricyclohexylphosphine C-9: 4,4-thiobis (3-methyl-6) -T-butylphenol)
C-10: Dilauryl thiodipropionate C-11: Distearyl thiodipropionate C-12: 2-mercaptobenzothiazole

[[X] peroxide decomposer]
X-1: Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]
X-2: 3,9-bis (octadecyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane X-3: bis (2,2,6,6-tetra Methyl-4-piperidyl) sebacate X-4: pentaerythritol tetrakis (3-mercaptobutyrate)

[[D] radical scavenger]
D-1: 2,2′-thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (“IRGANOX® 1035” from BASF)

[[E] polymerizable compound]
E-1: Dipentaerythritol hexaacrylate E-2: Ditrimethylolpropane tetraacrylate

[[F] radiation sensitive compound]
F-1: Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide (“LUCIRIN® TPO” from BASF)
F-2: Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (“IRGACURE® 819” from BASF)
F-3: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (“IRGACURE® 907” from BASF)
F-4: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime) (“Irgacure® OXE02” from BASF)
F-5: 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonic acid ester F— 6: 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)] (“Irgacure® OXE01” from BASF)

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

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

[Examples 2 to 18 and Comparative Examples 1 to 8]
Each resin composition was prepared in the same manner as in Example 1 except that the types and blending amounts of the blending components were as described in Table 1 below. In Table 1, “-” indicates that the corresponding component was not used.

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

[Patternability]
The patterning property was observed with an optical microscope for the QD-containing pattern film obtained by the following forming method, and the development residue was defined as A (good) when there was no development residue and the linear portion of the pattern was formed in a straight line. The case where it exists and / or the case where the linear part of a pattern is not formed linearly was judged as B (defect).

(Method for forming QD-containing pattern film of Example 1)
After applying the resin composition of Example 1 on a non-alkali glass substrate with a spinner, a coating film was formed by pre-baking on a hot plate at 90 ° C. for 2 minutes. Next, the radiation containing each wavelength of 365 nm, 405 nm, and 436 nm was irradiated at an integrated dose of 700 J / m ² using a high-pressure mercury lamp through a photomask having a predetermined pattern. Next, development was performed in a 0.04 mass% potassium hydroxide aqueous solution at 25 ° C. for 90 seconds to form a QD-containing pattern film having an average thickness of 5 μm.

(Methods for forming QD-containing pattern films of Examples 2 to 18 and Comparative Examples 1 to 8)
The QD-containing pattern film of Example 2 used the resin composition of Example 2 in the method for forming the QD-containing pattern film of Example 1 above, and the cumulative irradiation dose was 1,000 J / m ^2. Except for the above, the same method was used. In addition, the QD-containing pattern films of Examples 14, 17 and 18 and Comparative Examples 6 to 7 are the same as the QD-containing pattern film forming method of Example 1 described above in Examples 14, 17 and 18 and Comparative Examples 6 to 7, respectively. The resin composition was used in the same manner except that the resin composition was used and the cumulative dose was 800 J / m ² . Further, the QD-containing pattern film of Example 13 uses the resin composition of Example 13 in the method for forming the QD-containing pattern film of Example 1 above, and the integrated irradiation amount is set to 2,000 J / m ^2, and further development The latter pattern was formed in the same manner except that ultraviolet irradiation was performed using a high-pressure mercury lamp with an integrated irradiation amount of 10,000 J / m ² . Furthermore, the QD-containing pattern films of Examples 3 to 12, 15 and 16, and Comparative Examples 1 to 5 and 8 are the same as the QD-containing pattern films of Example 1 to Examples 3 to 12, 15 and 16 described above. And the resin compositions of Comparative Examples 1 to 5 and 8 were formed in the same manner except that the integrated dose was 1,500 J / m ² .

