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

Curable resin composition, cured film, and display device Download PDF

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CN108445714B
CN108445714B CN201810151753.0A CN201810151753A CN108445714B CN 108445714 B CN108445714 B CN 108445714B CN 201810151753 A CN201810151753 A CN 201810151753A CN 108445714 B CN108445714 B CN 108445714B
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resin
resin composition
curable resin
acid
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CN108445714A (en
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原田好宽
早坂惠
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Sumitomo Chemical Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • G09F9/35—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements being liquid crystals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements
    • H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
    • H01L33/502—Wavelength conversion materials

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  • Materials For Photolithography (AREA)
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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 from the curable resin composition, and a display device including the cured film.
Background
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 application laid-open No. JP 2015-028139). JP2005-128539 discloses a semiconductor nanocrystal having a compound having a photosensitive functional group coordinated to the surface thereof, and a photosensitive composition containing the same.
Disclosure of Invention
The invention provides a curable resin composition, a cured film and a display device shown below.
[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 organic ligands are coordinated, and 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.
[2] [1] the curable resin composition according to the above item, wherein the resin (B) comprises a resin (B-1) having a carboxyl group and/or a carboxylic anhydride group bonded to the molecular main chain via a linking group.
[3] The curable resin composition according to [1] or [2], wherein the resin (B) satisfies any one of the following [ i ] and [ ii ]:
[ i ] comprising a resin (B-1 a) 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,
the resin composition comprises 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 the carboxyl group and the carboxylic anhydride group are all bonded to the molecular main chain via a linking group; the resin (B-2) has at least 1 carboxyl group and a carboxylic acid anhydride group, and the carboxyl group and the carboxylic acid anhydride group are all directly bonded to the molecular main chain.
[4] The curable resin composition according to any one of [1] to [3], further comprising a light scattering agent.
[5] A cured film comprising 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) in which semiconductor particles having organic ligands coordinated thereto are present, a resin (B), and a polymerizable compound (C). According to the curable resin composition, a patterned cured film having a desired line width can be formed with high accuracy (hereinafter, this effect is referred to as "good pattern formability", and the accuracy of pattern formation is referred to as "pattern formability"). According to the curable resin composition, even when the line width is small, a patterned cured film can be formed with high accuracy.
In the present specification, the compounds listed as examples of each component contained or capable of being contained in the curable resin composition may be used alone or in combination of two or more unless otherwise specified.
[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 particles to which the organic ligand is coordinated are preferably luminescent (fluorescent) semiconductor particles. The cured film formed from the curable resin composition containing light-emitting semiconductor particles may be a film exhibiting fluorescence emission in a desired wavelength range and having excellent color reproducibility.
The luminescent semiconductor particles are particles composed of semiconductor crystals, and preferably nanoparticles composed of semiconductor crystals. Preferred examples of luminescent semiconductor particles are semiconductor quantum dots. The average particle diameter of the semiconductor quantum dots is, for example, 0.5nm to 20nm, preferably 1nm to 15nm (for example, 2nm to 15 nm). The average particle diameter of the semiconductor quantum dots can be determined by using a Transmission Electron Microscope (TEM).
The semiconductor quantum dot may be made of a semiconductor material containing 1 or 2 or more elements selected from the group consisting of group 2 elements, group 11 elements, group 12 elements, group 13 elements, group 14 elements, group 15 elements, and group 16 elements of the periodic table, for example.
Specific examples of semiconductor materials that can constitute semiconductor quantum dots include SnS 2 Compounds of group 14 elements and group 16 elements such as SnS, snSe, snTe, pbS, pbSe, pbTe, etc.; compounds of group 13 elements and group 15 elements such as GaN, gaP, gaAs, gaSb, inN, inP, inAs, inSb, inGaN, and InGaP; 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 A compound of an isogroup 13 element and a group 16 element; znO, ZCompounds of group 12 elements and group 16 elements such as nS, znSe, znTe, cdO, cdS, cdSe, cdTe, hgO, hgS, hgSe, hgTe, etc.; 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 、Bi 2 Se 3 、Bi 2 Te 3 Compounds of group 15 elements and group 16 elements; compounds of group 2 elements and group 16 elements such as MgS, mgSe, mgTe, caS, caSe, caTe, srS, srSe, srTe, baS, baSe, baTe, etc.; simple substance of group 14 element, group 15 element or group 16 element such as Si, ge, etc.
