KR20180094807A - Curable resin composition, cured film and display device - Google Patents

Abstract

The present invention provides a curable resin composition which can form a cured film having small roughness and reduced color unevenness. The curable resin composition of the present invention comprises: semiconductor particles (A), a resin (B), a polymerizable compound (C) and an organic solvent (D). The organic solvent (D) comprises a compound having at least one group selected from the group consisting of a cycloalkane ring and a group consisting of -O-, -OC(= O)-, -C(=O)-O- and -C(=O)-.

Description

TECHNICAL FIELD [0001] The present invention relates to a curable resin composition, a cured film,

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

A display device such as an image display device usually has a cured film such as a wavelength conversion film. As the curable resin composition for forming the cured film, a composition containing semiconductor particles such as semiconductor quantum dots is known (for example, JP 2015-028139 A). JP 2005-128539 A discloses a semiconductor nanocrystal having a surface-coordinated compound having a photosensitive functional group and a photosensitive composition containing the same.

The present invention provides the following curable resin composition, cured film and display device.

[1] A resin composition comprising semiconductor particles (A), a resin (B), a polymerizable compound (C) and an organic solvent (D)

The organic solvent (D) is at least one member selected from the group consisting of a cycloalkane ring and a group selected from the group consisting of -O-, -OC (= O) -, -C (= O) -O- and -C A compound having at least one group.

[2] A cured film formed from the curable resin composition according to [1].

[3] A display device comprising the cured film according to [2].

<Curable resin composition>

The curable resin composition according to the present invention comprises a semiconductor particle (A), a resin (B), a polymerizable compound (C) and an organic solvent (D), wherein the organic solvent (D) A compound having at least one group selected from the group consisting of -O-, -OC (= O) -, -C (= O) -O- and -C (= O) - D1). According to the curable resin composition, the surface roughness is small, and thus the cured film in which the color unevenness is reduced can be formed.

Reduction of the color unevenness is advantageous in increasing the in-plane uniformity of the luminescent characteristics of the cured film. According to this curable resin composition, it is possible to form a patterned cured film having a desired line width with good precision (hereinafter, this effect is referred to as "good patterning property" and the patterning accuracy is referred to as "patterning property" .). According to the curable resin composition, even if the line width is relatively narrow, it is possible to form the patterned cured film with good precision.

In the present specification, the compounds exemplified as the respective components included in the curable resin composition or contained may be used alone or in combination of two or more, unless otherwise specified.

[1] Semiconductor particle (A)

The curable resin composition comprises semiconductor particles (A). The semiconductor particle (A) is preferably a semiconductor particle of luminescent (fluorescent luminescent) property. The cured film formed from the curable resin composition containing the luminescent semiconductor particles may be excellent in color reproduction showing fluorescence emission in a desired wavelength range.

The luminescent semiconductor particles are nanoparticles composed of semiconductor crystals, preferably semiconductor crystals. A preferable example of the luminescent semiconductor particles is semiconductor quantum dots. The average particle diameter of the semiconductor quantum dots is, for example, 0.5 nm or more and 20 nm or less, preferably 1 nm or more and 15 nm or less (for example, 2 nm or more and 15 nm or less). The average particle diameter of the semiconductor quantum dots can be obtained by using a transmission electron microscope (TEM).

The semiconductor quantum dots are 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, for example. Or a semiconductor material containing at least one element selected from the group consisting of silicon and silicon.

Specific examples of the semiconductor material that can constitute the semiconductor quantum dots include a compound of Group 14 elements and Group 16 elements such as SnS ₂ , SnS, SnSe, SnTe, PbS, PbSe, and PbTe; A compound of a Group 13 element and a Group 15 element such as GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, InGaN and InGaP; Group 13 elements such as 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 and In ₂ Te ₃ , &Lt; / RTI &gt; A compound of Group 12 elements and Group 16 elements such as ZnO, ZnS, ZnSe, ZnTe, CdO, CdS, CdSe, CdTe, HgO, HgS, HgSe and HgTe; 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 ₂ O ₃ , Bi ₂ S ₃ , A compound of a Group 15 element and a Group 16 element such as Bi ₂ Se ₃ and Bi ₂ Te ₃ ; A compound of a Group 2 element and a Group 16 element such as MgS, MgSe, MgTe, CaS, CaSe, CaTe, SrS, SrSe, SrTe, BaS, BaSe and BaTe; Si, Ge and the like, a single element of a Group 15 element or a Group 16 element.

The semiconductor quantum dots may be a single layer structure made of a single semiconductor material and the surface of the core particles (core layer) made of a single semiconductor material may be coated with a coating layer (shell layer) made of one or more kinds of semiconductor materials different from this, Or may be a core shell structure covered with a core. In the latter case, the semiconductor material constituting the shell layer generally has a larger band gap energy than the semiconductor material constituting the core layer. The semiconductor quantum dots may have two or more types of shell layers. The shape of the semiconductor quantum dots is not particularly limited and may be spherical, substantially spherical, rod-like, disk-like, or the like.

The semiconductor particle (A) may be a ligand-containing semiconductor particle containing an organic ligand to be added to semiconductor particles. The organic ligand coordinated to the semiconductor particles may be an organic compound having a polar group showing coordination ability with respect to semiconductor particles. The organic ligand contained in the ligand-containing semiconductor particles may be an organic ligand added for restricting the synthesis of the ligand-containing semiconductor particles or for stabilization. For example, the ligand-containing semiconductor particles disclosed in JP2015-529698 contain hexanoic acid as an organic ligand from the viewpoint of particle size control, and furthermore, the organic ligand is substituted with DDSA (dodecenylsuccinic acid) for stabilization after synthesis .

The organic ligand can be coordinated to, for example, the surface of the semiconductor particle.

The organic ligand coordinated to the semiconductor particles may be one ligand or two or more ligands. When the organic ligand is an organic compound having a polar group, the organic ligand ordinarily coordinates to the semiconductor particle through the polar group. The coordination of the organic ligand is confirmed in that the semiconductor particles are uniformly dispersed in the dispersion medium preferable 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 can be advantageous in facilitating coordination with the semiconductor particles, i.e., raising the satellites for the semiconductor particles. High saturation satellites can contribute to improvement of the color unevenness of the cured film and / or improvement of the patterning property of the curable resin composition. Among them, from the viewpoint of obtaining a cured film (a wavelength conversion film or the like) having better luminescence characteristics, it is more preferable that the polar group is at least one group selected from the group consisting of a thiol group and a carboxyl group. The organic ligand may have at least one polar group.

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

The organic ligand can be, for example,

Y ¹ -Z

. Wherein Y ¹ is the above polar group and Z is a monovalent hydrocarbon group which may contain a hetero atom (N, O, S, halogen atom, etc.). The hydrocarbon group may have at least one unsaturated bond such as a carbon-carbon double bond. The hydrocarbon group may have a straight chain, branched chain or cyclic structure. The number of carbon atoms in the hydrocarbon group is, for example, 1 or more and 40 or less, and may be 1 or more and 30 or less. The methylene group contained in the hydrocarbon group may be replaced by -O-, -S-, -C (= O) -, -C (= O) -O-, -OC -, -NH-, and the like. Such a hydrocarbon group usually contains no heteroatom in many cases because of simplicity of preparation of the ligand-containing semiconductor particles.

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 include a polar group. However, the polar group of the group Z 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 polar groups. For the specific examples of the polar group, the above-mentioned technique relating to the polar group Y ¹ is cited. The group Z usually contains no polar group in many cases because of simplicity of preparation of the ligand-containing semiconductor particles.

