JP2017025165A - Composition for forming cured film, cured film, light-emitting display element, method for forming cured film and dispersion liquid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for forming a cured film that can suppress the reduction of a fluorescence quantum yield of a semiconductor quantum dot, to provide a cured film produced from the composition for forming a cured film, to provide a light-emitting display element using the cured film, to provide a method for forming a cured film by using the composition for forming a cured film and to provide a dispersion liquid suitable for the composition for forming a cured film.SOLUTION: The composition for forming a cured film contains a binder polymer, a polymerizable compound, a semiconductor quantum dot and a dispersant including an acidic functional group in which the dispersant has an acid value of not less than 5 mgKOH/g to not more than 150 mgKOH/g. The dispersant may include a carboxyl group, a sulfo group or a combination thereof as an acidic functional group. The dispersant may be a block copolymer having a first block composed of a first repeating unit and a second block composed of a second repeating unit having higher hydrophilicity than the first repeating unit.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a cured film forming composition, a cured film, a light emitting display element, a method for forming a cured film, and a dispersion.

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

  Specifically, a blue light-emitting organic EL element, a semiconductor quantum dot (hereinafter also referred to as “G-QD”) that emits green fluorescence when excited by light from the blue light-emitting organic EL element, and a blue light-emitting organic EL element A display combined with a semiconductor quantum dot (hereinafter also referred to as “R-QD”) that emits red fluorescence when excited by light from the light attracts attention. In such a display, various hues are obtained by combining green fluorescence from G-QD, red fluorescence from R-QD, and unconverted blue light emitted from a blue light emitting organic EL element. The light is reproduced.

  However, such QD is easily affected by oxygen, moisture, and the like. For example, when oxygen, moisture, or the like adheres to the QD, the crystal structure of the QD may change near the surface, and the QD fluorescence quantum yield may decrease. In such a display including a QD, oxygen or moisture adheres to the QD over time, so that the green fluorescence from the G-QD is increased with respect to the intensity of blue light from the blue light emitting organic EL element. And the intensity of red fluorescence from the R-QD may be reduced, which may reduce the color reproducibility of the display.

JP 2014-174406 A

  This invention is made | formed based on the above-mentioned situation, The objective is the cured film formation composition which can suppress the fall of the fluorescence quantum yield of QD, and the cured film obtained by the said composition for cured film formation Another object of the present invention is to provide a light emitting display element using the cured film, a method for forming a cured film using the cured film forming composition, and a dispersion suitable for the cured film forming composition.

  The invention made to solve the above problems includes a binder polymer (hereinafter also referred to as “[A] binder polymer”), a polymerizable compound (hereinafter also referred to as “[B] polymerizable compound”), a semiconductor quantum dot ( Hereinafter referred to as “[C] QD”) and a dispersant containing an acidic functional group (hereinafter also referred to as “[D] dispersant”), and the acid value of [D] dispersant is 5 mgKOH / g or more and 150 mgKOH. / G or less of the composition for forming a cured film.

  Moreover, this invention includes a light emitting display element provided with the cured film obtained with the above-mentioned composition for cured film formation, and the cured film formed with the above-mentioned composition for cured film formation.

  Furthermore, the present invention provides a step of forming a coating film on one surface side of the substrate with the above-described cured film forming composition, a step of irradiating at least a part of the coating film, and the coating film after radiation irradiation. And a method for forming a cured film, which includes a step of developing the film and a step of heating the coated film after development.

  Another invention made to solve the above-mentioned problems includes a semiconductor quantum dot, a dispersant containing an acidic functional group, and a solvent, and the acid value of the dispersant is 5 mgKOH / g or more and 150 mgKOH / g or less. It is a dispersion.

  Here, the “acidic functional group” means a functional group having at least one hydrogen atom that can be ionized as a hydrogen ion, and examples thereof include a carboxy group, a sulfo group, a hydroxy group, and a phosphate group. Further, the “acid value” is the number of mg of potassium hydroxide (KOH) necessary for neutralizing the acidic functional group contained in 1 g of the dispersant, according to JIS-K-0070 (1992). Required in compliance.

  ADVANTAGE OF THE INVENTION According to this invention, the cured film formation composition which can suppress the fall of the fluorescence quantum yield of QD, the cured film obtained by the said cured film formation composition, The cured film formed with the said composition for cured film formation The dispersion liquid suitable for the light emitting display element provided with this, the formation method of the said cured film, and the said composition for cured film formation 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.

<Composition for forming cured film>
The composition for forming a cured film contains [A] a binder polymer, [B] a polymerizable compound, [C] QD and a [D] dispersant, and the acid value of the [D] dispersant is 5 mgKOH / g or more and 150 mgKOH. / G or less of the composition for forming a cured film. The cured film-forming composition may contain a radiation-sensitive compound (hereinafter also referred to as “[E] radiation-sensitive compound”), and a solvent (hereinafter referred to as “[F] solvent”). May also be included).

  By having the said structure, the said composition for cured film formation can suppress the fall of the fluorescence quantum yield of QD. The reason why the composition for forming a cured film has the above-described configuration has the above-mentioned effects is not necessarily clear, but is presumed as follows, for example. That is, when the [D] dispersant is attached to the surface of [C] QD via an acidic functional group, oxygen, moisture, etc. that cause a decrease in the fluorescence quantum yield of [C] QD are attached to the surface This is considered to suppress the decrease in the fluorescence quantum yield of [C] QD.

  In addition, when QD is applied to a display using a blue light-emitting organic EL element, in the conventional cured film forming composition, oxygen or moisture adheres to the surface of R-QD or G-QD, thereby causing blue light emission. The intensity of red fluorescence from R-QD and the intensity of green fluorescence from G-QD may decrease with respect to the intensity of blue light emitted from the organic EL element, and color reproducibility may decrease. On the other hand, when the cured film forming composition is used, the [D] dispersant adheres to the surface of [C] QD such as R-QD or G-QD as described above. The reduction of QD fluorescence quantum yield can be suppressed, and the intensity of fluorescence from [C] QD can be maintained with respect to the intensity of blue light emitted from a blue light emitting organic EL device, and high color reproducibility can be maintained. It is thought that you can.

  Hereinafter, each component of the composition for forming a cured film will be described in detail.

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

  Moreover, [A '] alkali-soluble resin which is illustrated below as a [A] binder polymer can also be used. [A] By using [A ′] alkali-soluble resin as the binder polymer, patterning with an alkali developer becomes possible.

[[A '] alkali-soluble resin]
[A ′] The alkali-soluble resin is a resin that is soluble in an alkaline solution. [A ′] As the alkali-soluble resin, a polymer obtained by radical polymerization using an unsaturated compound containing a carboxy group as a monomer (hereinafter, also referred to as “[a] polymer”), polyimide, polysiloxane, novolak resin , And combinations thereof are preferred. Hereinafter, each of [a] polymer, polyimide, polysiloxane, and novolak resin will be described in detail.

[[A] polymer]
[A] The polymer has a structural unit containing a carboxy group. Moreover, you may have a structural unit containing a polymeric group for a sensitivity improvement. The structural unit containing a polymerizable group is preferably a structural unit containing an epoxy group, a structural unit containing a (meth) acryloyl group, or a structural unit containing a vinyl group. [A] When the polymer has a structural unit containing the specific polymerizable group, a cured film forming composition having excellent surface curability and deep part curability can be obtained.

  [A] The polymer may have a structural unit containing a hydroxyl group and other structural units.

  The structural unit containing the carboxy group includes, for example, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, anhydrides of unsaturated dicarboxylic acids, and mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids. Using a saturated compound as a monomer, it can be formed by radical polymerization with other monomers as appropriate.

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

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

  Examples of the anhydride of the unsaturated dicarboxylic acid include anhydrides of the compounds exemplified as the unsaturated dicarboxylic acid.

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

  Among these carboxylic acid-based unsaturated compounds, acrylic acid, methacrylic acid, maleic anhydride and mono [2- (meth) acryloyloxyethyl] succinate are preferable from the viewpoint of polymerizability.

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

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

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

  Examples of the unsaturated compound having an oxiranyl group include glycidyl acrylate, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, and 6,7 acrylic acid. -Epoxyheptyl, methacrylic acid 6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, 3,4-epoxycyclohexyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether , P-vinylbenzyl glycidyl ether and the like.

Examples of the unsaturated compound having an oxetanyl group include 3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- ( Acryloyloxymethyl) -2-phenyloxetane, 3- (2-acryloyloxyethyl) oxetane, 3- (2-acryloyloxyethyl) -2-ethyloxetane, 3- (2-acryloyloxyethyl) -3-ethyloxetane , Acrylic acid esters such as 3- (2-acryloyloxyethyl) -2-phenyloxetane;
3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -2-methyloxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 3- (2-methacryloyloxyethyl) oxetane, 3- (2-methacryloyloxyethyl) -2-ethyloxetane, 3- (2-methacryloyloxyethyl) -3-ethyloxetane, 3- (2-methacryloyloxyethyl) -2 -Methacrylic acid esters such as phenyl oxetane and 3- (2-methacryloyloxyethyl) -2,2-difluorooxetane.

