JP6834213B2 - Resin composition, film, wavelength conversion member, and method for forming the film - Google Patents

Description

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

In recent years, semiconductor quantum dots (hereinafter, also referred to as “QD”) obtained by forming semiconductors such as cadmium sulfide (CdS) and cadmium telluride (CdTe) to a nanometer size have attracted attention. Since such a QD exhibits a special optical property of exhibiting broad light absorption and emitting fluorescence having a narrow spectrum width, various applications are currently being studied. For example, the above-mentioned QD has come to be used for a display using an organic electroluminescence (EL) element or the like (see JP-A-2014-174406).

Specifically, a blue-emitting organic EL element, a semiconductor quantum dot (hereinafter, also referred to as “G-QD”) that is excited by light from the blue-emitting organic EL element and emits green fluorescence, and a blue-emitting organic EL element. A display that combines semiconductor quantum dots (hereinafter, also referred to as "R-QD") that are excited by light from an OLED and emit red fluorescence is attracting 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 a 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 can be made by combining the green fluorescence from the G-QD layer, the red fluorescence from the R-QD layer, and the unconverted blue light emitted from the blue-emitting organic EL element. It reproduces the light of various hues.

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

Further, the film containing QD can be applied not only to the above-mentioned display applications but also to wavelength conversion films used as, for example, solar cell sealing sheets, agricultural films, lighting components and the like. Such a film can be obtained, for example, by applying a resin composition containing QD on a substrate and then heat-treating the obtained coating film.

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

Japanese Unexamined Patent Publication No. 2014-174406

The present invention has been made based on the above circumstances, and an object of the present invention is a resin composition capable of suppressing a decrease in the fluorescence quantum yield of QD after heat treatment, a film obtained by the resin composition, and the film. It is an object of the present invention to provide a wavelength conversion member using the above, 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, "[C"). ] Compound] is contained in the resin composition.

The present invention also includes a wavelength conversion member including a film obtained from the above-mentioned resin composition and a film formed from the above-mentioned resin composition.

Furthermore, the present invention includes a first method for forming a film, which comprises a step of forming a coating film on one surface side of the substrate with the above-mentioned resin composition and a step of heating the coating film.

Further, the present invention comprises a step of forming a coating film on one surface side of the substrate with the above-mentioned resin composition, a step of irradiating at least a part of the coating film with radiation, and developing the above-mentioned coating film after irradiation. The present invention includes a second method for forming a film, which comprises 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 by the resin composition, a wavelength conversion member provided with the film obtained by the resin composition, and the present invention. 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] binder resin, [B] QD and [C] compound. The [C] compound is selected from the group consisting of a compound having a phenylphosphine structure, a compound having a cycloalkylphosphine structure, a compound having a thiobisphenol structure, a compound having a dialkylthiodipropionate structure, and a compound having a benzothiazole structure. It is at least one kind and is considered to function as an antioxidant as described later. In addition, the resin composition may contain an antioxidant other than the [C] compound. Examples of the antioxidant other than the [C] compound include a peroxide decomposing agent not corresponding to the [C] compound (hereinafter, also referred to as “[X] peroxide decomposing agent”) and a radical not corresponding to the [C] compound. Examples thereof include a scavenger (hereinafter, also referred to as “[D] radical scavenger”). Further, the resin composition includes 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 also contain "[G] solvent"). The resin composition may contain two or more of the above components.

By having the above-mentioned structure, the resin composition can suppress a decrease in the fluorescence quantum yield of [B] QD after the heat treatment. The reason why the resin composition exerts the above effect by having the above composition is not always clear, but it is presumed as follows, for example. That is, the [C] compound used in the resin composition has a peroxide decomposition function of blocking the chain initiation reaction by, for example, decomposing hydroperoxide (ROOH) generated during the oxidation reaction into a stable compound. Since it is a particularly excellent compound, 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 when forming a film (wavelength conversion layer) with the resin composition, the peroxide that is the source of free radicals is decomposed by the [C] compound, so that [B] after the heat treatment ] It is considered that the decrease in the fluorescence quantum yield of QD can be suppressed.

Further, when applying QD to a display using a blue light emitting organic EL element, in the conventional resin composition, as described above, red color from R-QD with respect to the intensity of blue light due to free radicals during heat treatment. The intensity of fluorescence and the intensity of green fluorescence from G-QD may decrease, resulting in a decrease in color reproducibility. 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, so that the fluorescence of [B] QDs such as R-QD and G-QD is fluorescent. 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 may be any binder resin as long as it can serve as a base material for the film.

It is preferable to use a binder resin having an alicyclic structure in the side chain as the [A] binder resin because the deterioration of the fluorescence quantum yield of [B] QD with time can be suppressed. [A] The reason why the above effect is obtained by using a binder resin having an alicyclic structure in the side chain is not always clear, but it is presumed as follows, for example. That is, the hydrophobicity of the alicyclic structure can prevent moisture, which can cause deterioration of the fluorescence quantum yield over time, from adhering to the surface of [B] QD. Therefore, the fluorescence quantum yield of [B] QD can be reduced. It is considered 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 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 monocyclic structure such as a cyclopentene structure, a cyclohexene structure, and a cyclopentadiene structure. Cycloalkene structure; a polycyclic cycloalkane structure such as norbornane structure, adamantan structure, tricyclodecane structure, and tetracyclododecane structure; a polycyclic cycloalkene structure such as norbornene structure and tricyclodecene structure can be mentioned.

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, deterioration of the fluorescence quantum yield of [B] QD with time can be further suppressed.

The [A] binder resin having an alicyclic structure in the side chain is selected from the group consisting of, for example, methacrylic acid 3,4-epoxycyclohexyl, methacrylic acid cyclic alkyl ester, acrylic acid cyclic alkyl ester and N-cyclohexyl maleimide, which will be described later. Examples thereof include the [a] resin having a structural unit derived from at least one compound, a cyclic olefin polymer, and the like.

When the resin composition is applied to a photosensitive resin composition that can be patterned with an alkaline developer, the [A'] alkali-soluble resin as exemplified below may be used as the [A] binder resin. preferable.

[[A'] Alkali-soluble resin]
[A'] The alkali-soluble resin is a resin that is soluble in an alkaline solution. As the [A'] 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”), a polyimide, a polysiloxane, or a novolak resin. , Alkaline-soluble polyolefin, resin having a cardo skeleton, and a combination thereof are preferable. Hereinafter, each of the resin [a], 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. Further, in order to improve the sensitivity, it may have a structural unit containing a polymerizable group. As the structural unit containing a polymerizable group, a structural unit containing an epoxy group, a structural unit containing a (meth) acryloyl group, and a structural unit containing a vinyl group are preferable. [A] Since the resin has a structural unit containing the above-mentioned specific polymerizable group, it is possible to obtain a resin composition having excellent surface curability and deep curability when forming a cured film.