Concrete examples of the organic ligand having a carboxyl group for the polar group Y ¹ include saturated or unsaturated fatty acids in addition to formic acid, acetic acid and propionic acid. Specific examples of the saturated or unsaturated fatty acid include saturated fatty acids such as butyric acid, pentanoic acid, capronic acid, caprylic acid, capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, Saturated fatty acids such as hexanoic acid, lignoceric acid and the like; Monounsaturated fatty acids such as myristoleic acid, palmitoleic acid, oleic acid, icosenic acid, erucic acid and nerubic acid; Polyunsaturated fatty acids such as linoleic acid,? -Linolenic acid,? -Linolenic acid, stearidonic acid, dihomo-? -Linolenic acid, arachidonic acid, eicosatetraenoic acid, docosadienic acid and adrenic acid (docosatetraenoic acid) .

Specific examples of the organic ligand having a thiol group or an amino group for the polar group Y ¹ include an organic ligand in which the carboxyl group is substituted with a thiol group or an amino group in the exemplified compound of an organic ligand having a carboxyl group.

The content of the semiconductor particles (A) is, for example, not less than 0.1 parts by mass and not more than 50 parts by mass, preferably not less than 1 part by mass and not more than 45 parts by mass, and more preferably not more than 5 parts by mass based on 100 parts by mass of the solid content of the curable resin composition Not less than 40 parts by mass. When the content of the semiconductor particles (A) is within the above range, a sufficient luminescence intensity can be obtained in the cured film (wavelength conversion film or the like), and the patterning property tends to be excellent. In the present specification, the "solid content of the curable resin composition" refers to the total of components other than the organic solvent (D) contained in the curable resin composition.

[2] Resin (B)

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

(A) (hereinafter also referred to as "(a)") selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, a cyclic ether structure having 2 to 4 carbon atoms and ethylene (B) (also referred to as &quot; (b) &quot; hereinafter) having an unsaturated bond,

Resin [K2]: Monomers (c) copolymerizable with (a) and (b) and (a) (which are different from (a) and (b)) (hereinafter also referred to as "(c)"). , &Lt; / RTI &gt;

Resin [K3]: a copolymer of (a) and (c)

Resin [K4]: a resin obtained by reacting (b) a copolymer of (a) and (c)

Resin [K5]: a resin obtained by reacting the copolymer (b) and (c) with (a)

Resin [K6]: a resin obtained by reacting (a) a copolymer of (b) and (c) with a carboxylic acid anhydride.

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

(a), specifically,

(Meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, mono [2- (meth) acryloyloxyethyl] succinate and phthalic acid mono [2- (meth) acryloyloxyethyl] Unsaturated monocarboxylic acids;

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, Unsaturated dicarboxylic acids such as tetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid, and compounds represented by the following formula (a1);

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept- 5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept- [2.2.1] hept-2-ene, and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;

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 dimethyl tetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (himic acid anhydride);

and unsaturated (meth) acrylic acid having a hydroxyl group and a carboxyl group in the same molecule, such as? - (hydroxymethyl) (meth) acrylic acid.

In the present specification, "(meth) acrylic" means at least one kind selected from the group consisting of acrylic and methacrylic. (Meth) acryloyl &quot;, &quot; (meth) acrylate &quot;, and the like.

(b) is a polymer having a cyclic ether structure having at least 2 carbon atoms and at most 4 carbon atoms (for example, at least one member selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring (oxolane ring)) and an ethylenically unsaturated bond &Lt; / RTI &gt; (b) is preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth) acryloyloxy group.

(b1) (hereinafter also referred to as "(b1)") having an oxiranyl group and an ethylenically unsaturated bond, a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond (hereinafter referred to as " b2) ", a monomer (b3) having a tetrahydrofuryl group and an ethylenic unsaturated bond (hereinafter also referred to as" (b3) "), and the like.

(b1-1) (hereinafter also referred to as "(b1-1)") having a structure in which an unsaturated aliphatic hydrocarbon is epoxidized, a monomer (b1) having a structure in which an unsaturated alicyclic hydrocarbon is epoxidized -2) (hereinafter also referred to as &quot; (b1-2) &quot;).

(meth) acrylate,? -methyl glycidyl (meth) acrylate,? -ethyl glycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl Vinylbenzyl glycidyl ether,? -Methyl-o-vinylbenzyl glycidyl ether,? -Methyl-o-vinylbenzyl glycidyl ether,? Methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5- Styrenes such as 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, (Glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (glycidyloxymethyl) .

(b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000 manufactured by Daicel Chemical Industries, Ltd.) 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 [5.2.1.0 ^2,6 ] 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. (meth) acryloyloxymethyloxetane, 3-methyl-3- (meth) acryloyloxymethyloxetane, 3-methyl-3- ) Acryloyloxyethyl oxetane, 3-ethyl-3- (meth) acryloyloxyethyl oxetane.

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. (b3) include tetrahydrofurfuryl acrylate (for example, Viscot V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

(c)

Butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (Meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl Tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (also referred to in the art as "dicyclopentanyl (meth) acrylate" (Also referred to as "tricyclodecyl (meth) acrylate"), tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate (Meth) acrylate], dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (Meth) acrylic acid esters such as propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate and benzyl (meth) acrylate;

(Meth) acrylic acid esters having a hydroxy group such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate; Succinic acid 1- [2- (methacryloyloxy) ethyl]

2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept- Ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept- 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, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept- Cyclohexyl [2.2.1] hept-2-ene, 5,6-bis 2,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene and the like such as bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept- Cyclounsaturated compounds;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N- Dicarbonylimide derivatives such as N-succinimidyl-3-maleimidepropionate and N- (9-acridinyl) maleimide;

And examples thereof include styrene,? -Methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, Vinyl, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene; Etc

.

Among them, (c) is preferably selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, benzyl (meth) acrylate, (Meth) acrylate, dicyclopentenyl (meth) acrylate, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] Hept-2-ene, and tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate.

In the resin [K1], the ratio of the respective structural units derived from each of the resins [K1] is preferably within the following range among the total structural units constituting the resin [K1].

(a); 2 mol% or more and 50 mol% or less (more preferably 10 mol% or more and 45 mol% or less)

a structural unit derived from the structural unit (b), particularly a structural unit derived from the structural unit (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 the structural unit of the resin [K1] is within the above range, storage stability, developability and solvent resistance of the resulting pattern tends to be excellent.

Resin [K1] can be synthesized by a method described in the document &quot; Experimental Method of Polymer Synthesis &quot; (published by Kagaku Dojin, 1st Edition, 1st Edition, March 1, 1972 by Takayuki Otsu) . &Lt; / RTI &gt;

Specifically, there can be mentioned a method in which a predetermined amount of (a) and (b) (particularly (b1)), a polymerization initiator and a solvent are placed in a reaction vessel and stirred, heated and maintained in a deoxygenated atmosphere. The polymerization initiator and solvent used herein are not particularly limited, and any of those conventionally used in the art can be used. Examples of the polymerization initiator include azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), and organic peroxides (such as benzoyl peroxide) have. As the solvent, any one that dissolves each monomer may be used, and an organic solvent (D) described later or the like may be used.

As the obtained copolymer, the solution after the reaction may be used as it is, or a concentrated or diluted solution may be used, or it may be taken out as a solid (powder) by a method such as re-precipitation.

In the resin [K2], the proportion of the respective structural units derived from each other is preferably within the following range among the total structural units constituting the resin [K2].

