CN108445714B - Curable resin composition, cured film, and display device - Google Patents

Abstract

A curable resin composition comprising ligand-containing semiconductor particles (A) which are semiconductor particles to which organic ligands are coordinated, a resin (B), and a polymerizable compound (C), wherein the content ratio of the organic ligands to the semiconductor particles in the ligand-containing semiconductor particles (A) is 0.1 or more and less than 5.0 by mass ratio.

Description

Curable resin composition, cured film and display device

technical field

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

Background technique

As a curable resin composition for forming a cured film such as a wavelength conversion film contained in a display device such as an image display device, a composition containing semiconductor particles such as semiconductor quantum dots is known [for example, Japanese Patent No. JP2015-028139]. JP2005-128539 A describes a semiconductor nanocrystal in which a compound having a photosensitive functional group is coordinated on the surface, and a photosensitive composition containing the same.

Contents of the invention

The present invention provides curable resin compositions, cured films, and display devices shown below.

[1] A curable resin composition comprising a ligand-containing semiconductor particle (A), a resin (B), and a polymerizable compound (C), wherein the ligand-containing semiconductor particle (A) is coordinated with an organic ligand The content ratio of the organic ligand to the semiconductor particle in the ligand-containing semiconductor particle (A) is 0.1 or more and less than 5.0 in terms of mass ratio.

[2] The curable resin composition according to [1], wherein the resin (B) includes a resin (B-1) having a carboxyl group and/or a carboxylic anhydride group bonded to a molecular main chain via a linking group.

[3] The curable resin composition described in [1] or [2], wherein the resin (B) satisfies any of the following items [i] and [ii]:

[i] includes a resin (B-1a) having a carboxyl group and/or a carboxylic acid anhydride group bonded to the main chain of the molecule through a linking group and a carboxyl group directly bonded to the main chain of the molecule and / or carboxylic acid anhydride groups,

[ii] including resin (B-1b) and resin (B-2), the resin (B-1b) has at least one carboxyl group and carboxylic anhydride group, and the carboxyl group and the carboxylic anhydride group are all connected through a linking group Bonding to the main chain of the molecule; the resin (B-2) has at least one carboxyl group and carboxylic anhydride group, and all the carboxyl group and the carboxylic anhydride group are directly bonded to the main chain of the molecule.

[4] The curable resin composition according to any one of [1] to [3], further comprising a light scattering agent.

[5] A cured film formed from the curable resin composition according to any one of [1] to [4].

[6] A display device comprising the cured film according to [5].

detailed description

＜Curable resin composition＞

The curable resin composition according to the present invention contains ligand-containing semiconductor particles (A), a resin (B) and a polymerizable compound (C) comprising semiconductor particles coordinated with an organic ligand. According to this curable resin composition, a patterned cured film having a desired line width can be formed with good precision (hereinafter, this effect is referred to as "good pattern formability", and the accuracy of pattern formation is referred to as "pattern formation sex" situation.). According to this curable resin composition, even when the above-mentioned line width is narrow, a patterned cured film can be formed with high precision.

In addition, in this specification, unless otherwise specified, the compound mentioned as an example of each component which is contained or may be contained in a curable resin composition can be used individually or in combination of multiple types.

[1] Ligand-containing semiconductor particles (A)

The curable resin composition contains ligand-containing semiconductor particles (A) which are semiconductor particles coordinated with an organic ligand. The semiconductor particle to which the organic ligand is coordinated is preferably a light-emitting (fluorescent) semiconductor particle. A cured film formed from a curable resin composition containing light-emitting semiconductor particles can be a film that exhibits fluorescent light in a desired wavelength range and has excellent color reproducibility.

The light-emitting semiconductor particles are particles composed of semiconductor crystals, preferably nanoparticles composed of semiconductor crystals. A preferable example of the luminescent semiconductor particle is a semiconductor quantum dot. The average particle diameter 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 diameter of semiconductor quantum dots can be obtained using a transmission electron microscope (TEM).

The semiconductor quantum dots may be selected from the group consisting of, for example, elements of group 2, element 11, element 12, element 13, element 14, element 15, and element 16 of the periodic table. Composed of semiconductor materials of one or more elements.

Specific examples of semiconductor materials that can constitute semiconductor quantum dots include compounds of Group 14 elements such as SnS ₂ , SnS, SnSe, SnTe, PbS, PbSe, and PbTe, and Group 16 elements; GaN, GaP, GaAs, GaSb, InN, InP , InAs, InSb, InGaN, InGaP and other compounds of group 13 elements and group 15 elements; Ga ₂ O ₃ , Ga ₂ S ₃ , Ga ₂ Se ₃ , Ga ₂ Te ₃ , In ₂ O ₃ , In ₂ S ₃ , In ₂ Se ₃ , In ₂ Te ₃ and other Group 13 elements and Group 16 elements compounds; ZnO, ZnS, ZnSe, ZnTe, CdO, CdS, CdSe, CdTe, HgO, HgS, HgSe, HgTe and other Group 12 elements Compounds of elements with Group 16 elements; As ₂ O ₃ , As ₂ S ₃ , As ₂ Se ₃ , As ₂ Te ₃ , Sb ₂ O ₃ , Sb ₂ S ₃ , Sb ₂ Se ₃ , Sb ₂ Te ₃ , Bi Compounds of Group 15 elements such as ₂ O ₃ , Bi ₂ S ₃ , Bi ₂ Se ₃ , Bi ₂ Te ₃ and Group 16 elements; MgS, MgSe, MgTe, CaS, CaSe, CaTe, SrS, SrSe, SrTe, BaS Compounds of group 2 elements such as BaSe and BaTe and group 16 elements; simple substances of group 14 elements such as Si and Ge, group 15 elements or group 16 elements.

Semiconductor quantum dots can be a single-layer structure made of a single semiconductor material, or can be coated with a surface of a nuclear particle (nuclear layer) made of a single semiconductor material that is made of one or more than two different semiconductor materials. A core-shell structure covered by a coating (shell). In the latter case, the semiconductor material constituting the shell layer generally has a band gap energy greater than that of the semiconductor material constituting the core layer.

A semiconductor quantum dot may have two or more types of shell layers. The shape of the semiconductor quantum dots is not particularly limited, and may be spherical or nearly spherical, rod-shaped, disc-shaped, or the like.

The organic ligand that coordinates with the semiconductor particles may be, for example, an organic compound having a polar group that exhibits coordination ability to the semiconductor particles. The organic ligand contained in the ligand-containing semiconductor particle (A) may be an organic ligand added for the synthesis of the ligand-containing semiconductor particle (A) or for stabilization. For example, in Japanese Patent No. JP2015-529698, the ligand-containing semiconductor particles contain hexanoic acid as an organic ligand from the viewpoint of controlling the particle size. In addition, in order to stabilize after synthesis, the organic ligand uses DDSA (dodecenyl Succinic anhydride).

Organic ligands can be coordinated to, for example, the surface of semiconductor particles.

The organic ligands coordinated to the semiconductor particles may be one kind of ligands or two or more kinds of ligands. When the organic ligand is an organic compound having a polar group, the organic ligand usually coordinates with the semiconductor particle through the polar group. The fact that the organic ligand is coordinated can be confirmed by uniformly dispersing the semiconductor particles in a dispersion medium suitable for the organic ligand.

The polar group 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 ). The polar group selected from this group is beneficial to facilitate coordination with semiconductor particles, that is, to improve coordination with semiconductor particles. A high coordination property can contribute to the improvement of the pattern formability of a curable resin composition. Among these, the polar group is more preferably at least one group selected from the group consisting of a thiol group and a carboxyl group from the viewpoint of obtaining a cured film (wavelength conversion film, etc.) with more excellent luminescent properties. An organic ligand may have one or more polar groups.

The molecular weight of the organic ligand coordinated to the semiconductor particles is not particularly limited, and is, for example, 50 to 500, preferably 80 to 400. When the molecular weight of the organic ligand is within this range, the ligand-containing semiconductor particle (A) can be prepared with excellent reproducibility.

The organic ligand can be, for example, an organic compound represented by the following formula:

Y ¹ -Z

In the formula, ^Y1 is the above-mentioned polar group, and Z is a monovalent hydrocarbon group that may contain a heteroatom (N, O, S, halogen atom, etc.). This hydrocarbon group may have one or more unsaturated bonds such as carbon-carbon double bonds. This hydrocarbon group may be linear, branched or have a cyclic structure. The number of carbon atoms in the hydrocarbon group is, for example, 1 to 40, and may be 1 to 30. The methylene contained in the hydrocarbon group can be replaced by -O-, -S-, -C(=O)-, -C(=O)-O-, -OC(=O)-, -C(=O) -NH-, -NH- and other substitutions. In view of the simplicity of preparing the ligand-containing semiconductor particle (A), the hydrocarbon group usually does not contain heteroatoms in many cases.