The semiconductor quantum dot may have a single-layer structure made of a single semiconductor material, or may have a core-shell structure in which the surface of a core particle (core layer) made of a single semiconductor material is coated with a coating layer (shell layer) made of 1 or 2 or more different semiconductor materials. In the latter case, the band gap energy of the semiconductor material constituting the shell layer is generally larger than that of the semiconductor material constituting the core layer.
The semiconductor quantum dot may have more than 2 kinds of shell layers. The shape of the semiconductor quantum dot is not particularly limited, and may be spherical or approximately spherical, rod-like, disk-like, or the like.
The organic ligand coordinated to the semiconductor particle may be, for example, an organic compound having a polar group showing coordination energy to the semiconductor particle. The organic ligand contained in the ligand-containing semiconductor particles (a) may be an organic ligand added for the synthesis of the ligand-containing semiconductor particles (a) or for stabilization. For example, in JP2015-529698 a, the ligand-containing semiconductor particles contain caproic acid as an organic ligand from the viewpoint of controlling the particle size, and DDSA (dodecenylsuccinic anhydride) is used as the organic ligand for stabilization after synthesis.
The organic ligand may be coordinated to, for example, the surface of the semiconductor particle.
The organic ligand coordinated to the semiconductor particle may be 1 type of ligand or 2 or more types of ligands. When the organic ligand is an organic compound having a polar group, the organic ligand is usually coordinated to the semiconductor particle through the polar group. The coordination of the organic ligand can be confirmed by uniformly dispersing the semiconductor particles in a dispersion medium suitable for the organic ligand.
The polar group is preferably selected from the group consisting of a thiol group (-SH), a carboxyl group (-COOH), and an amino group (-NH) 2 ) At least 1 group selected from the group consisting of. The polar group selected from the group may be advantageous in facilitating coordination with the semiconductor particle, that is, in improving coordination with the semiconductor particle. The high coordination may contribute to improving the pattern formability of the curable resin composition. Among them, from the viewpoint of obtaining a cured film (such as a wavelength conversion film) having more excellent light emission characteristics, the polar group is more preferably at least 1 group selected from the group consisting of a thiol group and a carboxyl group. The organic ligand may have 1 or more polar groups.
The molecular weight of the organic ligand coordinated to the semiconductor particle 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 particles (a) can be prepared with excellent reproducibility.
The organic ligand may be, for example, an organic compound represented by the following formula:
Y 1 -Z
in the formula, Y 1 Is the above polar group, and Z is a 1-valent hydrocarbon group which may contain a hetero atom (N, O, S, halogen atom, etc.). The hydrocarbon group may have 1 or more unsaturated bonds such as carbon-carbon double bonds. The hydrocarbon group may be linear, branched or have a cyclic structure. The number of carbon atoms of the hydrocarbon group is, for example, 1 to 40, and may be 1 to 30. The methylene group contained in the hydrocarbon group may be replaced by-O-,; -S-, -C (= O) -, or-C (= O) -O-, -O-C (= O) -, -C (= O) -NH-, -NH-and the like. In general, the hydrocarbon group does not contain a heteroatom in many cases because of the ease of preparing the ligand-containing semiconductor particle (a).
Y 1 The organic ligand represented by-Z is preferably a saturated fatty acid having 5 to 12 carbon atoms or a non-saturated fatty acid having 5 to 12 carbon atomsA saturated fatty acid.
The group Z may contain a polar group. Specific examples of the polar group may be cited a polar group Y 1 The above description is related. However, the group Z has a polar group different from Y 1 Polar groups as indicated. I.e. Y when the group Z has a polar group 1 The organic ligand represented by-Z has 2 or more polar groups. In general, the group Z does not contain a polar group in many cases because of the ease of preparing the ligand-containing semiconductor particle (a).
Having carboxyl groups as polar groups Y 1 Specific examples of the organic ligand of (2) include formic acid, acetic acid, propionic acid and saturated or unsaturated fatty acids. Specific examples of the saturated or unsaturated fatty acids include saturated fatty acids such as butyric acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, and the like; monounsaturated fatty acids such as myristoleic acid, palmitoleic acid, oleic acid, eicosenoic acid, erucic acid, and nervonic acid; and polyunsaturated fatty acids such as linoleic acid, alpha-linolenic acid, gamma-linolenic acid, stearidonic acid, dihomo-gamma-linolenic acid, arachidonic acid, eicosatetraenoic acid, docosadienoic acid, and adrenal acid (docosatetraenoic acid).