As the structural unit containing a carboxy group, a carboxylic acid-based unsaturated compound such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, or a mono-[(meth) acryloyloxyalkyl] ester of a polyvalent carboxylic acid is used 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, crotonic acid and the like.

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] and the like. Be done.

Among these carboxylic acid-based unsaturated compounds, acrylic acid, methacrylic acid and monosuccinic acid [2- (meth) acryloyloxyethyl] are preferable from the viewpoint of polymerizable property.

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

[A] The lower limit of the content ratio of the structural unit containing the carboxy group in the resin is preferably 1 mol%, more preferably 5 mol%, and 10 mol% with respect to all the structural units constituting the [a] resin. Is even more preferable. The upper limit of the content ratio of the structural unit is preferably 80 mol%, more preferably 70 mol%, still more preferably 60 mol%. When the content ratio of the structural unit containing a carboxy group is within the above range, the solubility in an alkaline developer can be further improved.

The structural unit containing an epoxy group can be formed by, for example, using an epoxy group-containing unsaturated compound as a monomer and radically polymerizing it together with another monomer as appropriate. Examples of the epoxy group-containing unsaturated compound include unsaturated compounds containing an oxylanyl group (1,2-epoxy structure) and an oxetanyl group (1,3-epoxy structure).

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

Examples of the unsaturated compound having an oxetanyl group include 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -2-methyloxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, and 3-(. Methacryloyloxymethyl) -2-phenyloxetane, 3- (2-methacryloyloxyethyl) oxetane, 3- (2-methacryloyloxyethyl) -2-ethyloxetane, 3- (2-methacryloyloxyethyl) -3-ethyloxetane Oxetane ester and the like.

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

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

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% and 5 mol% with respect to all the structural units constituting the resin [a]. More preferably, 10 mol% is further preferable. The upper limit of the content ratio is preferably 80 mol%, more preferably 70 mol%, and even more preferably 60 mol%. When the content ratio of the structural unit containing the epoxy group is in the above range, a film having higher hardness and better solvent resistance can be formed.

The structural unit containing the (meth) acryloyl group is, for example, a method of reacting a polymer having an epoxy group with (meth) acrylic acid, or reacting a polymer having a carboxy group with 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 with (meth) acrylic acid, or the like.

Examples of the monomer giving the other structural unit include (meth) acrylic acid chain alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated dicarboxylic acid diester, maleimide compound, and unsaturated. Examples thereof include aromatic compounds, conjugated dienes, unsaturated compounds having an tetrahydrofuran skeleton, hydroxyl group-containing unsaturated compounds, and other unsaturated compounds.

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, and 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 tricyclo acrylate. [5.2.1.0 ^2,6 ] Decane-8-yl, isobornyl acrylate and the like can be mentioned.

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

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, p-methoxystyrene and the like.

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, and α-methyl-p-hydroxystyrene. And so on.

Examples of the other unsaturated compound include acrylonitrile.

Among the monomers giving the other structural units, styrene, methyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, t-butyl methacrylate, n-lauryl methacrylate, benzyl methacrylate, and methacrylic, among the monomers giving the other structural units. Preferables are tricyclodecanyl acid acid, p-methoxystyrene, 2-methylcyclohexylacrylate, N-phenylmaleimide, N-cyclohexylmaleimide, tetrahydrofurfuryl methacrylate and 2-hydroxyethyl methacrylate.

The monomer giving the other structural unit may be used alone or in combination of two or more.

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%, based on all the structural units constituting the resin [a]. 10 mol% is more preferred. The upper limit of the content ratio is preferably 80 mol%, more preferably 70 mol%. When the content ratio is within the above range, for example, the molecular weight of the resin [a] can be adjusted without interfering with the above-mentioned effect.

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

The ratio of the above Mw to the number average molecular weight (Mn) of the [a] resin, that is, the lower limit of the molecular weight distribution (Mw / Mn) is usually 1, preferably 1.2, and more preferably 1.5. preferable. As the upper limit of Mw / Mn, 5 is preferable, 4 is more preferable, and 3 is further preferable. [A] By setting the Mw / Mn of the resin in the above range, 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 subjecting the above-mentioned monomers to a polymerization reaction in the presence of a polymerization initiator in a solvent.

[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, and a thiol group are included in the structural unit. , Or a polyimide containing a combination thereof is preferable. The polyimide can be provided with alkali developability (alkali soluble) by containing these alkali-soluble groups in the structural unit, and as a result, scum generation in the exposed portion can be suppressed during alkaline development. The polyimide can be synthesized, for example, by the methods described in 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 JP2010-152302.

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

[Alkali-soluble polyolefin]
The alkali-soluble polyolefin used in the resin composition is not particularly limited, but a cyclic olefin polymer having a protonic polar group is preferable from the viewpoint of alkali solubility. Here, the protic polar group refers to a group in which a hydrogen atom is directly bonded to an atom belonging to Group 15 or Group 16 of the periodic table. As the protonic 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 with 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 two other cyclic structures are bonded to a ring carbon atom constituting the cyclic structure. For example, two aromatic rings (for example, two aromatic rings) are attached to the carbon atom at the 9-position of the fluorene ring. A structure in which a benzene ring) is bonded can be mentioned. 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 [A'] alkali-soluble resin]
When the resin composition is not applied to a photosensitive resin composition that can be patterned with an alkaline developer, an alkali-insoluble [A] binder resin can be used. Examples of the alkali-insoluble [A] binder resin include alkali-insoluble polyolefins.

[Alkali-insoluble polyolefin]
The alkali-insoluble polyolefin used in the resin composition is not particularly limited, but the polyolefin having no protonic 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). Coalescence) and the like. Examples of the alkene include ethylene, propylene, butene and the like. 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 an alkyl group having 1 to 5 carbon atoms, a group in which the alkyl group is combined with at least one selected from the group consisting of -CO- and -O-, and the like. Methyl and methoxycarbonyl groups are preferred. As the alkali-insoluble polyolefin, a cyclic olefin polymer is preferable, a polymer having a substituted or unsubstituted cycloalkene as a monomer is more preferable, and a polymer having norbornan and a substituted or unsubstituted tetracyclododecene as a monomer is preferable. More preferred. Specific examples of the alkali-insoluble polyolefin include those described in Japanese Patent Application Laid-Open No. 2015-127733.

The lower limit of the content of the [A] binder resin in the resin composition is preferably 1% by mass, more preferably 5% by mass. The upper limit of the content is preferably 50% by mass, more preferably 40% by mass. [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 better solvent resistance while further increasing the sensitivity. On the other hand, by setting the content to the above upper limit or less, the storage stability can be further improved.

[[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) as a constituent element without Cd or Pb as a constituent element is preferable.

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

Examples of the above elements include Be (berylium), Mg (magnium), Ca (calcium), Sr (strontium), Ba (barium), Cu (copper), Ag (silver), gold (Au), and zinc (Zn). , B (boron), Al (aluminum), Ga (gallium), In (indium), Tell (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 preferable from the viewpoint of improving the fluorescence characteristics.