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

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

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

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

  Examples of the (meth) acrylic acid ester having an epoxy group include glycidyl acrylate, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, and acrylic acid. Examples include 6,7-epoxyheptyl, 6,7-epoxyheptyl methacrylate, α-ethylacrylic acid-6,7-epoxyheptyl, 3,4-epoxycyclohexyl methacrylate, and the like.

  Of these (meth) acrylic acid esters having an epoxy group, glycidyl methacrylate and 3,4-epoxycyclohexyl methacrylate are preferred from the viewpoint of reactivity.

  These (meth) acrylic acid esters having an epoxy group may be used alone or in combination of two or more.

  [A] When the polymer has a structural unit containing a (meth) acryloyl group, the lower limit of the content ratio of the structural unit is preferably 1 mol% with respect to all the structural units constituting the polymer. Mole% is more preferable, and 10 mol% is more preferable. Moreover, as an upper limit of the said content rate, 80 mol% is preferable, 70 mol% is more preferable, and 60 mol% is further more preferable. When the content ratio of the structural unit containing a (meth) acryloyl group is within the above range, a cured film having higher hardness and better solvent resistance can be formed.

  The structural unit containing a vinyl group can be formed, for example, by a method of reacting a polymer having a carboxy group with a compound having an epoxy group and a vinyl group.

  Examples of the compound having an epoxy group and a vinyl group include vinyl glycidyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether.

  Of these compounds having an epoxy group and a vinyl group, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether and p-vinyl benzyl glycidyl ether are preferable from the viewpoint of reactivity.

  These compounds having an epoxy group and a vinyl group may be used alone or in combination of two or more.

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

  The structural unit containing a hydroxyl group can be formed, for example, by radical polymerization with another monomer as appropriate using a hydroxyl group-containing unsaturated compound as a monomer.

  Examples of the hydroxyl group-containing unsaturated compound include (meth) acrylic acid ester having an alcoholic hydroxyl group, (meth) acrylic acid ester having a phenolic hydroxyl group, and hydroxystyrene.

  Examples of the acrylic acid ester having an alcoholic hydroxyl group include 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, and 6-hydroxyhexyl acrylate. .

  Examples of the methacrylic acid ester having an alcoholic hydroxyl group include 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, and 6-hydroxyhexyl methacrylate. .

  Examples of the acrylic acid ester having a phenolic hydroxyl group include 2-hydroxyphenyl acrylate and 4-hydroxyphenyl acrylate.

  Examples of the methacrylic acid ester having a phenolic hydroxyl group include 2-hydroxyphenyl methacrylate and 4-hydroxyphenyl methacrylate.

  Examples of the hydroxystyrene include o-hydroxystyrene, p-hydroxystyrene, and α-methyl-p-hydroxystyrene.

  Of these hydroxyl group-containing unsaturated compounds, 2-hydroxyethyl methacrylate and α-methyl-p-hydroxystyrene are preferred from the viewpoint of polymerizability.

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

  [A] When the polymer has a structural unit containing a hydroxyl group, the lower limit of the content ratio of the structural unit is preferably 1 mol%, more preferably 5 mol% with respect to all structural units constituting the polymer [a]. Preferably, 10 mol% is more preferable. Moreover, as an upper limit of the said content rate, 30 mol% is preferable and 20 mol% is more preferable. When the content rate of the structural unit containing a hydroxyl group is in the above range, the solubility in an alkali developer can be further improved.

  Examples of the monomer that gives other structural units include methacrylic acid chain alkyl ester, methacrylic acid cyclic alkyl ester, acrylic acid chain alkyl ester, acrylic acid cyclic alkyl ester, methacrylic acid aryl ester, acrylic acid aryl ester, unsaturated Examples include dicarboxylic acid diesters, maleimide compounds, unsaturated aromatic compounds, conjugated dienes, unsaturated compounds having a tetrahydrofuran skeleton, and other unsaturated compounds.

  Examples of the methacrylic acid chain alkyl ester include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, and n methacrylate. -Lauryl, tridecyl methacrylate, n-stearyl methacrylate and the like.

Examples of the methacrylic acid cyclic alkyl ester include cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, and tricyclomethacrylate [5.2. 1.0 ^2,6 ] decan-8-yloxyethyl, isobornyl methacrylate and the like.

  Examples of the acrylic acid chain alkyl ester include methyl acrylate, ethyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, and n-acrylate. -Lauryl, tridecyl acrylate, n-stearyl acrylate and the like.

Examples of the acrylic acid cyclic alkyl ester include cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate, and tricyclo [5.2 acrylate]. 1.0 ^2,6 ] decan-8-yloxyethyl, isobornyl acrylate, and the like.

  Examples of the methacrylic acid aryl ester include phenyl methacrylate and benzyl methacrylate.

  Examples of the acrylic acid aryl ester include phenyl acrylate and benzyl acrylate.

  Examples of the unsaturated dicarboxylic acid diester include diethyl maleate, diethyl fumarate, diethyl itaconate and the like.

  Examples of the maleimide compound include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N- (4-hydroxyphenyl) maleimide, N- (4-hydroxybenzyl) maleimide, N-succinimidyl-3-maleimidobenzoate. N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide and the like.

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

  Examples of the conjugated diene include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

  Examples of the unsaturated compound having a tetrahydrofuran skeleton include tetrahydrofurfuryl methacrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, 3- (meth) acryloyloxytetrahydrofuran-2-one, and the like.

  Examples of the other unsaturated compounds include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, and vinyl acetate.

Among the monomers giving the other structural units, from the viewpoint of polymerizability, styrene, methyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, t-butyl methacrylate, n-lauryl methacrylate, benzyl methacrylate, methacryl Acid tricyclo [5.2.1.0 ^2,6 ] decan-8-yl, p-methoxystyrene, 2-methylcyclohexyl acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, and tetrahydrofurfuryl methacrylate are preferred. .

  The monomer which gives the said other structural unit may be used independently, and 2 or more types may be mixed and used for it.

  [A] When the polymer 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 structural units constituting the [a] polymer. 10 mol% is more preferable. Moreover, as an upper limit of the said content rate, 80 mol% is preferable and 70 mol% is more preferable. When the said content rate is in the said range, the molecular weight etc. of [a] polymer can be adjusted, for example, without preventing the effect mentioned above.

  [A] The lower limit of the weight average molecular weight (Mw) of the polymer is preferably 1,000, more preferably 2,000, and still more preferably 3,000. The upper limit of the Mw is preferably 30,000, more preferably 20,000, and further preferably 15,000. [A] By making Mw of a polymer into the said range, storage stability and a sensitivity can be improved more.

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

In addition, Mw and Mn in this specification are values measured by gel permeation chromatography (GPC) under the following conditions.
Equipment: For example, “GPC-101” from Showa Denko
Column: For example, “GPC-KF-801”, “GPC-KF-802”, “GPC-KF-803”, and “GPC-KF-804” manufactured by Showa Denko KK Mobile phase: Tetrahydrofuran Column temperature: 40 ℃
Flow rate: 1.0 mL / min Sample concentration: 1.0% by mass
Sample injection volume: 100 μL
Detector: Differential refractometer Standard material: Monodisperse polystyrene

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

  Examples of the solvent include alcohol, glycol ether, ethylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, dipropylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, propylene glycol monoalkyl. Examples include ether propionate, other esters, and ketones.

  As said polymerization initiator, what is generally known as a radical polymerization initiator can be used. Examples of the radical polymerization initiator include 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis- (4- And azo compounds such as methoxy-2,4-dimethylvaleronitrile).

[Polyimide]
As said polyimide, the polyimide which contains a carboxy group, a phenolic hydroxyl group, a sulfo group, a thiol group, or these combination in a structural unit is preferable. By containing these alkali-soluble groups in the structural unit, alkali developability (alkali solubility) is provided, and the occurrence of scum in the exposed portion can be suppressed during alkali development.

  The polyimide is obtained, for example, by condensing an acid component and an amine component. The acid component is preferably tetracarboxylic dianhydride, and the amine component is preferably diamine.

  Examples of the tetracarboxylic dianhydride used for forming the polyimide include 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride. 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenonetetra Carboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis ( 3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2 , 3- Carboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 2,2-bis (3,4-dicarboxy) Phenyl) hexafluoropropane dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, 9,9 -Bis {4- (3,4-dicarboxyphenoxy) phenyl} fluorene dianhydride and the like. These may be used alone or in combination of two or more.

  Examples of diamines used for forming polyimide include, for example, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenylmethane, 3,4′- Diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfide, 3,4 '-Diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, m-phenylenediamine, p-phenylenediamine, 1,4-bis (4-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) fluorene Etc. These may be used alone or in combination of two or more.