Having thiol or amino groups as polar groups Y 1 Specific examples of the organic ligand of (1) include those having a carboxyl group as the polar group Y exemplified above 1 The organic ligand of (2) wherein the carboxyl group is substituted with a thiol group or an amino group.
The content ratio of the organic ligand to the semiconductor particles in the ligand-containing semiconductor particles (a) [ hereinafter also referred to as "L/P mass ratio". And a mass ratio of less than 5.0, preferably 4.5 or less, more preferably 3 or less, still more preferably 2 or less, still more preferably 1 or less, and particularly preferably 0.6 or less. When the L/P mass ratio is within this range, it is possible to contribute to formation of a patterned cured film with good accuracy. The reason why the patterned cured film can be formed with high accuracy is considered to be that the affinity of the ligand-containing semiconductor particles (a) for the resin (B) is easily improved by setting the L/P mass ratio within the above range, and as a result, the solubility in an alkali developing solution is improved. In addition, the L/P mass ratio is 0.1 or more from the viewpoint of dispersibility of the ligand-containing semiconductor particles (a) in the curable resin composition. The L/P mass ratio can be measured as described in the later-mentioned examples.
The content of the ligand semiconductor-containing particles (a) in 100 parts by mass of the solid content of the curable resin composition is, for example, 0.1 part by mass or more and 50 parts by mass or less, preferably 1 part by mass or more and 45 parts by mass or less, and more preferably 5 parts by mass or more and 40 parts by mass or less. When the content of the ligand-containing semiconductor particles (a) is too small, a cured film (a wavelength conversion film or the like) tends to be difficult to obtain sufficient light emission intensity. When the content of the ligand-containing semiconductor particles (a) is too large, a patterned cured film tends not to be formed with good accuracy. In the present specification, "solid component of the curable resin composition" refers to the total of components other than the solvent (E) contained in the curable resin composition.
[2] resin (B)
The curable resin composition contains a resin (B). The curable resin composition may contain 1 or more kinds of resins as the resin (B). The resin (B) is preferably an alkali-soluble resin. The alkali solubility refers to a property of being soluble in a developer as an aqueous solution of an alkali compound. Examples of the resin (B) include the following resins [ K1] to [ K6 ].
Resin [ K1]: at least 1 kind (a) (hereinafter also referred to as "(a)") selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides. And a monomer (b) having a cyclic ether structure of 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter also referred to as "(b)"). Copolymers of (A) and (B),
Resin [ K2]: (a) and (b) and a monomer (c) copolymerizable with (a) (wherein (a) and (b).) are different from each other and are hereinafter also referred to as "(c)". Copolymers of (A) and (B),
Resin [ K3]: (a) A copolymer with (c),
Resin [ K4]: (a) A resin obtained by reacting the copolymer (c) with the copolymer (b),
Resin [ K5]: (b) A resin obtained by reacting the copolymer (c) with the copolymer (a),
Resin [ K6]: (b) A resin obtained by reacting the copolymer (c) with (a) and then with a carboxylic acid anhydride.
The resin (B) is preferably a resin [ K3].
(a) Specific examples thereof include the following:
unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, succinic acid mono [2- (meth) acryloyloxyethyl ] and phthalic acid mono [2- (meth) acryloyloxyethyl ];
unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5, 6-tetrahydrophthalic acid, 1,2,3, 6-tetrahydrophthalic acid, dimethyl tetrahydrophthalic acid, 1, 4-cyclohexene dicarboxylic acid, and the compounds represented by the formula (a 1) described later;
carboxyl group-containing bicyclic unsaturated compounds such as 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, etc.;
unsaturated dicarboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5, 6-tetrahydrophthalic anhydride, 1,2,3, 6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, bicyclo [2.2.1] -2-heptene-5, 6-dicarboxylic anhydride (nadic anhydride), and the like;
unsaturated (meth) acrylic acid such as α - (hydroxymethyl) (meth) acrylic acid containing a hydroxyl group and a carboxyl group in the same molecule.