[Shrink resistance]
The QD-containing pattern film formed by the same method as in the case of the above patterning evaluation is further irradiated with ultraviolet rays with a cumulative irradiation amount of 10,000 J / m ² using a high-pressure mercury lamp, and the QD-containing patterns before and after the ultraviolet irradiation. The average thickness of the film was measured with a stylus-type film thickness measuring device (“Alphastep IQ” manufactured by KLA Tencor). Then, the remaining film rate is calculated by the following formula, and when the remaining film rate is 99% or more, A (shrinkage resistance is good) is judged, and when it is less than 99%, B (shrinkage resistance is bad) is judged. did.
Residual film ratio (%) = (average thickness after treatment / average thickness before treatment) × 100

[Light resistance]
With respect to the QD-containing pattern film formed by the same method as in the case of the above patterning evaluation, an ultraviolet ray irradiation device (Ushio's “UVX-02516S1JS01”) is used to emit 800,000 J / m ² of ultraviolet rays at an illuminance of 130 mW. After irradiation, the average thickness of the QD-containing pattern film before and after the ultraviolet irradiation was measured with a stylus type film thickness measuring device (“Alphastep IQ” manufactured by KLA Tencor). Then, the amount of film loss was calculated by the following formula, and when the amount of film loss was 2% or less, A (light resistance was good), and when it was more than 2%, B (light resistance was poor) was judged.
Film loss (%) = {(average thickness before treatment−average thickness after treatment) / average thickness before treatment} × 100

[Fluorescence quantum yield]
The fluorescence quantum yield was measured at 25 ° C. using an absolute PL fluorescence quantum yield measurement apparatus (“C11347-01” from Hamamatsu Photonics) for a QD-containing pattern film formed by the same method as in the case of the above patterning evaluation. Measured in The wavelength of the excitation light was 450 nm. Separately, a QD-containing pattern film formed by the same method as in the case of the patterning property evaluation is heated at 180 ° C. for 20 minutes (post-baking) in a clean oven to form a cured film, and The fluorescence quantum yield was measured by the same method. Table 1 shows the former fluorescence quantum yield as “untreated” and the latter fluorescence quantum yield as “after heat treatment”.

[Change rate of fluorescence quantum yield]
The rate of change of fluorescence quantum yield, fluorescence quantum yield of the untreated and [Phi _1, was calculated by the following formula fluorescence quantum yield after the heat treatment as [Phi _2. It can be evaluated that the lower the change rate of the fluorescence quantum yield, the more the decrease in the fluorescence quantum yield of [B] QD after heat treatment (after post-baking) is suppressed.
Change rate of fluorescence quantum yield (%) = {(Φ ₁ −Φ ₂ ) / Φ ₁ } × 100

[Wavelength conversion evaluation]
For wavelength conversion evaluation, an absolute PL fluorescence quantum yield measurement apparatus (C11347-01 manufactured by Hamamatsu Photonics Co., Ltd.) was used for a QD-containing pattern film after heat treatment (after post-baking) formed by the same method as in the case of patterning property evaluation. )) And measured at 25 ° C. Specifically, it was carried out by reading the numerical value of the fluorescence maximum wavelength measured simultaneously with the quantum yield. The wavelength of the excitation light was 450 nm. This fluorescence maximum wavelength (nm) was defined as wavelength conversion evaluation (nm). The wavelength conversion evaluation indicates that the closer to 630 nm, the better the conversion to the desired wavelength even after the heat treatment.

[Fluorescence half width]
The full width at half maximum of the fluorescence was measured using an absolute PL fluorescence quantum yield measurement apparatus (C11347-01 manufactured by Hamamatsu Photonics Co., Ltd.) for a QD-containing pattern film after heat treatment (post-bake) formed by the same method as in the case of the above patterning evaluation. )) And measured at 25 ° C. Specifically, it was performed by reading the numerical value of the half width of fluorescence measured simultaneously with the quantum yield. The wavelength of the excitation light was 450 nm. The fluorescence half-value width (nm) indicates that the smaller the value, the better the wavelength conversion to fluorescence with high color purity even after the heat treatment.