  The polyimide can be synthesized, for example, by obtaining a polyimide precursor using a known method and then imidizing the polyimide precursor using a known imidization reaction method. Known synthesis methods for polyimide precursors include, for example, a method of reacting tetracarboxylic dianhydride and diamine at low temperature, a diester obtained by tetracarboxylic dianhydride and alcohol, and then in the presence of a condensing agent. There is a method of reacting with diamine.

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

[Polysiloxane]
As said polysiloxane, the hydrolysis-condensation product of a hydrolysable silane compound is mentioned. Here, the “hydrolyzable silane compound” refers to a compound containing a group that can be hydrolyzed to form a silanol group or a group that can form a siloxane condensate. Further, in the hydrolysis reaction of the hydrolyzable silane compound, some hydrolyzable groups may remain in an unhydrolyzed state in the produced polysiloxane. Here, the “hydrolyzable group” refers to a group capable of forming a silanol group by hydrolysis as described above or a group capable of forming a siloxane condensate. In addition, in the cured film forming composition, some hydrolyzable silane compounds may have a part or all of the hydrolyzable groups in the molecule in an unhydrolyzed state and other hydrolyzable silanes. It may remain in the monomer state without condensing with the compound. The “hydrolysis condensate” means a condensate obtained by condensing silanol groups of a hydrolyzed silane compound.

  The hydrolysis condensate is preferably a hydrolysis condensate containing a radical reactive functional group. In this case, the hydrolysis condensate can be cured by radical polymerization, and the curing shrinkage of the film can be minimized. Examples of the radical reactive functional group include unsaturated organic groups such as a vinyl group, an α-methylvinyl group, a (meth) acryloyl group, and a styryl group. Among these, a (meth) acryloyl group is preferable because the curing reaction proceeds smoothly.

  Among the hydrolyzed condensates of the hydrolyzable silane compound, a hydrolyzable silane compound represented by the following formula (S-1) (hereinafter also referred to as “(s1) compound”) and the following formula (S-2) A hydrolyzable condensate of a hydrolyzable silane compound including the hydrolyzable silane compound (hereinafter also referred to as “(s2) compound”) is preferable.

In the above formula ^{(S-1), R 11} is an alkyl group having 1 to 6 carbon atoms. R ¹² is an organic group containing a radical reactive functional group. p is an integer of 1 to 3. However, when a plurality of R ¹¹ and R ¹² are included, the plurality of R ¹¹ and R ¹² may be the same or different.

In the above formula ^{(S-2), R 13} is an alkyl group having 1 to 6 carbon atoms. R ¹⁴ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a fluorinated alkyl group having 1 to 20 carbon atoms, a phenyl group, a tolyl group, a naphthyl group, an epoxy group, an amino group, or an isocyanate group. n is an integer of 0-20. q is an integer of 0-3. However, when a plurality of R ¹³ and R ¹⁴ are included, the plurality of R ¹³ and R ¹⁴ may be the same or different.

((S1) compound)
(S1) The compound is a hydrolyzable silane compound represented by the above formula (S-1).

The alkyl group having 1 to 6 carbon atoms represented by R ^11, a methyl group, an ethyl group, n- propyl group, i- propyl group, a butyl group. Among these, it is preferable that R ¹¹ is a methyl group or an ethyl group because the (s1) compound is easily hydrolyzed. As said p, 1 and 2 are preferable and 1 is more preferable since a hydrolysis-condensation reaction advances smoothly.

Examples of the organic group containing a radical reactive functional group represented by R ¹² include a hydrocarbon group in which one or more hydrogen atoms are substituted with the above-described radical reactive functional group. Examples of the hydrocarbon group include linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms, aryl groups having 6 to 12 carbon atoms, aralkyl groups having 7 to 12 carbon atoms, and the like. The organic group represented by R ¹² may have a hetero atom. Examples of such an organic group include organic groups containing heteroatom-containing groups such as ether groups, ester groups, and sulfide groups.

  Examples of the compound (s1) when p is 1 include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, o-styryltrimethoxysilane, o-styryltriethoxysilane, m-styryltrimethoxysilane, m-styryltriethoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, methacryloyloxytrimethoxysilane, methacryloyloxytriethoxysilane, methacryloyloxytripropoxysilane, acryloyl Oxytrimethoxysilane, acryloyloxytriethoxysilane, acryloyloxytripropoxysilane, 2-methacryloyloxyethyltrimethoxysilane, 2- Tacryloyloxyethyltriethoxysilane, 2-methacryloyloxyethyltripropoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyltripropoxysilane, 2-acryloyloxyethyltri Methoxysilane, 2-acryloyloxyethyltriethoxysilane, 2-acryloyloxyethyltripropoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltripropoxysilane, 3- Methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-meta Examples include trialkoxysilane compounds such as liloyloxypropyltripropoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, trifluorobutyltrimethoxysilane, and 3- (trimethoxysilyl) propyl succinic anhydride. .

  Examples of the compound (s1) when p is 2 include vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylphenyldimethoxysilane, vinylphenyldiethoxysilane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, and phenyltrifluoro. And dialkoxysilane compounds such as propyldimethoxysilane.

  Examples of the compound (s1) when p is 3 include allyldimethylmethoxysilane, allyldimethylethoxysilane, divinylmethylmethoxysilane, divinylmethylethoxysilane, 3-methacryloyloxypropyldimethylmethoxysilane, and 3-acryloyloxypropyldimethylmethoxy. Silane, 3-methacryloyloxypropyldiphenylmethoxysilane, 3-acryloyloxypropyldiphenylmethoxysilane, 3,3′-dimethacryloyloxypropyldimethoxysilane, 3,3′-diacryloyloxypropyldimethoxysilane, 3,3 ′, 3 '' -Trimethacryloyloxypropylmethoxysilane, 3,3 ', 3' '-triacryloyloxypropylmethoxysilane, dimethyltrifluoropropyl Monoalkoxysilane compounds such Tokishishiran the like.

  Among these (s1) compounds, the scratch resistance of the cured film can be achieved at a high level and the condensation reactivity is increased. Therefore, vinyltrimethoxysilane, p-styryltriethoxysilane, 3-methacryloyloxypropyltrimethyl. Methoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, and 3- (trimethoxysilyl) propyl succinic anhydride are preferred.

((S2) compound)
(S2) The compound is a hydrolyzable silane compound represented by the above formula (S-2).

The alkyl group having 1 to 6 carbon atoms which is represented by the above R ^13, for example, methyl, ethyl, n- propyl, i- propyl, and butyl. Among these, it is preferable that R ¹³ is a methyl group or an ethyl group because the (s2) compound is easily hydrolyzed. The above q is preferably 1 or 2 and more preferably 1 because the hydrolysis and condensation reaction proceeds smoothly.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ¹⁴ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, n-pentyl group, 3-methylbutyl group, 2-methylbutyl group, 1-methylbutyl group, 2,2-dimethylpropyl group, n-hexyl group, 4-methylpentyl group, 3-methylpentyl group, 2-methylpentyl group 1-methylpentyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 1,2-dimethylbutyl group, 1,1 -Dimethylbutyl group, n-heptyl group, 5-methylhexyl group, 4-methylhexyl group, 3-methylhexyl group, 2-methylhexyl group, 1-methylhexyl group, 4,4-di- Methylpentyl group, 3,4-dimethylpentyl group, 2,4-dimethylpentyl group, 1,4-dimethylpentyl group, 3,3-dimethylpentyl group, 2,3-dimethylpentyl group, 1,3-dimethylpentyl group Group, 2,2-dimethylpentyl group, 1,2-dimethylpentyl group, 1,1-dimethylpentyl group, 2,3,3-trimethylbutyl group, 1,3,3-trimethylbutyl group, 1,2, 3-trimethylbutyl group, n-octyl group, 6-methylheptyl group, 5-methylheptyl group, 4-methylheptyl group, 3-methylheptyl group, 2-methylheptyl group, 1-methylheptyl group, 2-ethylhexyl Group, n-nonanyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-heptadecyl group, n-hex Decyl group, n- heptadecyl group, n- octadecyl, n- nonadecyl group and the like. Especially, a C1-C10 alkyl group is preferable and a C1-C3 alkyl group is more preferable.

  As the compound (s2) when q is 0, for example, a silane compound substituted with four hydrolyzable groups, that is, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetra-n-propoxysilane, tetra -I-propoxysilane etc. are mentioned.

  In the case where q is 1, the (s2) compound is a silane compound substituted with one non-hydrolyzable group and three hydrolyzable groups, such as methyltrimethoxysilane, methyltriethoxysilane, methyltri- i-propoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-i-propoxysilane, ethyltributoxysilane, butyltrimethoxysilane, phenyltrimethoxysilane, naphthyltrimethoxysilane, phenyltriethoxy Silane, naphthyltriethoxysilane, aminotrimethoxysilane, aminotriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy, γ-glycidoxypropyltrimethoxysilane, 3-isocyanopropyltrimethoxy Silane, 3-isocyanoacetate triethoxysilane, o- tolyl trimethoxysilane, m- tolyl trimethoxysilane, p- tolyl trimethoxysilane, and the like.