The organic ligand represented by Y ¹ -Z is preferably a saturated fatty acid having 5 to 12 carbon atoms or an unsaturated fatty acid having 5 to 12 carbon atoms.

The group Z may contain polar groups. As a specific example of the polar group, the above-mentioned description regarding the polar group ^Y1 can be cited. However, the polar group that group Z has is different from the polar group represented by Y ¹ . That is, when the group Z has a polar group, the organic ligand represented by Y ¹ -Z has two or more kinds of polar groups. Based on the simplicity of preparing the ligand-containing semiconductor particle (A), usually the group Z does not contain a polar group in many cases.

Specific examples of organic ligands having a carboxyl group as the polar group Y ¹ include formic acid, acetic acid, propionic acid, and saturated or unsaturated fatty acids. Specific examples of saturated or unsaturated fatty acids include butyric acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, behenic acid, Saturated fatty acids such as henic acid and lignoceric acid; monounsaturated fatty acids such as myristic acid, palmitoleic acid, oleic acid, eicosenoic acid, erucic acid, and nervonic acid; linoleic acid, α-linolenic acid, γ- Linolenic acid, stearidonic acid, dihomo-γ-linolenic acid, arachidonic acid, eicosadonic acid, docosadienoic acid, adrenal acid (docosatetraenoic acid), etc. polyunsaturated fatty acids.

Specific examples of organic ligands having a thiol group or an amino group as ^a polar group Y include organic ligands in which the carboxyl group is substituted by a thiol group or an amino group in the organic ligands having a carboxyl group as ^a polar group Y exemplified above. body.

Content ratio of the organic ligand to the semiconductor particle in the ligand-containing semiconductor particle (A) [hereinafter also referred to as "L/P mass ratio". ], the mass ratio is less than 5.0, preferably 4.5 or less, more preferably 3 or less, further preferably 2 or less, still more preferably 1 or less, particularly preferably 0.6 or less. When the L/P mass ratio is within this range, it is advantageous to form a patterned cured film with high precision. As the reason why the patterned cured film can be formed with good precision, it is considered that by making the L/P mass ratio within the above range, the affinity of the ligand-containing semiconductor particle (A) to the resin (B) is easily improved, and as a result It is to improve the solubility of alkaline developer. In addition, from the viewpoint of the dispersibility of the ligand-containing semiconductor particles (A) in the curable resin composition, the L/P mass ratio is 0.1 or more. The L/P mass ratio can be measured as described in the section of Examples described later.

The content of the ligand-containing semiconductor particles (A) is, for example, 0.1 to 50 parts by mass, preferably 1 to 45 parts by mass, more preferably 5 parts by mass in 100 parts by mass of the solid content of the curable resin composition. More than 40 parts by mass. When the content of the ligand-containing semiconductor particles (A) is too small, it tends to be difficult to obtain sufficient emission intensity of the cured film (wavelength conversion film, etc.). When the content of the ligand-containing semiconductor particles (A) is too large, a patterned cured film tends not to be formed accurately. The "solid content of curable resin composition" in this specification means the sum of components other than the solvent (E) contained in curable resin composition.

[2] Resin (B)

Curable resin composition contains resin (B). Curable resin composition may contain 1 or more types of resin as resin (B). The resin (B) is preferably an alkali-soluble resin. Alkali solubility refers to the property of being soluble in a developing solution which is an aqueous alkali compound solution. As the resin (B), the following resins [K1] to [K6] and the like are exemplified.

Resin [K1]: At least one type (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides [hereinafter also referred to as "(a)". ], and a monomer (b) having a cyclic ether structure with 2 to 4 carbon atoms and an ethylenically unsaturated bond [hereinafter also referred to as "(b)". ] copolymer,

Resin [K2]: (a) and (b) and (a) copolymerizable monomer (c) (herein, different from (a) and (b).) [hereinafter also referred to as "(c)". ] copolymer,

Resin [K3]: 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 with carboxylic anhydride.

As the resin (B), resin [K3] is preferable.

(a) Specifically, the following can be listed:

(Meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, succinic acid mono[2-(meth)acryloyloxyethyl], phthalic acid mono[2-(meth)acryloyl] Oxyethyl] and other unsaturated monocarboxylic acids;

Maleic acid, fumaric acid, citraconic acid, methyl fumaric acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1 , unsaturated dicarboxylic acids such as 2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexenedicarboxylic acid, and compounds represented by formula (a1) described later;

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]-2-heptene, 5,6-dicarboxybicyclo[2.2.1]-2-heptene, 5-carboxy-5-methylbicyclo[2.2.1]-2-heptene, 5-carboxy-5-ethylbicyclo[2.2.1]-2-heptene, 5-carboxy-6-methylbicyclo[ 2.2.1]-2-heptene, 5-carboxy-6-ethylbicyclo[2.2.1]-2-heptene and other carboxyl-containing bicyclic unsaturated compounds;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride Unsaturated dicarboxylic anhydrides such as acid anhydride, dimethyltetrahydrophthalic anhydride, bicyclo[2.2.1]-2-heptene-5,6-dicarboxylic anhydride (nadic anhydride);

Unsaturated (meth)acrylic acid containing a hydroxyl group and a carboxyl group in the same molecule, such as α-(hydroxymethyl)(meth)acrylic acid, and the like.

In this specification, "(meth)acrylic acid" means at least 1 sort(s) selected from the group which consists of acrylic acid and methacrylic acid. Expressions such as "(meth)acryloyl" and "(meth)acrylate" also have the same meaning.

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

(b) The monomer (b1) which has an oxiranyl group and an ethylenically unsaturated bond is mentioned [it may also be called "(b1)" hereafter. ], a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond [hereinafter also referred to as "(b2)". ], a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond [hereinafter also referred to as "(b3)". 〕Wait.

Examples of (b1) include a monomer (b1-1) having a structure after epoxidation of an unsaturated aliphatic hydrocarbon [hereinafter also referred to as "(b1-1)". ], a monomer (b1-2) having an epoxidized structure of an unsaturated alicyclic hydrocarbon [hereinafter also referred to as "(b1-2)". ].

Examples of (b1-1) include: glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, vinyl glycidyl ether , o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinyl Benzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2,4-bis(glycidyloxymethyl) ) styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tris(glycidyloxy methyl) styrene, 2,3,5-tris(glycidyloxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5 - Tris(glycidyloxymethyl)styrene, 2,4,6-tris(glycidyloxymethyl)styrene and the like.

Examples of (b1-2) include vinylcyclohexene monoxide, 1,2-epoxy4-vinylcyclohexane (for example, CELLOXIDE 2000; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexyl Methyl (meth)acrylate (e.g. Cyclomer A400; manufactured by Daicel Chemical Industry Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g. Cyclomer M100; manufactured by Daicel Chemical Industry Co., Ltd. ), 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate, etc.

The monomer (b2) 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 Butane, 3-methyl-3-(meth)acryloyloxyethyloxetane, 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. Preferable examples of (b3) include tetrahydrofurfuryl acrylate (for example, Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

Specific examples of (c) include:

Methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-(meth)acrylate Ethylhexyl, Lauryl (meth)acrylate, Lauryl (meth)acrylate, Stearyl (meth)acrylate, Cyclopentyl (meth)acrylate, Cyclohexyl (meth)acrylate , (meth)acrylate-2-methylcyclohexyl ester, (meth)acrylate tricyclo[5.2.1.0 ^2,6 ]decane-8-yl ester [in this technical field, as the common name "( Dicyclopentyl methacrylate". In addition, it may be called "tricyclodecanyl (meth)acrylate". ], Tricyclo[5.2.1.0 ^2,6 ]decen-8-yl (meth)acrylate [In this technical field, it is called "dicyclopentenyl (meth)acrylate" as a common name. ], Dicyclopentyloxyethyl (meth)acrylate, Isobornyl (meth)acrylate, Adamantyl (meth)acrylate, Allyl (meth)acrylate, Propargyl (meth)acrylate , (meth)acrylates such as phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth)acrylate;

Hydroxyl-containing (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;

Dibasic carboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate;

Bicyclo[2.2.1]-2-heptene, 5-methylbicyclo[2.2.1]-2-heptene, 5-ethylbicyclo[2.2.1]-2-heptene, 5-hydroxybicyclo[2.2 .1]-2-heptene, 5-hydroxymethylbicyclo[2.2.1]-2-heptene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]-2-heptene, 5- Methoxybicyclo[2.2.1]-2-heptene, 5-ethoxybicyclo[2.2.1]-2-heptene, 5,6-dihydroxybicyclo[2.2.1]-2-heptene, 5,6-bis(hydroxymethyl)bicyclo[2.2.1]-2-heptene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]-2-heptene, 5,6 -Dimethoxybicyclo[2.2.1]-2-heptene, 5,6-diethoxybicyclo[2.2.1]-2-heptene, 5-hydroxy-5-methylbicyclo[2.2.1 ]-2-heptene, 5-hydroxy-5-ethylbicyclo[2.2.1]-2-heptene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]-2-heptene, 5 -tert-butoxycarbonylbicyclo[2.2.1]-2-heptene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]-2-heptene, 5-phenoxycarbonylbicyclo[2.2.1]- 2-heptene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]-2-heptene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]-2- Bicyclic unsaturated compounds such as heptene;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3-maleimide Imide propionate, N-(9-acridyl)maleimide and other dicarbonyl imide derivatives;

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, propylene Amide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene; etc.

