JP7512071B2 - CURABLE RESIN COMPOSITION, CURED FILM AND DISPLAY DEVICE - Google Patents

Description

The present invention relates to a curable resin composition, a cured film formed from the composition, and a display device including the cured film.

Curable resin compositions containing semiconductor particles such as semiconductor quantum dots are known for forming cured films such as wavelength conversion films included in display devices such as image display devices [for example, JP 2015-028139 A (Patent Document 1)]. JP 2005-128539 A (Patent Document 2) describes semiconductor nanocrystals with a compound having a photosensitive functional group coordinated on the surface, and a photosensitive composition containing the same.

JP 2015-028139 A JP 2005-128539 A

Cured films such as wavelength conversion films are required to be patterned by photolithography or the like. The object of the present invention is to provide a curable resin composition containing semiconductor particles and having good patterning properties, a cured film formed therefrom, and a display device including the cured film.

The present invention provides the following curable resin composition, cured film, and display device.
[1] A curable resin composition comprising semiconductor particles (A), a compound (B) containing a polyalkylene glycol structure and having a polar group at a molecular end, a resin (C), and a polymerizable compound (D).

[2] The curable resin composition according to [1], in which at least a portion of the compound (B) is coordinated to the semiconductor particles (A).

[3] The curable resin composition according to [1] or [2], wherein the polar group is at least one group selected from the group consisting of a thiol group, a carboxyl group, and an amino group.

[4] The curable resin composition according to any one of [1] to [3], wherein the compound (B) has a molecular weight of 500 or more and 5,000 or less.

[5] The semiconductor particle (A) further includes a compound (L) other than the compound (B), the compound (L) having a coordination ability with the semiconductor particle (A),
The ratio of the total amount of the compound (B) and the compound (L) to the semiconductor particles (A) is 0.1 to 1.5 in terms of mass ratio. The curable resin composition according to any one of [1] to [4].

[6] A cured film formed from the curable resin composition described in any one of [1] to [5].

[7] A display device including the cured film described in [6].

According to the present invention, it is possible to provide a curable resin composition containing semiconductor particles and having good patterning properties, a cured film formed therefrom, and a display device containing the cured film.

<Curable resin composition>
The curable resin composition according to the present invention includes semiconductor particles (A), a compound (B) having a polyalkylene glycol structure and a polar group at the molecular end (hereinafter also referred to as "compound (B)"). ), a resin (C) and a polymerizable compound (D). The curable resin composition can exhibit good patterning properties. For example, the curable resin composition can accurately form a patterned cured film having a desired line width. The curable resin composition can accurately form a patterned cured film even when the line width is relatively narrow.

In addition, the curable resin composition according to the present invention can form a cured film that retains quantum yield (QY) even after post-baking, and a patterned cured film (such as a wavelength conversion film). In this specification, the quantum yield (%) of a cured film (after post-baking) formed from the curable resin composition when the quantum yield of the curable resin composition (before curing) is taken as 100% is referred to as "QY retention" (%). The QY retention is measured as described in the Examples section below.

In addition, the compounds exemplified in this specification as components that are or can be contained in the curable resin composition can be used alone or in combination, unless otherwise specified.

[1] Semiconductor particles (A)
The curable resin composition contains semiconductor particles (A). The semiconductor particles (A) are preferably luminescent (fluorescent) semiconductor particles. A cured film such as a wavelength conversion film formed from the curable resin composition containing the luminescent semiconductor particles can have excellent color reproducibility and exhibit fluorescent emission in a desired wavelength range.

The luminescent semiconductor particles are particles made of semiconductor crystals, preferably nanoparticles made of semiconductor crystals. A preferred example of the luminescent semiconductor particles is semiconductor quantum dots. The average particle size of the semiconductor quantum dots is, for example, 0.5 nm to 20 nm, preferably 1 nm to 15 nm (for example, 2 nm to 15 nm). The average particle size of the semiconductor quantum dots can be determined using a transmission electron microscope (TEM).

The semiconductor quantum dots can be composed of a semiconductor material containing one or more elements selected from the group consisting of Group 2 elements, Group 11 elements, Group 12 elements, Group 13 elements, Group 14 elements, Group 15 elements, and Group 16 elements of the periodic table.

Specific examples of semiconductor materials that can form semiconductor quantum dots include compounds of Group 14 elements and Group 16 elements, such as _SnS2 , SnS, SnSe, SnTe, PbS, PbSe, and PbTe; compounds of Group 13 elements and Group 15 elements, such as GaN, GaP, GaAs, GaSb, InN, InP _, InAs, InSb, InGaN, and InGaP; _Ga2O3 , _{Ga2S3 , Ga2Se3 , Ga2Te3 , In2O3 , In2S3 , In2Se3} , _{and In2Te .} compounds of Group 13 elements and Group 16 elements, such as ZnO, ZnS, _ZnSe , ZnTe, CdO, CdS, CdSe, CdTe, HgO, _{HgS ,} HgSe, HgTe; compounds of Group ₁₂ elements and Group 16 elements, such as _{As2O3, As2S3 , As2Se3 , As2Te3 , Sb2O3 , Sb2S3 , Sb2Se3 , Sb2Te3 , Bi2O3 , Bi2S3} , _{Bi2Se3 , Bi2Te} compounds of Group ₁₅ elements and Group 16 elements, such as CaS, CaSe, CaTe, SrS, SrSe, SrTe, BaS, BaSe, BaTe; and simple substances of Group 14 elements, Group 15 elements, or Group 16 elements, such as Si and Ge.

The semiconductor quantum dots may have a single-layer structure made of a single semiconductor material, or a core-shell structure in which the surface of a core particle (core layer) made of a single semiconductor material is covered with a coating layer (shell layer) made of one or more different semiconductor materials. In the latter case, the semiconductor material constituting the shell layer is usually one having a larger band gap energy than the semiconductor material constituting the core layer. The semiconductor quantum dots may have two or more shell layers. The shape of the semiconductor quantum dots is not particularly limited, and may be, for example, spherical or nearly spherical, rod-like, disc-like, etc.

The content of the semiconductor particles (A) is, for example, 0.1 parts by mass or more and 50 parts by mass or less, preferably 1 part by mass or more and 40 parts by mass or less, and more preferably 2 parts by mass or more and 30 parts by mass or less, per 100 parts by mass of the solid content of the curable resin composition. If the content of the semiconductor particles (A) is excessively small, it tends to be difficult to obtain sufficient luminescence intensity in the cured film (wavelength conversion film, etc.). If the content of the semiconductor particles (A) is excessively large, the mechanical strength and patterning property of the cured film (wavelength conversion film, etc.) tend to decrease. In this specification, the "solid content of the curable resin composition" refers to the total of the components other than the solvent (F) contained in the curable resin composition.

[2] Compound (B)
The compound (B) contained in the curable resin composition is an organic compound containing a polyalkylene glycol structure and having a polar group at the molecular end. By including the compound (B) in the curable resin composition, it is possible to improve the patterning property of the curable resin composition containing the semiconductor particles (A). In addition, including the compound (B) in the curable resin composition can also contribute to increasing the QY retention rate. The molecular end is preferably the end of the longest carbon chain in the compound (B) (the carbon atom in the carbon chain may be replaced with another atom such as an oxygen atom).

The polyalkylene glycol structure is the following formula:

(n is an integer of 2 or more) In the formula, R ¹ is an alkylene group, for example, an ethylene group, a propylene group, etc.
Specific examples of the compound (B) include the compound represented by the following formula (B-1):

In formula (B-1), X is a polar group, Y is a monovalent group, and Z is a divalent or trivalent group. n is an integer of 2 or more. m is 1 or 2. R ¹ is an alkylene group, for example, an ethylene group or a propylene group. The curable resin composition may contain only one type of compound (B), or may contain two or more types.

In the curable resin composition, at least a part of the molecules of the compound (B) are preferably coordinated to the semiconductor particle (A), and all or almost all of the molecules may be coordinated to the semiconductor particle (A). That is, the curable resin composition preferably contains the compound (B) coordinated to the semiconductor particle (A), but may contain the compound (B) not coordinated to the semiconductor particle (A) together with the compound (B) coordinated to the semiconductor particle (A). The inclusion of the compound (B) coordinated to the semiconductor particle (A) can be advantageous in improving the patterning property of the curable resin composition and/or in increasing the QY retention rate. The compound (B) can usually be coordinated to the semiconductor particle (A) via the polar group X. When the group Y contains a polar group, the compound (B) can also be coordinated to the semiconductor particle (A) via the polar group of the group Y, or via the polar groups of the polar group X and the group Y. The coordination of the compound (B) is confirmed by the fact that the semiconductor particle (A) is uniformly dispersed in a dispersion medium suitable for the compound (B).
The compound (B) can be coordinated, for example, to the surface of the semiconductor particle (A).