(a); 4 mol% or more and 45 mol% or less (more preferably 10 mol% or more and 30 mol% or less)

a structural unit derived from the structural unit (b), particularly a structural unit derived from the structural unit (b1); 2 mol% or more and 95 mol% or less (more preferably 5 mol% or more and 80 mol% or less)

(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 the structural unit of the resin [K2] is within the above range, the storage stability, developability, solvent resistance of the obtained pattern, heat resistance and mechanical strength tend to be excellent.

The resin [K2] can be produced in the same manner as the method described as the method for producing the resin [K1]. Specifically, a method of putting a predetermined amount of (a), (b) (particularly (b1)) and (c), a polymerization initiator and a solvent in a reaction vessel and stirring, heating and maintaining them in a deoxygen atmosphere have. As the obtained copolymer, the solution after the reaction may be used as it is, or a concentrated or diluted solution may be used, or it may be taken out as a solid (powder) by a method such as re-precipitation.

In the resin [K3], the ratio of the respective structural units derived from each of the resins [K3] is preferably within the following range among the total structural units constituting the resin [K3].

(a); 2 mol% or more and 55 mol% or less (more preferably 10 mol% or more and 50 mol% or less), a structural unit derived from (c); And more preferably 45 mol% or more and 98 mol% or less (more preferably 50 mol% or more and 90 mol% or less).

The resin [K3] can be produced in the same manner as the method described as the method for producing the resin [K1].

The resin [K4] is obtained by obtaining a copolymer of (a) and (c), and a cyclic ether structure having 2 or more and 4 or less carbon atoms in (b), particularly, an oxirane ring having (b1) To the parent and / or carboxylic acid anhydrides. Specifically, first, a copolymer of (a) and (c) is prepared in the same manner as described for the method of producing the resin [K1]. In this case, the ratio of the respective structural units derived from each other preferably falls within the following range among the total structural units constituting the copolymer of (a) and (c).

(a); 5 mol% or more and 50 mol% or less (more preferably 10 mol% or more and 45 mol% or less)

(c); 50 mol% or more and 95 mol% or less (more preferably 55 mol% or more and 90 mol% or less).

Next, a cyclic ether structure having a carbon number of 2 to 4, particularly, an oxirane ring having (b1) in the copolymer (b) is added to a part of the carboxylic acid and / or carboxylic acid anhydride derived from the copolymer . Specifically, following the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced with air from nitrogen, and the reaction between the carboxylic acid or carboxylic acid anhydride and the cyclic ether (b1) (For example, tris (dimethylaminomethyl) phenol) and polymerization inhibitor (for example, hydroquinone) are placed in a flask and heated at 60 ° C or more and 130 ° C or less for 1 hour or more and 10 hours or less To obtain a resin [K4].

(b) is preferably 5 mol or more and 80 mol or less, more preferably 10 mol or more and 75 mol or less, per 100 mol of (a). When the content is in this range, the balance between storage stability, developability, solvent resistance, heat resistance, mechanical strength and sensitivity tends to be good. (B1) is more preferable, and (b1-1) is more preferable for the resin (K4) because the reactivity of the cyclic ether structure is high and the unreacted (b)

The amount of the reaction catalyst to be used is preferably 0.001% by mass or more and 5% by mass or less based on the total amount of (a) and (b) (particularly, (b1)) and (c). The amount of the polymerization inhibitor to be 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 introduction method, the reaction temperature and the time can be appropriately adjusted in consideration of the production equipment or the amount of heat generated by polymerization. Further, in the same manner as the polymerization conditions, the introduction method and the reaction temperature can be appropriately adjusted in consideration of the production facility and the amount of heat generated by polymerization.

As the first step, the resin [K5] is obtained in the same manner as in the production of the resin [K1] described above to obtain a copolymer of (b) (particularly (b1)) and (c). As in the case of the above, the solution after the reaction may be used as it is, or a concentrated or diluted solution may be used as the obtained copolymer, or it may be taken out as a solid (powder) by a method such as re-precipitation.

the proportion of the structural units derived from the structural units (b) (particularly (b1)) and (c) is preferably in the following range with respect to the total number of moles of the total structural units constituting the copolymer.

a structural unit derived from the structural unit (b), particularly a structural unit derived from the structural unit (b1); 5 mol% or more and 95 mol% or less (more preferably 10 mol% or more and 90 mol% or less)

(c); 5 mol% or more and 95 mol% or less (more preferably 10 mol% or more and 90 mol% or less).

In the same manner as in the production of the resin (K4), the cyclic ether structure derived from the copolymer (b) (particularly the copolymer (b1)) and the copolymer (c) Or a carboxylic acid anhydride is reacted to obtain a resin [K5]. The amount of (a) to be reacted with the copolymer is preferably from 5 to 80 moles per 100 moles of (b) (particularly (b1)). (B1) is preferable and (b1-1) is more preferable for the resin (K5) because the reactivity of the cyclic ether structure is high and the unreacted (b) is difficult to remain.

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

Examples of the 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, and 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hydroamic anhydride).

Among them, the resin (B) is preferably a resin (B-1) having a carboxyl group (-COOH) and / or a carboxylic acid anhydride group (-C (= O) 1). The linking group is a group which is not a direct bond, which binds the molecular main chain of the polymer to the carboxyl group and / or the carboxylic acid anhydride group, and is, for example, a hydrocarbon group having 1 or more carbon atoms. The hydrocarbon group may include straight chain, branched chain and / or cyclic structures. The at least one methylene group contained in the hydrocarbon group may be replaced by -O-, -S-, -C (= O) -, -C (= O) -O-, -OC O) -NH-, -NH-, or the like.

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 acid anhydride group, the linking group has two bonds with the carboxylic acid anhydride group.

The fact that the resin (B) contains the resin (B-1) can contribute to enhance the dispersibility of the semiconductor particles (A) in the curable resin composition. This is because the resin having a polar group can be coordinated to semiconductor particles through the polar group, and the carboxyl group and / or the carboxylic acid anhydride group of the resin (B-1) has a relatively high coordination ability, It is considered that the effect of increasing the dispersibility of the semiconductor particles (A) is further enhanced by the coordination with the particles. The high dispersibility of the semiconductor particles (A) can contribute to reduction of surface roughness of a cured film such as a wavelength conversion film and reduction of color unevenness thereby improving in-plane uniformity of light emission characteristics of the cured film.

Examples of the resin (B-1) include a resin (B-1a) having a carboxyl group and / or a carboxylic anhydride group bonded to a molecular main chain via a linking group, a carboxyl group and / or a carboxylic anhydride group directly bonding to a molecular main chain, And a resin (B-1b) having at least one carboxylic anhydride group and both of the carboxyl group and the carboxylic acid anhydride group bonded to the molecular main chain through a linking group.

The resin (B-1a) is a resin having a structure (b1-1) having a carboxyl group and / or a carboxylic acid anhydride group bonded to a main chain of a molecule through a linking group and a carboxyl group and / or a carboxylic acid anhydride group Is preferably a copolymer containing units (b2-2).

In the resin (B-1a), the proportion of the structural unit (b1-1) in the total structural units is preferably 8 to 62% by mass, more preferably 16 to 49% by mass, Is 24 to 37%.

In the resin (B-1a), the proportion of the structural unit (b1-2) in the total structural units is preferably 0 to 23 mass%, more preferably 6 to 15 mass% Is 6 to 12%.

The resin (B-1b) comprises 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 structural unit having no carboxyl group and / or carboxylic acid anhydride group directly bonded to the main chain of the molecule Is preferably a copolymer.

The resin (B) may have at least one of a carboxyl group and a carboxylic anhydride group, and both the carboxyl group and the carboxylic acid anhydride group may contain a resin (B-2) directly bonded to the molecular main chain.