Among them, (c) is preferably methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, Benzyl (meth)acrylate, Tricyclodecanyl (meth)acrylate, Dicyclopentenyl (meth)acrylate, Styrene, N-Phenylmaleimide, N-Cyclohexylmaleimide Amine, N-benzylmaleimide, bicyclo[2.2.1]-2-heptene, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl (meth)acrylate, etc.

In the resin [K1], the ratio of the structural units derived from each monomer is preferably in the following range among all the structural units constituting the resin [K1]:

Structural unit derived from (a); 2 mol% to 50 mol% (more preferably 10 mol% to 45 mol%)

The structural unit derived from (b), especially the structural unit derived from (b1): 50 mol% to 98 mol% (more preferably 55 mol% to 90 mol%).

When the ratio of the structural unit of resin [K1] exists in the said range, it tends to be excellent in storage stability, developability, and the solvent resistance of the pattern obtained.

Resin [K1] can be, for example, the method described in the document "Experimental Method for Polymer Synthesis" (by Takayuki Otsu, Publishing Co., Ltd. Chemical Doujin 1st Edition, 1st Printing, Issued on March 1, 1972) and the method described above. Citations cited in the literature are made by reference.

Specifically, a method of adding predetermined amounts of (a) and (b) (especially (b1)), a polymerization initiator, a solvent, etc. to a reaction container, stirring, heating, and keeping warm in a deoxygenated atmosphere is exemplified. In addition, the polymerization initiator, solvent, and the like used here are not particularly limited, and any of those commonly used in this 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.). As a solvent, what is necessary is just to dissolve each monomer, and the solvent (E) etc. mentioned later can also be used.

The obtained copolymer may be used as a solution after the reaction, may be used as a concentrated or diluted solution, or may be obtained as a solid (powder) by reprecipitation or the like.

In the resin [K2], the ratio of the structural units derived from each monomer is preferably in the following range among all the structural units constituting the resin [K2]:

Structural unit derived from (a); 4 mol% to 45 mol% (more preferably 10 mol% to 30 mol%),

The structural unit derived from (b), especially the structural unit derived from (b1); 2 mol% to 95 mol% (more preferably 5 mol% to 80 mol%),

Structural unit derived from (c): 1 mol% to 65 mol% (more preferably 5 mol% to 60 mol%).

When the ratio of the structural unit of resin [K2] exists in the said range, it tends to be excellent in storage stability, developability, the solvent resistance of the obtained pattern, heat resistance, and mechanical strength.

Resin [K2] can be produced in the same manner as the method described as the production method of resin [K1]. Specifically, a method of adding predetermined amounts of (a), (b) (especially (b1)) and (c), a polymerization initiator, a solvent, etc. into a reaction vessel, stirring, heating, and keeping warm under a deoxygenated atmosphere is exemplified. The obtained copolymer may be used as a solution after the reaction, may be used as a concentrated or diluted solution, or may be obtained as a solid (powder) by reprecipitation or the like.

In the resin [K3], the ratio of the structural units derived from each monomer is preferably in the following range among all the structural units constituting the resin [K3]:

Structural unit derived from (a); 2 mol% to 55 mol% (more preferably 10 mol% to 50 mol%),

Structural unit derived from (c): 45 mol% to 98 mol% (more preferably 50 mol% to 90 mol%).

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

The resin [K4] can be produced by obtaining a copolymer of (a) and (c), and making (b) have a cyclic ether structure with 2 or more and 4 or less carbon atoms, especially the cyclic ether structure of (b1) The oxirane ring is added to the carboxylic acid and/or carboxylic anhydride contained in (a). Specifically, first, a copolymer of (a) and (c) is produced in the same manner as the method described as the production method of resin [K1]. In this case, it is preferable that the ratio of each structural unit in all structural units constituting the copolymer of (a) and (c) be in the following range.

Structural unit derived from (a); 5 mol% to 50 mol% (more preferably 10 mol% to 45 mol%),

Structural unit derived from (c): 50 mol% to 95 mol% (more preferably 55 mol% to 90 mol%).

Next, the cyclic ether structure having 2 to 4 carbon atoms in (b), especially the oxirane ring in (b1), is combined with the carboxylic acid derived from (a) and / or a part of the carboxylic anhydride is reacted. Specifically, after the copolymer of (a) and (c) is produced, the atmosphere in the flask can be replaced from nitrogen to air, and (b) (especially (b1)), carboxylic acid or carboxylic anhydride and cyclic ether Structure reaction catalysts (such as tris(dimethylaminomethyl)phenol, etc.) Reaction time is carried out, thereby obtaining resin [K4].

The usage-amount of (b), especially the usage-amount of (b1), is preferably 5 mol or more and 80 mol or less, more preferably 10 mol or more and 75 mol or less, based on 100 mol of (a). By setting it as this range, the balance of storage stability, developability, solvent resistance, heat resistance, mechanical strength, and sensitivity tends to become favorable. (b1) is preferable, and (b1-1) is more preferable as (b) used for resin [K4] from the viewpoint that the reactivity of a cyclic ether structure is high and unreacted (b) is hard to remain|survive.

The usage-amount of the said reaction catalyst is preferably 0.001 mass % or more and 5 mass % or less with respect to the total amount of (a), (b) (especially (b1)), and (c). The usage-amount of the said polymerization inhibitor is preferably 0.001 mass % or more and 5 mass % or less with respect to the total amount of (a), (b) and (c).

Reaction conditions such as a charging method, reaction temperature, and time can be appropriately adjusted by considering production facilities, heat generated by polymerization, and the like. In addition, the charging method and the reaction temperature can be appropriately adjusted by considering the production equipment, the calorific value of polymerization, and the like, similarly to the polymerization conditions.

About resin [K5], the copolymer of (b) (especially (b1)) and (c) is obtained by carrying out similarly to the manufacturing method of resin [K1] mentioned above as a 1st stage. In the same manner as above, the obtained copolymer may be used as a solution after the reaction, may be used as a concentrated or diluted solution, or may be obtained as a solid (powder) by reprecipitation or the like.

It is preferable that the ratio of the structural unit derived from (b) (especially (b1)) and (c) exists in the following range with respect to the total number of moles of all the structural units which comprise the said copolymer.

A structural unit derived from (b), especially a structural unit derived from (b1); 5 mol% to 95 mol% (more preferably 10 mol% to 90 mol%),

Structural unit derived from (c): 5 mol% to 95 mol% (more preferably 10 mol% to 90 mol%).

Furthermore, under the same conditions as the production method of resin [K4], by combining (b) (especially (b1)) and (c) the cyclic ether structure derived from (b) and ( a) Resin [K5] can be obtained by reacting the carboxylic acid or carboxylic acid anhydride which it has. The usage-amount of (a) reacted with the said copolymer is preferably 5 mol or more and 80 mol or less with respect to 100 mol of (b) (particularly (b1)). (b1) is preferable, and (b1-1) is more preferable as (b) used for resin [K5] from the viewpoint that the reactivity of a cyclic ether structure is high and unreacted (b) is hard to remain|survive.

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

Examples of carboxylic 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, bicyclo[2.2.1]-2-heptene-5,6-dicarboxylic anhydride (nadic anhydride), etc.

The resin (B) preferably includes a resin (B- 1). The linking group is an indirect bonded group that bonds the molecular main chain of the polymer to the carboxyl group and/or carboxylic acid anhydride group, for example, a hydrocarbon group having 1 or more carbon atoms. The hydrocarbon group may include linear, branched and/or cyclic structures. In addition, one or more methylene groups contained in the hydrocarbon group may be replaced by -O-, -S-, -C(=O)-, -C(=O)-O-, -O-C(=O)- , -C(=O)-NH-, -NH-, etc. for substitution.

The linking group may have one bond or two or more bonds with the molecular main chain of the polymer. When the resin (B-1) has a carboxylic anhydride group, there are two bonds between the linking group and the carboxylic anhydride group.

When the resin (B) contains the resin (B-1), it can contribute to the improvement of the dispersibility of the ligand-containing semiconductor particles (A) in the curable resin composition. This is considered to be due to the fact that the carboxyl group and/or carboxylic acid anhydride group of the resin (B-1) has a relatively high coordination energy when a resin having a polar group can coordinate with the semiconductor particles through its polar group. , the effect of improving the dispersibility of the ligand-containing semiconductor particles (A) is further increased by the coordination with the semiconductor particles based on the high coordination energy. The high dispersibility of the ligand-containing semiconductor particles (A) can contribute, for example, to an improvement in the in-plane uniformity of light emission characteristics of cured films such as wavelength conversion films.