As the [B] QD containing In, semiconductor quantum dots having a core-shell structure, which will be described later, semiconductor quantum dots made of AgInS ₂ , and semiconductor quantum dots made of Zn-doped AgInS ₂ are preferable.

Further, as [B] QD, Si-based semiconductor quantum dots such as semiconductor quantum dots made of Si and semiconductor quantum dots made of a compound of Si and other elements are also preferable.

Further, [B] a compound (A) in which the QD has a fluorescence maximum in the wavelength region of green light of 500 nm or more and 600 nm or less, and / or a compound (B) having a fluorescence maximum in the wavelength region of red light of 600 nm or more and 700 nm or less. Is preferably included. [B] As a resin composition for forming a wavelength conversion layer of a light emitting display element that displays an image using visible light by containing the compound (A) and / or the compound (B) having the above fluorescence characteristics in QD. The resin composition can be applied.

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

The core-shell structure type [B] QD is constructed by forming a core structure with one kind of compound and covering the core structure with another kind of compound. For example, by coating the semiconductor of the core with a semiconductor having a larger bandgap, 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 preferably contains In as a constituent element of the core from the viewpoint of improving the fluorescence characteristics, and 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 preferable. 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 structural semiconductor quantum dots.

[B] The lower limit of the average particle size of QD is preferably 0.5 nm, more preferably 1.0 nm. The upper limit of the average particle size is preferably 20 nm, more preferably 10 nm. If 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 size of [B] QD is observed by using a transmission electron microscope after the sample is dried, and the longest width of each of any 10 [B] QDs contained in the visual field is averaged. It is required by doing.

The wavelength region of fluorescence of [B] QD can be controlled by appropriately selecting the constituent materials and average particle diameter of [B] QD.

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

As a method for obtaining [B] QD, for example, a known method of thermally decomposing an organometallic compound in a coordinating organic solvent can be used. Further, in the core-shell structure type [B] QD, for example, after forming a homogeneous core structure by a reaction, a precursor for forming a shell on the core surface is added to the reaction system to form a shell on the core surface. After that, the reaction is stopped and the mixture is separated from the solvent. [B] Examples of the method of controlling the average particle size of QD include a method of adjusting the reaction temperature, reaction time, and the like. It is also possible to use a commercially available product.

InP / ZnS, which is a core-shell structure type semiconductor quantum dot, can also be synthesized by referring to, for example, the method described in the technical document "Journal of the American Chemical Society. 2007, 129, 15432-15433". _{Further, CuInS 2} / ZnS, which is a core-shell structure type semiconductor quantum dot, is described in, for example, the method described in the technical document "Journal of American Chemical Society. 2009, 131, 5691-5697" and the technical document "Chemistry of Materials. , 21, 242 2-2429 ”, can also be referred to and synthesized.

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

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

[[C] compound]
The [C] compound is selected from the group consisting of a compound having a phenylphosphine structure, a compound having a cycloalkylphosphine structure, a compound having a thiobisphenol structure, a compound having a dialkylthiodipropionate structure, and a compound having a benzothiazole structure. At least one compound. Since the [C] compound has an excellent peroxide decomposition function of blocking the chain initiation reaction by, for example, decomposing the hydroperoxide (ROOH) produced during the oxidation reaction into a stable compound, [B] ] 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 considered that the resin composition can suppress the decrease in the fluorescence quantum yield of QD after the heat treatment by containing the [C] compound.

(Compound having a phenylphosphine structure)
The compound having a phenylphosphine structure is a compound represented by the 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. Examples of the compound having a phenyl phosphine structure, a compound having a triphenyl phosphine structure is a three also R ² are both a substituted or unsubstituted phenyl group in the above general formula are preferred.

Examples of compounds having a phenylphosphine structure include tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tri-2,5-kisilylphosphine, and tri-3,5-kisilylphosphine. , 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-triphenylphosphine and tri-m-tril from the viewpoint of more effectively suppressing the generation of free radicals that cause a decrease in the fluorescence quantum yield of [B] QD. Phosphine, tri-p-trilphosphine, tri-2,5-kisilylphosphine, diphenyl (p-vinylphenyl) phosphine, triphenylphosphine and tris (2,4,6-trimethylphenyl) phosphine are preferred, tri-o -Trilphosphine, tri-m-trilphosphine, tri-p-trilphosphine 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 of the cycloalkyl group include an alkyl group having 1 to 5 carbon atoms and an alkenyl group having 2 to 5 carbon atoms. Examples of the compound having a cycloalkyl phosphine structure, compound 3 R ³ in the general formula has a tricycloalkyl phosphine structure cycloalkyl group either substituted or unsubstituted are preferred.

As the compound having a cycloalkylphosphine structure, tricyclohexylphosphine is preferable.

(Compound with thiobisphenol structure)
The compound having a thiobisphenol structure is a compound represented by the general formula: S- (R ⁴ ) ₂ . Here, R ⁴ is a substituted or unsubstituted hydroxyphenyl group. Two R ⁴ may be the same or different. Examples of the substituent of the hydroxyphenyl group include an alkyl group having 1 to 5 carbon atoms. The substituted hydroxyphenyl group preferably does not have 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 dialkyl thiodipropionate structural _formula: is ^{_{S- (CH 2 -CH 2 -COO-}} R 5) a compound represented by _2. Here, R ⁵ is an alkyl group. Two R ⁵ can be the same or different. As the alkyl group, a linear alkyl group having 10 or more and 20 or less carbon atoms is preferable.

Examples of the compound having a dialkylthiodipropionate structure include dilaurylthiodipropionate, ditridecylthiodipropionate, dimyristylthiodipropionate, and distearylthiodipropionate.

Compounds having a dialkylthiodipropionate structure include dilaurylthiodipropionate and distearyl 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 a benzothiazole structure)
The compound having a benzothiazole structure is a substituted or unsubstituted benzothiazole. Examples of the substituent of the 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.

The lower limit of the content of the [C] compound in the resin composition is preferably 0.1 part by mass, more preferably 1 part by mass, and even more preferably 2 parts by mass with respect to 100 parts by mass of the [A] binder resin. .. The upper limit of the content is preferably 15 parts by mass, more preferably 10 parts by mass, and even more preferably 8 parts by mass with respect to 100 parts by mass of the binder resin [A]. 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. Further, when the resin composition has curability, it is possible to suppress hindering the curing reaction of the resin composition.

[[X] Peroxide Decomposing Agent]
The [X] peroxide decomposing agent is an antioxidant that does not correspond to the [C] compound and has a peroxide decomposing function. The [X] peroxide decomposing agent is an antioxidant that does not correspond to the [C] compound and has a peroxide decomposing function. [X] Examples of the peroxide decomposing agent include a phosphorus compound, a sulfur compound, a compound containing a phosphorus atom and a sulfur atom, and specifically, a compound having a phosphite structure and a compound having a thioether structure ( However, compounds having a thiobisphenol structure and compounds having a dialkylthiodipropionate structure), compounds having a benzotriazole structure, compounds having a thiophosphite structure and the like can be mentioned.