The polar group X is preferably at least one group selected from the group consisting of a thiol group (-SH), a carboxyl group (-COOH) and an amino group (-NH ₂ ). A polar group selected from this group can be advantageous in increasing the coordination with the semiconductor particles (A). High coordination can contribute to improving the patterning properties of the curable resin composition and/or improving the QY retention rate. In particular, from the viewpoint of obtaining a cured film (such as a wavelength conversion film) having superior light-emitting properties, the polar group X is more preferably at least one group selected from the group consisting of a thiol group and a carboxyl group, and even more preferably a thiol group.

The group Y is a monovalent group. The group Y is not particularly limited, and may be a monovalent hydrocarbon group which may have a substituent (N, O, S, halogen atom, etc.). The methylene group contained in the hydrocarbon group may be substituted with -O-, -S-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -C(=O)-NH-, -NH-, etc. The number of carbon atoms in the hydrocarbon group is, for example, 1 to 12. The hydrocarbon group may have an unsaturated bond. Examples of the group Y include an alkyl group having 1 to 12 carbon atoms and a linear, branched, or cyclic structure; an alkoxy group having 1 to 12 carbon atoms and a linear, branched, or cyclic structure. The number of carbon atoms in the alkyl group and alkoxy group is preferably 1 to 8, more preferably 1 to 6, and even more preferably 1 to 4. The methylene groups contained in the alkyl and alkoxy groups may be substituted with -O-, -S-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -C(=O)-NH-, -NH-, etc. Among these, the group Y is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms, and more preferably a linear alkoxy group having 1 to 4 carbon atoms.

The group Y may contain a polar group. Specific examples of the polar group are as described above for the polar group X. The polar group is preferably located at the terminal of the group Y.

The group Z is a divalent or trivalent group. The group Z is not particularly limited, and examples thereof include divalent or trivalent hydrocarbon groups that may contain heteroatoms (N, O, S, halogen atoms, etc.). The number of carbon atoms in the hydrocarbon group is, for example, 1 to 24. The hydrocarbon group may have an unsaturated bond. Examples of the group Z that is a divalent group include an alkylene group having a linear, branched, or cyclic structure and a carbon number of 1 to 24; an alkenylene group having a linear, branched, or cyclic structure and a carbon number of 1 to 24. The number of carbon atoms in the alkyl group and the alkenylene group is preferably 1 to 12, more preferably 1 to 8, and even more preferably 1 to 4. The methylene group contained in the alkyl group and the alkenylene group may be substituted with -O-, -S-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -C(=O)-NH-, -NH-, etc. An example of the trivalent group Z is a group obtained by removing one hydrogen atom from the divalent group Z.

The group Z may have a branched structure. The group Z having a branched structure may have a polyethylene glycol structure other than the polyethylene glycol structure shown in the above formula (B-1) in a branched chain other than the branched chain containing the polyethylene glycol structure shown in the above formula (B-1).

Among these, the group Z is preferably a linear or branched alkylene group having 1 to 6 carbon atoms, and more preferably a linear alkylene group having 1 to 4 carbon atoms.

In formula (B-1), n is an integer of 2 or more, preferably 4 or more and 540 or less, and more preferably 8 or more and 120 or less.

The molecular weight of compound (B) may be, for example, about 200 or more and 10,000 or less, but from the viewpoint of improving the patterning properties of the curable resin composition and/or increasing the QY retention rate, it is preferably 500 or more and 5,000 or less, more preferably 600 or more and 4,000 or less, and may be 700 or more and 3,000 or less.

The above molecular weight may be a number average molecular weight or a weight average molecular weight. In other words, the molecular weight of compound (B) being 200 or more and 10,000 or less means that the number average molecular weight and/or weight average molecular weight of compound (B) is 200 or more and 10,000 or less. The number average molecular weight and weight average molecular weight are the number average molecular weight and weight average molecular weight, respectively, calculated in terms of standard polystyrene as measured by gel permeation chromatography.

The curable resin composition may further contain a compound (L) other than the compound (B) that has a coordination ability with the semiconductor particles (A).
Examples of the compound (L) include organic acids, organic amine compounds, and thiol compounds.
In addition, the compound (L) does not include the resin (C), the polymerizable compound (D), the polymerization initiator (E), the polymerization initiation aid (E1), the solvent (F), the leveling agent (G), the antioxidant (H), and other components shown in the following [10].
The content ratio of the total amount of the compound (B) and the compound (L) to the semiconductor particles (A) in the curable resin composition [hereinafter also referred to as "(B, L) / (A) mass ratio"] is preferably 0.1 or more and 1.5 or less in mass ratio. The content ratio within this range can be advantageous in improving the patterning property of the curable resin composition and / or in increasing the QY retention rate. The patterning property is improved because the semiconductor particles (A) become more easily compatible with the resin (C) and the solubility in an alkaline developer is improved. In addition, the QY retention rate is increased because the semiconductor particles (A) become more easily dispersed in the curable resin composition. The (B, L) / (A) mass ratio is more preferably 0.1 or more and 1.4 or less, and even more preferably 0.2 or more and 1.4 or less. The (B, L) / (A) mass ratio is measured according to the description in the Examples section described later. Alternatively, it can also be measured by nuclear magnetic resonance (NMR).

The content of compound (B) is, for example, 0.4 parts by mass or more and 27 parts by mass or less, preferably 0.9 parts by mass or more and 24 parts by mass or less, and more preferably 1.8 parts by mass or more and 24 parts by mass or less, per 100 parts by mass of the solid content of the curable resin composition. The content of compound (B) in the above-mentioned range can be advantageous in improving the patterning properties of the curable resin composition and/or in increasing the QY retention rate.

[3] Resin (C)
The curable resin composition contains a resin (C). The curable resin composition may contain one or more resins as the resin (C). The resin (C) is preferably an alkali-soluble resin. Alkali-solubility refers to the property of dissolving in a developer, which is an aqueous solution of an alkaline compound. Examples of the resin (C) include the following resins [K1] to [K6].

Resin [K1]: a copolymer of at least one (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter also referred to as "(a)"). and a monomer (b) having a cyclic ether structure and an ethylenically unsaturated bond and having from 2 to 4 carbon atoms (hereinafter also referred to as "(b)").
Resin [K2]: A copolymer of (a), (b), and a monomer (c) copolymerizable with (a) (but different from (a) and (b)) (hereinafter also referred to as "(c)");
Resin [K3]: a copolymer of (a) and (c),
Resin [K4]: a resin obtained by reacting a copolymer of (a) and (c) with (b);
Resin [K5]: a resin obtained by reacting a copolymer of (b) and (c) with (a);
Resin [K6]: A resin obtained by reacting a copolymer of (b) and (c) with (a) and then reacting it with a carboxylic acid anhydride.

Specifically, (a) is
Unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid, mono[2-(meth)acryloyloxyethyl] succinate, and mono[2-(meth)acryloyloxyethyl] phthalate;
Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, and 1,4-cyclohexenedicarboxylic acid;
Bicyclounsaturated compounds containing a carboxy group, such as methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, and 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene;
Unsaturated dicarboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride (himic anhydride);
Examples of such compounds include unsaturated (meth)acrylic acids containing a hydroxy group and a carboxy group in the same molecule, such as α-(hydroxymethyl)(meth)acrylic acid.

Among these, from the viewpoint of copolymerization reactivity and solubility in an alkaline aqueous solution, (a) is preferably (meth)acrylic acid, maleic anhydride, etc.

In this specification, "(meth)acrylic" refers to at least one selected from the group consisting of acrylic and methacrylic. The same applies to the terms "(meth)acryloyl" and "(meth)acrylate".

(b) refers to a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (e.g., at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring (oxolane ring)) and an ethylenically unsaturated bond. (b) is preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth)acryloyloxy group.

Examples of (b) include monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter also referred to as "(b1)"); monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond (hereinafter also referred to as "(b2)"); and monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter also referred to as "(b3)").

Examples of (b1) include monomer (b1-1) having a structure in which an unsaturated aliphatic hydrocarbon has been epoxidized (hereinafter also referred to as "(b1-1)"); and monomer (b1-2) having a structure in which an unsaturated alicyclic hydrocarbon has been epoxidized (hereinafter also referred to as "(b1-2)").