The resin (B-1a), the resin (B-1b) and the resin (B-2) can be obtained by using at least one (a) selected from the group consisting of the unsaturated carboxylic acid and the unsaturated carboxylic acid anhydride, can do. (B-1a), the resin (B-1b) and the resin (B-2) can be prepared by selecting an appropriate monomer as the monomer (a). (a) are as described above, but the present invention is not limited to these specific examples.

(A) is at least one compound selected from the group consisting of vinylbenzoic acid, 1,2,3,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, Methyl-5-norbornene-2,3-dicarboxylic acid, methyl-5-norbornene-2,3-dicarboxylic anhydride and the like can be used.

In order to introduce a carboxyl group and / or a carboxylic acid anhydride group to be bonded to the molecular backbone through a linking group into the resin, for example, at least one of monomers represented by formula (a1) may be used as (a).

[In the formula (a1)

R ¹ represents a hydrogen atom or a methyl group.

R ² represents an alkanediyl group having 2 to 6 carbon atoms or a cycloalkanediyl group having 5 to 12 carbon atoms or a trivalent group obtained by extracting one hydrogen atom from the alkanediyl group.

R ³ represents an alkanediyl group having 2 to 6 carbon atoms, a cycloalkanediyl group having 5 to 12 carbon atoms, a cycloalkenediyl group having 5 to 12 carbon atoms, or a divalent aromatic group.

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

Examples of the alkanediyl group having 2 to 6 carbon atoms in R ² and R ³ include an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane- A straight chain alkanediyl group such as a methyl group, a hexane-1, 6-diyl group and the like; A propane-1,2-diyl group, a butane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane- , A pentane-1,4-diyl group, and a 2-methylbutane-1,4-diyl group.

Examples of the cycloalkanediyl group having 5 to 12 carbon atoms in R ² and R ³ include cyclopentane-1,2-diyl group, cyclopentane-1,3-diyl group, cyclopentane- A cyclohexane-1,2-diyl group, a cyclohexane-1,3-diyl group, a cyclohexane-1,4-diyl group, a cycloheptane- Dihexyl group, cycloheptane-1, 4-diyl group, adamantane-1,2-diyl group, adamantane-1,3-diyl group and the like.

Examples of the cycloalkenediyl group having 5 to 12 carbon atoms in R ³ include groups in which any of the carbon-carbon single bonds in the cycloalkanediyl ring structure is substituted with carbon-carbon double bonds.

Examples of the divalent aromatic group in R ³ include aromatic hydrocarbons having 5 to 12 carbon atoms, specifically, benzene-1,2-diyl group, benzene-1,3-diyl group, benzene- Naphthalene-1,3-diyl group, naphthalene-1,4-diyl group, naphthalene-1,5-diyl group, naphthalene-1,8-diyl group, naphthalene- Diyl group, a naphthalene-2,4-diyl group, and a naphthalene-2,6-diyl group.

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

Examples of the monomer represented by the formula (a1) include mono [(meth) acrylate] dicarboxylic acids such as mono [2- (meth) acryloyloxyethyl succinate], phthalic acid mono [2- (meth) acryloyloxyethyl] Acryloyloxyalkyl] esters and the like. The use of the monomer represented by the formula (a1) such as mono [(meth) acryloyloxyalkyl] ester of dicarboxylic acid is advantageous from the viewpoint of dispersibility of the semiconductor particle (A) in the organic solvent.

(Meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, maleic anhydride, 3,4,5,6-tetramethyluronium hexafluorophosphate and the like are used as (a) the carboxyl group and / Tetrahydrophthalic acid, and 3,4,5,6-tetrahydrophthalic anhydride. (Meth) acrylic acid, maleic anhydride and the like are preferable in view of the copolymerization reactivity and the solubility of the resulting resin in an aqueous alkali solution.

The resin (B) is obtained by reacting the following [i] and [ii]:

(I) a resin (B-1a) having a carboxyl group and / or a carboxylic anhydride group bonded to the molecular backbone through a linking group and a carboxyl group and / or a carboxylic anhydride group directly bonded to the molecular backbone,

(Ii) at least one of a carboxyl group and a carboxylic anhydride group, wherein the carboxyl group and the carboxylic acid anhydride group both have at least one of a resin (B-1b) bonded to a molecular main chain through a linking group and a carboxyl group and a carboxylic acid anhydride group, Both the carboxyl group and the carboxylic acid anhydride group include the resin (B-2) directly bonded to the molecular main chain,

Is satisfied.

Satisfying one or both of [i] and [ii] above can contribute to enhancement of the dispersibility of the semiconductor particles (A) in the curable resin composition, and can improve the patterning property of the curable resin composition You can contribute.

The resin (B) may contain only the resin (B-1a), the resin (B-1a) and the resin (B-1b) And may contain the resin (B-2).

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

Among the acid value represented by the resin (B), the acid value X based on the carboxyl group directly bonded to the molecular main chain and / or the carboxylic acid anhydride and the acid value Y ^a based on the carboxyl group bonded to the molecular main chain via the linkage group and / with the ratio X / Y ^a is, for example, (0mg-KOH / g or more 150mg-KOH / g or less) / a (20mg-KOH / g or more 150mg-KOH / g or less), preferably (40mg-KOH (40 mg-KOH / g or more and 80 mg-KOH / g or less) / (60 mg-KOH / g or more and 100 mg-KOH / g or less) / g to 90 mg-KOH / g).

When the ratio X / Y ^a is within the above range, the dispersibility of the resin (B) and the developability (developing speed and patternability) of the curable resin composition can be increased. The high dispersibility of the resin (B) can also contribute to the reduction of the surface roughness of the cured film such as the wavelength conversion film and the reduction of the color unevenness thereby improving the in-plane uniformity of the light emitting property of the cured film.

The acid value of the resin (B) is, for example, 20 mgKOH / g or more and 200 mgKOH / g or less, preferably 40 mgKOH / g or more and 170 mgKOH / g or less, more preferably 60 mgKOH / g or more and 150 mg-KOH / g or less.

Within the above range, both developability and high dispersibility can be achieved.

The solution acid value of the resin (B) is preferably 5 mgKOH / g or more and 180 mgKOH / g or less, more preferably 10 mgKOH / g or more and 100 mgKOH / g or less, KOH / g and not more than 50 mg-KOH / g. The acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the resin, and the solution acid value is a value measured as the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the solution, (Titration) using a potassium aqueous solution.

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

The weight average molecular weight of the resin (B) in terms of polystyrene is preferably from 3,000 to 100,000, more preferably from 5,000 to 50,000, and still more preferably from 5,000 to 30,000. When the molecular weight is within the above range, the solubility of the unexposed portion in the developer is high, and the residual film ratio 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 the resin (B) is preferably 1.1 or more and 6 or less, and more preferably 1.2 or more and 4 or less.

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

[3] The polymerizable compound (C)

The polymerizable compound (C) is not particularly limited as long as it is a compound which can be polymerized by an active radical or the like generated from the polymerization initiator (D) by light irradiation or the like, and a compound having a polymerizable ethylenically unsaturated bond . The weight average molecular weight of the polymerizable compound (C) is preferably 3000 or less.

The polymerizable compound (C) is preferably a photopolymerizable compound having three or more ethylenic unsaturated bonds. Specific examples of the photopolymerizable compound having three or more ethylenic unsaturated bonds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta Acrylate, tripentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (metha) acrylate, tripentaerythritol octa (metha) acrylate, tripentaerythritol hepta (Meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol hexa Modified pentaerythritol tetra (meth) acrylate, propylene glycol-modified dipenta Less erythritol, and the like hexa (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate.