  In the case where q is 2, the (s2) compound is a silane compound substituted with two non-hydrolyzable groups and two hydrolyzable groups, such as dimethyldimethoxysilane, diphenyldimethoxysilane, ditolyldimethoxysilane. And dibutyldimethoxysilane.

  In the case where q is 3, the (s2) compound includes a silane compound substituted with three non-hydrolyzable groups and one hydrolyzable group, such as trimethylmethoxysilane, triphenylmethoxysilane, and tolylmethoxyl. Silane, tributylmethoxysilane, etc. are mentioned.

  Of these (s2) compounds, silane compounds substituted with four hydrolyzable groups and silane compounds substituted with one non-hydrolyzable group and three hydrolyzable groups are preferred, More preferred are silane compounds substituted with one non-hydrolyzable group and three hydrolyzable groups. Particularly preferred hydrolyzable silane compounds include tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-i-propoxysilane, methyltributoxysilane, phenyltrimethoxysilane, tolyltrimethoxysilane, and ethyltrimethoxysilane. , Ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, butyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, naphthyltrimethoxysilane, γ-aminopropyltrimethoxysilane, and γ-isocyanatopropyl A trimethoxysilane is mentioned. Such hydrolyzable silane compounds may be used alone or in combination of two or more.

  (S1) As a minimum of the usage-amount of a compound, 5 mol% is preferable with respect to the total mole number of a (s1) compound and a (s2) compound. When the (s1) compound is less than 5 mol%, the scratch resistance and the like of the resulting cured film tend to be reduced.

(Hydrolytic condensation of (s1) compound and (s2) compound)
The method of hydrolyzing and condensing the compound (s1) and the compound (s2) described above includes hydrolyzing at least a part of the compound (s1) and the compound (s2) to convert the hydrolyzable group into a silanol group, The method is not particularly limited as long as it causes a condensation reaction, and a conventionally known method can be employed.

  Examples of water used for the hydrolysis-condensation reaction include water purified by a method such as reverse osmosis membrane treatment, ion exchange treatment, and distillation. By using such purified water, side reactions can be suppressed and the reactivity of hydrolysis can be improved. As a minimum of the usage-amount of water with respect to 1 mol total amount of the hydrolysable group of the said (s1) compound and (s2) compound, 0.1 mol is preferable, 0.3 mol is more preferable, 0.5 mol is Further preferred. Moreover, as an upper limit of the usage-amount of the said water, 3 mol is preferable, 2 mol is more preferable, and 1.5 mol is further more preferable. By using such an amount of water, the reaction rate of hydrolysis condensation can be optimized.

  The solvent used for the hydrolysis condensation reaction is not particularly limited, and examples thereof include alcohol solvents, ester solvents, ether solvents, and ketone solvents. In addition, a solvent may be used independently or may be used in combination of 2 or more type.

Examples of alcohol solvents include methanol, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, t-butyl alcohol, 1-hexanol, 1-octanol, 1-nonanol, 1-dodecanol, diacetone alcohol, and the like. Alkyl alcohols of
And aromatic alcohols such as benzyl alcohol.

Examples of ether solvents include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether;
Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;
Diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether;
Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether and diethylene glycol ethyl methyl ether;
Examples include dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and dipropylene glycol monobutyl ether.

Examples of the ester solvent include carboxylic acid esters such as ethyl acetate, i-propyl acetate, n-butyl acetate, amyl acetate, ethyl lactate, methyl 3-methoxypropionate and ethyl 3-ethoxypropionate;
Polyhydric alcohol carboxylate solvents such as propylene glycol diacetate;
Examples thereof include polyhydric alcohol partial ether carboxylate solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate.

  Examples of the ketone solvent include acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, methyl amyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, and cycloheptanone.

  Among these, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, methyl isobutyl ketone, cyclopentanone and cyclohexanone are preferred, and diethylene glycol dimethyl ether. Diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether are more preferred.

  A catalyst may be added in the hydrolysis condensation reaction. Examples of the catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and polyphosphoric acid; formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, (anhydrous) maleic acid, tartaric acid, lactic acid, citric acid, and the like Organic acid; acidic ion exchange resin; base catalysts such as aqueous ammonia, triethylamine, tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide, and the like.

  When adding a catalyst, as a minimum of the usage-amount of a catalyst, 0.00001 mol is preferable with respect to a total of 1 mol of the hydrolysable group of a hydrolysable silane compound, and 0.0001 mol is more preferable. Moreover, as an upper limit of the usage-amount of a catalyst, 0.2 mol is preferable with respect to a total of 1 mol of the hydrolysable group of a hydrolysable silane compound, and 0.1 mol is more preferable. By making the usage-amount of a catalyst into the said range, a hydrolysis condensation reaction can be accelerated | stimulated effectively. The catalyst may be charged into the reaction system from the beginning, or may be charged when the temperature reaches a predetermined temperature, or may be charged stepwise or continuously.

  As a minimum of the weight average molecular weight (Mw) of the said polysiloxane, 500 are preferable and 1,000 are more preferable. Moreover, as an upper limit of said Mw, 10,000 are preferable and 5,000 are more preferable. By setting the Mw to the above lower limit or more, the film formability of the cured film forming composition can be improved. On the other hand, a decrease in sensitivity can be suppressed by setting the Mw to the upper limit or less.

[Novolac resin]
The novolak resin can be obtained by polycondensing phenols with aldehydes such as formaldehyde using a known method.

  Examples of the phenols used for obtaining the novolak resin include phenol, p-cresol, m-cresol, o-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2 , 6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2,4 , 5-trimethylphenol, methylene bisphenol, methylene bis p-cresol, resorcin, catechol, 2-methyl resorcin, 4-methyl resorcin, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3-dichlorophenol, m-methoxyphenol, -Methoxyphenol, p-butoxyphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, 2,3-diethylphenol, 2,5-diethylphenol, p-isopropylphenol, α-naphthol, β-naphthol Etc. These may be used alone or in combination of two or more.

  In addition to formaldehyde, aldehydes used to obtain a novolak resin include paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde, and the like. These may be used alone or in combination of two or more.

  As a minimum of the weight average molecular weight (Mw) of the said novolak resin, 2,000 are preferable and 3,000 are more preferable. Further, the upper limit of the Mw is preferably 50,000, and more preferably 40,000. By setting the Mw to the above lower limit or more, the film formability of the cured film forming composition can be improved. On the other hand, a decrease in sensitivity can be suppressed by setting the Mw to the upper limit or less.

  As a minimum of content of [A] binder polymer in the composition for cured film formation, 1 mass% is preferred and 5 mass% is more preferred. Moreover, as an upper limit of the said content, 50 mass% is preferable and 40 mass% is more preferable. [A] By making content of a binder polymer more than the said minimum, the cured film which is higher in hardness and excellent in solvent resistance can be formed, improving a sensitivity more. On the other hand, storage stability can be improved more by making the said content below into the said upper limit.

[[B] polymerizable compound]
[B] The polymerizable compound is not particularly limited as long as it is a compound that is polymerized by irradiation or heating, but a compound having a (meth) acryloyl group, an epoxy group, a vinyl group, or a combination thereof is preferable from the viewpoint of improving sensitivity. A compound having two or more (meth) acryloyl groups in the molecule is more preferable.

  Examples of the [B] polymerizable compound having two or more (meth) acryloyl groups in the molecule include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, Tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, neopentyl Glycol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate 1,6-hexanediol diacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate , Pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol heptaacrylate, tripentaerythritol octaacrylate, tetrapentaerythritol nonaacrylate, tetrapentaerythritol decaacrylate, pentapentaerythritol undecaacrylate, penta Pentaerythritol Decaacrylate, tripentaerythritol heptamethacrylate, tripentaerythritol octamethacrylate, tetrapentaerythritol nonamethacrylate, tetrapentaerythritol decamethacrylate, pentapentaerythritol undecamethacrylate, pentapentaerythritol dodecamethacrylate, dimethylol-tricyclodecane diacrylate, ethoxylation 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-methacryloyloxyethoxy) -3,5 -Dimethylphenyl] fluorene and the like.

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

  [A] The lower limit of the content of the polymerizable compound [B] with respect to 100 parts by mass of the binder polymer is preferably 1 part by mass, more preferably 10 parts by mass, and still more preferably 20 parts by mass. Moreover, as an upper limit of the said content, 200 mass parts is preferable, 150 mass parts is more preferable, and 120 mass parts is further more preferable. By setting the content within the above range, it is possible to form a cured film having higher hardness and higher solvent resistance while further improving storage stability and sensitivity.