(b1-1) includes glycidyl (meth)acrylate, β-methyl glycidyl (meth)acrylate, β-ethyl glycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyl Examples include 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tris(glycidyloxymethyl)styrene, 2,3,5-tris(glycidyloxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene, and 2,4,6-tris(glycidyloxymethyl)styrene.

Examples of (b1-2) include vinylcyclohexene monoxide, 1,2-epoxy 4-vinylcyclohexane (e.g., Celloxide 2000; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer A400; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer M100; manufactured by Daicel Chemical Industries, Ltd.), and 3,4-epoxytricyclo[ ^5.2.1.02,6 ]decyl (meth)acrylate.

The monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond is preferably a monomer having an oxetanyl group and a (meth)acryloyloxy group. Preferred examples of (b2) include 3-methyl-3-(meth)acryloyloxymethyloxetane, 3-ethyl-3-(meth)acryloyloxymethyloxetane, 3-methyl-3-(meth)acryloyloxyethyloxetane, and 3-ethyl-3-(meth)acryloyloxyethyloxetane.

The monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond is preferably a monomer having a tetrahydrofuryl group and a (meth)acryloyloxy group. Preferred examples of (b3) include tetrahydrofurfuryl acrylate (e.g., Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, etc.

Specific examples of (c) are:
Methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decan-8-yl (meth)acrylate (commonly known in the art as "dicyclopentanyl (meth)acrylate" and sometimes also called "tricyclodecyl (meth)acrylate"). ], tricyclo[5.2.1.0 ^2,6 ]decen-8-yl(meth)acrylate (commonly known in the technical field as "dicyclopentenyl(meth)acrylate")], dicyclopentanyloxyethyl(meth)acrylate, isobornyl(meth)acrylate, adamantyl(meth)acrylate, allyl(meth)acrylate, propargyl(meth)acrylate, phenyl(meth)acrylate, naphthyl(meth)acrylate, benzyl(meth)acrylate and other (meth)acrylic acid esters;
Hydroxy group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;
dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate;
Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, chloro[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept -2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene bicyclounsaturated compounds such as ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, and 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene;
dicarbonyl imide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, and N-(9-acridinyl)maleimide;
Examples of the copolymer include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene.

Among these, from the viewpoints of copolymerization reactivity, heat resistance, developability during patterning, etc., (c) is preferably methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, benzyl (meth)acrylate, tricyclodecyl (meth)acrylate, dicyclopentenyl (meth)acrylate, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene, etc.

In the resin [K1], the ratio of the structural units derived from each of them to all the structural units constituting the resin [K1] is preferably within the following range.
Structural units derived from (a): 2 mol % or more and 50 mol % or less (more preferably 10 mol % or more and 45 mol % or less),
Structural units derived from (b), particularly structural units derived from (b1): 50 mol % or more and 98 mol % or less (more preferably 55 mol % or more and 90 mol % or less).

When the ratio of structural units in resin [K1] is within the above range, the storage stability, developability, and solvent resistance of the resulting pattern tend to be excellent.

Resin [K1] can be produced by referring to the method described in the literature "Experimental Methods for Polymer Synthesis" (written by Otsu Takayuki, published by Kagaku Dojin Co., Ltd., 1st edition, 1st printing, published March 1, 1972) and the references cited therein.

Specific examples of the method include a method in which predetermined amounts of (a) and (b) (particularly (b1)), a polymerization initiator, a solvent, and the like are charged into a reaction vessel, and the mixture is stirred, heated, and kept warm in a deoxygenated atmosphere. The polymerization initiator and solvent used here are not particularly limited, and any of those commonly used in the relevant field can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.). The solvent may be any that dissolves each monomer, and solvent (F) described below may be used.

The copolymer obtained may be used as it is in the form of a solution after the reaction, or in the form of a concentrated or diluted solution, or may be extracted as a solid (powder) by a method such as reprecipitation.

In the resin [K2], the ratio of the structural units derived from each of them to all the structural units constituting the resin [K2] is preferably within the following range.
Structural units derived from (a): 4 mol % or more and 45 mol % or less (more preferably 10 mol % or more and 30 mol % or less),
Structural units derived from (b), particularly structural units derived from (b1); 2 mol % or more and 95 mol % or less (more preferably 5 mol % or more and 80 mol % or less),
Structural units derived from (c): 1 mol % or more and 65 mol % or less (more preferably 5 mol % or more and 60 mol % or less).

When the ratio of structural units in resin [K2] is within the above range, the storage stability, developability, and solvent resistance, heat resistance, and mechanical strength of the resulting pattern tend to be excellent.

Resin [K2] can be produced in the same manner as described for the production method of resin [K1]. Specifically, a method can be mentioned in which predetermined amounts of (a), (b) (particularly (b1)), and (c), a polymerization initiator, and a solvent are charged into a reaction vessel, and the mixture is stirred, heated, and kept warm in a deoxygenated atmosphere. The resulting copolymer may be used as a solution after the reaction as is, or a concentrated or diluted solution may be used, or a solid (powder) extracted by a method such as reprecipitation may be used.

In the resin [K3], the ratio of the structural units derived from each of them to all the structural units constituting the resin [K3] is preferably within the following range.
Structural units derived from (a): 2 mol % or more and 55 mol % or less (more preferably 10 mol % or more and 50 mol % or less),
Structural units derived from (c): 45 mol % or more and 98 mol % or less (more preferably 50 mol % or more and 90 mol % or less).

Resin [K3] can be produced in the same manner as described for the production method of resin [K1].

Resin [K4] can be produced by obtaining a copolymer of (a) and (c), and adding a cyclic ether structure having 2 to 4 carbon atoms contained in (b), particularly an oxirane ring contained in (b1), to a carboxylic acid and/or a carboxylic acid anhydride contained in (a). Specifically, a copolymer of (a) and (c) is first produced in the same manner as described as the production method of resin [K1]. In this case, the ratio of the structural units derived from each of them is preferably within the following range among all the structural units constituting the copolymer of (a) and (c).
Structural units derived from (a): 5 mol % or more and 50 mol % or less (more preferably 10 mol % or more and 45 mol % or less),
Structural units derived from (c): 50 mol % or more and 95 mol % or less (more preferably 55 mol % or more and 90 mol % or less).

Next, a part of the carboxylic acid and/or carboxylic anhydride derived from (a) in the copolymer is reacted with the cyclic ether structure having 2 to 4 carbon atoms contained in (b), particularly the oxirane ring contained in (b1). Specifically, following the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced with air instead of nitrogen, and (b) (particularly (b1)), a reaction catalyst for the reaction of the carboxylic acid or carboxylic anhydride with the cyclic ether structure (e.g., tris(dimethylaminomethyl)phenol, etc.), and a polymerization inhibitor (e.g., hydroquinone, etc.) are placed in the flask, and the reaction is carried out at 60°C to 130°C for a reaction time of 1 hour to 10 hours, thereby obtaining the resin [K4].

The amount of (b), particularly (b1), used is preferably 5 to 80 moles, more preferably 10 to 75 moles, per 100 moles of (a). This range tends to provide a good balance between storage stability, developability, solvent resistance, heat resistance, mechanical strength, and sensitivity. As the cyclic ether structure has high reactivity and unreacted (b) is unlikely to remain, (b1) is preferred as (b) used in resin [K4], and (b1-1) is more preferred.

The amount of the reaction catalyst used is preferably 0.001% by mass or more and 5% by mass or less based on the total amount of (a), (b) (especially (b1)), and (c). The amount of the polymerization inhibitor used is preferably 0.001% by mass or more and 5% by mass or less based on the total amount of (a), (b), and (c).

The reaction conditions such as the charging method, reaction temperature and time can be adjusted as appropriate, taking into consideration the production equipment, the amount of heat generated by polymerization, etc. As with the polymerization conditions, the charging method and reaction temperature can be adjusted as appropriate, taking into consideration the production equipment, the amount of heat generated by polymerization, etc.

In the first step, resin [K5] is produced by obtaining a copolymer of (b) (particularly (b1)) and (c) in the same manner as in the production method of resin [K1] described above. As in the above, the obtained copolymer may be used as it is in the form of a solution after the reaction, or a concentrated or diluted solution, or it may be extracted as a solid (powder) by a method such as reprecipitation.

The ratio of the structural units derived from (b) (particularly (b1)) and (c) to the total number of moles of all structural units constituting the above copolymer is preferably within the following range.
Structural units derived from (b), particularly structural units derived from (b1); 5 mol % or more and 95 mol % or less (more preferably 10 mol % or more and 90 mol % or less),
Structural units derived from (c): 5 mol % or more and 95 mol % or less (more preferably 10 mol % or more and 90 mol % or less).