The curable resin composition may contain at least one kind of polymerizable compound (C). The content of the polymerizable compound (C) 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, based on 100 parts by mass of the resin (B) in the curable resin composition .

[4] Organic solvent (D)

The curable resin composition includes the organic solvent (D). The organic solvent (D) contains a cycloalkane ring and an ether group (-O-), an ester group (-C (= O) -O-, -OC (= O) -) and a carbonyl group (-C And an organic solvent (D1) which is an organic compound having at least one group selected from the group consisting of an organic solvent (D1).

By including the organic solvent (D1) in the organic solvent (D), it is possible to form a cured film such as a wavelength conversion film in which the surface roughness is small and thus the color unevenness is reduced. Such an organic solvent (D1) tends to have affinity for both the resin (B) and the semiconductor particles (A), so that the aggregation of the resin (B) and the semiconductor particles (A) It is thought that it can be prevented. The curable resin composition may include at least one organic solvent (D1).

The organic solvent (D1) is preferably a compound represented by the formula (1).

In the formula (1)

Ring T represents a cycloalkane ring of a k-membered ring.

k represents an integer of 3 to 12;

X ¹ and X ² each independently represent -O-, -OC (= O) -, -C (= O) -O- or -C (= O) -.

A ¹ represents an alkanediyl group having 1 to 12 carbon atoms or a cycloalkanediyl group having 3 to 12 carbon atoms.

A ² and A ⁴ each independently represent a monovalent hydrocarbon group of 1 to 12 carbon atoms.

A ³ represents a single bond, an alkanediyl group having 1 to 12 carbon atoms, or a cycloalkanediyl group having 3 to 12 carbon atoms.

m represents an integer of 1 to 6;

n represents an integer of 0 to 5;

p represents an integer of 0 to 5;

However, m + p is less than or equal to k.

The inclusion of the organic solvent (D1) represented by the formula (1) may be advantageous from the viewpoint of reducing the color unevenness and / or from the viewpoint of enhancing the patterning property of the curable resin composition.

K representing the number of carbon atoms constituting the cycloalkane ring T is preferably an integer of 4 to 6 from the viewpoint of reducing the color unevenness and / or increasing the patterning property of the curable resin composition. Specifically, the cycloalkane ring T is preferably a cyclobutane ring, a cycloheptane ring, or a cyclohexane ring.

A ¹ is preferably an alkanediyl group having 1 to 6 carbon atoms or a cycloalkanediyl group having 3 to 6 carbon atoms from the viewpoints of reducing color heterogeneity and / or enhancing the patternability of the curable resin composition, Represents an alkanediyl group having 1 to 3 carbon atoms or a cycloalkanediyl group having 4 to 6 carbon atoms. The alkanediyl group may be linear or branched.

Examples of the alkanediyl group having 1 to 6 carbon atoms include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane- 1-yl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, Diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group and the like.

Examples of the cycloalkanediyl group having 3 to 6 carbon atoms include a cyclopropane-1,3-diyl group, a cyclobutane-2,2-diyl group, a cyclopentane-1,5-diyl group, And the like.

Examples of the monovalent hydrocarbon group having 1 to 12 carbon atoms in A ² and A ⁴ include linear or branched monovalent aliphatic hydrocarbon groups, monovalent alicyclic hydrocarbon groups, monovalent aromatic hydrocarbon groups, and combinations thereof have.

Examples of the linear or branched monovalent aliphatic hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, And an alkyl group such as a 2-ethylhexyl group.

The monovalent alicyclic hydrocarbon group may be monocyclic or polycyclic. Examples of the monovalent monovalent alicyclic hydrocarbon group include a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclodecyl group. Examples of the polycyclic monovalent alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group and norbornyl group.

Examples of the monovalent aromatic hydrocarbon group include an aryl group such as a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.

Examples of the group in which a monovalent aliphatic hydrocarbon group and a monovalent alicyclic hydrocarbon group are combined include a methylcyclohexyl group, a dimethylcyclohexyl group, and a methylnorbornyl group.

The monovalent hydrocarbon group having 1 to 12 carbon atoms is preferably an alkyl group having 1 to 6 carbon atoms from the viewpoint of reducing the color unevenness and / or increasing the patterning property of the curable resin composition.

A ³ is preferably a single bond, an alkanediyl group having 1 to 6 carbon atoms, or a cycloalkanediyl group having 3 to 6 carbon atoms, from the viewpoint of reducing color heterogeneity and / or increasing the patternability of the curable resin composition, More preferably a single bond, an alkanediyl group having 1 to 3 carbon atoms, or a cycloalkanediyl group having 4 to 6 carbon atoms. The alkanediyl group may be linear or branched.

Specific examples of the alkanediyl group having 1 to 6 carbon atoms and the cycloalkanediyl group having 3 to 6 carbon atoms are the same as those exemplified for A ¹ .

The total number of carbon atoms contained in A ¹ to A ⁴ is usually 1 to 24, and preferably 1 to 12 from the viewpoint of reducing the color unevenness and / or improving the patterning property of the curable resin composition.

m is preferably an integer of 1 to 3, more preferably an integer of 1 to 2, from the viewpoint of reducing the color heterogeneity and / or increasing the patterning property of the curable resin composition.

n is preferably an integer of 0 to 3, more preferably an integer of 0 to 1, from the viewpoint of reducing color heterogeneity and / or improving the patternability of the curable resin composition.

p is preferably an integer of 0 to 3 from the viewpoint of reducing the color unevenness and / or improving the patterning property of the curable resin composition.

The organic solvent D1 may have two or more identical groups selected from the group consisting of -O-, -OC (= O) -, -C (= O) -O- and -C (= O) And two or more different groups selected from the above group may be present.

As the organic solvent (D1), an ester solvent (a solvent containing a cycloalkyl ring and -C (= O) -O-), an ether solvent (a solvent containing a cycloalkane ring and -O-) other than an ester solvent, (Solvent containing a cycloalkane ring, -OC (= O) - and / or -C (= O) -O- and -O-), a ketone solvent other than an ester solvent (a cycloalkane ring and -C = O) -), and the like.

Examples of the ester solvent include cyclohexyl acetate, 2-methylcyclohexyl acetate, cyclohexylpropionate, cis-3,3,5-trimethylcyclohexyl acetate, 4-tert-butylcyclohexyl acetate, cyclohexyl butyrate, cyclohexanecarboxylic acid iso Propyl, ethyl cyclohexyl acetate, and the like.

Examples of the ether solvent include methoxycyclohexane, ethoxycyclohexane, propoxycyclohexane, 1-methoxy-4-methylcyclohexane, and 1,1-diisopropoxycyclohexane.

As the ether ester solvent, ethyl 2-ethoxycyclohexanecarboxylate and the like can be given.

Examples of the ketone solvent include dicyclohexyl ketone, ethyl 3-cyclohexyl-3-oxopropionate, and cyclohexyl phenyl ketone.

The organic solvent (D1) is preferably at least one selected from the group consisting of cis-3,3,5-trimethylcyclohexyl acetic acid, 4-tert-butylcyclohexyl acetate, cyclohexyl acetic acid and the like, from the viewpoint of reducing color heterogeneity and / or increasing the patternability of the curable resin composition Hexyl cyclohexanecarboxylate, isopropyl cyclohexanecarboxylate, 1-methoxy-4-methylcyclohexane, 1,1-diisopropoxycyclohexane, dicyclohexylketone, ethyl 3-cyclohexyl-3-oxopropionate and cyclohexylphenyl Ketones, and more preferably at least one member selected from the group consisting of cyclohexyl acetate and isopropyl cyclohexanecarboxylate.