In the present specification, "(meth) acrylic acid" means at least 1 selected from the group consisting of acrylic acid and methacrylic acid. The expressions "(meth) acryloyl" and "(meth) acrylate" and the like have the same meaning.
(b) The polymerizable compound has a cyclic ether structure having 2 to 4 carbon atoms (for example, at least 1 selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring (an oxolane ring)) and an ethylenically unsaturated bond. (b) Preferably, the monomer has a cyclic ether structure having 2 to 4 carbon atoms and a (meth) acryloyloxy group.
(b) Examples thereof include: a monomer (b 1) [ hereinafter also referred to as "(b 1)") having an oxiranyl group and an ethylenically unsaturated bond. A monomer (b 2) [ hereinafter also referred to as "(b 2)") having an oxetanyl group and an ethylenically unsaturated bond. A monomer (b 3) [ hereinafter also referred to as "(b 3)") having a tetrahydrofuranyl group and an ethylenically unsaturated bond. And so on.
(b1) Examples thereof include: a monomer (b 1-1) [ hereinafter also referred to as "(b 1-1)" ] having a structure obtained by epoxidizing an unsaturated aliphatic hydrocarbon. And a monomer (b 1-2) [ hereinafter also referred to as "(b 1-2)") having a structure obtained by epoxidizing an unsaturated alicyclic hydrocarbon. And a separate component.
Examples of (b 1-1) include: glycidyl (meth) acrylate, β -methylglycidyl (meth) acrylate, β -ethylglycidyl (meth) acrylate, vinylglycidyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α -methyl-o-vinylbenzyl glycidyl ether, α -methyl-m-vinylbenzyl glycidyl ether, α -methyl-p-vinylbenzyl glycidyl ether, 2, 3-bis (glycidyloxymethyl) styrene, 2, 4-bis (glycidyloxymethyl) styrene, 2, 5-bis (glycidyloxymethyl) styrene, 2, 6-bis (glycidyloxymethyl) styrene, 2,3, 4-tris (glycidyloxymethyl) styrene, 2,3, 5-tris (glycidyloxymethyl) styrene, 2,3, 6-tris (glycidyloxymethyl) styrene, 3,4, 5-tris (glycidyloxymethyl) styrene, 2,4, 6-tris (glycidyloxymethyl) styrene and the like.
Examples of (b 1-2) include: vinylcyclohexene monoxide, 1, 2-epoxy-4-vinylcyclohexane (for example, CELL OXIDE2000; manufactured by Daiiol Chemicals Co., ltd.), 3, 4-epoxycyclohexylmethyl (meth) acrylate (for example, cyclomer A400; manufactured by Daiiol Chemicals Co., ltd.), 3, 4-epoxycyclohexylmethyl (meth) acrylate (for example, cyclomer M100; manufactured by Daiiol Chemicals Co., ltd.), 3, 4-epoxytricyclo [5.2.1.0 2,6 ]Decyl (meth) acrylate, and the like.
The monomer (b 2) is preferably a monomer having an oxetanyl group and a (meth) acryloyloxy group. (b2) Preferred examples of (B) include 3-methyl-3- (meth) acryloyloxymethyloxetane, 3-ethyl-3- (meth) acryloyloxymethyloxetane, 3-methyl-3- (meth) acryloyloxyethyleneoxetane and 3-ethyl-3- (meth) acryloyloxyethyleneoxetane.
The monomer (b 3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond is preferably a monomer having a tetrahydrofuranyl group and a (meth) acryloyloxy group. (b3) Preferable examples of the (d) include tetrahydrofurfuryl acrylate (e.g., viscoat V #150, manufactured by Osaka organic chemical industry Co., ltd.), tetrahydrofurfuryl methacrylate, and the like.