Furthermore, under the same conditions as in the manufacturing method of resin [K4], resin [K5] can be obtained by reacting a cyclic ether structure derived from (b) contained in a copolymer of (b) (particularly (b1)) and (c) with a carboxylic acid or carboxylic anhydride contained in (a). The amount of (a) reacted with the above copolymer is preferably 5 to 80 moles per 100 moles of (b) (particularly (b1)). As the reactivity of the cyclic ether structure is high and unreacted (b) is unlikely to remain, (b1) is preferred as (b) used in resin [K5], and (b1-1) is more preferred.

Resin [K6] is a resin obtained by further reacting resin [K5] with a carboxylic acid anhydride. The hydroxyl group generated by the reaction of the cyclic ether structure with a carboxylic acid or a carboxylic acid anhydride is reacted with the carboxylic acid anhydride.

Examples of carboxylic acid anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride (himic anhydride), etc.

The polystyrene-equivalent weight average molecular weight of resin (C) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 5,000 to 30,000. When the molecular weight is within the above range, the solubility of the unexposed parts in the developer is high, and the residual film rate and hardness of the obtained pattern tend to be high. The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of resin (C) is preferably 1.1 to 6, and more preferably 1.2 to 4.

The acid value of the resin (C) is, for example, 20 mg-KOH/g or more and 200 mg-KOH/g or less, preferably 40 mg-KOH/g or more and 170 mg-KOH/g or less, and more preferably 60 mg-KOH/g or more and 150 mg-KOH/g or less. When the acid value of the resin (C) is in the above range, both developability and high dispersibility can be achieved.
The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of resin, and can be determined, for example, by titration using an aqueous potassium hydroxide solution.

The solution acid value of the resin (C) is preferably 5 mg-KOH/g or more and 180 mg-KOH/g or less, more preferably 10 mg-KOH/g or more and 100 mg-KOH/g or less, and even more preferably 12 mg-KOH/g or more and 50 mg-KOH/g or less. The solution acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin solution, and can be determined, for example, by titration using an aqueous potassium hydroxide solution.
The solution acid value is a value measured by dissolving the resin (C) in a predetermined solvent, and the resin concentration in the solution is, for example, 10% by mass or more and 50% by mass or less.
When the solution acid value of the resin (C) is within the above-mentioned range, the semiconductor particles and the resin (C) can be mixed without causing aggregation of either of them.

The content of resin (C) is preferably 5% by mass or more and 70% by mass or less, more preferably 10% by mass or more and 65% by mass or less, and even more preferably 15% by mass or more and 60% by mass or less, based on 100% by mass of the solid content of the curable resin composition. When the content of resin (C) is within the above range, the solubility of the unexposed portion in the developer tends to be high.

[4] Polymerizable compound (D)
The polymerizable compound (D) is not particularly limited as long as it is a compound that can be polymerized by active radicals generated from the polymerization initiator (E) by light irradiation, etc., and examples thereof include compounds having a polymerizable ethylenically unsaturated bond, etc. The weight average molecular weight of the polymerizable compound (D) is preferably 3000 or less.

Among them, the polymerizable compound (D) is preferably a photopolymerizable compound having three or more ethylenically unsaturated bonds. Specific examples of photopolymerizable compounds having three or more ethylenically unsaturated bonds include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, and tetrapentaerythritol nona(meth)acrylate. acrylate, tris(2-(meth)acryloyloxyethyl)isocyanurate, ethylene glycol modified pentaerythritol tetra(meth)acrylate, ethylene glycol modified dipentaerythritol hexa(meth)acrylate, propylene glycol modified pentaerythritol tetra(meth)acrylate, propylene glycol modified dipentaerythritol hexa(meth)acrylate, caprolactone modified pentaerythritol tetra(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate, etc.

The curable resin composition may contain one or more polymerizable compounds (D). The content of the polymerizable compound (D) is preferably 20 parts by mass or more and 150 parts by mass or less, more preferably 80 parts by mass or more and 120 parts by mass or less, per 100 parts by mass of the resin (C) in the curable resin composition.

[5] Polymerization initiator (E)
The curable resin composition may contain a polymerization initiator (E). The polymerization initiator (E) is not particularly limited as long as it is a compound that can generate active radicals, acids, etc. by the action of light or heat and initiate polymerization, and any known polymerization initiator can be used.

Examples of the polymerization initiator (E) include oxime compounds such as O-acyloxime compounds, alkylphenone compounds, biimidazole compounds, triazine compounds, acylphosphine oxide compounds, and the like. Two or more types of polymerization initiator (E) may be used in combination, taking into consideration the sensitivity, patterning properties, and the like. It is preferable that the polymerization initiator (E) contains an oxime compound such as O-acyloxime compounds, as this is advantageous in precisely creating a pattern shape having sensitivity and a desired line width.

An O-acyloxime compound is a compound having a structure represented by the following formula (d). Hereinafter, * represents a bond.

Examples of such O-acyloxime compounds include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine, N-acetyloxy-1-[4-(2-hydroxyethyloxy)phenylsulfanylphenyl]propan-1-one-2-imine, N-acetyloxy-1-[4-(1-methyl-2-methoxyethoxy)-2-methylphenyl]-1-(9-ethyl-6-nitro-9H-carbazol-3-yl)methane-1-imine, and the like. Commercially available products such as Irgacure (registered trademark) OXE01, OXE02, and OXE03 (all manufactured by BASF), N-1919, NCI-930, and NCI-831 (all manufactured by ADEKA) may also be used. These O-acyloxime compounds are advantageous in that they can improve lithography performance.

The alkylphenone compound is a compound having a partial structure represented by the following formula (d4) or a partial structure represented by the following formula (d5). In these partial structures, the benzene ring may have a substituent.

Examples of compounds having the structure represented by formula (d4) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one. Commercially available products such as Irgacure (registered trademark) 369, 907, and 379 (all manufactured by BASF) may also be used.

Examples of compounds having a structure represented by formula (d5) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α,α-diethoxyacetophenone, and benzyl dimethyl ketal.

In terms of sensitivity, the alkylphenone compound is preferably a compound having a structure represented by formula (d4).

Examples of biimidazole compounds include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl ) biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl) biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl) biimidazole (see, for example, JP-B-48-38403 and JP-A-62-174204), imidazole compounds in which the phenyl groups at the 4,4',5,5'-positions are substituted with carboalkoxy groups (see, for example, JP-A-7-10913), etc. Among these, compounds represented by the following formula or mixtures thereof are preferred.

Triazine compounds include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-( 5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine, etc.

Examples of acylphosphine oxide compounds include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

Further examples of the polymerization initiator (E) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, o-benzoyl methyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with the polymerization initiator aid (E1) (particularly amines) described below.

As the polymerization initiator (E), a polymerization initiator containing at least one selected from the group consisting of an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an O-acyloxime compound, and a biimidazole compound is preferred, and a polymerization initiator containing an O-acyloxime compound is more preferred.

The content of the polymerization initiator (E) is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 1 part by mass or more and 25 parts by mass or less, and even more preferably 1 part by mass or more and 20 parts by mass or less, relative to 100 parts by mass of the total amount of the resin (C) and the polymerizable compound (D). When the content of the polymerization initiator (E) is within the above range, the sensitivity tends to be increased and the exposure time tends to be shortened, so that the productivity of the cured film such as the wavelength conversion film tends to be improved.

[6] Polymerization initiator aid (E1)
The curable resin composition may contain a polymerization initiation aid (E1). The polymerization initiation aid (E1) is a compound used to promote the polymerization of the polymerizable compound (D) whose polymerization has been initiated by the polymerization initiator (E), or a sensitizer. When the polymerization initiation aid (E1) is contained, it is used in combination with the polymerization initiator (E).

Examples of the polymerization initiation aid (E1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds. Among these, thioxanthone compounds are preferred. Two or more types of polymerization initiation aids (E1) may be used in combination.

Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, etc., of which 4,4'-bis(diethylamino)benzophenone is preferred. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may also be used.

Examples of alkoxyanthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, and 2-ethyl-9,10-dibutoxyanthracene.

Examples of thioxanthone compounds include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

Examples of carboxylic acid compounds include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc.

The content of the polymerization initiation aid (E1) is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 1 part by mass or more and 20 parts by mass or less, relative to 100 parts by mass of the total amount of the resin (C) and the polymerizable compound (D). When the content of the polymerization initiation aid (E1) is within the above range, the productivity of the cured film such as the wavelength conversion film can be further improved.