(Compound with 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, and the like. Tris (p-2-butenylphenyl) phosphite, bis (p-nonylphenyl) cyclohexylphosphite, tris (2,4-di-t-butylphenyl) phosphite, 3,9-bis (octadecyloxy)- 2,4,8,10-Tetraoxa-3,9-diphosphaspiro [5.5] undecane, triphenylphosphite, 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 JP-A-2003-26715, JP-A-2009-97010, JP-A-2012-211975, JP-A-2014-126811, and JP-A-2014-134763. Examples thereof include compounds described in Japanese Patent Publication No.

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

Examples of commercially available compounds having a thioether structure include the compounds described in JP-A-2014-48428, JP-A-2014-134763, and the like.

(Compound having a benzotriazole structure)
Examples of the compound having a benzotriazole structure include 2- (2-hydroxy-5-methylphenyl) benzotriazole and 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 products of compounds having a benzotriazole structure include compounds described in JP-A-2003-26715, JP-A-2009-97010, JP-A-2012-211975 and the like.

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

[[D] Radical scavenger]
The resin composition may further contain the [D] radical scavenger. The [D] radical scavenger is an antioxidant that does not correspond to the [C] compound, and has a function of preventing oxidation by capturing 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 an electronic device. There is. In this way, when free radicals are generated in the membrane, these free radicals are chemically unstable and therefore easily react with other compounds to produce new free radicals while deteriorating the QD in a chain reaction. , Causes a decrease in membrane function. When the resin composition contains the [D] radical scavenger, even if the above-mentioned free radicals are generated, the free radicals are trapped by the [D] radical scavenger, so that the fluorescence of [B] QD after the heat treatment is performed. The decrease in radical yield can be further suppressed. The [D] radical scavenger also includes those having a function of decomposing peroxide. Further, in the present specification, a substance having a function of decomposing peroxide and a function of capturing free radicals is referred to as [D] radical scavenger.

[D] The radical scavenger is not particularly limited as long as it can capture free radicals and inactivate radicals, but for example, phenols and aromatic amines can be used and have a hindered phenol structure. And a compound having a hindered amine structure are preferable. [D] By using the above-mentioned specific compound as a radical scavenger, free radicals can be more reliably captured.

[Compound with hindered phenol structure]
Examples of the hindered phenol structure include a structure having a hydroxyphenyl group substituted with two or more monovalent organic groups having 3 or more and 10 or less carbon atoms. Examples of the compound having a hindered phenol structure include pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and 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-t-butyl-4-hydroxy-5-methylfienyl) propionyloxy] ethyl] 2,4,8,10-tetraoxaspiro [5,5] -undecane and Examples thereof include polymers of these compounds.

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

[Compound with 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 and 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-2,2,2) 6,6-Tetramethylpiperidine-4-yl) amino] -triazine-2-yl] -4,7-Diazadecane-1,10-diamine and other low-molecular-weight compounds, piperidine rings were multiple-bonded via the triazine skeleton. Examples thereof include a polymer in which a plurality of piperidine rings are bonded via an ester bond.

Examples of commercially available products of the compound having a hindered amine structure include the compounds described in JP-A-2011-11823, JP-A-2014-134763, and the like.

[D] As the radical trapping agent, a compound having a hindered phenol structure is preferable from the viewpoint of more reliably trapping free radicals, and 2,2'-thiodiethylenebis [3- (3,5-di-t-butyl). -4-Hydroxyphenyl) propionate], and 3,9-bis [1,1-dimethyl-2- [β- (3-t-butyl-4-hydroxy-5-methylfienyl) propionyloxy] ethyl] 2 , 4,8,10-Tetraoxaspiro [5,5] -undecan is more preferred.

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

[[E] Polymerizable compound]
The resin composition may further contain the [E] polymerizable compound. When the resin composition contains the [E] polymerizable compound, the curing reaction of the resin composition can be accelerated. The [E] polymerizable compound is not particularly limited as long as it is a compound that polymerizes by irradiation, heating, or the like, 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. , Compounds having two or more (meth) acryloyl groups in the molecule are more preferred.

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, and triethylene glycol dimethacrylate. Tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropanedimethacrylate, trimethylolpropanetrimethacrylate, 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 -Tricyclodecanediacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, ditrimethylolpropanetetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol heptaacrylate, Tripentaerythritol octaacrylate, tetrapentaerythritol nonaacrylate, tetrapentaerythritol decaacrylate, pentapentaerythritol undecaacrylate, pentapentaerythritol dodecaacrylate, tripentaerythritol heptamethacrylate, tripentaerythritol octamethacrylate, tetrapentaerythritol nonamethacrylate, tetra Pentaerythritol decamethacrylate, pentapentaerythritol undecamethacrylate, pentapentaerythritol dodecamethacrylate, dimethylol-tricyclodecanediacrylate, 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] fluorene , (2-Acryloyloxypropoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2-acryloyloxyethoxy) -3,5-dimethylphenyl] fluorene, 9,9-bis [4- ( 2-Methylloyloxyethoxy) -3,5-dimethylphenyl] fluorene and the like can be mentioned.

Among them, 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, and pentaerythritol tetraacrylate and ditrimethylol. More preferred are propanetetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol heptaacrylate and tripentaerythritol octaacrylate.

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

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

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

[Radiation-sensitive radical polymerization initiator]
When a radically polymerizable compound is used as the [E] polymerizable compound, for example, 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, an active species capable of initiating a radical polymerization reaction of the [E] polymerizable compound is generated by exposure to radiation such as visible light, ultraviolet rays, far ultraviolet rays, electron beams, and X-rays. Examples include compounds that can be used.

Specific examples of the radiation-sensitive radical polymerization initiator include, for example.
Etanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime), etanone, 1- [9-ethyl -6- {2-Methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9H-carbazole-3-yl]-, 1- (O-acetyloxime), etanone, 1- [9-Ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime), 1,2-octanedione-1- [4] -(Phenylthio) -2- (O-benzoyl oxime)], Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime) ) Etc. O-acyloxime compounds;
2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholine-4-yl-phenyl) ) -Butan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one and other α-aminoketone compounds;
Α-Hydroxyketones such as 1-phenyl-2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone Compound;
Examples thereof include 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-carbazole-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- Morphorinopropan-1-one, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide are preferred.

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

Examples of the quinone diazide compound include, for example.
1,2-Naphthoquinone diazide sulfonic acid ester such as 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone azide-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- Examples thereof include 1,2-naphthoquinonediazide sulfonic acid ester of (polyhydroxyphenyl) alkane such as hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid ester. Specific examples of the quinone diazide compound include those described in Japanese Patent No. 5454321, Japanese Patent No. 5630068, Japanese Patent No. 5592664, and the like.