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

  [C] The material constituting the QD includes a group 2 element, a group 11 element, a group 12 element, a group 13 element, a group 14 element, a group 15 element, a group 16 element element, and a compound containing a combination thereof. It is done.

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

  In addition, [C] QD has a compound (A) having a fluorescence maximum in a green light wavelength region of 500 nm to 600 nm and / or a compound (B) having a fluorescence maximum in a red light wavelength region of 600 nm to 700 nm. It is preferable to contain.

  [C] A composition for forming a cured film for a light-emitting layer of a light-emitting display element that displays an image using visible light, when QD includes the compound (A) and / or the compound (B) having the above-described fluorescence emission characteristics The cured film forming composition can be applied to a product.

  [C] QD may be a homogenous structure type composed of one compound or a core-shell structure type composed of two or more compounds.

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

[C] As QD, semiconductor quantum dots made of a compound containing In as a constituent element are preferable, and InP / ZnS, InP / ZnSe, CuInS ₂ / ZnS, and (ZnS / AgInS ₂ ) solid solutions that are core-shell structure type semiconductor quantum dots / ZnS and homogeneous structure type semiconductor quantum dots AgInS ₂ and Zn-doped AgInS ₂ are more preferable, and InP / ZnS is more 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 structure type semiconductor quantum dots.

  [C] The lower limit of the average particle diameter of QD is preferably 0.5 nm, and more preferably 1.0 nm. Moreover, as an upper limit of the said average particle diameter, 20 nm is preferable and 10 nm is more preferable. When the average particle size is less than the above lower limit, the fluorescence characteristics of [C] QD may become unstable. On the other hand, when the average particle size of [C] QD exceeds the above upper limit, the quantum confinement effect may not be obtained, and the desired fluorescence characteristics may not be obtained. Here, the average particle diameter refers to the average particle diameter represented by the volume center diameter D50 of the particle size distribution of [C] QD in the dispersion.

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

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

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

  InP / ZnS, which is a core-shell structure type semiconductor quantum dot, can also be synthesized with reference to a method described in, for example, a technical document “Chemistry of Materials. 2015, 27, 4893-4898” relating to semiconductor quantum dots. .

  As a minimum of content of [C] QD in the said composition for cured film formation, 1 mass part is preferable with respect to 100 mass parts of [A] binder polymers, and 10 mass parts is more preferable. Moreover, as an upper limit of the said content, 150 mass parts is preferable with respect to 100 mass parts of [A] binder polymer, and 100 mass parts is more preferable. [C] By setting the content of QD in the above range, a cured film (light emitting layer) having excellent fluorescence characteristics can be formed.

[[D] Dispersant]
[D] Dispersant adheres to the surface of [C] QD as described above, suppresses adhesion of oxygen, moisture, etc. to the surface of [C] QD, and reduces the fluorescence quantum yield of [C] QD. It suppresses the decrease.

  Such a [D] dispersant is not particularly limited as long as it has a site that adheres to the surface of [C] QD. However, the first block consisting of the first repeating unit (hereinafter referred to as polymer block (I)) And a block copolymer (hereinafter simply referred to as “block copolymer”) having at least a second block (hereinafter also referred to as polymer block (II)) composed of a second repeating unit having a higher hydrophilicity than the first repeating unit. Also referred to as “union”). [D] By using the block copolymer as a dispersant, the highly hydrophilic polymer block (II) and [C] QD interact with each other, so that [D] the dispersant is a relatively low hydrophilic polymer. The block (I) is attached to the [C] QD with the outside facing outward. As a result, [C] QDs are uniformly dispersed in the composition for forming a cured film by causing [C] QDs to be separated from each other. Thereby, when a cured film is formed using the composition for forming a cured film, [C] QD is uniformly dispersed, so that the brightness variation of the cured film can be reduced.

  [D] Examples of the acidic functional group contained in the dispersant include a carboxy group, a sulfo group, a hydroxy group, and a phosphate group. Since these acidic functional groups have high adsorptivity to [C] QD, it is possible to effectively suppress the attachment of oxygen, moisture, etc. to the surface of [C] QD. [D] The dispersant may contain one or more of these acidic functional groups. As said acidic functional group, a carboxy group, a sulfo group, and these combination are preferable, and a carboxy group is more preferable. By using these specific acidic functional groups, a decrease in the fluorescence quantum yield of [C] QD can be sufficiently suppressed even after a step of heating after irradiation (hereinafter also referred to as “post-bake”). In these acidic functional groups, hydrogen atoms may be substituted with metal atoms or the like in the composition for forming a cured film.

  The polymer block (I) is preferably composed of the first block composed of the first repeating unit and having hydrophobicity. Specific examples of the first repeating unit include, for example, styrene, α-methylstyrene, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, 2-methylpropane methacrylate, t-butyl methacrylate, pentyl methacrylate, hexyl methacrylate. , Octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, isodecyl methacrylate, lauryl methacrylate, tetradecyl methacrylate, octadecyl methacrylate, behenyl methacrylate, isostearyl methacrylate, cyclohexyl methacrylate, t-butylcyclohexyl methacrylate, isobornyl Methacrylate, trime Le cyclohexyl methacrylate, tricyclodecyl methacrylate, tricyclodecyl methacrylate, tricyclodecyl methacrylate, benzyl methacrylate, phenyl methacrylate, naphthyl methacrylate, allyl methacrylate, phenyl maleimide, those derived from the cyclohexyl maleimide.

  The polymer block (II) is composed of a second block composed of a second repeating unit having higher hydrophilicity than the above-mentioned first repeating unit. For example, the second block contains the above-mentioned acidic functional group and exhibits hydrophilicity. . Specific examples of the second repeating unit include, for example, (meth) acrylic acid, hydroxyethyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethylphthalic acid, and 2-methacryloyl. Oxyethylhexahydrophthalic acid, p-hydroxyphenyl (meth) acrylate, 2- (methacryloyloxy) ethyl phosphate, 3-chloro-2- (phosphonooxy) propyl methacrylate, 2- (methacryloyloxy) propyl phosphate, methacryl Acid 2- (phenoxyphosphonyloxy) ethyl, acid phosphooxypolyoxyethylene glycol monomethacrylate, acid phosphooxypolyoxypropylene glycol monomethacrylate, 2-acryloyloxyethanesulfonic acid, 2 Those derived from methacryloyloxy ethane sulfonic acid and the like.

  Examples of the [D] dispersant composed of the polymer block (I) and the polymer block (II) as described above include a methacrylic acid / methyl methacrylate block copolymer, a methacrylic acid / ethylhexyl methacrylate copolymer, and a methacrylic acid. Acid / benzyl methacrylate block copolymer, methacrylic acid / cyclohexyl methacrylate block copolymer, methacrylic acid / tricyclodecyl methacrylate block copolymer, 2-methacryloyloxyethyl succinic acid / methyl methacrylate block copolymer, 2-methacryloyloxy Ethyl succinic acid / ethyl hexyl methacrylate block copolymer, 2-methacryloyloxyethyl succinic acid / benzyl methacrylate block copolymer, 2-methacryloyloxyethyl succinate / Cyclohexyl methacrylate block copolymer, 2- (methacryloyloxy) ethyl phosphate / methyl methacrylate block copolymer, 2- (methacryloyloxy) ethyl phosphate / ethylhexyl methacrylate block copolymer, 2- (methacryloyloxy) phosphate Ethyl / benzyl methacrylate block copolymer, 2- (methacryloyloxy) ethyl phosphate / cyclohexyl methacrylate block copolymer, 2- (methacryloyloxy) ethyl phosphate / tricyclodecyl methacrylate block copolymer, 2-methacryloyloxyethane Sulfonic acid / methyl methacrylate block copolymer, 2-methacryloyloxyethanesulfonic acid / ethylhexyl methacrylate block copolymer, 2-methacryloyl o Shi ethanesulfonic acid / benzyl methacrylate block copolymer, 2-methacryloyloxy ethane sulfonic acid / cyclohexyl methacrylate block copolymer, 2-methacryloyloxy ethane sulfonic acid / tricyclodecylacrylate methacrylate block copolymer.

  [C] From the viewpoint of more effectively suppressing the adhesion of oxygen, moisture, etc. to the surface of QD, [D] As the dispersant, methacrylic acid / ethylhexyl methacrylate copolymer, methacrylic acid / benzyl methacrylate block copolymer Copolymer, methacrylic acid / cyclohexyl methacrylate block copolymer, methacrylic acid / tricyclodecyl methacrylate block copolymer, 2-methacryloyloxyethyl succinic acid / ethylhexyl methacrylate block copolymer, 2-methacryloyloxyethyl succinic acid / benzyl methacrylate block Copolymers and 2-methacryloyloxyethyl succinic acid / cyclohexyl methacrylate block copolymers are preferred, methacrylic acid / benzyl methacrylate copolymers, methacrylic acid / cyclohexyl Tacrylate block copolymer, methacrylic acid / tricyclodecyl methacrylate block copolymer, 2-methacryloyloxyethyl succinic acid / benzyl methacrylate block copolymer, 2-methacryloyloxyethyl succinic acid / cyclohexyl methacrylate block copolymer, and 2-Methacryloyloxyethyl succinic acid / tricyclodecyl methacrylate block copolymer is more preferred.