(c) Specific examples of (b) include:
methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 (meth) acrylate 2,6 ]Decan-8-yl ester [ in the art, known by the trivial name "(dicyclopentanyl (meth) acrylate) ]. Also, it is sometimes referred to as "tricyclodecyl (meth) acrylate". Tri-cyclic (meth) acrylic acid [5.2.1.0 ] 2,6 ]Decen-8-yl ester [ commonly known in the art as "(dicyclopentenyl (meth) acrylate"). (meth) acrylates such as dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, and benzyl (meth) acrylate;
hydroxyl group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate;
bicyclo [2.2.1] -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 [ 2.1] -2-heptene, 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-cyclohexyloxycarbonybicyclo [2.2.1] -2-heptene, 5-phenoxycarbonylbicyclo [2.2.1] -2-heptene, 5, 6-di (tert-butoxycarbonyl) bicyclo [2.2.1] -2-heptene, 5, 6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] -2-heptene and the like An unsaturated compound;
dicarbonylimide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-succinimidyl-3-maleimidopropionate and N- (9-acridinyl) maleimide;
styrene, alpha-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1, 3-butadiene, isoprene, 2, 3-dimethyl-1, 3-butadiene; and the like.
Among them, from the viewpoints of copolymerization reactivity, heat resistance, developability during pattern formation, and the like, (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, N-benzylmaleimide, bicyclo [2.2.1] maleimide]-2-heptene, (meth) acrylic acid tricyclo [5.2.1.0 2,6 ]Decan-8-yl esters and the like.
In the resin [ K1], the ratio of the structural units derived from the respective monomers is preferably in the following range in all the structural units constituting the resin [ K1]:
a building block from (a); 2 to 50 mol% (more preferably 10 to 45 mol%)
A structural unit from (b), in particular a structural unit from (b 1); 50 to 98 mol% (more preferably 55 to 90 mol%).
When the ratio of the structural unit of the resin [ K1] is in the above range, the storage stability, the developability, and the solvent resistance of the obtained pattern tend to be excellent.
The resin [ K1] can be produced, for example, by a method described in "Experimental method for Polymer Synthesis" (published by Otsuka corporation, 1 st edition, chemical Co., ltd., 1972, 3/1), and a cited document described in the document.
Specifically, the following are listed: a method comprising charging the predetermined amounts of (a) and (b) (particularly (b 1)), a polymerization initiator, a solvent and the like into a reaction vessel, stirring the mixture in a deoxygenated atmosphere, heating the mixture, and keeping the temperature. The polymerization initiator and the solvent used herein are not particularly limited, and any of those generally used in the art can be used. As the polymerization initiator, there are exemplified azo compounds (2, 2 '-azobisisobutyronitrile, 2' -azobis (2, 4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.). The solvent may be any solvent that dissolves the monomers, and a solvent (E) described later may be used.
The copolymer obtained may be used as it is as a solution after the reaction, may be used as a solution obtained by concentration or dilution, or may be used as a solid (powder) obtained by a method such as reprecipitation.
In the resin [ K2], the ratio of the structural units derived from the respective monomers is preferably in the following range among all the structural units constituting the resin [ K2]:
a building block from (a); 4 to 45 mol% (more preferably 10 to 30 mol%)
A structural unit from (b), in particular a structural unit from (b 1); 2 to 95 mol% (more preferably 5 to 80 mol%)
The building block from (c); 1 mol% to 65 mol% (more preferably 5 mol% to 60 mol%).
When the ratio of the structural unit of the resin [ K2] is within the above range, the storage stability, the developability, and the solvent resistance, the heat resistance, and the mechanical strength of the obtained pattern tend to be excellent.
The resin [ K2] can be produced in the same manner as described for the production method of the resin [ K1 ]. Specifically, the following are listed: a method comprising charging the predetermined amounts of (a), (b) (particularly (b 1)) and (c), a polymerization initiator, a solvent and the like into a reaction vessel, stirring in a deoxygenated atmosphere, heating, and keeping the temperature. The copolymer obtained may be used as it is as a solution after the reaction, may be used as a solution obtained by concentration or dilution, or may be used as a solid (powder) obtained by a method such as reprecipitation.
In the resin [ K3], the ratio of the structural units derived from the respective monomers is preferably in the following range in all the structural units constituting the resin [ K3]:
a building block from (a); 2 to 55 mol% (more preferably 10 to 50 mol%)
The building block from (c); 45 mol% to 98 mol% (more preferably 50 mol% to 90 mol%).
The resin [ K3] can be produced in the same manner as described for the production method of the resin [ K1 ].