As is clear from the results in Table 1, Examples 1 to 18 using the resin composition containing the [C] compound all have good patternability, shrinkage resistance and light resistance, and Comparative Example 1 Compared with ˜8, the change rate of fluorescence quantum yield, wavelength conversion evaluation, and fluorescence half width were small. Among Examples 1 to 18, Examples 1 to 8, 13 and 15 to 18 using a compound having a phenylphosphine structure or a compound having a cycloalkylphosphine structure as the [C] compound are different from the other examples. Also, the change rate of the fluorescence quantum yield and the half width of the fluorescence were small. Furthermore, Examples 2 to 5, 16 and 18 using (C-2) to (C-5) as the [C] compound are the change rate of fluorescence quantum yield and the half width of fluorescence among Examples 1 to 18. Was particularly small.

[Examples 19 to 22 and Comparative Example 9]
Each resin composition was prepared in the same manner as in Example 1 except that the types and amounts of each component were as described in Table 2 below. In Table 2, “-” indicates that the corresponding component was not used.

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

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

A QD-containing film is used instead of the QD-containing pattern film, and the other points are operated in the same manner as in Examples 1 to 18 and Comparative Examples 1 to 8, and shrink resistance, light resistance, fluorescence quantum yield, and fluorescence quantum The rate of change in yield, wavelength conversion evaluation, and fluorescence half width were evaluated.

As is clear from the results in Table 2, Examples 19 to 22 have good shrinkage resistance, and compared with Comparative Example 9, the fluorescence quantum yield and the rate of change thereof, wavelength conversion evaluation, and fluorescence half-value width evaluation The item was good. Moreover, Example 19, 21, and 22 which made content of the [C] compound 2 mass parts or more with respect to 100 mass parts of [A] binder resin were also favorable also about light resistance.

ADVANTAGE OF THE INVENTION According to this invention, the resin composition which can suppress the fall of the fluorescence quantum yield of QD after heat processing, the film | membrane obtained by the said resin composition, the wavelength conversion member using the said film, and the said resin composition are used. A method of forming a film can be provided.

11 wavelength conversion substrate 12 first base material 13 wavelength conversion layer 13a first wavelength conversion layer 13b second wavelength conversion layer 13c third wavelength conversion layer 14 black matrix 15 adhesive layer 16 second base material 17 light source 17a first light source 17b Second light source 17c Third light source 18 Light source substrate 100 Light emitting display element

Claims (15)

1. Binder resin,
   Semiconductor quantum dots and at least 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 dialkylthiodipropionate structure, and a compound having a benzothiazole structure A resin composition containing one kind of compound.
2. The resin composition according to claim 1, further comprising a radical scavenger.
3. The resin composition according to claim 1 or 2, further comprising a polymerizable compound.
4. The resin composition according to claim 1, wherein the binder resin has an alicyclic structure in a side chain.
5. The resin composition according to any one of claims 1 to 4, wherein the binder resin is an alkali-soluble resin.
6. The resin composition according to claim 5, wherein the alkali-soluble resin has a carboxy group in a side chain.
7. The semiconductor quantum dot includes at least two elements 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, a group 15 element, and a group 16 element. The resin composition according to claim 6.
8. The resin composition according to claim 7, wherein the semiconductor quantum dot contains In.
9. The resin composition according to claim 8, wherein the semiconductor quantum dot has a core-shell structure containing In as a constituent element of the core.
10. The resin composition according to any one of claims 1 to 6, wherein the semiconductor quantum dots contain Si.
11. The resin composition according to any one of claims 1 to 10, further comprising a radiation sensitive compound.
12. A film formed from the resin composition according to any one of claims 1 to 11.
13. A wavelength conversion member provided with the film | membrane formed with the resin composition of any one of Claims 1-11.
14. A step of forming a coating film on one surface side of the substrate, and a step of heating the coating film,
    The film formation method which forms the said coating film with the resin composition of any one of Claims 1-11.
15. Forming a coating film on one side of the substrate;
    Irradiating at least a part of the coating film with radiation,
    A step of developing the coating film after irradiation, and a step of heating the coating film after development,
    The film formation method which forms the said coating film with the resin composition of Claim 11.

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