[7] Solvent (F)
The curable resin composition preferably contains one or more solvents (F). Examples of the solvent (F) include ester solvents (solvents containing -C(=O)-O-), ether solvents other than ester solvents (solvents containing -O-), ether ester solvents (solvents containing -C(=O)-O- and -O-), ketone solvents other than ester solvents (solvents containing -C(=O)-), alcohol solvents, aromatic hydrocarbon solvents, amide solvents, and dimethyl sulfoxide.

Examples of ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexyl acetate, 2-methylcyclohexyl acetate, cyclohexyl propionate, cis-3,3,5-trimethylcyclohexyl acetate, 4-tert-butylcyclohexyl acetate, cyclohexyl butyrate, isopropyl cyclohexanecarboxylate, and γ-butyrolactone.

Ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, methylanisole, and methoxycyclohexane.

Ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate, Examples of such ether acetates include ethyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and dipropylene glycol methyl ether acetate.

Ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, 2-acetylcyclopentanone, cyclohexanone, 2-acetylcyclohexanone, and isophorone.

Examples of alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin. Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, and mesitylene. Examples of amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

From the viewpoints of application and drying properties, the following solvents are selected as the solvent (F): propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide, cyclohexyl acetate, methoxycyclohexane, isopropyl cyclohexanecarboxylate, cyclopentanone, cyclohexanone, cyclohexafluoropropane ... It is preferable that the solvent contains at least one selected from the group consisting of ethanol, benzene, toluene, xylene, and mesitylene, and it is more preferable that the solvent contains at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate, cyclohexyl acetate, methoxycyclohexane, isopropyl cyclohexanecarboxylate, cyclopentanone, cyclohexanone, and cyclohexanol.

The content of the solvent (F) is preferably 60% by mass or more and 95% by mass or less, more preferably 65% by mass or more and 92% by mass or less, based on 100% by mass of the curable resin composition. In other words, the solid content of the curable resin composition is preferably 5% by mass or more and 40% by mass or less, more preferably 8% by mass or more and 35% by mass or less. When the content of the solvent (F) is within the above range, the coatability of the curable resin composition and the flatness during application tend to be good, and the light-emitting properties of the cured film such as the wavelength conversion film tend to be good.

[8] Leveling agent (G)
The curable resin composition may contain one or more leveling agents (G). Examples of the leveling agent (G) include silicone surfactants, fluorine surfactants, and silicone surfactants having fluorine atoms. These may have a polymerizable group in the side chain.

Examples of silicone surfactants include surfactants having a siloxane bond in the molecule. Specific examples include Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, and SH8400 (product names: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, and KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan, LLC).

Examples of fluorosurfactants include surfactants having a fluorocarbon chain in the molecule. Specific examples include Fluorad (registered trademark) FC430 and FC431 (manufactured by Sumitomo 3M Limited), Megafac (registered trademark) F142D, F171, F172, F173, F177, F183, F554, R30, and RS-718-K (manufactured by DIC Corporation), EF-TOP (registered trademark) EF301, EF303, EF351, and EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, S382, SC101, and SC105 (manufactured by Asahi Glass Co., Ltd.), and E5844 (manufactured by Daikin Fine Chemicals Research Institute, Ltd.).

Examples of silicone surfactants having fluorine atoms include surfactants having siloxane bonds and fluorocarbon chains in the molecule. Specific examples include Megafac (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation).

The content of the leveling agent (G) is usually 0.001% by mass or more and 0.2% by mass or less, preferably 0.002% by mass or more and 0.1% by mass or less, and more preferably 0.005% by mass or more and 0.05% by mass or less, based on 100% by mass of the curable resin composition.

[9] Antioxidant (H)
From the viewpoint of improving the heat resistance and light resistance of the curable resin composition, the curable resin composition may contain an antioxidant (H). The antioxidant (H) is not particularly limited as long as it is an antioxidant generally used industrially, and phenol-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, etc. may be used. Two or more types of antioxidants (H) may be used in combination.

Phenol-based antioxidants include Irganox (registered trademark) 1010 (Irganox 1010: pentaerythritol tetrakis [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], manufactured by BASF Corporation), Irganox 1076 (Irganox 1076: octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, manufactured by BASF Corporation), Irganox 1330 (Irganox 1330: 3,3',3'',5,5',5''-hexa-t-butyl-a,a',a''-(mesitylene-2,4,6-triyl)tri-p-cresol, manufactured by BASF Corporation), and Irganox 3114 (Irganox Irganox 3114: 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Corporation, Irganox 3790: 1,3,5-tris((4-t-butyl-3-hydroxy-2,6-xylyl)methyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Corporation, Irganox 1035: thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], manufactured by BASF Corporation, Irganox 1135: Irganox 1135: benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy, C7-C9 side chain alkyl ester, manufactured by BASF Corporation; Irganox 1520L (Irganox 1520L: 4,6-bis(octylthiomethyl)-o-cresol, manufactured by BASF Corporation); Irganox 3125 (Irganox 3125, manufactured by BASF Corporation); Irganox 565 (Irganox 565: 2,4-bis(n-octylthio)-6-(4-hydroxy-3',5'-di-t-butylanilino)-1,3,5-triazine, manufactured by BASF Corporation); Adeka STAB (registered trademark) AO-80 (Adeka STAB AO-80: 3,9-bis(2-(3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5,5)undecane, manufactured by ADEKA Co., Ltd., Sumilizer (registered trademark) BHT, Sumilizer GA-80, Sumilizer GS (all manufactured by Sumitomo Chemical Co., Ltd.), Cyanox (registered trademark) 1790 (manufactured by Cytec Co., Ltd.), and Vitamin E (manufactured by Eisai Co., Ltd.), etc.

Phosphorus-based antioxidants include Irgafos (registered trademark) 168 (Irgafos 168: tris(2,4-di-t-butylphenyl)phosphite, manufactured by BASF Corporation), Irgafos 12 (Irgafos 12: tris[2-[[2,4,8,10-tetra-t-butyldibenzo[d,f][1,3,2]dioxaphosphine-6-yl]oxy]ethyl]amine, manufactured by BASF Corporation), Irgafos 38 (Irgafos 38: bis(2,4-bis(1,1-dimethylethyl)-6-methylphenyl)ethyl ester phosphorous acid, manufactured by BASF Corporation), Adekastab (registered trademark) 329K, Adekastab PEP36, Adekastab PEP-8 (all manufactured by ADEKA Corporation), and Sandstab Examples include P-EPQ (Clariant), Weston (registered trademark) 618, Weston (registered trademark) 619G (both manufactured by GE), Ultranox 626 (manufactured by GE), and Sumilizer (registered trademark) GP (6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenz[d,f][1.3.2]dioxaphosphepine) (manufactured by Sumitomo Chemical Co., Ltd.).

Examples of sulfur-based antioxidants include dialkyl thiodipropionate compounds such as dilauryl, dimyristyl, or distearyl thiodipropionate, and β-alkyl mercaptopropionate compounds of polyols such as tetrakis[methylene(3-dodecylthio)propionate]methane.

[10] Other Components The curable resin composition may contain, as necessary, one or more additives such as a filler, a polymer compound other than the resin (C), an adhesion promoter, an ultraviolet absorber, an anti-aggregation agent, a curing agent, and a light scattering agent.

Examples of fillers include glass, silica, and alumina. Examples of polymer compounds other than resin (C) include polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate.

Examples of adhesion promoters include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane.

Examples of ultraviolet absorbers include benzotriazole-based compounds such as 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole; benzophenone-based compounds such as 2-hydroxy-4-octyloxybenzophenone; benzoate-based compounds such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate; and triazine-based compounds such as 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol. Examples of anti-aggregation agents include sodium polyacrylate.

Examples of the curing agent include compounds that can react with carboxy groups in the resin (C) when heated to crosslink the resin (C), and compounds that can be polymerized and cured by themselves, such as epoxy compounds and oxetane compounds.

Examples of the light scattering agent include metal or metal oxide particles, glass particles, etc. Examples of metal oxides include TiO ₂ , SiO ₂ , BaTiO ₃ , ZnO, etc. The particle size of the light scattering agent is, for example, about 0.03 μm or more and 20 μm or less, preferably 0.05 μm or more and 1 μm or less, and more preferably 0.05 μm or more and 0.3 μm or less. The content of the light scattering agent is usually 0.001 mass% or more and 50 mass% or less, preferably 1 mass% or more and 40 mass% or less, and more preferably 5 mass% or more and 30 mass% or less in 100 mass% of the curable resin composition.