The organic solvent (D) may include an organic solvent (D2) which is an organic solvent other than the organic solvent (D1). The curable resin composition may contain one or more organic solvents (D2). Examples of the organic solvent (D2) include ester solvents (solvents containing -C (= O) -O-), ether solvents (solvents containing -O-) other than ester solvents, ether ester solvents (-C (A solvent containing -O- and -O-), a ketone solvent other than an ester solvent (a solvent containing -C (= O) -), an alcohol solvent, an aromatic hydrocarbon solvent, an amide solvent and dimethylsulfoxide .

The organic solvent (D2) is a compound wherein at least one methylene group contained in the cycloalkyl ring is -O-, -S-, -C (= O) -, -C (= O) -, -C (= O) -NH-, -NH-, and the like, but may be a compound having the same structure as the organic solvent (D1).

Examples of the ester solvent 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, Butyl propionate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate and? -Butyrolactone.

Examples of the ether solvent 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 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, And the like.

Examples of the ether ester solvent 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 propionate, methyl propionate, methyl 2-ethoxy-2-methyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono Propyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether Ether acetate, diethylene glycol monobutyl ether acetate and dipropylene glycol methyl ether acetate.

Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3- Pentanone, cyclohexanone, and isophorone.

Examples of the alcohol solvent 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.

The organic solvent (D2) is preferably selected from the group consisting of propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene Methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone and N, N'-diethyleneglycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, , N-dimethylformamide, and it is preferable to use 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 and ethyl 3-ethoxypropionate. It is preferred to have.

The organic solvent (D) may contain only the organic solvent (D1) or may contain the organic solvent (D1) and the organic solvent (D2). The content of the organic solvent (D1) is preferably 20% by mass or more, more preferably 20% by mass or more, from the viewpoint of reducing color heterogeneity and / or increasing the patterning property of the curable resin composition, Is at least 40% by mass, and more preferably at least 50% by mass.

The content of the organic solvent (D) is preferably 60 mass% or more and 95 mass% or less, and more preferably 65 mass% or more and 92 mass% or less, based on 100 mass% of the curable resin composition. In other words, the solid content of the curable resin composition is preferably 5 mass% or more and 40 mass% or less, and more preferably 8 mass% or more and 35 mass% or less. When the content of the organic solvent (D) is in the above range, the coating property of the curable resin composition and the flatness at the time of coating tends to be good, and the cured film such as a wavelength conversion film tends to have good luminescent properties.

[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 capable of initiating polymerization by generating an active radical or an acid by the action of light or heat, and a known polymerization initiator can be used.

Examples of the polymerization initiator (E) include oxime compounds such as O-acyl oxime compounds, alkylphenone compounds, imidazole compounds, triazine compounds, and acylphosphine oxide compounds. The polymerization initiator (E) may be used in combination of two or more in consideration of sensitivity, patterning property, and the like. The polymerization initiator (E) preferably contains an oxime-based compound such as an O-acyloxime compound in that it is advantageous to precisely form a pattern having sensitivity and a desired line width.

The O-acyloxime compound is a compound having a structure represented by the formula (d). Herein, * denotes a combined hand.

Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy- 2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan- -Acetoxy-l- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl Benzoyl} -9H-carbazol-3-yl] ethan-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- ] -3-cyclopentylpropan-1-one-2-imine, N-acetyloxy-1- [4- (2-hydroxyethyloxy) phenylsulfanylphenyl] propan- Methyl-2-methoxyethoxy) -2-methylphenyl] -1- (9-ethyl- - Immigration. Commercially available products such as Irgacure (registered trademark) OXE01, copper OXE02, copper OXE03 (manufactured by BASF), N-1919, NCI-930 and NCI-831 (manufactured by ADEKA Corporation) may be used. These O-acyloxime compounds are advantageous in that they can improve the lithography performance.

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

Examples of the compound having the structure represented by the formula (d4) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan- 2-benzylbutan-1-one and 2- (dimethylamino) -2 - [(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan- And the like. IRGACURE (registered trademark) 369, 907, and 379 (manufactured by BASF Co., Ltd.) may be used.

Examples of the compound having a structure represented by the formula (d5) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2- Propoxy) phenyl] propane-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomers of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan- Diethoxyacetophenone, benzyldimethylketal, and the like.

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

Examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- 4,4 ', 5,5'-tetraphenylbiimidazole (see JP-A 6-75372, JP-A 6-75373, etc.), 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (alkoxyphenyl) biimidazole, 2,2'-bis Bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole (Japanese Patent Publication No. 48-38403 (JP-A-62-174204, etc.)), an imidazole compound in which the phenyl group at the 4,4 ', 5,5'-position is substituted by a carboalkoxy group (JP- 10913, etc.), and the like. Among them, a compound represented by the following formula or a mixture thereof is preferable.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4- Methyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (Trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2, Bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- - [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

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

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, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert- butylperoxycarbonyl) benzophenone, Benzophenone compounds such as 2,4,6-trimethylbenzophenone; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethyl anthraquinone, camphorquinone, etc .; Butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with a polymerization initiator (E1) (particularly an amine compound) to be described later.

As the polymerization initiator (E), a polymerization initiator containing at least one member selected from the group consisting of alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds and imidazole compounds is preferable, and O -Acyloxime compound is more preferable.

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

[6] Polymerization initiator (E1)

The curable resin composition may contain a polymerization initiator (E1). The polymerization initiator (E1) is a compound or a sensitizer used for promoting polymerization of the polymerizable compound (C) initiated polymerization by the polymerization initiator (E).

When the polymerization initiator (E1) is included, it is used in combination with the polymerization initiator (E).

Examples of the polymerization initiator (E1) include an amine compound, an alkoxyanthracene compound, a thioxanthone compound, and a carboxylic acid compound. Of these, thioxanthone compounds are preferred. The polymerization initiator (E1) may be used in combination of two or more.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethylbenzoate, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 4,4'- -Bis (ethylmethylamino) benzophenone, and among them, 4,4'-bis (diethylamino) benzophenone is preferable. And commercially available products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) may be used.

Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, Ethoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, and the like.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- Oakstone, and the like.

Examples of the carboxylic acid compound include phenylsulfanyl acetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, Diphenylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

The content of the polymerization initiator (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 more, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C) Parts by mass or less. When the content of the polymerization initiator (E1) is within the above range, the productivity of the cured film such as a wavelength converting film can be further improved.

[7] Leveling agent (F)

The curable resin composition may include at least one leveling agent (F). Examples of the leveling agent (F) include a silicone surfactant, a fluorinated surfactant, and a silicon surfactant having a fluorine atom. These may have a polymerizable group in the side chain.

Examples of the silicone surfactant include a surfactant having a siloxane bond in the molecule. Specifically, TORAY Silicon DC3PA, copper SH7PA, copper DC11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, copper SH8400 (trade name, manufactured by Toray Dow Corning Co.), KP321, KP322, KP323, KP324, KP326 , KP340, KP341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan Co., have.

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain in the molecule. Concretely, it is possible to use a flour (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Corporation), Megapack (registered trademark) F142D, copper F171, copper F172, copper F173, copper F177 copper copper F554 copper R30, RS-718-K (manufactured by DIC Corporation), Epson (registered trademark) EF301, EF303, EF351 and EF352 (manufactured by Mitsubishi Materials Electronics Co., , S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Research Co., Ltd.).

Examples of the silicone surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples thereof include Megapac (registered trademark) R08, Copolymer BL20, Copolymer F475, Copolymer F477 and Copolymer F443 (manufactured by DIC Corporation).

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

[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 generally used industrially, and phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants can be used. The antioxidant (G) may be used in combination of two or more.