As the resin (B-1), there are carboxyl groups and/or carboxylic anhydride groups bonded to the main chain of the molecule through a linking group, and resins (B-1) having carboxyl groups and/or carboxylic anhydride groups directly bonded to the main chain of the molecule. -1a), and a resin (B-1b) having at least one carboxyl group and a carboxylic acid anhydride group, and the carboxyl group and the carboxylic anhydride group are all bonded to the main chain of the molecule through a linking group.

The resin (B-1a) is preferably a copolymer containing the following structural units: a structural unit having a carboxyl group and/or a carboxylic acid anhydride group bonded to the main chain of the molecule through a linking group, and a carboxyl group directly bonded to the main chain of the molecule And/or structural units of carboxylic acid anhydride groups. The resin (B-1b) is preferably a copolymer containing the following structural units: a structural unit having a carboxyl group and/or a carboxylic acid anhydride group bonded to the main chain of the molecule through a linking group, and not having a carboxyl group directly bonded to the main chain of the molecule. Structural unit of carboxyl group and/or carboxylic acid anhydride group.

The curable composition of the present invention may include, as the resin (B), a resin (B-2) having at least one carboxyl group and a carboxylic anhydride group, and the carboxyl group and the carboxylic anhydride group are all linked to the molecular main body. Resins in which the chains are directly bonded.

Resin (B-1a), resin (B-1b) and resin (B-2) can be obtained by using at least one kind (a) selected from the group consisting of the above-mentioned unsaturated carboxylic acid and unsaturated carboxylic acid anhydride as a monomer Use to prepare. By selecting an appropriate monomer as (a), resin (B-1a), resin (B-1b) and resin (B-2) can be prepared separately. Although specific examples of (a) are mentioned above, it is not limited to these specific examples.

In order to introduce a carboxyl group and/or carboxylic acid anhydride group bonded to the main chain of the molecule through a linking group into the resin, as (a), vinylbenzoic acid, 1,2,3,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic acid, methyl-5-norbornene-2,3-dicarboxylic anhydride, etc.

In order to introduce a carboxyl group and/or carboxylic acid anhydride group bonded to the molecular main chain via a linking group into the resin, as (a), for example, one or more monomers represented by formula (a1) may be used.

[In formula (a1),

R ¹ represents a hydrogen atom or a methyl group.

R ² represents an alkylene group having 2 to 6 carbon atoms or a cycloalkylene group having 5 to 12 carbon atoms, or a trivalent group obtained by removing one hydrogen atom from the alkylene group.

R ³ represents an alkylene group having 2 to 6 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, or a cycloalkenylene group having 5 to 12 carbon atoms, or a divalent aromatic group.

Y is a hydrogen atom or an alkyl group with 1 to 8 carbon atoms, and the methylene group contained in the alkyl group can be replaced by -O-, -S-, -C(=O)-, -C(=O)-O -, -O-C(=O)-, -C(=O)-NH- or -NH-substitution.

Examples of the alkylene group having ² to 6 carbon atoms in R2 and ^R3 include 1,2-ethylene, 1,3-propylene, 1,4-butylene, and 1,5-pentylene 1,6-hexylene and other linear alkylene groups; 1,1-ethylene, 1,2-propylene, 1,3-butylene, 2-methyl-1,3-propylene Branched alkylene groups such as 2-methyl-1,2-propylene, 1,4-pentylene, 2-methyl-1,4-butylene, etc.

Examples of cycloalkylene groups having 5 to ¹² carbon atoms in R and ^R include 1,2-cyclopentylene, 1,3-cyclopentylene, 1,4-cyclopentylene, 1 ,2-Cyclohexylene, 1,3-Cyclohexylene, 1,4-Cyclohexylene, 1,2-Cycloheptylene, 1,3-Cycloheptylene, 1,4-Cycloheptylene, Adamantane-1,2-diyl, adamantane-1,3-diyl, etc.

Examples of the cycloalkenylene group having 5 to 12 carbon atoms in R ³ include groups in which any one of the carbon-carbon single bonds in the ring structure of the above-mentioned cycloalkylene group is replaced with a carbon-carbon double bond.

Examples of divalent aromatic groups in ^R3 include aromatic hydrocarbons with 5 to 12 carbon atoms, specifically 1,2-phenylene, 1,3-phenylene, and 1,4-phenylene. , 1,2-naphthylene, 1,3-naphthylene, 1,4-naphthylene, 1,5-naphthylene, 1,8-naphthylene, 2,3-naphthylene, 2 , 4-naphthylene, 2,6-naphthylene, etc.

Examples of the alkyl group having 1 to 8 carbon atoms in Y include linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, pentyl, and octyl.

Examples of the monomer represented by the formula (a1) include mono[2-(meth)acryloyloxyethyl]succinate and mono[2-(meth)acryloyloxyethyl]phthalate. Mono [(meth)acryloyloxyalkyl] esters of dicarboxylic acids, etc. Mono[(meth)acryloyloxyalkyl]esters of dicarboxylic acids represented by the formula (a1) are advantageous from the standpoint of dispersibility of the ligand-containing semiconductor particles (A) in organic solvents .

In order to introduce a carboxyl group and/or carboxylic anhydride group directly bonded to the main chain of the molecule into the resin, as (a), (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, maleic anhydride, 3,4,5,6-tetrahydrophthalic acid, 3,4,5,6-tetrahydrophthalic anhydride, etc. From the viewpoint of copolymerization reactivity and the solubility of the obtained resin in an aqueous alkali solution, (meth)acrylic acid, maleic anhydride, and the like are preferable.

The resin (B) preferably satisfies any of the following (i) and (ii):

[i] includes a resin (B-1a) having a carboxyl group and/or a carboxylic acid anhydride group bonded to the main chain of the molecule through a linking group, and a carboxyl group directly bonded to the main chain of the molecule and / or carboxylic acid anhydride group;

[ii] Comprising resin (B-1b) and resin (B-2), resin (B-1b) has at least one carboxyl group and carboxylic acid anhydride group, and the carboxyl group and the carboxylic anhydride group are all connected to the main chain of the molecule through a linking group Bonding: Resin (B-2) has at least one carboxyl group and carboxylic acid anhydride group, and the carboxyl group and the carboxylic anhydride group are all directly bonded to the molecular main chain.

Satisfying any one or both of [i] and [ii] can help to improve the dispersibility of the ligand-containing semiconductor particles (A) in the curable resin composition, and at the same time contribute to the improvement of the composition of the curable resin. Pattern formation of objects.

In [i], resin (B) may contain only resin (B-1a), may also contain resin (B-1a) and resin (B-1b), may also contain resin (B-1a) and resin (B-1a) 2).

The resin (B) is preferably composed of the resin (B-1), more preferably composed of the resin (B-1), and contains the resin (B-1a).

Among the acid values shown by the resin (B), the acid value X based on the carboxyl group and/or carboxylic acid anhydride group directly bonded to the main chain of the molecule, and the acid value X based on the carboxyl group and/or the carboxyl group bonded to the main chain of the molecule through a linking group Or the ratio ^{X/Y a of} the acid value Ya of the carboxylic anhydride group is, for example, (more than 0 mg-KOH/g and less than 150 mg-KOH/g)/(more than 20 mg-KOH/g and less than 150 mg-KOH/g), preferably ( 40mg-KOH/g to 100mg-KOH/g)/(40mg-KOH/g to 120mg-KOH/g), more preferably (40mg-KOH/g to 80mg-KOH/g)/(60mg- KOH/g or more and 90mg-KOH/g or less).

When the ratio X/Y ^a is within the above range, the dispersibility of the resin (B) and the developability (development speed and pattern formability) of the curable resin composition can be improved.

The acid value of the resin (B) is, for example, 20 mg-KOH/g to 200 mg-KOH/g, preferably 40 mg-KOH/g to 170 mg-KOH/g, more preferably 60 mg-KOH/g to 150 mg-KOH/g below g. By being within the above range, both developability and high dispersibility can be made compatible.

The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of resin, and can be obtained by titration using an aqueous potassium hydroxide solution, for example.

The solution acid value of the resin (B) 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, still more preferably 12 mg-KOH/g or more and 50 mg-KOH/g or less. 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 solution, and can be obtained, for example, by titration using an aqueous potassium hydroxide solution.

The solution acid value is a value measured by dissolving the resin (B) in a predetermined solvent, and the concentration is, for example, 10% by mass or more and 50% by mass or less. When the acid value of the solution is within the aforementioned range, both the semiconductor particles and the resin (B) can be mixed without aggregation.