<Method for preparing curable resin composition>
The curable resin composition can be prepared by mixing the semiconductor particles (A), the compound (B), the resin (C), the polymerizable compound (D), and other components used as necessary. However, when using the semiconductor particles (A) coordinated with a ligand such as an organic ligand [hereinafter also referred to as "ligand M". The ligand M is, for example, the above-mentioned compound (L). ] as a raw material, in order to obtain a curable resin composition containing the semiconductor particles (A) coordinated with at least a part of the compound (B), it is preferable to previously subject the semiconductor particles (A) coordinated with the ligand M to a ligand exchange reaction to obtain the semiconductor particles (A) coordinated with the compound (B) (or the compound (B) and the ligand M), and then mix the semiconductor particles (A) with the resin (C), the polymerizable compound (D), and other components used as necessary to prepare the curable resin composition.

The ligand exchange reaction is a reaction in which at least a portion of the ligand M coordinated to the semiconductor particle (A) is replaced with the compound (B). The reaction can be carried out, for example, by heating a mixture of the semiconductor particle (A) having the ligand M and the compound (B) in a solvent. The heating temperature is, for example, 50°C or higher and 180°C or lower.

<Cured film, patterned cured film, wavelength conversion film, and display device>
A cured film can be obtained by curing a film (layer) made of a curable resin composition. In this case, a patterned cured film can be obtained by patterning using a method such as a photolithography method, an inkjet method, or a printing method. The cured film or the patterned cured film can be suitably used as a wavelength conversion film (wavelength conversion filter) that emits light with a wavelength different from the wavelength of incident light. The wavelength conversion film can be suitably used in a display device such as a liquid crystal display device or an organic EL device. The patterning method is preferably a photolithography method. The photolithography method is a method in which a curable resin composition is applied to a substrate, dried to form a curable resin composition layer, and the curable resin composition layer is exposed to light through a photomask and developed.

As the substrate, glass plates such as quartz glass, borosilicate glass, alumina silicate glass, and soda lime glass with a silica-coated surface, resin plates such as polycarbonate, polymethylmethacrylate, and polyethylene terephthalate, silicon, and the above substrates on which thin films of aluminum, silver, and silver/copper/palladium alloys have been formed can be used.

The formation of a patterned cured film by photolithography can be carried out using known or conventional equipment and conditions, and can be formed, for example, as follows. First, a curable resin composition is applied onto a substrate, and then the substrate is dried by heating and drying (pre-baking) and/or drying under reduced pressure to remove volatile components such as solvents, thereby obtaining a curable resin composition layer. Examples of application methods include spin coating, slit coating, and slit and spin coating.

When drying by heating, the temperature is preferably 30°C or more and 120°C or less, and more preferably 50°C or more and 110°C or less. The heating time is preferably 10 seconds or more and 10 minutes or less, and more preferably 30 seconds or more and 5 minutes or less. When drying under reduced pressure, it is preferably performed under a pressure of 50 Pa or more and 150 Pa or less, and at a temperature range of 20°C or more and 25°C or less. The film thickness of the curable resin composition layer is not particularly limited, and can be appropriately selected according to the film thickness of the desired cured film such as a wavelength conversion film.

Next, the curable resin composition layer is exposed through a photomask to form a desired pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used. As the light source used for exposure, a light source that generates light with a wavelength of 250 nm or more and 450 nm or less is preferable. For example, light less than 350 nm may be cut using a filter that cuts this wavelength range, or light near 436 nm, near 408 nm, and near 365 nm may be selectively extracted using a bandpass filter that extracts these wavelength ranges. Examples of light sources include mercury lamps, light-emitting diodes, metal halide lamps, halogen lamps, etc.

For exposure, it is preferable to use an exposure device such as a mask aligner or stepper, since it is possible to uniformly irradiate the entire exposure surface with parallel light rays and to perform accurate alignment between the photomask and the substrate on which the curable resin composition layer is formed.

The exposed curable resin composition layer is brought into contact with a developer and developed to form a pattern of the curable resin composition layer on the substrate. The unexposed portion of the curable resin composition layer is dissolved in the developer and removed by development. The developer is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.03% by mass or more and 5% by mass or less. The developer may further contain a surfactant. Examples of the development method include a paddle method, a dipping method, and a spray method. Furthermore, the substrate may be tilted at any angle during development. After development, it is preferable to wash with water.

Furthermore, the obtained pattern of the curable resin composition layer is preferably post-baked. The post-baking temperature is preferably 60°C or more and 250°C or less, and more preferably 110°C or more and 240°C or less. The post-baking time is preferably 1 minute or more and 120 minutes or less, and more preferably 10 minutes or more and 60 minutes or less. The film thickness of the cured film after post-baking is, for example, 1 μm or more and 10 μm or less, and preferably 3 μm or more and 10 μm or less.

The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples. In the examples, percentages and parts indicating the content or amount used are based on mass unless otherwise specified.

<Production Example 1-1: Preparation of Semiconductor Particles (A) Coordinated with Compound (B)-1>
(1) Preparation of semiconductor quantum dots (semiconductor particles (A)) As the semiconductor quantum dots, core-shell type semiconductor quantum dots INP530 [manufactured by NN-LABS] having a structure of InP (core)/ZnS (first shell)/ZnS (second shell) were used. Oleylamine is coordinated to the surface of this semiconductor quantum dot.

(2) Ligand reduction treatment Next, the above semiconductor quantum dots (QDs) were subjected to a ligand reduction treatment according to the following procedure. First, 2 parts by volume of hexane was added to 1 part by volume of the dispersion containing QDs obtained in (1) above to dilute it. Then, 30 parts by volume of ethanol was added to precipitate the QDs, and a centrifugation treatment was performed. The supernatant was removed, and 3 parts by volume of hexane was added to redisperse the QDs. This treatment (precipitation by adding ethanol → centrifugation → removal of the supernatant → redispersion by adding hexane) was performed a total of three times. However, at the third redispersion, toluene was added instead of hexane so that the concentration of QDs (containing oleylamine ligands) was 20% by mass, and QD dispersion liquid-A was obtained. In the same manner as in (4) of Production Example 1-1 described later, the (B, L)/(A) mass ratio was measured for the obtained QD dispersion liquid-A.

(3) Preparation of semiconductor particles (A) coordinated with compound (B) (ligand exchange treatment)
To 1 part of the QD dispersion-A obtained in (2) above, 0.1 part of poly(ethylene glycol) methyl ether thiol (Sigma-Aldrich, number average molecular weight 800, a compound in the above formula (B-1) where X = -SH, Y = _-OCH3 , Z = _-CH2CH2- , ^R1 = _-CH2CH2- , and m = 1) as compound ( _B ) was added, and the mixture was heated and stirred at 80°C for 12 hours to carry out _a ligand exchange reaction, thereby obtaining a dispersion containing QDs coordinated with poly(ethylene glycol) methyl ether thiol.

19.7 parts of hexane was added to the dispersion to precipitate the QDs, and the mixture was centrifuged. The supernatant was removed, and the QDs were dispersed in propylene glycol monomethyl ether acetate (PGMEA) to obtain QD dispersion-B, which is a PGMEA dispersion containing 20% by weight of QDs coordinated with poly(ethylene glycol) methyl ether thiol (number average molecular weight 800).
In the QD dispersion-A obtained by the ligand reduction treatment, the QDs were dispersed in toluene, a nonpolar solvent, and were difficult to disperse in polar solvents. On the other hand, in the QD dispersion-B obtained by the ligand exchange treatment, the QDs were dispersed in PGMEA, a polar solvent. This indicates that at least a portion of the ligands were exchanged, and poly(ethylene glycol) methyl ether thiol (compound (B)) was coordinated to the QDs.
In the other production examples described below, it was determined that compound (B) was coordinated to QDs by being dispersed in the polar solvent PGMEA.

(4) Measurement of (B, L)/(A) mass ratio The (B, L)/(A) mass ratio [mass ratio of the total amount of compound (B) and compound (L) oleylamine to semiconductor quantum dots (semiconductor particles (A)] for the obtained QD dispersion-B was measured by the following procedure. 30 μL of the QD dispersion was measured in an aluminum pan, and thermogravimetric measurements were performed in the temperature range from 45 ° C. to 550 ° C. at a heating rate of 5 ° C./min under a nitrogen gas flow using a thermogravimetric analyzer "TGDTA6200" (Seiko Instrument Co., Ltd.). The weight change from 130°C, which is the temperature at which the PGMEA volatilization ends, to 500°C was taken as the total weight (total mass) of compound (B) and compound (L), the weight of the residue after the measurement was taken as the weight (mass) of the semiconductor quantum dots, and the (B, L)/(A) mass ratio was calculated by dividing the total mass of compound (B) and compound (L) by the mass of the semiconductor quantum dots.