As the quinone diazide compound, 1,2-naphthoquinone diazide sulfonic acid ester of (polyhydroxyphenyl) alkane is preferable from the viewpoint of increasing the radiosensitivity 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 resin composition contains the [F] radiation-sensitive compound, the lower limit of the content of the [F] radiation-sensitive compound is preferably 1 part by mass with respect to 100 parts by mass of the [A] binder resin. Parts by mass are more preferred. The upper limit of the content is preferably 150 parts by mass, more preferably 100 parts by mass, based on 100 parts by mass of the binder resin [A]. By setting the content in the above range, the radiation sensitivity of the resin composition can be further enhanced.

[[G] solvent]
The resin composition may further contain the [G] solvent. When the resin composition contains the [G] solvent, its coatability is improved. The [G] solvent is not particularly limited as long as each of the above components can be dissolved or dispersed, and examples thereof include a solvent used when synthesizing a resin such as the above-mentioned [a] resin. The [G] solvent may be used alone or in combination of two or more.

[[H] Other ingredients]
In addition to the above-mentioned components, the resin composition may contain [H] and other components such as a thermal polymerization initiator, a storage stabilizer, and an adhesion aid 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 resin composition contains [H] and other components, the upper limit of the content is preferably 10 parts by mass and more preferably 1 part by mass with respect to 100 parts by mass of the [A] binder resin.

The resin composition can be prepared by an appropriate method, and for example, in the [G] solvent, the [A] binder resin, the [B] QD, the [C] compound and, if necessary, any component are added. It can be prepared by mixing. As the lower limit of the concentration of the solid content in the composition at the time of mixing, 5% by mass is preferable, and 10% by mass is more preferable. The upper limit of the concentration is preferably 80% by mass, more preferably 70% by mass. By setting the concentration of the solid content in the above range, the coatability can be improved. The above-mentioned "solid content" refers to the residue obtained by drying the 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 film is obtained from the resin composition, a decrease in the fluorescence quantum yield of QD after heat treatment is suppressed, and for example, a film as a wavelength conversion layer having high color reproducibility can be provided. The film may or may not be patterned, but if the film is patterned, it can be applied to a wavelength conversion layer useful as a sub-pixel. The film is usually heat-treated to remove volatile components and promote various chemical reactions so that it 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 a “cured film”) or a film using a non-crosslinked resin as a base material. The cured film can be obtained, for example, by using the resin composition having curability. Examples of the method for imparting curability to the resin composition include a method of using a curable resin such as a thermosetting resin as the [A] binder resin, and [E] containing a polymerizable compound and other cross-linking agents. The method etc. can be mentioned.

<Wavelength conversion member>
The film is suitable as a wavelength conversion layer included in a wavelength conversion member such as a light emitting display element or a wavelength conversion film. Hereinafter, a wavelength conversion film and a light emitting display element will be described as examples of a preferred embodiment of the wavelength conversion member provided with the film.

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

[Light emitting display element]
FIG. 1 is a cross-sectional view schematically showing a light emitting display element 100 of one embodiment. The light emitting display element 100 includes a wavelength conversion substrate 11 formed by providing a wavelength conversion layer 13 (13a, 13b, 13c) and a black matrix 14 on the first base material 12, and an adhesive layer 15 on the wavelength conversion substrate 11. It has a light source substrate 18 bonded to each other via.

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

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

The wavelength conversion substrate 11 wavelength-converts the excitation light from the light source 17 of the light source substrate 18 by the QD contained in each of the wavelength conversion layers 13, and emits fluorescence of a desired wavelength. In the wavelength conversion substrate 11, the first wavelength conversion layer 13a, the second wavelength conversion layer 13b, and the third wavelength conversion layer 13c are 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 converts the excitation light into green light. Can be configured to convert to blue light.

In that case, the QD contained in each of the wavelength conversion layers 13a, 13b, and 13c is selected so that each has the desired fluorescence characteristics. Therefore, in forming the wavelength conversion layers 13a, 13b, and 13c of the wavelength conversion substrate 11, for example, three kinds of resin compositions containing QDs having different emission characteristics are prepared.

The lower limit of the average thickness of the wavelength conversion layer 13 of the wavelength conversion substrate 11 is preferably 100 nm, more preferably 1 μm. The upper limit of the average thickness is preferably 100 μm. If the average thickness is less than the above lower limit, the excitation light cannot be sufficiently absorbed, and the light conversion efficiency is lowered, which may cause a problem that the brightness of the light emitting display element cannot be sufficiently secured.

A black matrix 14 is arranged between the wavelength conversion layers 13 on the first base material 12. The black matrix 14 can be formed by patterning according to a known method using a known light-shielding material. The black matrix 14 is not an indispensable component of the wavelength conversion board 11, and the wavelength conversion board 11 may be configured not to be provided with the black matrix 14.

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

The light source substrate 18 includes a second base material 16 and a light source 17 arranged on the wavelength conversion board 11 side of the second base material 16. Ultraviolet light or blue light is emitted from the light source 17 as excitation light, respectively.

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

The light emission display element 100 converts the excitation light from the first light source 17a into wavelength by the QD of the first wavelength conversion layer 13a of the wavelength conversion substrate 11. Similarly, the excitation light from the second light source 17b is wavelength-converted by the QD of the second wavelength conversion layer 13b of the wavelength conversion substrate 11, and the excitation light from the third light source 17c is wavelength-converted by the third wavelength conversion layer 13c of the wavelength conversion substrate 11. Wavelength conversion is performed by the QD of. 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 displays red. That is, the first wavelength conversion layer 13a of the wavelength conversion substrate 11 converts the excitation light from the opposite first light source 17a of the light source substrate 18 into red light. Further, the portion provided with the second wavelength conversion layer 13b constitutes a sub-pixel that displays green. That is, the second wavelength conversion layer 13b converts the excitation light from the opposite second light source 17b of the light source substrate 18 into green light. Further, the portion provided with the third wavelength conversion layer 13c constitutes a sub-pixel that displays blue. For example, when ultraviolet light is used as the excitation light, the third wavelength conversion layer 13c converts the ultraviolet light from the opposite third light source 17c of the light source substrate 18 into blue light.

In the light emitting display element 100, blue light can also be used as the excitation light from the third light source 17c. In this case, the wavelength conversion substrate 11 can use a light scattering layer formed by dispersing light scattering particles in a resin instead of the third wavelength conversion layer 13c. By doing so, the blue light, which is the excitation light, can be used as it is without wavelength conversion.

The light emitting display element 100 is composed of three types of sub-pixels, a sub-pixel having a first wavelength conversion layer 13a, a sub-pixel having a second wavelength conversion layer 13b, and a sub-pixel having a third wavelength conversion layer 13c. It constitutes one pixel which is the smallest unit which constitutes.