The polystyrene-equivalent weight average molecular weight of the resin (B) is preferably from 3,000 to 100,000, more preferably from 5,000 to 50,000, still more preferably from 5,000 to 30,000. When the molecular weight is within the above range, the solubility of the unexposed portion to the developing solution is high, and the remaining film rate and hardness of the obtained pattern also tend to be high. The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6 and more preferably 1.2 to 4.

The content of the resin (B) is preferably not less than 5% by mass and not more than 70% by mass, more preferably not less than 10% by mass and not more than 65% by mass, and still more preferably not less than 15% by mass, in 100% by mass of the solid content of the curable resin composition. 60% by mass or less. When content of resin (B) exists in the said range, the solubility with respect to the developing solution of an unexposed part tends to be high.

[3] Polymerizable compound (C)

The polymerizable compound (C) is not particularly limited as long as it is a compound that can be polymerized by light irradiation or the like via active radicals generated from the polymerization initiator (D), and examples thereof include compounds having a polymerizable ethylenically unsaturated bond, etc. . The weight average molecular weight of the polymerizable compound (C) is preferably 3,000 or less.

The polymerizable compound (C) 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, and pentaerythritol tetra(meth)acrylate. , dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tetrapentaerythritol deca(meth)acrylate , Pentaerythritol nona(meth)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 (C). The content of the polymerizable compound (C) is preferably not less than 20 parts by mass and not more than 150 parts by mass, more preferably not less than 80 parts by mass and not more than 120 parts by mass, based on 100 parts by mass of the resin (B) in the curable resin composition.

[4] Polymerization initiator (D)

The curable resin composition may contain a polymerization initiator (D). The polymerization initiator (D) is not particularly limited as long as it is a compound that generates active radicals, acids, etc. by the action of light or heat to initiate polymerization, and known polymerization initiators can be used.

Examples of the polymerization initiator (D) include oxime compounds such as O-acyl oxime compounds, benzokyne ketone compounds, bisimidazole compounds, triazine compounds, acyl phosphine oxide compounds, and the like. In consideration of sensitivity, pattern formability, etc., a polymerization initiator (D) may use 2 or more types together. The polymerization initiator (D) preferably contains an oxime compound such as an O-acyl oxime compound from the viewpoint of being advantageous for precise production of a pattern shape having sensitivity and a desired line width.

The O-acyl oxime compound is a compound having a structure represented by formula (d). The following * indicates the key position.

O-acyl oxime compounds can be listed: N-benzoyloxy-1-(4-phenylthiophenyl) butane-1-one-2-imine, N-benzoyloxy-1-( 4-Phenylthiophenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)-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-dioxolylmethyloxy)benzoyl }-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole- 3-yl]-3-cyclopentylpropane-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole- 3-yl]-3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[4-(2-hydroxyethyloxy)phenylthiophenyl]propane-1 -Keto-2-imine, N-acetoxy-1-[4-(1-methyl-2-methoxyethoxy)-2-methylphenyl]-1-(9-ethyl -6-nitro-9H-carbazol-3-yl)methane-1-imine, etc. Commercially available items such as Irgacure (registered trademark) OXE01, Irgacure OXE02, Irgacure OXE03 (the above are manufactured by BASF Corporation), N-1919, NCI-930, NCI-831 (the above are all manufactured by ADEKA Corporation) can be used. These O-acyl oxime compounds are advantageous in improving lithographic performance.

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

The compound having the structure shown in formula (d4) can enumerate: 2-methyl-2-morpholino-1-(4-methylthiophenyl) propane-1-one, 2-dimethylamino-1- (4-morpholinophenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4- (4-morpholinyl)phenyl]butan-1-one, etc. Commercially available items such as Irgacure (registered trademark) 369, Irgacure 907, and Irgacure 379 (all of which are manufactured by BASF Corporation) can be used.

The compound having the structure shown in formula (d5) can enumerate: 2-hydroxyl-2-methyl-1-phenylpropan-1-ketone, 2-hydroxyl-2-methyl-1-[4-(2-hydroxyl Oligomerization of ethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one substances, α,α-diethoxyacetophenone, benzyl dimethyl ketal, etc.

From the viewpoint of sensitivity, the phenylalkyl ketone compound is preferably a compound having a structure represented by formula (d4).

Examples of bisimidazole compounds include: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2,3-dichlorobenzene base)-4,4',5,5'-tetraphenylbiimidazole (refer to Japanese Patent Laid-Open Publication No. 6-75372, Japanese Patent Laid-Open Publication No. 6-75373, etc.), 2,2'-bis( 2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5 '-Tetrakis(dialkoxyphenyl)bisimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)bisimidazole ( Refer to Japanese Patent Publication No. 48-38403, Japanese Patent Publication No. 62-174204, etc.), 4,4', 5,5'-position phenyl is substituted by alkoxycarbonyl imidazole compound (refer to Japanese Japanese Patent Application Laid-Open Publication No. 7-10913, etc.), etc. Among them, compounds represented by the following formulas 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)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl] -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)vinyl]-1,3,5-triazine, etc.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like.

Examples of the polymerization initiator (D) include: benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Methanone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra( tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone and other benzophenone compounds; 9,10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone and other quinones Compounds; 10-butyl-2-chloroacridone, dibenzoyl, methyl phenylglyoxylate, titanocene compounds, etc. These are preferably used in combination with a polymerization initiation adjuvant (D1) (especially an amine compound) described later.

The polymerization initiator (D) preferably contains at least one kind of polymerization initiator selected from the group consisting of phenalkyl ketone compounds, triazine compounds, acyl phosphine oxide compounds, O-acyl oxime compounds and bis-imidazole compounds, more preferably A polymerization initiator containing an O-acyl oxime compound.

The content of the polymerization initiator (D) is preferably not less than 0.1 parts by mass and not more than 30 parts by mass, more preferably not less than 1 part by mass and not more than 25 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). , More preferably at least 1 part by mass and at most 20 parts by mass. When content of a polymerization initiator (D) exists in the said range, since it exists in the tendency to shorten exposure time by high sensitivity, it tends to improve the productivity of cured films, such as a wavelength conversion film.

[5] Polymerization initiation aid (D1)

The curable resin composition may contain a polymerization initiation adjuvant (D1). The polymerization initiation adjuvant (D1) is a compound for accelerating the polymerization of the polymerizable compound (C) whose polymerization is initiated by the polymerization initiator (D), or a sensitizer. When containing a polymerization initiation adjuvant (D1), it is used in combination with a polymerization initiator (D).

As a polymerization start adjuvant (D1), an amine compound, an alkoxy anthracene compound, a thioxanthone compound, a carboxylic acid compound, etc. are mentioned. Among them, thioxanthone compounds are preferable. The polymerization initiation adjuvant (D1) can be used in combination of 2 or more types.

Amine compounds include: triethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethylaminobenzoic acid methyl ester, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid iso Pentyl ester, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethyl Amino) benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, etc., among which , preferably 4,4'-bis(diethylamino)benzophenone. Commercial items such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can 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, 2-ethyl-9,10-dibutoxyanthracene, etc.

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

Carboxylic acid compounds include: phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, Dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid, etc. .

The content of the polymerization initiation adjuvant (D1) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). the following. When the content of the polymerization initiation adjuvant (D1) is within the above range, the productivity of cured films such as wavelength conversion films can be further improved

〔6〕Solvent (E)

Curable resin composition It is preferable that a curable resin composition contains 1 or more types of solvent (E). Examples of the solvent (E) include ester solvents (solvents containing -C(=O)-O-), ether solvents other than ester solvents (solvents containing -O-), ether ester solvents (containing -C(=O)- O- and -O- solvents), ketone solvents other than ester solvents (solvents containing -C(=O)-), alcohol solvents, aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

Examples of ester solvents include: methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, propyl butyl butyrate, 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, cyclohexanecarboxylic acid Isopropyl and γ-butyrolactone, etc.

Examples of 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 Alcohol 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, methyl anisole, methoxycyclohexane, etc.

Examples of 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, 2-Ethoxy Ethyl-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether ethyl Ester, 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, etc.

Examples of ketone solvents include: 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone , Cyclopentanone, 2-acetyl cyclopentanone, cyclohexanone, 2-acetyl cyclohexanone and isophorone, etc.

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

From the viewpoint of applicability and drying properties, the solvent (E) preferably contains propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate Esters, 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 and N,N-dimethylformamide, cyclohexyl acetate, methoxycyclohexane, isopropyl cyclohexanecarboxylate, cyclopentanone, cyclohexanone, cyclohexanone At least one selected from the group consisting of hexanol, benzene, toluene, xylene, and mesitylene, more preferably containing propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and dipropylene glycol monomethyl ether acetate , ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 3-ethoxy ethyl propionate, cyclohexyl acetate, methoxycyclohexane, cyclo At least one selected from the group consisting of isopropyl hexanecarboxylate, cyclopentanone, cyclohexanone, and cyclohexanol.