<Production Example 1-2: Preparation of Semiconductor Particles (A) Coordinated with Compound (B)-2>
QD dispersion-C was obtained as a PGMEA dispersion containing 20 mass% QDs coordinated with poly(ethylene glycol) methyl ether thiol (weight average molecular weight 2000) in the same manner as in Production Example 1-1, except that in Production Example 1-1 ( ₃ ), poly(ethylene glycol) methyl ether thiol (manufactured by Sigma-Aldrich, number average molecular weight 800) was used as compound (B) ("Sunbright ME- _020SH " manufactured by NOF Corporation, _weight average molecular weight 2000, a compound in which X=-SH, Y=-OCH3, Z= _-CH2CH2- , ^R1 = _-CH2CH2- , and m=1 in the above formula (B-1)). In the same manner as in (4) of Production Example 1-1, the (B, L)/(A) mass ratio of the obtained QD dispersion-C was measured.

<Production Example 1-3: Preparation of Semiconductor Particles (A) Coordinated with Compound (B)-3>
In (3) of Production Example 1-1, instead of poly(ethylene glycol) methyl ether thiol (Sigma-Aldrich, number average molecular weight 800), methoxypolyethylene glycolamine (Sigma-Aldrich, number average molecular weight 750, compound in the above formula (B-1) where X= _-NH2 , Y= _-OCH3 , Z= _-CH2CH2- , ^R1 = _-CH2CH2- , and m= ₁ ) was used as compound ( _B ), in the same manner as in Production Example 1-1, to obtain QD dispersion-D as a PGMEA dispersion having a concentration of 20 mass% QDs coordinated with methoxypolyethylene glycolamine (number average molecular weight 750). The (B, L)/(A) mass ratio of the obtained QD dispersion-D was measured in the same manner as in (4) of Production Example 1-1.

<Production Example 1-4: Preparation of Semiconductor Particles (A) Coordinated with Compound (B)-4>
In (3) of Production Example 1-1, except that the amount of poly(ethylene glycol) methyl ether thiol [Sigma-Aldrich, number average molecular weight 800] added as compound (B) was changed to 0.05 parts, the same procedure as in Production Example 1-1 was repeated to obtain QD dispersion-E as a PGMEA dispersion having a concentration of QDs coordinated with poly(ethylene glycol) methyl ether thiol (number average molecular weight 800) of 20 mass%. The (B, L)/(A) mass ratio of the obtained QD dispersion-E was measured in the same manner as in (4) of Production Example 1-1.

<Production Example 1-5: Preparation of Semiconductor Particles (A) Coordinated with Compound (B)-5>
In (3) of Production Example 1-1, except that the amount of poly(ethylene glycol) methyl ether thiol [Sigma-Aldrich, number average molecular weight 800] added as compound (B) was changed to 0.2 parts, the same procedure as in Production Example 1-1 was repeated to obtain QD dispersion-F as a PGMEA dispersion having a concentration of QDs coordinated with poly(ethylene glycol) methyl ether thiol (number average molecular weight 800) of 20 mass%. The (B, L)/(A) mass ratio of the obtained QD dispersion-F was measured in the same manner as in (4) of Production Example 1-1.

<Production Example 1-6: Preparation of Semiconductor Particles (A) Coordinated with Compound (B)-6>
In (3) of Production Example 1-1, except that the amount of poly(ethylene glycol) methyl ether thiol [Sigma-Aldrich, number average molecular weight 800] added as compound (B) was changed to 0.3 parts, the same procedure as in Production Example 1-1 was repeated to obtain QD dispersion-G as a PGMEA dispersion having a concentration of QDs coordinated with poly(ethylene glycol) methyl ether thiol (number average molecular weight 800) of 20 mass%. The (B, L)/(A) mass ratio of the obtained QD dispersion-G was measured in the same manner as in (4) of Production Example 1-1.

<Production Example 1-7: Preparation of Semiconductor Particles (A) Coordinated with Compound (B)-7>
In (3) of Production Example 1-1, the QD concentration when QDs were redispersed by adding PGMEA was set to 30 mass% at the final redispersion in the same manner as in Production Example 1-1, and QD dispersion liquid-H was obtained as a PGMEA dispersion liquid having a concentration of QDs coordinated with poly(ethylene glycol) methyl ether thiol (number average molecular weight 800) of 30 mass%. The (B, L)/(A) mass ratio of the obtained QD dispersion liquid-H was measured in the same manner as in (4) of Production Example 1-1.

<Production Example 1-8: Preparation of Semiconductor Particles (A) Coordinated with Compound (B)-8>
In (3) of Production Example 1-1, the QD concentration when redispersing QDs by adding PGMEA was set to 35 mass% at the final redispersion, and the same procedure was followed as in Production Example 1-1 to obtain QD dispersion-I as a PGMEA dispersion having a concentration of QDs coordinated with poly(ethylene glycol) methyl ether thiol (number average molecular weight 800) of 35 mass%. In addition, the (B, L)/(A) mass ratio of the obtained QD dispersion-I was measured in the same manner as in (4) of Production Example 1-1.

<Production Example 1-9: Preparation of Semiconductor Particles (A) Coordinated with Oleylamine-1>
In (2) of Production Example 1-1, QD dispersion-J was obtained in the same manner as in Production Example 1-1, except that in the third redispersion, cyclohexane carboxylate isopropyl (CHCI) was added instead of toluene so that the concentration of QD (including oleylamine ligand) was 20 mass%. In this production example, the step (3) of Production Example 1-1 (ligand exchange treatment) was not performed. The (B, L)/(A) mass ratio of the obtained QD dispersion-J was measured in the same manner as in (4) of Production Example 1-1.

<Production Example 1-10: Preparation of Semiconductor Particles (A) Coordinated with Compound (B)-9>
QD dispersion liquid-K was obtained in the same manner as in Production Example 1-1, except that in (3) of Production Example 1-1, ethanol was added instead of toluene during dispersion so that the concentration of QD (containing PEG-thiol ligand) was 20% by mass. The (B, L)/(A) mass ratio of the obtained QD dispersion liquid-K was measured in the same manner as in Production Example 1-1 (4). In measuring the (B, L)/(A) mass ratio, the change in weight from 100°C, which is the temperature at which ethanol volatilizes, to 550°C was taken as the weight (mass) of compound (B).

A summary of Production Examples 1-1 to 1-10 is shown in Table 1. In the table, "PEG-thiol" represents poly(ethylene glycol) methyl ether thiol. "PEG-amine" represents methoxypolyethylene glycol amine. The molecular weights of PEG-thiol and PEG-amine shown in the table are number average molecular weights or weight average molecular weights measured by gel permeation chromatography (standard polystyrene equivalent values).

<Production Example 2-1: Preparation of solution containing resin (C)-1>
A flask equipped with a cooling tube and a stirrer was charged with 100 parts of PGMEA and substituted with nitrogen. While stirring at 70 ° C., a mixed solution of 14.3 parts of methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 5.6 parts by mass of dicyclopentanyl methacrylate (FA-513M, manufactured by Hitachi Chemical Co., Ltd.), 2.4 parts by mass of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.1 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.), 1.4 parts by mass of pentaerythritol tetrakis (3-mercaptopropionate) [PEMP] (manufactured by SC Organic Chemical Co., Ltd.) and 100 parts of PGMEA was dropped over 30 minutes at the same temperature, and a polymerization reaction was carried out at the same temperature for 2 hours. The reaction solution was gradually cooled to room temperature, then dropped into ethanol, and the precipitate was collected by filtration and dried in a vacuum dryer at 40 ° C. 20 parts of the obtained white powder was dissolved in 80 parts of PGMEA to obtain a resin solution-a (resin concentration: 20% by mass). The weight average molecular weight of the obtained resin was 17,000 (standard polystyrene equivalent value by gel permeation chromatography).

<Production Example 2-2: Preparation of solution containing resin (C)-2>
A resin solution-b was obtained in the same manner as in Production Example 2-1, except that 20 parts of the obtained white powder was dissolved in 46.7 parts of PGMEA (resin concentration: 30% by mass).

<Production Example 2-3: Preparation of solution containing resin (C)-3>
A resin solution was prepared according to the description of paragraph [0191] of the above-mentioned Patent Document 1, and then PGMEA was added to obtain a resin solution-c having a resin concentration of 20 mass %.

<Production Example 2-4: Preparation of polyethylene oxide solution>
Polyethylene oxide (Sigma-Aldrich, weight average molecular weight 200,000 to 400,000) was dissolved in ethanol to prepare a resin solution-d, which was a polyethylene oxide (PEO) solution with a concentration of 20% by mass.