The resin [ K4] can be produced by the following method: a copolymer of (a) and (c) is obtained by adding a cyclic ether structure having 2 to 4 carbon atoms, particularly an oxirane ring of (b 1), to a carboxylic acid and/or a carboxylic acid anhydride of (a). Specifically, first, the copolymer of (a) and (c) is produced in the same manner as the method described as the method for producing the resin [ K1 ]. In this case, it is preferable that the ratio of each structural unit in the total structural units constituting the copolymer of (a) and (c) is in the following range.
A building block from (a); 5 to 50 mol% (more preferably 10 to 45 mol%),
The building block from (c); 50 to 95 mol% (more preferably 55 to 90 mol%).
Then, the cyclic ether structure having 2 to 4 carbon atoms of (b), particularly the oxirane ring of (b 1), is reacted with a part of the carboxylic acid and/or carboxylic acid anhydride derived from (a) in the copolymer. Specifically, after the copolymer of (a) and (c) is produced, the atmosphere in the flask may be replaced with air from nitrogen, and (b) (particularly (b 1)), a reaction catalyst of a carboxylic acid or a carboxylic acid anhydride and a cyclic ether structure (for example, tris (dimethylaminomethyl) phenol) and a polymerization inhibitor (for example, hydroquinone) and the like may be added to the flask, and the reaction may be carried out at 60 ℃ to 130 ℃ for a reaction time of 1 hour to 10 hours to obtain the resin [ K4].
(b) The amount of (b 1) to be used, particularly the amount of (b 1) to be used, is preferably 5 to 80 moles, more preferably 10 to 75 moles, based on 100 moles of (a). By setting the range, the balance of storage stability, developability, solvent resistance, heat resistance, mechanical strength, and sensitivity tends to be good. From the viewpoint of high reactivity of the cyclic ether structure and difficulty in remaining unreacted (b), the (b) used in the resin [ K4] is preferably (b 1), and more preferably (b 1-1).
The amount of the reaction catalyst used is preferably 0.001 mass% or more and 5 mass% or less with respect to the total amount of (a), (b) (particularly (b 1)) and (c). The amount of the polymerization inhibitor used is preferably 0.001 mass% or more and 5 mass% or less based on the total amount of (a), (b) and (c).
The reaction conditions such as the method of feeding, the reaction temperature and time can be appropriately adjusted in consideration of the production equipment and the amount of heat generated by polymerization. In addition, as in the case of the polymerization conditions, the feeding method and the reaction temperature can be appropriately adjusted by taking into consideration the production facilities, the amount of heat generated by polymerization, and the like.
The resin [ K5] is subjected to the same operation as in the above-mentioned method for producing the resin [ K1] as the first stage, thereby obtaining a copolymer of (b) (particularly (b 1)) and (c). As described above, the obtained copolymer may be used as it is as a solution after the reaction, may be used as a solution obtained by concentration or dilution, or may be used as a substance obtained as a solid (powder) by a method such as reprecipitation.
(b) The ratio of the structural units (b 1) and (c) to the total number of moles of all the structural units constituting the copolymer is preferably in the following range.
A structural unit from (b), in particular a structural unit from (b 1); 5 to 95 mol% (more preferably 10 to 90 mol%),
The building block from (c); 5 to 95 mol% (more preferably 10 to 90 mol%).
Further, the resin [ K5] can be obtained by reacting the cyclic ether structure derived from (b) which is contained in the copolymer of (b) (particularly (b 1)) and (c) with the carboxylic acid or carboxylic acid anhydride which is contained in (a) under the same conditions as the process for producing the resin [ K4]. The amount of (a) to be used in the reaction with the copolymer is preferably 5 to 80 moles per 100 moles of (b) (particularly (b 1)). From the viewpoint that the cyclic ether structure has high reactivity and unreacted (b) hardly remains, the (b) used in the resin [ K5] is preferably (b 1), and more preferably (b 1-1).
The resin [ K6] is a resin obtained by further reacting a carboxylic acid anhydride with the resin [ K5]. The carboxylic anhydride is further reacted with a hydroxyl group 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), and the like.