From the viewpoint of the dispersibility of the ligand-containing semiconductor particles (A) and the resin (B) in the curable resin composition, the solvent (E) preferably contains an alicyclic hydrocarbon group (non-aromatic cyclic hydrocarbon group) and an ether bond ( A solvent (E-a) of at least one of -O-), an ester bond (-C(=O)-O-), and a ketone bond (-C(=O)-).

The solvent (E) may consist of only the solvent (E-a), or may be a mixture of the solvent (E-a) and other solvents. In the case of a mixture, from the viewpoint of the dispersibility of the ligand-containing semiconductor particles (A) and the resin (B) in the curable resin composition, the solvent (E-a) is preferably contained at 20% by mass or more, more preferably at least 30% by mass , It is more preferable to contain 40 mass % or more.

Solvent (E-a) includes: cyclohexyl acetate, 2-methylcyclohexyl acetate, cyclohexyl propionate, cis-3,3,5-trimethylcyclohexyl acetate, 4-tert-butylcyclohexyl acetate , cyclohexyl butyrate, isopropyl cyclohexanecarboxylate, methoxycyclohexane, cyclopentanone, 2-acetylcyclopentanone, cyclohexanone, 2-acetylcyclohexanone, etc.

The content of the solvent (E) in 100% by mass of the curable resin composition is preferably not less than 60% by mass and not more than 95% by mass, more preferably not less than 65% by mass and not more than 92% by mass. In other words, the solid content of the curable resin composition is preferably not less than 5% by mass and not more than 40% by mass, more preferably not less than 8% by mass and not more than 35% by mass. When the content of the solvent (E) is within the above range, the applicability of the curable resin composition and the flatness at the time of coating tend to be favorable, and the light emission characteristics of cured films such as wavelength conversion films tend to be favorable.

〔7〕Leveling agent (F)

The curable resin composition may be one or more leveling agents (F). As a leveling agent (F), the silicone type surfactant which has a silicone type surfactant, a fluorine type surfactant, and a fluorine atom, etc. are mentioned. These may have a polymerizable group in a side chain.

Examples of silicone-based surfactants include surfactants having a siloxane bond in the molecule, and the like. Specifically, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (trade name, manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF -4446, TSF4452 and TSF4460 (manufactured by Momentive Advanced Materials Nippon Contracting Co., Ltd.), etc.

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule, and the like. Specifically, Fluorad (registered trademark) FC430, Fluorad FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafac (registered trademark) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac F554, Megafac R30, Megafac RS-718-K (manufactured by DIC Co., Ltd.), F-TOP (registered trademark) EF301, F-TOPEF303, F-TOP EF351, F-TOP EF352 (manufactured by Mitsubishi Materials Corporation), Surflon (registered trademark) ) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemical Research Institute, Ltd.), etc.

Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule, and the like. Specifically, Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477, and Megafac F443 (manufactured by DIC Co., Ltd.) etc. are mentioned.

The content of the leveling agent (F) in 100% by mass of the curable resin composition is usually 0.001% by mass to 0.2% by mass, preferably 0.002% by mass to 0.1% by mass, more preferably 0.005% by mass to 0.05% by mass the following.

[8] Antioxidant (G)

From the viewpoint of improving the heat resistance and light resistance of the curable resin composition, the curable resin composition may contain an antioxidant (G). The antioxidant (G) is not particularly limited as long as it is an antioxidant commonly used industrially, and phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like can be used. Antioxidant (G) can use 2 or more types together.

Phenolic antioxidants include: Irganox (registered trademark) 1010 (Irganox 1010: pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], manufactured by BASF Co., Ltd.) , Iluganox 1076 (Irganox 1076: octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, manufactured by BASF Co., Ltd.), Iluganox 1330 (Irganox 1330: 3, 3',3",5,5',5"-hexa-tert-butyl-a,a',a"-(mesitylene-2,4,6-triyl)tri-p-cresol, BASF Co., Ltd. manufactured), Irganox 3114 (Irganox 3114: 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6-( 1H, 3H, 5H)-trione, manufactured by BASF Co., Ltd.), Ilganox 3790 (Irganox 3790: 1,3,5-tris((4-tert-butyl-3-hydroxy-2,6-xylyl )methyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, manufactured by BASF Co., Ltd.), Irganox 1035 (Irganox 1035: Thiodiethylene Bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], manufactured by BASF Co., Ltd.), Irganox 1135 (Irganox 1135: phenylpropionic acid, 3,5-bis(1 ,1-Dimethylethyl)-4-hydroxy-C7-C9 side chain alkyl ester, manufactured by BASF Co., Ltd.), Irganox 1520L (Irganox 1520L: 4,6-bis(octylthiomethyl)-o- Cresol, BASF Co., Ltd.), Iluganox 3125 (Irganox 3125, BASF Co., Ltd.), Iluganox 565 (Irganox 565: 2,4-bis(n-octylthio)-6-(4-hydroxy- 3',5'-di-tert-butylanilino)-1,3,5-triazine, manufactured by BASF Co., Ltd.), Adecastab (registered trademark) AO-80 (Adecastab AO-80: 3,9-bis( 2-(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl)-2,4,8,10-tetraoxo Aspiro(5,5)undecane, manufactured by ADEKA Co., Ltd.), Sumilizer (registered trademark) BHT, Sumilizer GA-80, Sumilizer GS (Sumilizer, all of which are manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer (registered trademark) Trademark) 1790 (Cyanox 1790, manufactured by Saitama Industrial Technology Center (SAITEC)), vitamin E (manufactured by Eisai Co., Ltd.), etc.

Examples of phosphorus-based antioxidants include Ilugafos (registered trademark 168 (Irgafos 168: tris(2,4-di-tert-butylphenyl) phosphite, manufactured by BASF Co., Ltd.), Ilugafos 12 (Irgafos 12: tris[2- [[2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphospin-6-yl]oxy]ethyl]amine, BASF( Co., Ltd.), Irgafos 38 (Irgafos 38: bis(2,4-bis(1,1-dimethylethyl)-6-methylphenyl) ethyl phosphite, manufactured by BASF Co., Ltd.), Adecastab (registered trademark) 329K, Adecastab PEP 36, Adecastab PEP-8 (all of the above are manufactured by ADEKA Co., Ltd.), Sandstab P-EPQ (manufactured by Clariant), Weston (registered trademark) 618, Weston 619G (all of the above are manufactured by GE), Ultranox 626 (manufactured by GE), and Sumilizer (registered trademark) GP (Sumilizer GP: 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy] -2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphaheptin) (manufactured by Sumitomo Chemical Co., Ltd.), etc.

Sulfur-based antioxidants include: dialkyl thiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl thiodipropionate, or distearyl thiodipropionate, and four [Methylene(3-dodecylthio)propionate] β-alkylmercaptopropionate compounds of polyhydric alcohols such as methane, etc.

[9] Other ingredients

If necessary, the curable resin composition may contain one or more fillers, polymer compounds other than the resin (B), adhesion promoters, ultraviolet absorbers, anti-coagulation agents, organic acids, and organic amine compounds. , thiol compounds, curing agents, light scattering agents and other additives.

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

Adhesion promoters include: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-amino Propylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyl Trimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethylsilane Oxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane, etc.

Examples of ultraviolet absorbers include: benzotriazole compounds such as 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole; 2-hydroxy-4-octyl Benzophenone-based compounds such as oxybenzophenone; benzoate-based compounds such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate ; 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol and other triazine compounds; etc. Sodium polyacrylate etc. are mentioned as an anti-agglomeration agent.

Examples of the curing agent include compounds capable of crosslinking the resin (B) by reacting with carboxyl groups in the resin (B) by heating, compounds capable of homopolymerization and curing, and the like. Examples thereof include epoxy compounds, oxetane compounds, and the like.

Examples of the light-scattering agent include metal or metal oxide particles, glass particles, and the like. Examples of metal oxides include TiO ₂ , SiO ₂ , BaTiO ₃ , ZnO, and the like.

The light-scattering agent includes metal oxide particles, more preferably TiO ₂ , SiO ₂ , and the like.

The particle size of the light scattering agent is, for example, about 0.03 μm to 20 μm, preferably 0.05 μm to 1 μm, more preferably 0.05 μm to 300 nm. The content of the light scattering agent is usually 0.001 to 50 mass % in 100 mass % of the curable resin composition, preferably 1 to 40 mass %, more preferably 5 to 30 mass %.

<Preparation method of curable resin composition>

The curable resin composition can be prepared by mixing the ligand-containing semiconductor particles (A), the resin (B), the polymerizable compound (C) and other components used as necessary.

The ligand-containing semiconductor particle (A) is preferably subjected to the following treatment: prepare or prepare a semiconductor particle to which an organic ligand has been coordinated, and then perform a ligand-reducing treatment for reducing the amount of coordination of the organic ligand to the semiconductor particle, The L/P mass ratio is set to be 0.1 or more and less than 5.0. The ligand reduction treatment is usually performed before mixing with the resin (B) or the polymerizable compound (C).