  The [D] dispersant having a phosphate group is preferably a polyoxyethylene alkyl phosphate ester represented by the following formula (1).

In the above formula (1), ^{R 3} _{is, C q H 2q + 1 -CH} 2 O- (CH 2 CH 2 O) q '-CH 2 CH 2 is O-. q is an integer of 8-10. q 'is an integer of 12-16. k is an integer of 1 to 3.

  [D] The lower limit of the acid value of the dispersant is 5 mgKOH / g, preferably 7 mgKOH / g, and more preferably 10 mgKOH / g. [D] The upper limit of the acid value of the dispersant is 150 mgKOH / g, preferably 140 mgKOH / g, and more preferably 130 mgKOH / g. By making the acid value of the dispersant within the above-mentioned preferable range, it is possible to further suppress the adhesion of oxygen and moisture to [C] QD, and as a result, further suppress the decrease in the fluorescence quantum yield of [C] QD. can do.

  [A] As a minimum of content of [D] dispersing agent to 100 mass parts of binder polymers, 0.1 mass part is preferred, 0.5 mass part is more preferred, and 1 mass part is still more preferred. Moreover, as an upper limit of the said content, 20 mass parts is preferable, 15 mass parts is more preferable, and 10 mass parts is further more preferable. By making the content within the above range, it is possible to further suppress the adhesion of oxygen and moisture to [C] QD, and as a result, further suppress the decrease in the fluorescence quantum yield of [C] QD. Can do.

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

  [E] Examples of the radiation sensitive compound include a radiation sensitive radical polymerization initiator, a radiation sensitive acid generator, a radiation sensitive base generator, and combinations thereof.

  For example, when a radical polymerizable compound is used as the [B] polymerizable compound, the radiation sensitive radical polymerization initiator can further promote the curing reaction by radiation of the cured film forming composition.

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

  Specific examples of the radiation-sensitive radical polymerization initiator include, for example, O-acyl oxime compounds, α-amino ketone compounds, α-hydroxy ketone compounds, acyl phosphine oxide compounds, and the like.

  Examples of the O-acyloxime compound include 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate, 1- [9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -octane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxy Benzoyl} -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone, 1- [9 -Ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime) and the like.

  Examples of the α-aminoketone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- ( 4-morpholin-4-yl-phenyl) -butan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, and the like.

  Examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one and 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one. 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone and the like.

  Examples of the acylphosphine oxide compound include diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like.

  The radiation sensitive radical polymerization initiator is preferably an O-acyl oxime compound, an α-aminoketone compound and an acyl phosphine oxide compound from the viewpoint of further promoting the curing reaction by radiation. Etanone, 1- [9-ethyl-6 -(2-Methylbenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)], 2-methyl-1- (4-Methylthiophenyl) -2-morpholinopropan-1-one and diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide are more preferred.

  The radiation sensitive acid generator can increase the radiation sensitivity of the composition for forming a cured film when a compound whose curing reaction is accelerated by an acid such as polysiloxane is used as the [A] binder polymer. Examples of the radiation sensitive acid generator include compounds that generate an acid upon exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray.

  Specific examples of the radiation-sensitive acid generator include, for example, an iodonium salt-based radiation sensitive acid generator, a sulfonium salt-based radiation sensitive acid generator, a tetrahydrothiophenium salt-based radiation sensitive acid generator, and an imide sulfonate system. A radiation sensitive acid generator, an oxime sulfonate type radiation sensitive acid generator, a quinonediazide compound, etc. are mentioned.

  Examples of the iodonium salt-based radiation-sensitive acid generator include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium pyrenesulfonate, diphenyliodonium dodecylbenzenesulfonate, diphenyliodonium nonafluoro n-butanesulfonate, and bis (4-t-butylphenyl) iodonium. Trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium dodecylbenzenesulfonate, bis (4-t-butylphenyl) iodonium naphthalenesulfonate, bis (4-t-butylphenyl) iodonium hexafluoroantimonate, bis (4- t-butylphenyl) iodonium nonafluoro n-butanesulfonate, diphenyliodonium hexafluoroantimony Over doors and the like.

  Examples of the sulfonium salt-based radiation-sensitive acid generator include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium naphthalenesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, and (hydroxyphenyl). Benzenemethylsulfonium toluenesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, dicyclohexyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, dimethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonate, 4-hydroxy Phenyl) benzylmethylsulfonium toluenesulfonate, 1-naphthyldimethylsulfonium trifluoromethanesulfonate, 1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-cyano-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-nitro-1-naphthyldimethylsulfonium trifluoromethane Sulfonate, 4-methyl-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-cyano-1-naphthyl-diethylsulfonium trifluoromethanesulfonate, 4-nitro-1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-methyl-1-naphthyldiethyl Sulfonium trifluoromethanesulfonate, 4-hydroxy-1- Borderless Le dimethyl sulfonium trifluoromethanesulfonate, and the like.

  Examples of the tetrahydrothiophenium salt-based radiation sensitive acid generator include 4-hydroxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-methoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, and 4-ethoxy. -1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-methoxymethoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-ethoxymethoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4- (1-methoxy Ethoxy) -1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4- (2-methoxyethoxy) -1-naphthyltetrahydrothioff Nium trifluoromethanesulfonate, 4-methoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-ethoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-n-propoxycarbonyloxy-1-naphthyl Tetrahydrothiophenium trifluoromethanesulfonate, 4-i-propoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-n-butoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-t- Butoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4- ( -Tetrahydrofuranyloxy) -1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4- (2-tetrahydropyranyloxy) -1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-benzyloxy-1-naphthyltetrahydrothiofe Examples thereof include nium trifluoromethanesulfonate, 1- (naphthylacetomethyl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4,7-dibutoxy-1-naphthyl) tetrahydrothiophenium trifluoromethanesulfonate, and the like.

  Examples of the imide sulfonate-based radiation-sensitive acid generator include trifluoromethylsulfonyloxybicyclo [2.2.1] hept-5-enedicarboximide, succinimide trifluoromethyl sulfonate, phthalimide trifluoromethyl sulfonate, and N-hydroxy. Naphthalimidomethanesulfonate, N-hydroxy-5-norbornene-2,3-dicarboximidepropanesulfonate, and the like can be given.

  Examples of the oxime sulfonate-based radiation-sensitive acid generator include (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (5-octylsulfonyloxyimino-5H-thiophene). -2-ylidene)-(2-methylphenyl) acetonitrile, (camphorsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl) acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophene) 2-ylidene)-(2-methylphenyl) acetonitrile, (5-octylsulfonyloxyimino)-(4-methoxyphenyl) acetonitrile, and the like.

  Examples of the quinonediazide compound include 1,2-naphthoquinone diazide sulfonate of trihydroxybenzophenone, 1,2-naphthoquinone diazide sulfonate of tetrahydroxybenzophenone, 1,2-naphthoquinone diazide sulfonate of pentahydroxybenzophenone, hexa 1,2-naphthoquinone diazide sulfonic acid ester of hydroxybenzophenone, 1,2-naphthoquinone diazide sulfonic acid ester of (polyhydroxyphenyl) alkane, and the like.

  Examples of the 1,2-naphthoquinonediazide sulfonic acid ester of trihydroxybenzophenone include 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone azido-4-sulfonic acid ester and 2,3,4-trihydroxybenzophenone. -1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2 -Naphthoquinonediazide-5-sulfonic acid ester etc. are mentioned.

  Examples of the 1,2-naphthoquinone diazide sulfonic acid ester of tetrahydroxybenzophenone include 2,2 ′, 4,4′-tetrahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,2 ′, 4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,3′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2, 3,4,3′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,4'-tetrahydroxybenzofe 1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,2′-tetrahydroxy-4′-methylbenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4 4,2′-tetrahydroxy-4′-methylbenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,4′-tetrahydroxy-3′-methoxybenzophenone-1,2-naphtho Examples thereof include quinonediazide-4-sulfonic acid ester and 2,3,4,4′-tetrahydroxy-3′-methoxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester.

  Examples of the 1,2-naphthoquinone diazide sulfonic acid ester of pentahydroxybenzophenone include 2,3,4,2 ′, 6′-pentahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,3 , 4,2 ′, 6′-pentahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester and the like.

  Examples of the 1,2-naphthoquinone diazide sulfonic acid ester of hexahydroxybenzophenone include 2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 3,4,5,3 ′, 4 ′, 5′-hexahydroxybenzophenone -1,2-naphthoquinonediazide-4-sulfonic acid ester, 3,4,5,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, and the like.