The light emitting display element 100 having the above configuration is red for each sub-pixel having the first wavelength conversion layer 13a, the sub-pixel having the second wavelength conversion layer 13b, and the sub-pixel having the third wavelength conversion layer 13c. , Green or blue light emission is controlled and 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 base material 12. That is, a red color filter is provided between the first wavelength conversion layer 13a and the first base material 12, a green color filter is provided between the second wavelength conversion layer 13b and the first base material 12, and a third. A blue color filter can be provided between the wavelength conversion layer 13c and the first base material 12. As a result, the purity of the displayed color can be increased. Here, as the color filter, a color filter known for a liquid crystal display element or the like can be formed and used by a known method.

<First method of forming a film>
The first method for forming the film can preferably form an unpatterned film used as a wavelength conversion layer or the like of a wavelength conversion film. The first method for forming the film is a step of forming a coating film on one surface side of the substrate (hereinafter, also referred to as a “coating film forming step”) and a step of heating the coating film (hereinafter, “heating step”). 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 surely form a film in which a decrease in the fluorescence quantum yield of QD after heat treatment is suppressed. it can. Here, the "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, a coating film is formed by applying the resin composition onto a substrate. In the coating film forming step, after applying the resin composition, the solvent or the like may be removed by heating the coated surface with an appropriate heating device such as a hot plate or an oven. The heating conditions may be, for example, a heating temperature of 70 ° C. or higher and 130 ° C. or lower and a heating time of 1 minute or longer and 10 minutes or shorter.

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

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

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

Since a film laminated on the substrate is obtained by the heating step, the substrate and the laminated body of the film can be used as a wavelength conversion film or the like. Further, when the resin composition having curability is used in this method, a cured film is obtained by causing a cross-linking reaction in the resin composition by the above heating.

<Second method of forming a film>
The second method of forming the film can preferably form a patterned film. The second method of forming the film is a step of forming a coating film on one surface side of the substrate (hereinafter, also referred to as a "coating film forming step"), and irradiating (exposing) at least a part of the coating film with radiation. (Hereinafter, also referred to as “irradiation step”), step of developing the coating film after irradiation (hereinafter, also referred to as “development step”), and step of heating the coating film (hereinafter, also referred to as “heating step”). The coating film is formed by the resin composition comprising (referred to as) and containing a radiation-sensitive compound. Further, the second forming method of the film may include a step of exposing the developed pattern (hereinafter, also referred to as “post-exposure step”) between the developing step and the heating step.

According to the second method for forming the film, since the resin composition described above is used, it is possible to easily and surely form a film in which the decrease in the fluorescence quantum yield of QD after the heat treatment is suppressed. it can. The film obtained by the second method of forming the film is usually a cured film. Hereinafter, each step will be described.

[Coating film forming process]
In the coating film forming step, for example, a coating film is formed by applying the resin composition onto a substrate. After applying the resin composition, the solvent or the like may be removed by heating (prebaking) the coated 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 polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, polyimide, an addition polymer of a cyclic olefin, a ring-opening polymer of a cyclic olefin, and a hydrogenated product thereof. Be done. Further, these substrates may be subjected to pretreatment such as chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, vacuum deposition, etc., if desired.

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

[Irradiation process]
In the 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, for example, the radiation may be irradiated through a photomask having a pattern of a desired shape. By using this photomask, a part of the irradiated radiation passes through the photomask, and a part of the radiation is irradiated to the coating film.

Examples of the 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 or more and 450 nm or less is preferable, and radiation containing ultraviolet rays having a wavelength of 365 nm is more preferable.

As the lower limit of the integrated irradiation amount (exposure amount) in the irradiation step, 100 J / m ² is preferable, and 200 J / m ² is more preferable. Further, as the upper limit of the integrated irradiation amount, 2,000 J / m ² is preferable, and 1,000 J / m ² is more preferable. In the present specification, the “integrated irradiation amount” refers to an integrated value of values measured by an illuminance meter (for example, “OAI model 356” of OAI Optical Associates Inc.) at a wavelength of 365 nm of radiation.

[Development process]
In the developing step, the coating film after irradiation is developed to remove unnecessary parts.

The developer used for development is at least one of alkaline compounds 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 to be used.

Examples of the developing method include a liquid filling method, a dipping method, a rocking dipping method, a spray method and the like. The developing time varies depending on the composition of the resin composition, but the lower limit of the developing time is preferably 5 seconds, more preferably 10 seconds. The upper limit of the developing time is preferably 300 seconds, more preferably 180 seconds. A desired pattern can be obtained by, for example, washing with running water for a time of 30 seconds or more and 90 seconds or less after the development treatment, and then drying with compressed air or compressed nitrogen.

[Post-exposure process]
For example, when a quinonediazide compound is used as the [F] radiation-sensitive compound, the unexposed portion exhibits a red color. Therefore, the coating film can be made colorless by post-exposure to the unexposed portion after development in this step. it can. The post-exposure conditions at this time may be, for example, the same conditions as those in the above-mentioned exposure step.

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

The lower limit of the heating temperature is preferably 150 ° C. The upper limit of the heating temperature is preferably 250 ° C. When heating is performed on 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 method of forming the wavelength conversion layer including the above step is repeated using each of the three types of resin compositions to obtain the first wavelength. The conversion layer 13a, the second wavelength conversion layer 13b, and the third wavelength conversion layer 13c may be formed, respectively.

<Other embodiments>
Although preferred embodiments of the present invention have been described above, 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 sub-pixels of a light emitting display element has been described, but the present invention is not limited to this, and is also applied to a backlight unit of a liquid crystal display or the like. be able to. For example, when a blue light emitting diode is used as the light source of the backlight unit, high-purity white light can be reproduced by combining with the film obtained by the resin composition of the present invention containing the above-mentioned G-QD and R-QD. Further, in the above preferred embodiment, a method of forming a film laminated on a substrate has been described as a first method of forming the film, but the film can also be formed by another film forming method 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: Showa Denko's "GPC-101"
Column: Showa Denko's "GPC-KF-801", "GPC-KF-802", "GPC-KF-803" and "GPC-KF-804" connected Mobile phase: tetrahydrofuran Column temperature: 40 ° C.
Flow velocity: 1.0 mL / min Sample concentration: 1.0 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) 150 parts by mass of propylene glycol monomethyl ether acetate was charged into a flask equipped with a cooling tube and a stirrer and substituted with nitrogen. Heated to 80 ° C., 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 monosuccinate [2-methacryloyloxyethyl]. A mixed solution of 3 parts by mass of 2-hydroxyethyl methacrylate, 15 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide and 6 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile). Was added dropwise over 2 hours, and the mixture was polymerized for 1 hour while maintaining this temperature. Then, the temperature of the reaction solution was raised to 90 ° C., and the mixture was further polymerized for 1 hour to obtain a propylene glycol monomethyl ether acetate solution (solid content concentration: 33% by mass) of the resin (A-1). The obtained resins had Mw = 10,800, Mn = 5,900, and Mw / Mn = 1.83.