The ligand reduction treatment can be performed by extracting organic ligands coordinated to the semiconductor particles with an appropriate solvent. Examples of the solvent for the extraction include ethanol, methanol, and the like. The extraction conditions are as follows: After the dispersion liquid containing the ligand-containing semiconductor particles (A) is added dropwise to the extraction solvent to precipitate it, the precipitate is separated by a centrifuge to remove the supernatant liquid, and then dispersed in a predetermined solvent (hexane, toluene, chloroform, etc.).

<Cured film, patterned cured film, wavelength conversion film, and display device>

A cured film can be obtained by curing a film (layer) composed of a curable resin composition. At this time, pattern formation may be performed by a method such as a photolithography method, an inkjet method, or a printing method, thereby obtaining a patterned cured film. A cured film or a patterned cured film can be suitably used as a wavelength conversion film (wavelength conversion filter) that emits light of a wavelength different from the wavelength of incident light. The wavelength conversion film can be applied to display devices such as liquid crystal display devices and organic EL devices. The patterning method is preferably photolithography. The photolithography method is a method of applying a curable resin composition on a substrate, drying it to form a curable resin composition layer, exposing and developing the curable resin composition layer through a photomask.

As the substrate, glass plates such as quartz glass, borosilicate glass, aluminosilicate glass, soda lime glass with silica coating on the surface, polycarbonate, polymethylmethacrylate, polyterephthalate, etc. can be used. Resin boards such as ethylene formate, silicon, substrates on which aluminum, silver, silver/copper/palladium alloy thin films, etc. are formed, etc.

Formation of the cured film patterned by photolithography can be carried out using known or commonly used equipment or conditions. For example, it can be produced as follows. First, a curable resin composition is applied on a substrate, and volatile components such as a solvent are removed and dried by heat drying (prebaking) and/or reduced pressure drying to obtain a curable resin composition layer. Examples of the coating method include a spin coating method, a slit coating method, a slit and spin coating method, and the like.

The temperature at the time of heat drying is preferably 30°C to 120°C, more preferably 50°C to 110°C. The heating time is preferably from 10 seconds to 10 minutes, more preferably from 30 seconds to 5 minutes. When performing reduced-pressure drying, it is preferable to carry out under the pressure of 50 Pa or more and 150 Pa or less, and the temperature range of 20 degreeC or more and 25 degreeC 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 a desired cured film such as a wavelength conversion film.

Next, the curable resin composition layer is exposed through a photomask for forming a desired pattern. The pattern on the photomask is not particularly limited, and a pattern matching the intended use can be used. As the light source for exposure, a light source emitting light having a wavelength of 250 nm to 450 nm is preferable. For example, light less than 350 nm can be cut using a filter that cuts this wavelength range, or light around 436 nm, 408 nm, and 365 nm can be selectively extracted using a bandpass filter that cuts out these wavelength ranges. Examples of the light source include mercury lamps, light-emitting diodes, metal halides, and halogen lamps.

Since it is possible to uniformly irradiate the entire exposure surface with parallel light, or to align the correct position of the photomask and the substrate on which the curable resin composition layer is formed, it is preferable to use an exposure device such as a mask aligner or a step-and-repeater for exposure. .

The pattern of the curable resin composition layer is formed on a board|substrate by making the exposed curable resin composition layer contact a developing solution, and developing. By image development, the unexposed part of a curable resin composition layer melt|dissolves in a developing solution, and is removed. As the developer, it is preferable to use an aqueous solution of a basic compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, tetramethylammonium hydroxide, or the like. The concentration of these basic compounds in the aqueous solution is preferably not less than 0.01% by mass and not more than 10% by mass, more preferably not less than 0.03% by mass and not more than 5% by mass. The developer may further contain a surfactant. As an image development method, a paddle stirring method, a dipping method, a spraying method, etc. are mentioned. Further, the substrate can be tilted at any angle during development. After image development, washing with water is preferred.

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

Example

Examples are given below to describe the present invention more specifically, but the present invention is not limited to these examples. In the examples, % and parts indicating the content or the amount used are mass standards unless otherwise specified.

<Manufacturing Example 1-1: Preparation of Ligand-Containing Semiconductor Particles (A)-1>

(1) Preparation of semiconductor quantum dots

As the semiconductor quantum dot, a core-shell type semiconductor quantum dot INP530 (manufactured by NN-LABS Co., Ltd.) having an InP (core)/ZnS (first shell)/ZnS (second shell) structure was used. Oleylamine is coordinated to the surface of the semiconductor quantum dot.

(2) Reduce ligand processing

Next, the above-mentioned semiconductor quantum dots (QDs) were subjected to ligand reduction treatment in the following order. First, 2 parts by volume of hexane was added to 1 part by volume of the dispersion containing the QDs obtained in (1) above to dilute. Thereafter, 30 parts by volume of ethanol was added to precipitate the QDs, followed by centrifugation. The supernatant was removed, and 3 parts by volume of hexane were added to redisperse the QDs. Such treatment (precipitation by adding ethanol→centrifugation→removal of the supernatant→addition of hexane and redispersion) was performed a total of 3 times. However, when performing the third redispersion, isopropyl cyclohexanecarboxylate (CHCI) was added instead of hexane so that the concentration of QDs (containing oleylamine ligand) was 20% by mass to obtain QD dispersion-A.

(3) Determination of L/P mass ratio

For the obtained QD dispersion-A, the L/P mass ratio [mass ratio of the organic ligand to the semiconductor quantum dot; [mass of the organic ligand]/[mass of the semiconductor quantum dot]] was measured in the following order.

Measure 30 μL of the QD dispersion liquid into an aluminum pot, and use a thermogravimetric analysis device "TGDTA6200" (manufactured by Nippon Seiko Co., Ltd.) to heat it in the temperature range of 45 °C to 550 °C at a heating rate of 5 °C/min under nitrogen flow. Re-determined. The weight change from 170°C to 550°C, which is the end temperature of CHCI volatilization, is taken as the weight (mass) of the organic ligand, and the weight of the residue after the measurement is taken as the weight (mass) of the semiconductor quantum dot. Divide by the mass of the semiconductor quantum dots to obtain the L/P mass ratio.

<Production Example 1-2: Production of Ligand-Containing Semiconductor Particles (A)-2>

Add 14.5 parts of oleic acid to 100 parts of QD dispersion-A, add CHCI so that the concentration of QD (containing oleylamine and oleic acid ligand) becomes 20% by mass, and stir at 80°C for 3 hours to obtain QD dispersion Liquid-B. In the same manner as (3) of Production Example 1-1, the L/P mass ratio of the obtained QD dispersion-B was measured.

<Production Example 1-3: Production of Ligand-Containing Semiconductor Particles (A)-3>

Add 49.0 parts of oleic acid to 100 parts of QD dispersion-A obtained in Production Example 1-1, add CHCI so that the concentration of QD (containing oleylamine and oleic acid ligand) is 20% by mass, and stir at 80°C for 3 hours, thus obtaining QD dispersion-C. In the same manner as (3) of Production Example 1-1, the L/P mass ratio of the obtained QD dispersion-C was measured.

The summary of Production Examples 1-1 to 1-3 is shown in Table 1.

【Table 1】

<Manufacturing example 2-1: Preparation of solution containing resin (B)-1>

100 parts of propylene glycol monomethyl ether acetate (PGMEA) was added to the flask equipped with the condenser tube and the stirrer, and nitrogen substitution was carried out. While stirring at 70° C., 7.6 parts of methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 7.6 parts of dicyclopentyl methacrylate (manufactured by Hitachi Chemical Co., Ltd. ") 5.6 parts, methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 2.7 parts, succinic acid 1-[2-(methacryloyloxy)ethyl] ester (manufactured by Sigma-Aldrich Nippon Kogyo Co., Ltd.) 6.4 parts , 2,2'-azobis(2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.) 2.1 parts, pentaerythritol tetrakis(3-mercaptopropionate) [PEMP] (SC Organic Chemicals Co., Ltd. Co., Ltd.) and a mixed solution of 1.4 parts by mass of PGMEA and 100 parts of PGMEA were polymerized at this temperature for 2 hours. After slowly cooling the reaction solution to room temperature, it was added dropwise to ethanol, and the precipitate was collected by filtration and dried with a vacuum dryer at 40°C. 20 parts of the obtained white powder were dissolved in a mixed solvent of 40 parts of PGMEA and 40 parts of CHCI 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 conversion value obtained by gel permeation chromatography). Based on the charged amount, the acid value of the solid content of the obtained resin was calculated as X/Y ^a =80/70 (mg-KOH/g).