Examples of the phenol antioxidant include Irganox 1010 (Irganox 1010: pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], BASF ), 1076 (Irganox 1076: octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, manufactured by BASF), 1330 , 3 ', 3 ", 5,5', 5" -hexa-t-butyl-a, a ', a " (Manufactured by BASF Corporation), 3114 (Irganox 3114: 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) 4,6 (1H, 3H, 5H) -tione, manufactured by BASF Corporation, 3790 (Irganox 3790: 1,3,5-tris ((4-t- (Xylyl) methyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -triene, manufactured by BASF Corporation, 1035 (Irganox 1035: thiodiethylenebis [ (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, manufactured by BASF Corporation, 1135 (Irganox 1135: benzenepropanoic acid, 3,5- -Dimethylethyl) -4-hydroxy, C7-C9 branched alkyl ester, BASF ( (Irganox 1525L: 4,6-bis (octylthiomethyl) -o-cresol manufactured by BASF), 3125 (Irganox 3125, manufactured by BASF), 565 : 2,4-bis (n-octylthio) -6- (4-hydroxy-3 ', 5'-di-t-butyl anilino) -1,3,5- ), Adecastab AO-80 (adecastab 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), Smiliger (registered trademark) BHT, copper GA-80, copper GS (trade name, manufactured by Sumitomo Chemical Co., Ltd.), Cyanox 1790 (Cyanox 1790, manufactured by Cytec), and vitamin E (manufactured by Eizo K.K.).

As the phosphorus antioxidant, Irgafos 168 (tris (2,4-di-t-butylphenyl) phosphite, manufactured by BASF), 12 (Irgafos 12: tris [2- [[2,4,8,10-tetra-t-butyldibenzo [d, f] [1,3,2] dioxaphosphper-6- yl] oxy] ethyl] amine, , 38 (Irgafos 38: bis (2,4-bis (1,1-dimethylethyl) -6-methylphenyl) ethyl ester phosphoric acid, manufactured by BASF), Adekastab (registered trademark) 329K, copper PEP36, PEP-8 (manufactured by ADEKA), Sandstab P-EPQ (manufactured by Clariant), Weston 618 and 619G (manufactured by GE), Ultranox 626 (manufactured by GE) ) GP (6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t- butyldibenzo [d, , 3,2] dioxaphosphepin) (manufactured by Sumitomo Chemical Co., Ltd.).

Examples of the sulfur-based antioxidant include dialkyl thiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl or distearyl, and polyols such as tetrakis [methylene (3-dodecylthio) propionate] methane ? -alkylmercaptopropionic acid ester compounds, and the like.

[9] Other components

The curable resin composition may contain one or two additives such as a filler, a polymer other than the resin (B), an adhesion promoter, an ultraviolet absorber, an aggregation inhibitor, an organic acid, an organic amine compound, a thiol compound, a curing agent, Or more.

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

Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethylmethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane Ethoxy silane, and the like.

Examples of the ultraviolet absorber 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; Triazine-based compounds such as 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol; And the like. Examples of the anti-aggregation agent include sodium polyacrylate and the like.

Examples of the curing agent include a compound capable of reacting with a carboxyl group in the resin (B) by heating and capable of crosslinking the resin (B), a compound capable of being cured by polymerization alone, and an epoxy compound, an oxetane compound, have.

Examples of the light scattering agent include particles of metal or metal oxide, glass particles and the like. Examples of the metal oxide include TiO ₂ , SiO ₂ , BaTiO ₃ , and ZnO. The particle diameter of the light-scattering agent is, for example, about 0.03 to 20 μm, preferably 0.05 to 1 μm, more preferably 0.05 to 300 nm. The content of the light scattering agent is usually 0.001 to 50% by mass, preferably 1 to 40% by mass, more preferably 5 to 30% by mass, based on 100% by mass of the curable resin composition .

&Lt; Preparation method of curable resin composition >

The curable resin composition can be prepared by mixing the semiconductor particles (A), the resin (B), the polymerizable compound (C) and the organic solvent (D), and other components as needed.

The ligand-containing semiconductor particles as the semiconductor particles (A) may be prepared by preparing or preparing semiconductor particles coordinated by an organic ligand and then performing a ligand reducing treatment for reducing the coordination amount of organic ligands to the semiconductor particles. The ligand abatement treatment is usually carried out before mixing with the resin (B) or the polymerizable compound (C).

The ligand abatement treatment can be performed by extracting the organic ligand coordinated to the semiconductor particles into an appropriate solvent. Examples of the solvent for the extraction include ethanol, methanol and the like. The extraction conditions are such that the dispersion of the ligand-containing semiconductor particles (A) is dropped and precipitated in a solvent for extraction, the precipitate is separated by a centrifuge, the supernatant is removed, and the precipitate is precipitated in a predetermined solvent (hexane, toluene, chloroform, etc.) Dispersed.

<Cured Film, Patterned Cured Film, Wavelength Conversion Film, and Display Device>

The cured film can be obtained by curing the film (layer) made of the curable resin composition. At this time, the patterned cured film can be obtained by patterning by a method such as photolithography, inkjet, or printing. The cured film or the patterned cured film can be suitably used as a wavelength conversion film (wavelength conversion filter) that emits light having a wavelength different from the wavelength of the incident light. The wavelength conversion film can be suitably used for 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, followed by drying to form a curable resin composition layer, and the curable resin composition layer is exposed and developed via a photomask.

Examples of the substrate include glass plates such as quartz glass, borosilicate glass, alumina silicate glass and soda lime glass whose surface is coated with a silica, resin plates such as polycarbonate, polymethylmethacrylate and polyethylene terephthalate, silicon, , Silver, a silver / copper / palladium alloy thin film, or the like may be formed.

Formation of the patterned cured film by the photolithography method can be performed by a known apparatus or condition, and can be formed as follows. First, a curable resin composition is coated on a substrate, followed by drying by heating (prebaking) and / or drying under reduced pressure to remove volatile components such as a solvent and drying to obtain a curable resin composition layer. Examples of the application method include a spin coating method, a slit coating method, and a slit and spin coating method.

The temperature in the case of performing heat drying is preferably 30 占 폚 or higher and 120 占 폚 or lower, more preferably 50 占 폚 or higher and 110 占 폚 or lower. The heating time is preferably not less than 10 seconds and not more than 10 minutes, more preferably not less than 30 seconds and not more than 5 minutes. In the case of performing the reduced-pressure drying, it is preferable that the drying is carried out in a temperature range of 20 ° C to 25 ° C under a pressure of 50 Pa or more and 150 Pa or less. The film thickness of the curable resin composition layer is not particularly limited and can be appropriately selected depending on the film thickness of a cured film such as a desired wavelength conversion film.

Subsequently, 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 according to the intended use is used. As a light source used for exposure, a light source that generates light having a wavelength of 250 nm or more and 450 nm or less is preferable. For example, light having a wavelength of less than 350 nm may be cut using a filter for cutting the wavelength region, or a band-pass filter for extracting light in the vicinity of 436 nm, around 408 nm, and around 365 nm, Or may be selectively taken out. Examples of the light source include a mercury lamp, a light emitting diode, a metal halide lamp, and a halogen lamp.

For exposure, it is preferable to use an exposure apparatus such as a mask aligner, a stepper, or the like because it is possible to uniformly irradiate the entire exposure surface with a parallel light beam or to precisely align the photomask with the substrate on which the curable resin composition layer is formed Do.