Example 1
25 parts of QD dispersion liquid-B obtained in Production Example 1-1, 56 parts of resin solution-a obtained in Production Example 2-1, and 1.85 parts of a PGMEA solution containing an antioxidant (H-1) at a concentration of 20% by mass were placed in a flask and stirred to obtain a liquid containing QDs and resin.

Next, 3.75 parts of polymerizable compound (D-1), 3.75 parts of polymerizable compound (D-2), 0.20 parts of polymerization initiator (E-1), 0.75 parts of antioxidant (H-2), 0.25 parts of PGMEA solution containing leveling agent (G-1) at a concentration of 10% by mass, and 8.50 parts of PGMEA were mixed. The resulting mixture was added to the above-mentioned liquid containing QDs and resin, and stirred and mixed to obtain a curable resin composition. The solid content concentration of the obtained curable resin composition was 25% by mass. The types of blending components used in this example and their amounts used are summarized in Table 2. In Table 2, the unit of amount used is parts by mass. It was confirmed by visual observation that the resin was uniformly dissolved and the QDs were uniformly dispersed in the obtained curable resin composition.

<Examples 2 to 8, Comparative Examples 1 to 4>
The curable resin composition was prepared in the same manner as in Example 1, except that the types of QD dispersion, resin solution, and other blending components used and their amounts used were as shown in Table 2 or Table 3. In Tables 2 and 3, the units of amounts used are parts by mass. The solid content concentrations of the curable resin compositions obtained in Examples 2 to 8 and Comparative Examples 1 to 4 are all 25% by mass. In the curable resin compositions obtained in Examples 2 to 8 and Comparative Examples 3 to 4, it was confirmed by visual observation that the resin was uniformly dissolved and the QDs were uniformly dispersed. On the other hand, in the curable resin compositions of Comparative Examples 1 and 2, the liquid dispersibility was poor and the QDs precipitated. For this reason, the evaluation tests described below were not performed on these comparative examples.

<Comparative Example 5>
In order to obtain a resin composition, 0.5 parts of the QD dispersion-K obtained in Production Example 1-10, 0.4 parts of the PEO solution obtained in Production Example 2-4, and 1.1 parts of ethanol were mixed by stirring, and the mixture gelled. For this reason, the evaluation test described below was not performed for this comparative example.

The details of the blended components shown in Tables 2 and 3 are as follows.
[1] Polymerizable compound (D-1): propoxylated pentaerythritol triacrylate ("NK Ester ATM-4PL" manufactured by Shin-Nakamura Chemical Co., Ltd.),
[2] Polymerizable compound (D-2): pentaerythritol triacrylate ("NK Ester A-TMM-3LM-N" manufactured by Shin-Nakamura Chemical Co., Ltd.),
[3] Polymerizable compound (D-3): mono-2-(methacryloyloxy)ethyl succinate (Sigma-Aldrich),
[4] Polymerization initiator (E-1): O-acyloxime polymerization initiator "NCI-930" manufactured by ADEKA Corporation,
[5] Solvent (F-1): PGMEA,
[6] Solvent (F-2): toluene,
[7] Solvent (F-3): ethanol,
[8] Leveling agent (G-1): Toray Dow Corning Co., Ltd.'s polyether-modified silicone oil-based leveling agent "Toray Silicone SH8400";
[9] Antioxidant (H-1): Hindered phenol-based antioxidant "ADEKA STAB (registered trademark) AO-60" manufactured by ADEKA Corporation;
[10] Antioxidant (H-2): Phenol-phosphorus antioxidant “Sumilizer (registered trademark) GP” manufactured by Sumitomo Chemical Co., Ltd.

[Evaluation test]
(1) Patterning property 0.45 mL of the curable resin composition was dropped onto a glass substrate, spin-coated at 150 rpm for 20 seconds, and then dried (pre-baked) at 100 ° C for 3 minutes to form a curable resin composition layer. Next, using a photomask having a line and space pattern with a line width of 50 μm, pattern exposure was performed at an exposure dose of 40 mJ / cm ² (based on 365 nm) in an air atmosphere. The distance between the substrate and the photomask was 120 μm. The curable resin composition layer after pattern exposure was immersed in an aqueous developer having a potassium hydroxide concentration of 0.04 mass% at 23 ° C for 70 seconds, washed with water, and then post-baked in an oven at 230 ° C for 20 minutes to obtain a patterned cured film. The thickness of each of the cured films was 5 μm or more and 6 μm or less.

A point on the line of the patterned cured film (a line with a mask width of 50 μm) was observed using a laser microscope (Olympus Corporation's "3D Measuring Laser Microscope OLS4100"), and the patterning property was evaluated according to the following evaluation criteria. The results are shown in Table 4.

A: The line width is within the range of [mask width (50 μm)-2 μm] or more and [mask width (50 μm)+3 μm] or less.
B: The line width is within the range of [mask width (50 μm)-6 μm] or more and less than [mask width (50 μm)-2 μm], or within the range of [mask width (50 μm)+3 μm] and less than [mask width (50 μm)+10 μm];
C: The line width is less than [mask width (50 μm)−6 μm] or more than [mask width (50 μm)+10 μm];
D: There are areas where development is insufficient, that is, there are areas where adjacent lines are connected to each other, or the lines are peeled off due to insufficient development adhesion.

(2) QY retention The quantum yield of the coating film (before curing) of the curable resin composition was measured using an absolute PL quantum yield measurement device "C9920-02G" manufactured by Hamamatsu Photonics K.K. The quantum yield of the cured film (after post-baking) formed from the curable resin composition was also measured using the same device. From these measurement results, the QY retention, which is the quantum yield (%) of the cured film (after post-baking) formed from the curable resin composition when the quantum yield of the curable resin composition (before curing) was taken as 100%, was calculated. The results are shown in Table 4.

When measuring the quantum yield of the curable resin composition (before curing), the measurement sample was a glass substrate coated with the curable resin composition. When measuring the quantum yield of the cured film (after post-baking), the measurement sample was a cured film prepared in the same manner as in the evaluation test for "patterning ability" above, except that a photomask was not used.

(3) Emission Intensity A cured film was formed on a glass substrate in the same manner as in the evaluation test for "patterning property" above, except that a photomask was not used. The glass substrate with the cured film was placed on a blue backlight, and the emission intensity was measured using a total luminous flux measuring device "CSTM-OP-RADIANT-FLUX" manufactured by Ocean Photonics Co., Ltd. Table 4 shows the emission intensity ratio when the emission intensity of the cured film of Example 1 is set to 1.0.

As described above, for Comparative Examples 1, 2, and 5, the liquid dispersibility of the curable resin composition was poor, and gelation occurred during the preparation of the resin composition, so the above evaluation tests could not be carried out.

The curable resin composition of Comparative Example 3 had good liquid dispersibility, but the curable resin composition layer did not cure even when exposed to light, so the above evaluation test could not be carried out. The curable resin composition of Comparative Example 4 had good liquid dispersibility, but patterning could not be achieved even when development processing was carried out after pattern exposure, and all the lines were connected to each other.

Claims (4)

The composition comprises semiconductor particles (A), a compound (B) containing a polyalkylene glycol structure and having a polar group at a molecular end, a resin (C), a polymerizable compound (D) , a solvent (F) and an antioxidant (H),
The semiconductor particle (A) further includes a compound (L) other than the compound (B) and having a coordination ability with the semiconductor particle (A),
The compound (B) is a compound represented by the following formula (B-1):

[In formula (B-1), X is the polar group selected from the group consisting of a carboxyl group and an amino group, Y is a monovalent group, Z is a divalent or trivalent group, n is an integer of 2 or more, m is 1 or 2, and R ¹ is an alkylene group.]
the compound (B) and the compound (L) are coordinated to the semiconductor particle (A);
The resin (C) is an alkali-soluble resin,
The polymerizable compound (D) is a photopolymerizable compound having three or more ethylenically unsaturated bonds,
The semiconductor particles (A) are uniformly dispersed,
a ratio of the total amount of the compound (B) and the compound (L) to the semiconductor particles (A) is 0.1 or more and 1.5 or less in terms of mass ratio,
The solvent (F) is one or more selected from the group consisting of ester solvents, ether solvents other than ester solvents, ether ester solvents, ketone solvents other than ester solvents, alcohol solvents, amide solvents, and dimethyl sulfoxide;
The curable resin composition, wherein the antioxidant (H) includes at least one of a phenol-based antioxidant and a phosphorus-based antioxidant. The curable resin composition according to claim 1, further comprising a leveling agent (G). A cured film formed from the curable resin composition according to claim 1 or 2. A display device comprising the cured film according to claim 3.