<Manufacturing example 2-2: Preparation of solution containing resin (B)-2>

As a monomer, 14.3 parts of methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 2.4 parts of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were used, and 1-[2-(methacryloyloxy) succinic acid was not used. Ethyl] ester (Sigma-Aldrich Nippon Contracting Co., Ltd.) was carried out in the same manner as in Production Example 2-1 to obtain resin solution-b (resin concentration: 20% by mass). The weight average molecular weight of the obtained resin was 17,000 (value in terms of standard polystyrene obtained by gel permeation chromatography). Based on the charged amount, the acid value of the obtained resin solid content was calculated as X/Y ^a =70/0 (mg-KOH/g).

<Production Example 2-3: Preparation of Solution Containing Resin (B)-3>

As a monomer, 10.3 parts of methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used, except that methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was not used, and it was carried out in the same manner as Production Example 2-1 to obtain Resin solution-c (resin concentration: 20% by mass). The weight average molecular weight of the obtained resin was 16,000 (value in terms of standard polystyrene obtained by gel permeation chromatography). Based on the charged amount, the acid value of the obtained resin solid content was calculated as X/Y ^a =0/70 (mg-KOH/g).

<Production Example 2-4: Preparation of Solution Containing Resin (B-4>

After preparing a resin solution according to the description in Japanese Patent No. JP2015-028139 [0191], PGMEA was added to obtain a resin solution-d having a resin concentration of 20% by mass. The acid value of the solid content of the obtained resin was calculated based on the amount charged, X/Y ^a =49/0 (mg-KOH/g).

<Example 1>

Put 25 parts of QD dispersion-A, 14.0 parts of resin solution-a, 42.0 parts of resin solution-b and 1.85 parts of PGMEA solution containing antioxidant (G-1) at a concentration of 20% by mass into a flask, stir and heat at 80°C 12 hours. Thereafter, it was left to cool to room temperature to obtain a solution containing QDs and resin.

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

<Examples 2-4, Comparative Examples 1-2>

A curable resin composition was prepared in the same manner as in Example 1, except that the types and amounts of the QD dispersion liquid, resin solution, and other mixing components used were as shown in Table 2. The solid content concentration of the curable resin composition obtained in Examples 2-4 and Comparative Examples 1-2 was 25 mass % for all. In the curable resin compositions obtained in Examples 2 to 4 and Comparative Examples 1 to 2, it was confirmed by visual observation that the resin was uniformly dissolved and the QDs were uniformly dispersed.

<Example 5>

Put 25 parts of QD dispersion-A, 11.4 parts of resin solution-a, 34.1 parts of resin solution-b and 1.50 parts of PGMEA solution containing antioxidant (G-1) at a concentration of 20% by mass into a flask, stir and heat at 80°C After 12 hours, it was left to cool to room temperature to obtain a solution containing QDs and resin.

Next, 3.05 parts of a polymerizable compound (C-1), 3.05 parts of a polymerizable compound (C-2), 0.15 parts of a polymerization initiator (D-1), and 0.60 parts of an antioxidant (G-2) were mixed at 10% by mass. Concentration Mix 0.25 parts of PGMEA solution containing leveling agent (F-1), 5.15 parts of light scattering agent and 16.0 parts of PGMEA. The obtained mixed liquid was added to the above-mentioned solution containing the QDs and the resin, and stirred and mixed to obtain a curable resin composition. The solid content concentration of the curable resin composition obtained was 25 mass %. Table 2 summarizes the types and amounts of the mixing components used in this example. Visual observation confirmed that the resin was uniformly dissolved and the QDs were uniformly dispersed in the obtained curable resin composition.

【Table 2】

The details of the mixing components shown in Table 2 are as follows.

[1] Polymerizable compound (C-1): Propoxylated pentaerythritol triacrylate ("NK ESTER ATM-4PL" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.),

[2] Polymerizable compound (C-2): pentaerythritol triacrylate ("NKESTER A-TMM-3LM-N" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.),

[3] Polymerization initiator (D-1): O-acyl oxime type polymerization initiator "NCI-930" manufactured by ADEKA Corporation,

[4] Solvent (E-1): PGMEA,

[5] Leveling agent (F-1): Polyether-modified silicone oil-based leveling agent "Toray Silicone SH8400" manufactured by Toray Silicone Co., Ltd.,

[6] Antioxidant (G-1): hindered phenolic antioxidant "Adeka Staub (registered trademark) AO-60" manufactured by ADEKA Co., Ltd.,

[7] Antioxidant (G-2): Sumitomo Chemical Co., Ltd. phenophospho-based antioxidant "Sumilaizer (registered trademark) GP",

[8] Light scattering agent: titanium oxide particle dispersion liquid "SF WHITE GC4134" (titanium oxide particle concentration: 73% by mass) manufactured by Sanyo Color Co., Ltd.

[Evaluation test]

(1) Pattern formation

0.45 mL of curable resin composition was dripped on the glass substrate, spin-coated at 150 rpm for 20 seconds, and 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 amount of 40 mJ/cm ² (based on 365 nm) under atmospheric air. The distance between the substrate and the photomask was 120 μm. The curable resin composition layer after the pattern exposure was immersed in an aqueous developer with a potassium hydroxide concentration of 0.04% by mass at 23°C for 70 seconds, washed with water, and post-baked in an oven at 230°C for 20 minutes to obtain Patterned cured film. The film thickness of the cured film is all 5 μm or more and 6 μm or less.

Using a laser microscope ("3D Measuring Laser Microscope OLS4100" manufactured by Olympus Corporation), one point of the patterned cured film lines (lines with a mask width of 50 μm) was observed, and the evaluation was based on the following The pattern formation property was evaluated as a benchmark. The results are shown in Table 2.

A: The line width is within the range of [mask width (50μm)-2μm] and [mask width (50μm)+3μm];

B: The line width is above [mask width (50μm)-6μm], less than [mask width (50μm)-2μm], or greater than [mask width (50μm)+3μm], [mask width ( 50μm)+10μm] within the range below;

C: The line width is less than [mask width (50μm)-6μm], or greater than [mask width (50μm)+10μm];

D: Insufficient development exists, that is, there is a junction between adjacent lines, or the lines are peeled off due to insufficient development adhesion.

(2) Luminous intensity

Except not having used the photomask, it carried out similarly to the evaluation test of said "pattern formability", and formed the cured film on the glass substrate. This cured film-attached glass substrate was placed on a blue backlight, and the luminous intensity was measured using a total luminous flux measuring device "CSTM-OP-RADIANT-FLUX" manufactured by Ocean Optical Co., Ltd. The luminous intensity of the cured film of Example 5 was nine times that of the cured film of Example 1.

Claims (8)

1. A curable resin composition comprising ligand-containing semiconductor particles A, a resin B and a polymerizable compound C, wherein the ligand-containing semiconductor particles A are semiconductor particles to which an organic ligand is coordinated,

the ligand-containing semiconductor particle A has a content ratio of the organic ligand to the semiconductor particle of 0.1 or more and less than 5.0 by mass ratio,

the resin B comprises a resin B-1 having a structural unit derived from a monomer having a carboxyl group and/or a carboxylic anhydride group bonded to the molecular main chain via a linking group.

2. The curable resin composition according to claim 1, wherein the monomer is represented by the following formula (a 1);

in the formula (a 1), the reaction mixture,

R ¹ represents a hydrogen atom or a methyl group,

R ² represents an alkylene group having 2 to 6 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, or a 3-valent group in which 1 hydrogen atom is removed from the alkylene group,

R ³ represents an alkylene group having 2 to 6 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms or a cycloalkenylene group having 5 to 12 carbon atoms, or a 2-valent aromatic group,

<xnotran> Y 1 ～ 8 , -O-, -S-, -C (= O) -, -C (= O) -O-, -O-C (= O) -, -C (= O) -NH- -NH- . </xnotran>

3. The curable resin composition according to claim 1, wherein the resin B satisfies any one of the following [ i ] and [ ii ]:

[ i ] comprising a resin B-1a having a carboxyl group and/or a carboxylic acid anhydride group bonded to the molecular main chain via a linking group and a carboxyl group and/or a carboxylic acid anhydride group directly bonded to the molecular main chain,

(ii) a resin B-1B and a resin B-2, wherein the resin B-1B has at least 1 carboxyl group and a carboxylic anhydride group, and all of the carboxyl group and the carboxylic anhydride group are bonded to the molecular main chain via a linking group; the resin B-2 has at least 1 carboxyl group and a carboxylic anhydride group, and the carboxyl group and the carboxylic anhydride group are all directly bonded to the molecular main chain.

4. The curable resin composition according to claim 1, further comprising a light scattering agent.

5. The curable resin composition according to claim 1, further comprising an antioxidant.

6. The curable resin composition according to claim 1, further comprising a leveling agent.

7. A cured film comprising the curable resin composition according to any one of claims 1 to 6.

8. A display device comprising the cured film according to claim 7.