[Synthesis Example 2] Synthesis of Resin (A-2) 150 parts by mass of propylene glycol monomethyl ether acetate was charged into a flask equipped with a cooling tube and a stirrer and substituted 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 succinate [2-methacryloyloxyethyl ] 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 mass of valeronitrile) was added dropwise over 2 hours, and the mixture was polymerized for 1 hour while maintaining this temperature. Then, the temperature of the reaction solution was raised to 90 ° C., and the mixture was further polymerized for 1 hour to obtain a propylene glycol monomethyl ether acetate solution (solid content concentration: 33% by mass) of the resin (A-2). The obtained resins had Mw = 11,100, Mn = 6,000, and Mw / Mn = 1.85.

[Synthesis Example 3] Synthesis of Resin (A-3) In a reaction vessel substituted with nitrogen, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . ^{430 parts by mass of a mixture of 80 mol: 20 mol of 17,10} ] -3-dodecene and bicyclo [2.2.1] hept-2-ene and 750 parts by mass of toluene were charged and heated to 60 ° C. .. This was modified with 0.62 parts by mass of a toluene solution of triethylaluminum (1.5 mol / L) and 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 with a hydrolyzed polymer. A resin (A-3) was obtained. The polymerization conversion rate 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>
The components used in the preparation of each resin composition are 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 size: 4 nm, quantum dot used in Example 4 in WO2006 / 103908).

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

[[C] Compound]
C-1: Triphenylphosphine C-2: Tri-o-trilphosphine C-3: Tri-m-trilphosphine C-4: Tri-p-trilphosphine C-5: Tris (2,4,6-trimethyl) Phosphine) phosphine C-6: tri-2,5-kisilylphosphine C-7: diphenyl (p-vinylphenyl) phosphine C-8: tricyclohexylphosphine C-9: 4,4-thiobis (3-methyl-6) -T-butylphenol)
C-10: Dilaurylthiodipropionate C-111: Distearylthiodipropionate C-12: 2-Mercaptobenzothiazole

[[X] Peroxide Decomposing Agent]
X-1: Pentaerythritol tetrakis [3- (3,5-di-t-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'-thiodiethylene bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (BASF's "IRGANOX® 1035")

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

[[F] Radiation-sensitive compounds]
F-1: Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide (BASF's "LUCIRIN® TPO")
F-2: Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (BASF's "Irgacure® 819")
F-3: 2-Methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (BASF's "Irgacure® 907")
F-4: Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazole-3-yl]-, 1- (O-acetyloxime) (BASF's "Irgacure® OXE02"
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)] (BASF's "Irgacure (registered trademark) OXE01")

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

[Example 1]
90 parts by mass of the propylene glycol monomethyl ether acetate solution of the synthesized resin (A-1) (30 parts by mass of (A-1) as the [A] binder resin and 60 parts by mass of (G-1) as the [G] solvent. (Contains parts), 10 parts by mass of (B-1) as [B] QD, 2 parts by mass of (C-1) as [C] compound, and (E-1) 30 as [E] polymerizable compound. The resin composition of Example 1 was prepared by adding parts by mass and 5 parts by mass of (F-1) as the [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 amounts of each compounding component were as shown in Table 1 below. In addition, "-" 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.

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

(Method for forming QD-containing pattern film of Example 1)
A coating film was formed by applying the resin composition of Example 1 on a non-alkali glass substrate with a spinner and then prebaking on a hot plate at 90 ° C. for 2 minutes. Next, through a photomask provided with a predetermined pattern, radiation containing each wavelength of 365 nm, 405 nm and 436 nm was irradiated using a high-pressure mercury lamp at an integrated irradiation amount of ^{700 J / m 2.} Next, development was carried out 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)
As the QD-containing pattern film of Example 2, the resin composition of Example 2 was used in the method for forming the QD-containing pattern film of Example 1 above, and the cumulative irradiation dose was set to 1,000 J / m ^2. Other than that, it was formed in the same way. Further, the QD-containing pattern films of Examples 14, 17 and 18 and Comparative Examples 6 to 7 were used in Examples 14, 17 and 18 and Comparative Examples 6 to 7, respectively, in the method for forming the QD-containing pattern film of Example 1. It was formed by the same method except that the resin composition of No. 1 was used and the cumulative irradiation dose was set to 800 J / m ^2. Further, the QD-containing pattern film of Example 13 was further developed by using the resin composition of Example 13 in the method for forming the QD-containing pattern film of Example 1 and setting the cumulative irradiation dose to 2,000 J / m ^2. The latter pattern was formed in the same manner except that ultraviolet irradiation was performed using a high-pressure mercury lamp at an integrated irradiation dose of 10,000 J / m ^2. Further, the QD-containing pattern films of Examples 3 to 12, 15 and 16 and Comparative Examples 1 to 5 and 8 are used in Examples 3 to 12, 15 and 16 in the method for forming the QD-containing pattern film of Example 1 above. , And the resin compositions of Comparative Examples 1 to 5 and 8 were used, and the resin compositions were formed in the same manner except that the ^{cumulative irradiation dose was 1,500 J / m 2.}

[Shrink resistance]
The QD-containing pattern film formed by the same method as in the above patterning property evaluation is further ^{irradiated with ultraviolet rays having an integrated irradiation amount of 10,000 J / m 2} using a high-pressure mercury lamp, and the QD-containing pattern before and after this ultraviolet irradiation is performed. The average thickness of the film was measured with a stylus type film thickness measuring machine (“Alpha Step IQ” manufactured by KLA Tencor). Then, the residual film ratio is calculated by the following formula, and when the residual film ratio is 99% or more, it is judged as A (good shrinkage resistance), and when it is less than 99%, it is judged as B (poor shrinkage resistance). did.
Residual film ratio (%) = (average thickness after treatment / average thickness before treatment) x 100

[Light resistance]
With respect to the QD-containing pattern film formed by the same method as in the case of the above patterning property evaluation, an ultraviolet irradiation device (“UVX-02516S1JS01” manufactured by Usio Co., Ltd.) was used to further 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 irradiation with ultraviolet rays was measured with a stylus type film thickness measuring machine (“Alpha Step 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, it was determined as A (good light resistance), and when it exceeded 2%, it was determined as B (poor light resistance).
Membrane loss (%) = {(average thickness before treatment-average thickness after treatment) / average thickness before treatment} x 100