  Examples of the 1,2-naphthoquinone diazide sulfonic acid ester of the above (polyhydroxyphenyl) alkane include, for example, bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinone diazide-4-sulfonic acid ester, bis (2,4 -Dihydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (p-hydroxyphenyl) methane- 1,2-naphthoquinonediazide-5-sulfonic acid ester, tri (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, tri (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide -5-sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-5 -Sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) methane-1,2- Naphthoquinonediazide-5-sulfonic acid ester, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2-bis (2,3, 4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,1,3-tris (2 5-Dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3- Phenylpropane-1,2-naphthoquinonediazide-5-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-hydroxyphenyl) -2-hydroxyphenylmethane -1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid ester, and the like. .

  As the radiation-sensitive acid generator, from the viewpoint of further promoting the curing reaction, an oxime sulfonate-based radiation-sensitive acid generator and a quinonediazide compound are preferable, and (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene) is preferable. )-(2-methylphenyl) acetonitrile and 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-5-sulfonic acid ester are more preferred.

  When the compound whose curing reaction is accelerated by a base such as polysiloxane is used as the [A] binder polymer, the radiation sensitive base generator can further enhance the radiation sensitivity of the cured film forming composition. Examples of the radiation sensitive base generator include compounds that generate a base upon exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray.

Specific examples of the radiation sensitive base generator include, for example, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoethane, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, 2-benzyl- Heterocyclic group-containing radiation sensitivity such as 2-dimethylamino-1- (4-morpholinophenyl) -butanone, N- (2-nitrobenzyloxycarbonyl) pyrrolidine, 1- (anthraquinone-2-yl) ethylimidazolecarboxylate Base generator;
2-nitrobenzylcyclohexylcarbamate, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, bis [[(2-nitrobenzyl) oxy] carbonyl] hexane-1,6-diamine, triphenylmethanol, o -Carbamoylhydroxylamide, o-carbamoyloxime, hexaamminecobalt (III) tris (triphenylmethylborate), 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidinium n-butyltriphenylborate From the viewpoint of further promoting the curing reaction, 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidinium n-butyltriphenylborate is preferable.

  When the said cured film formation composition contains a [E] radiation sensitive compound, as a minimum of content of a [E] radiation sensitive compound, 1 mass part is with respect to 100 mass parts of [A] binder polymers. Preferably, 10 parts by mass is more preferable. Moreover, as an upper limit of the said content, 50 mass parts is preferable with respect to 100 mass parts of [A] binder polymers, and 40 mass parts is more preferable. By setting the content in the above range, the radiation sensitivity of the cured film forming composition can be further increased.

[[F] solvent]
The composition for forming a cured film may contain a [F] solvent in addition to the above components. When the composition for forming a cured film contains a [F] solvent, the coating property is improved. [F] The solvent is not particularly limited as long as the above-described components can be dissolved or dispersed, and examples thereof include a solvent used when the above-described [a] polymer or polysiloxane is synthesized. In addition, a [F] solvent may be used independently and may be used in combination of 2 or more type.

[[G] Other ingredients]
In addition to the components described above, the cured film-forming composition may contain 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. [G] Other components may be used alone or in combination of two or more. When the said composition for cured film formation contains [G] other components, as an upper limit of the content, 10 mass parts is preferable with respect to 100 mass parts of [A] binder polymers, and 1 mass part is more preferable.

  The composition for forming a cured film can be prepared by an appropriate method. For example, in a [F] solvent, [A] a binder polymer, [B] a polymerizable compound, [C] QD, [D It can be prepared by mixing a dispersant and, if necessary, optional components. When preparing, [C] QD and a [D] dispersing agent can also be contained by mix | blending the said dispersion liquid mentioned later. As a minimum of the concentration of solid content in the composition at the time of mixing, 5 mass% is preferred and 10 mass% is more preferred. Moreover, as an upper limit of the said density | concentration, 80 mass% is preferable and 70 mass% is more preferable. By making the concentration of the solid content in the above range, the coating property can be improved. The “solid content” means a residue obtained by drying a sample on a hot plate at 175 ° C. for 1 hour to remove volatile substances.

<Curing film>
The cured film is obtained from the cured film forming composition. Since the said cured film is obtained with the said composition for cured film formation, the fall of the fluorescence quantum yield of QD is suppressed and the cured film which has high color reproducibility, for example can be provided. The cured film may be patterned or unpatterned. However, when the cured film is patterned, the cured film can be applied to a light-emitting layer useful as a subpixel. The method for forming the cured film is not particularly limited, and for example, a method of curing by radiation irradiation or a method of curing by heating may be used, but a method of curing by radiation irradiation described later can be applied. preferable. According to this method, a patterned cured film (light emitting layer) can be formed.

  The cured film is suitable for use as a light emitting layer of a light emitting display element. Hereinafter, preferred embodiments of the light-emitting display element will be described.

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

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

  The light emitting layer 13 of the wavelength conversion substrate 11 is formed by patterning using the cured film forming composition described above. Since the light emitting layer 13 is formed using the said composition for cured film formation, the fall of the fluorescence quantum yield of QD can be suppressed, for example, it can be set as a light emitting layer with high color reproducibility.

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

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

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

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

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

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

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

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

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

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

  The light-emitting display element 100 having the above configuration includes red, green, or green for each sub-pixel including the first light-emitting layer 13a, sub-pixel including the second light-emitting layer 13b, and sub-pixel including the third light-emitting layer 13c. The emission of blue light is controlled, and full color display is performed.

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

<Method for forming cured film>
The method for forming the cured film includes a step of forming a coating film on one surface side of the substrate (hereinafter also referred to as “coating film forming step”), and a step of irradiating (exposing) radiation to at least a part of the coating film. (Hereinafter also referred to as “radiation irradiation step”), a step of developing the coating film after radiation irradiation (hereinafter also referred to as “coating layer development step”), and a step of heating the coating layer (hereinafter referred to as “coating layer heating step”). The said coating film is formed with the said composition for cured film formation containing a radiation sensitive compound.

  According to the cured film forming method, since the cured film forming composition described above is used, it is possible to easily and reliably form a cured film in which a decrease in the fluorescence quantum yield of QD is suppressed. Hereinafter, each step will be described.

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

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

  The coating method of the cured film forming composition is not particularly limited, and for example, a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, or the like may be employed. it can. Among these coating methods, spin coating and slit die coating are preferable. The heating (pre-baking) conditions vary depending on the type of each component, the blending ratio, and the like.

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

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

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

[Coating film development process]
In the coating film developing process, the coating film after irradiation is developed to remove unnecessary portions.

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

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

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

  The lower limit of the heating temperature in this step is preferably 100 ° C. The upper limit of the heating temperature is preferably 250 ° C. When heating is performed with a hot plate, the lower limit of the heating time is preferably 5 minutes, and the upper limit is preferably 30 minutes. When heating is performed in an oven, the lower limit of the heating time is preferably 10 minutes, and the upper limit is preferably 180 minutes.

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

<Dispersion>
The dispersion contains QD, a dispersant containing an acidic functional group, and a solvent, and the dispersant has an acid value of 5 mgKOH / g or more and 150 mgKOH / g or less. The said dispersion liquid is suitable as a raw material liquid which mix | blends [C] QD and a [D] dispersing agent, when preparing the said composition for cured film formation mentioned above. That is, the dispersant containing QD and acidic functional group contained in the dispersion is the same as [C] QD and [D] dispersant of the cured film forming composition described above, respectively. The solvent contained in the dispersion is the same as the [F] solvent described as an optional component of the cured film-forming composition described above. Therefore, the QD of the dispersion, the dispersant containing an acidic functional group, and the solvent are described as [C] QD, [D] dispersant, and [F] solvent of the cured film forming composition, respectively. Therefore, explanation is omitted here. In addition, the said composition for cured film formation does not use the said dispersion liquid, for example, in [F] solvent, [A] binder polymer, [B] polymeric compound, [C] QD, [D] dispersing agent. Etc. can also be prepared by blending them sequentially.

  As a minimum of content of QD in solid content of the dispersion, 1 mass% is preferred, 2 mass% is more preferred, and 3 mass% is still more preferred. Further, the upper limit of the content of QD in the solid content of the dispersion is preferably 50% by mass, more preferably 40% by mass, and further preferably 30% by mass. By making the content within the above range, the preparation of the cured film forming composition becomes easier.

  As a minimum of content of a dispersing agent containing an acidic functional group in solid content of the dispersion, 1 mass% is preferred, 2 mass% is more preferred, and 3 mass% is still more preferred. Moreover, as an upper limit of content of the dispersing agent containing the acidic functional group in the solid content of the dispersion, 99% by mass is preferable, 95% by mass is more preferable, and 90% by mass is further preferable. By making the content within the above range, the preparation of the cured film forming composition becomes easier.