A pattern of the curable resin composition layer is formed on the substrate by bringing the exposed layer of the curable resin composition into contact with a developing solution. By the development, the unexposed portion of the curable resin composition layer is dissolved and removed in the developer. The developing solution is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, tetramethylammonium hydroxide or the like. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01% by mass or more and 10% by mass or less, and more preferably 0.03% by mass or more and 5% by mass or less. The developer may further contain a surfactant. Examples of the developing method include a paddle method, a dipping method, and a spray method. Further, the substrate may be inclined at an arbitrary angle during development. After development, it is preferable to rinse with water.

The pattern of the obtained curable resin composition layer is preferably post-baked. The post bake 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 longer and 120 minutes or shorter, and more preferably 10 minutes or longer and 60 minutes or shorter. The film thickness of the cured film after post-baking is, for example, from 1 占 퐉 to 10 占 퐉, and preferably from 3 占 퐉 to 10 占 퐉.

[Example]

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the examples, "%" and "parts" indicating the content or amount are based on mass unless otherwise stated.

&Lt; Preparation Examples A to E: Preparation of ligand-containing semiconductor particle dispersions a to e >

(1) Preparation of semiconductor quantum dots

A core-shell semiconductor quantum dot INP530 (manufactured by NN-LABS) having a structure of InP (core) / ZnS (first shell) / ZnS (second shell) was used as semiconductor quantum dots. Oleylamine is coordinated on the surface of the semiconductor quantum dots.

(2) Solvent substitution treatment

Subsequently, the semiconductor quantum dots QD were subjected to solvent substitution treatment in the following order. First, 2 parts by volume of hexane was added to 1 part by volume (volume) of the dispersion containing QD of the above (1) to dilute. Thereafter, 30 parts by volume of ethanol was added to precipitate QD, followed by centrifugation. The supernatant was removed, and 3 parts by volume of hexane was added to redisperse the QD. This treatment (precipitation by ethanol addition → centrifugation → supernatant removal → redispersion by hexane addition) was performed three times in total. However, in the third redispersion, the solvents shown in Table 1 were added so that the concentration of QD having the oleylamine ligand was 9.5% by mass to obtain QD dispersions -a to e.

&Lt; Preparation Example F: Preparation of solution containing resin (B) >

A flask equipped with a cooling tube and a stirrer was charged with 100 parts of propylene glycol monomethyl ether acetate (PGMEA), and the flask was purged with nitrogen. 7.6 parts of methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 5.6 parts of dicyclopentanyl methacrylate ("Pancryl FA-513M" manufactured by Hitachi Chemical Co., Ltd.), 5 parts of methacrylic acid (Manufactured by Sigma Aldrich Japan KK) (2.7 parts), succinic acid 1- [2- (methacryloyloxy) ethyl] (manufactured by Sigma Aldrich Japan KK), 2,2'-azobis (2,4-dimethylvaleronitrile Manufactured by Wako Pure Chemical Industries, Ltd.), 1.4 parts by mass of pentaerythritol tetrakis (3-mercaptopropionate) [PEMP] (SC Organic Chemicals Co., Ltd.) and 100 parts by mass of PGMEA was added dropwise over 30 minutes, The polymerization reaction was carried out at the same temperature for 2 hours. The reaction solution was cooled to room temperature and added dropwise to ethanol, and the precipitate was collected by filtration and dried in a vacuum drier at 40 ° C. 40 parts of the obtained white powder was dissolved in 60 parts of PGMEA to obtain a resin solution -a (resin concentration: 40% by mass). The weight average molecular weight of the obtained resin was 17000 (standard polystyrene reduced value by gel permeation chromatography). The acid value of the solid content of the resin obtained on the basis of the amount of addition was calculated as X / Y ^a = 80/70 (mg-KOH / g).

&Lt; Examples 1 to 3, Comparative Examples 1 and 2 >

52.7 parts of the QD dispersion shown in Table 2 and 27.7 parts of the resin solution-a were placed in a flask, and the mixture was heated and stirred at 50 DEG C for 12 hours. Thereafter, the mixture was allowed to cool to room temperature to obtain a liquid containing QD and a resin.

Subsequently, 3.7 parts of polymerizable compound (C-1), 3.7 parts of polymerizable compound (C-2), 0.7 part of polymerization initiator (E-1), 0.7 part of antioxidant (G- ) In a concentration of 10 mass% was mixed with 10.5 parts of the solvent (D-1). The obtained mixed solution was added to the liquid containing the QD and the resin described above and stirred and mixed to obtain a curable resin composition. The solid content concentration of the obtained curable resin composition was 25 mass%. Table 2 shows the types of the components used and their amounts used. In Table 2, the unit of usage is the mass part.

Details of the ingredients shown in Table 2 are as follows.

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

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

(3) Polymerization initiator (E-1): O-acyloxime polymerization initiator "NCI-930" manufactured by ADEKA,

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

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

[6] Antioxidant (G-1): Phenol phosphorus antioxidant "Sumilizer (registered trademark) GP" manufactured by Sumitomo Chemical Co., Ltd.

[Evaluation test]

0.45 mL of the curable resin composition was dropped on the glass substrate, spin-coated at 150 rpm for 20 seconds, and dried (prebaked) at 100 DEG C for 3 minutes to form a curable resin composition layer. Subsequently, post-baking was performed in an oven at 230 캜 for 20 minutes to obtain a cured film. The film thickness of the cured film was all 5 탆 or more and 6 탆 or less. The obtained cured film was subjected to the following evaluation test.

(1) Surface roughness

The roughness (Sa: arithmetic mean height) of the cured film was measured using a laser microscope ("3D Measuring Laser Microscope OLS4100" manufactured by Olympus Corporation) and evaluated according to the following evaluation criteria. The results are shown in Table 2.

?: Sa is 1.0 占 퐉 or less,

X: Sa exceeds 1.0 占 퐉.

(2) color unevenness

The surface of the cured film was visually observed and evaluated according to the following evaluation criteria. The results are shown in Table 2.

?: No irregularities in color were visually confirmed,

X: Uneven color is visually observed.

(3) QY retention rate

The quantum yield of the coating film (before curing) of the curable resin composition of Example 1 was measured using absolute PL quantum yield measuring apparatus &quot; C9920-02G &quot;, manufactured by Hamamatsu Photonics KK. The quantum yield of the cured film (after post-baking) formed of the curable resin composition was measured using this apparatus. From these measurement results, the QY retention ratio, 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 100% .

The QY retention rate was 87%, indicating good wavelength conversion characteristics.

(4) Patterning characteristics

0.45 mL of the curable resin composition prepared in Example 1 was dropped onto a glass substrate, spin-coated at 150 rpm for 20 seconds, and dried (prebaked) at 100 DEG C for 3 minutes to form a curable resin composition layer . Subsequently, pattern exposure was performed at an exposure dose of 40 mJ / cm ² (365 nm standard) in an air atmosphere using a photomask having a line-and-space pattern with a line width of 50 μm. The distance between the substrate and the photomask was 120 mu m. The patterned cured resin composition layer after pattern exposure was immersed in an aqueous developer having a concentration of potassium hydroxide of 0.04% by mass at 23 캜 for 70 seconds, and then post-baked in an oven at 230 캜 for 20 minutes to obtain a patterned cured film .

The film thickness of the cured film was 5 mu m and the line width was 54 mu m, showing good patterning characteristics.

Claims (3)

(A), a resin (B), a polymerizable compound (C) and an organic solvent (D)
The organic solvent (D) is at least one member selected from the group consisting of a cycloalkane ring and a group selected from the group consisting of -O-, -OC (= O) -, -C (= O) -O- and -C A curable resin composition comprising a compound having at least one group. A cured film formed from the curable resin composition according to claim 1. A display device comprising the cured film according to claim 2.