[Fluorescence quantum yield]
The fluorescence quantum yield was 25 ° C. using an absolute PL fluorescence quantum yield measuring device (“C11347-01” manufactured by Hamamatsu Photonics Co., Ltd.) for the QD-containing pattern film formed by the same method as in the above patterning property evaluation. Measured in. The wavelength of the excitation light was 450 nm. Separately, the QD-containing pattern film formed by the same method as in the above patterning property evaluation is heat-treated (post-baked) at 180 ° C. for 20 minutes in a clean oven to form a cured film. The fluorescence quantum yield was measured in the same manner. 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 smaller the rate of change in the fluorescence quantum yield is, the more the decrease in the fluorescence quantum yield of [B] QD after the heat treatment (after post-baking) is suppressed.
Rate of change in fluorescence quantum yield (%) = {(Φ _{1 − Φ 2} ) / Φ ₁ } × 100

[Wavelength conversion evaluation]
In the wavelength conversion evaluation, the QD-containing pattern film after heat treatment (after post-baking) formed by the same method as in the above patterning property evaluation was subjected to an absolute PL fluorescence quantum yield measuring device (Hamamatsu Photonics Co., Ltd. "C11347-01". ”) Was measured at 25 ° C. Specifically, it was carried out by reading the numerical value of the maximum fluorescence wavelength measured at the same time as 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 shows that the closer it is to 630 nm, the better it is because the wavelength can be converted to a desired wavelength even after the heat treatment.

[Fluorescence half width]
The fluorescence half width is the absolute PL fluorescence quantum yield measuring device (Hamamatsu Photonics Co., Ltd. "C11347-01") for the QD-containing pattern film after heat treatment (post-baking) formed by the same method as in the case of the above patterning property evaluation. ”) Was measured at 25 ° C. Specifically, it was carried out by reading the numerical value of the fluorescence half width measured at the same time as the quantum yield. The wavelength of the excitation light was 450 nm. The half width of fluorescence (nm) indicates that the smaller the value, the better the wavelength conversion to fluorescence with high color purity even after 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 patterning property, shrinkage resistance and light resistance, and Comparative Example 1 The rate of change in fluorescence quantum yield, wavelength conversion evaluation, and fluorescence half width were smaller than those in ~ 8. In addition, 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 compared with other examples. The rate of change in fluorescence quantum yield and the half width of fluorescence were small. Further, in Examples 2 to 5, 16 and 18 in which (C-2) to (C-5) were used as the [C] compounds, the rate of change in fluorescence quantum yield and the half width of fluorescence were found in 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 compounding component were as shown in Table 2 below. In addition, "-" 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 a non-alkali glass substrate with a spinner, and then heated on a hot plate at 90 ° C. 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 other points are operated in the same manner as in Examples 1 to 18 and Comparative Examples 1 to 8, and shrinkage resistance, light resistance, fluorescence quantum yield and its 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 the fluorescence quantum yield and its rate of change, wavelength conversion evaluation, and fluorescence half width evaluation are compared with those of Comparative Example 9. The item was good. Further, Examples 19, 21 and 22 in which the content of the [C] compound with respect to 100 parts by mass of the [A] binder resin was 2 parts by mass or more were also good in light resistance.

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 by the resin composition, a wavelength conversion member using the film, and the resin composition are used. It is possible to provide a method for forming a film.

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 2nd light source 17c 3rd light source 18 Light source substrate 100 Light emitting display element

Claims (14)

Binder resin,
At least selected from the group consisting of semiconductor quantum dots, compounds having a phenylphosphine structure, compounds having a cycloalkylphosphine structure, compounds having a thiobisphenol structure, compounds having a dialkylthiodipropionate structure, and compounds having a benzothiazole structure. Contains one compound ,
A resin composition further containing a radical scavenger. Binder resin,
At least selected from the group consisting of semiconductor quantum dots, compounds having a phenylphosphine structure, compounds having a cycloalkylphosphine structure, compounds having a thiobisphenol structure, compounds having a dialkylthiodipropionate structure, and compounds having a benzothiazole structure. Contains one compound ,
The resin composition in which the binder resin is Yes an alicyclic structure in the side chain. Binder resin,
At least selected from the group consisting of semiconductor quantum dots, compounds having a phenylphosphine structure, compounds having a cycloalkylphosphine structure, compounds having a thiobisphenol structure, compounds having a dialkylthiodipropionate structure, and compounds having a benzothiazole structure. Contains one compound ,
The semiconductor quantum dot contains at least two elements selected from the group consisting of Group 2 elements, Group 11 elements, Group 12 elements, Group 13 elements, Group 14 elements, Group 15 elements and Group 16 elements, and contains In. resin composition which have a core-shell structure including as a constituent element of the core. Binder resin,
At least selected from the group consisting of semiconductor quantum dots, compounds having a phenylphosphine structure, compounds having a cycloalkylphosphine structure, compounds having a thiobisphenol structure, compounds having a dialkylthiodipropionate structure, and compounds having a benzothiazole structure. Contains one compound ,
A resin composition in which the semiconductor quantum dots contain Si. Binder resin,
At least selected from the group consisting of semiconductor quantum dots, compounds having a phenylphosphine structure, compounds having a cycloalkylphosphine structure, compounds having a thiobisphenol structure, compounds having a dialkylthiodipropionate structure, and compounds having a benzothiazole structure. Contains one compound ,
A resin composition further containing a radiation-sensitive compound. Binder resin,
At least selected from the group consisting of semiconductor quantum dots, compounds having a phenylphosphine structure, compounds having a cycloalkylphosphine structure, compounds having a thiobisphenol structure, compounds having a dialkylthiodipropionate structure, and compounds having a benzothiazole structure. Contains one compound ,
The content of at least one compound, relative to the binder resin 100 parts by weight 1 part by weight to 15 parts by der Ru resin composition hereinafter. Binder resin,
At least selected from the group consisting of semiconductor quantum dots, compounds having a phenylphosphine structure, compounds having a cycloalkylphosphine structure, compounds having a thiobisphenol structure, compounds having a dialkylthiodipropionate structure, and compounds having a benzothiazole structure. A resin composition containing one kind of compound (however, the following curable composition is excluded) .
Further containing a polymerization initiator, a polymerizable compound and a thiol compound,
The binder resin is at least one monomer (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and a monomer copolymerizable with the monomer (a). A resin obtained by reacting a copolymer with c) with a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond.
A curable composition in which at least one of the above compounds is triphenylphosphine. The resin composition according to any one of claims 1 to 7, further comprising a polymerizable compound. The resin composition according to any one of claims 1 to 8 , wherein the binder resin is an alkali-soluble resin. The resin composition according to claim 9 , wherein the alkali-soluble resin has a carboxy group in the side chain. A film formed by the resin composition according to any one of claims 1 to 10. A wavelength conversion member including a film formed of the resin composition according to any one of claims 1 to 10. A step of forming a coating film on one surface side of the substrate and a step of heating the coating film are provided.
A method for forming a film by using the resin composition according to any one of claims 1 to 10. The process of forming a coating film on one side of the substrate,
The step of 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 are provided.
A method for forming a film by forming the coating film with the resin composition according to claim 5.

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