  The lower limit of the solid content concentration of the dispersion is preferably 1% by mass, more preferably 3% by mass, and even more preferably 5% by mass. Moreover, as an upper limit of the solid content density | concentration of the said dispersion liquid, 80 mass% is preferable, 70 mass% is more preferable, and 60 mass% is further more preferable. By making the said solid content density | concentration into the said range, preparation of the said composition for cured film formation becomes easier.

  The dispersion may contain other components such as a storage stabilizer and an adhesion aid in addition to the above components. The other components may be used alone or in combination of two or more. When the said dispersion contains the said other component, as an upper limit of the content, it is about 10 mass%.

  In addition, the said dispersion liquid is not limited to the use as a raw material liquid of the said composition for cured film formation. For example, a light-emitting film that can suppress a decrease in the fluorescence quantum yield of QD can be produced by preparing a resin composition obtained by mixing the dispersion and a thermoplastic resin and forming the resin composition. Moreover, the light emission pattern which can suppress the fall of the fluorescence quantum yield of QD by preparing the resin composition which mixed the resin and photocurable compound which are soluble in the said dispersion liquid and an alkali or a solvent, and patterning this Can also be manufactured. Moreover, white light emission which can suppress the fall of the fluorescence quantum yield of QD is prepared by preparing the resin composition which mixed the said dispersion liquid and a thermosetting composition, and potting this to the sealing part of a blue light emitting diode. Diodes can also be manufactured. Also, a luminescent glass capillary capable of suppressing a decrease in QD fluorescence quantum yield is prepared by preparing a resin composition in which the dispersion and the heat or photocurable composition are mixed, encapsulating the resin composition in a glass capillary, and curing the resin composition. It can also be manufactured.

<Other embodiments>
The preferred embodiments of the present invention have been described above, but the present invention is not limited to these embodiments. For example, in the above preferred embodiment, an example in which the composition for forming a cured film of the present invention is applied to a sub-pixel of a light-emitting display element has been described. However, the present invention is not limited to this, and is applied to a backlight unit of a liquid crystal display. Can also be applied. For example, when a blue light emitting diode is used as a light source of a backlight unit, white light with high purity can be obtained by combining with the cured film obtained by the cured film forming composition of the present invention including G-QD and R-QD described above. Can be reproduced.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples.

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

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

<Synthesis of binder polymer ([a] polymer)>
[Synthesis Example 1] Synthesis of Polymer (A-1) A flask equipped with a condenser and a stirrer was charged with 150 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. Heat to 80 ° C., and at the same temperature, 50 parts by weight of propylene glycol monomethyl ether acetate, 10 parts by weight of methacrylic acid, 30 parts by weight of cyclohexyl methacrylate, 10 parts by weight of styrene, 20 parts by weight of mono (2-methacryloyloxyethyl) succinate Solution of 3 parts by weight, 3 parts by weight of 2-hydroxyethyl methacrylate, 15 parts by weight of 2-ethylhexyl methacrylate, 12 parts by weight of N-phenylmaleimide and 6 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) Was added dropwise over 2 hours, and polymerization was carried out for 1 hour while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 90 ° C., and further polymerized for 1 hour to obtain a propylene glycol monomethyl ether acetate solution (solid content concentration: 33% by mass) of the polymer (A-1). The obtained polymer (A-1) was Mw = 10,800, Mn = 5,900, and Mw / Mn = 1.83.

<Preparation of composition for forming cured film, formation of cured film, and evaluation of physical properties>
Each component used for preparation of each composition for forming a cured film is shown below.

[[A] Binder polymer]
A-1: Polymer (A-1)

[[B] polymerizable compound]
B-1: Dipentaerythritol hexaacrylate

[[C] QD]
C-1: InP / ZnS (average particle diameter: 4 nm) which is a core-shell structure type semiconductor quantum dot

[[D] Dispersant]
D-1: Methacrylic acid / benzyl methacrylate block copolymer (acid value 101 mgKOH / g)
D-2: 2-methacryloyloxyethyl succinic acid / benzyl methacrylate block copolymer (acid value 53 mgKOH / g)
D-3: 2-methacryloyloxyethyl succinic acid / tricyclodecyl methacrylate block copolymer (acid value 11 mgKOH / g)
The above [D] dispersant is a block copolymer having a carboxy group and a polymer block (I) having a relatively low hydrophilicity and a polymer block (II) having a relatively high hydrophilicity.

[[E] Radiation sensitive compound]
E-1: Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide ("LUCIRIN TPO" from BASF)
E-2: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one ("Irgacure 907" from BASF)
E-3: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime) ("Irgacure OXE02" from BASF)
E-4: 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)] (“Irgacure OXE01” from BASF)

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

[Example 1]
90 parts by mass of propylene glycol monomethyl ether acetate solution of the synthesized polymer (A-1) (30 parts by mass of (A-1) as [A] binder polymer and 60 parts by mass of (F-1) as solvent [F]. (B-1) as a polymerizable compound (B-1) 30 parts by mass, [C] QD as (C-1) 10 parts by mass, [D] as a dispersant (D-1) 2 parts by mass and 5 parts by mass of (E-1) as a radiation sensitive compound [E] were added to prepare a composition for forming a cured film of Example 1.

[Example 2, Example 3 and Comparative Example 1]
Each cured film forming composition was prepared in the same manner as in Example 1 except that the types and blending amounts of the blending components were as shown in Table 1 below. In Table 1, “-” indicates that the corresponding component was not used.

  About each obtained composition for cured film formation, it evaluated in accordance with the following method. The evaluation results are shown in Table 1.

[Fluorescence quantum yield]
The fluorescence quantum yield was measured at 25 ° C. using an absolute PL fluorescence quantum yield measurement apparatus (“C11347-01” from Hamamatsu Photonics) for a cured film obtained by the following formation method. Separately, the cured film obtained by the following forming method was subjected to a heat treatment (post-baking) at 180 ° C. for 20 minutes in a clean oven, and then the fluorescence quantum yield was measured by the same method as described above. Table 1 shows the former fluorescence quantum yield as “untreated” and the latter fluorescence quantum yield as “after heat treatment”.

(Method for forming cured film)
After coating each composition for forming a cured film on an alkali-free glass substrate with a spinner, a coating film was formed by prebaking on a hot plate at 90 ° C. for 2 minutes. Next, the obtained coating film was irradiated with radiation including wavelengths of 365 nm, 405 nm, and 436 nm at a cumulative dose of 700 J / m ² using a high-pressure mercury lamp without using a photomask. A cured film having a thickness of 5 μm was formed.

[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 decrease in the fluorescence quantum yield of [C] QD after post-baking is suppressed as the change rate of the fluorescence quantum yield is smaller.
Change rate of fluorescence quantum yield (%) = {(Φ ₁ −Φ ₂ ) / Φ ₁ } × 100

  As is clear from the results in Table 1, in Examples, the fluorescence quantum yield after treatment and heat treatment, and the change rate of the fluorescence quantum yield were all good. On the other hand, Comparative Example 1 was inferior to Examples for any of the above evaluation items.

  ADVANTAGE OF THE INVENTION According to this invention, the cured film formation composition which can suppress the fall of the fluorescence quantum yield of QD, the cured film obtained by the said cured film formation composition, The cured film formed with the said composition for cured film formation The dispersion liquid suitable for the light emitting display element provided with this, the formation method of the said cured film, and the said composition for cured film formation can be provided.

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

Claims (9)

Binder polymer,
Polymerizable compounds,
Containing a semiconductor quantum dot and a dispersant containing an acidic functional group,
A composition for forming a cured film, wherein the acid value of the dispersant is from 5 mgKOH / g to 150 mgKOH / g.   The composition for forming a cured film according to claim 1, wherein the dispersant contains a carboxy group, a sulfo group, or a combination thereof as an acidic functional group.   The said dispersing agent is a block copolymer which has the 1st block which consists of a 1st repeating unit, and the 2nd block which consists of a 2nd repeating unit whose hydrophilicity is higher than a 1st repeating unit. 2. The composition for forming a cured film as described in 2.   The composition for forming a cured film according to claim 1, wherein the binder polymer contains an alkali-soluble resin.   The composition for forming a cured film according to any one of claims 1 to 4, further comprising a radiation-sensitive compound.   The cured film formed with the composition for cured film formation of any one of Claims 1-5.   A light emitting display element provided with the cured film formed of the composition for cured film formation of any one of Claims 1-5. Forming a coating film on one side of the substrate;
Irradiating at least a part of the coating film with radiation,
A step of developing the coating film after irradiation, and a step of heating the coating film after development,
The formation method of the cured film which forms the said coating film with the composition for cured film formation of Claim 5. Semiconductor quantum dots,
Containing a dispersant containing an acidic functional group, and a solvent,
A dispersion in which the acid value of the dispersant is 5 mgKOH / g or more and 150 mgKOH / g or less.

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