The resin (B) preferably contains a resin (B-1) having a carboxyl group (-COOH) and/or a carboxylic anhydride group (-C (= O) -O-C (= O) -) bonded to the molecular main chain via a linking group. The linking group is a group which is not directly bonded to the main molecular chain of the polymer and to the carboxyl group and/or carboxylic anhydride group, and is, for example, a hydrocarbon group having 1 or more carbon atoms. The hydrocarbon group may have a linear, branched and/or cyclic structure. <xnotran> , 1 -O-, -S-, -C (= O) -, -C (= O) -O-, -O-C (= O) -, -C (= O) -NH-, -NH- . </xnotran>
The linking group may have 1 bond or 2 or more bonds between itself and the molecular backbone of the polymer. When the resin (B-1) has a carboxylic anhydride group, 2 bonds are formed between the linking group and the carboxylic anhydride group.
When the resin (B) contains the resin (B-1), the dispersibility of the ligand-containing semiconductor particles (a) in the curable resin composition can be improved. This is presumably because, when the resin having a polar group is coordinated to the semiconductor particles via the polar group, the carboxyl group and/or carboxylic anhydride group of the resin (B-1) has a relatively high coordination energy, and the effect of improving the dispersibility of the ligand-containing semiconductor particles (A) is further enhanced by coordination to the semiconductor particles based on the high coordination energy. The high dispersibility of the ligand-containing semiconductor particles (a) can contribute to improvement of in-plane uniformity of the light emission characteristics of a cured film such as a wavelength conversion film, for example.
Examples of the resin (B-1) include a resin (B-1 a) 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, and a resin (B-1B) having at least one carboxyl group and at least one carboxylic acid anhydride group, all of which are bonded to the molecular main chain via a linking group.
The resin (B-1 a) 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 molecular main chain via a linking group, and a structural unit having a carboxyl group and/or a carboxylic acid anhydride group directly bonded to the molecular main chain. 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 molecular main chain via a linking group, and a structural unit having no carboxyl group and/or carboxylic acid anhydride group directly bonded to the molecular main chain.
The curable composition of the present invention may contain, as the resin (B), a resin (B-2) in which the resin (B-2) has at least one carboxyl group and at least one carboxylic anhydride group, and all of the carboxyl group and the carboxylic anhydride group are directly bonded to the molecular main chain.
The resin (B-1 a), the resin (B-1B) and the resin (B-2) can be prepared by using at least 1 kind (a) selected from the group consisting of the unsaturated carboxylic acid and the unsaturated carboxylic acid anhydride as a monomer. By selecting an appropriate monomer as (a), the resin (B-1B) and the resin (B-2) can be prepared separately. (a) The specific examples of (2) are as described above, but not limited to these.
In order to introduce a carboxyl group and/or a carboxylic anhydride group bonded to the molecular main chain via a linking group into the resin, (a) vinyl benzoic acid, 1,2,3, 6-tetrahydrophthalic anhydride, 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 anhydride group bonded to the molecular main chain via a linking group into the resin, (a) 1 or more kinds of monomers represented by the formula (a 1) may be used, for example.
Figure BDA0001580089800000121
[ in the formula (a 1),
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>
As R 2 And R 3 Examples of the alkylene group having 2 to 6 carbon atoms in (A) include linear alkylene groups such as 1, 2-ethylene group, 1, 3-propylene group, 1, 4-butylene group, 1, 5-pentylene group and 1, 6-hexylene group; branched alkylene groups such as 1, 1-ethylene, 1, 2-propylene, 1, 3-butylene, 2-methyl-1, 3-propylene, 2-methyl-1, 2-propylene, 1, 4-pentylene and 2-methyl-1, 4-butylene.
As R 2 And R 3 Examples of the cycloalkylene group having 5 to 12 carbon atoms in the above-mentioned group include 1, 2-cyclopentylene group, 1, 3-cyclopentylene group, 1, 4-cyclopentylene group, 1, 2-cyclohexylene group, 1, 3-cyclohexylene group, 1, 4-cyclohexylene group, 1, 2-cycloheptylene group, 1, 3-cycloheptylene group, 1, 4-cycloheptylene group, adamantane-1, 2-diyl group and adamantane-1, 3-diyl group.
As R 3 The cycloalkylene group having 5 to 12 carbon atoms in (b) includes a group in which any one of the carbon-carbon single bonds in the ring structure of the above cycloalkylene group is replaced with a carbon-carbon double bond.
As R 3 The 2-valent aromatic group in (A) may be an aromatic hydrocarbon having 5 to 12 carbon atoms, and specifically may be 1, 2-phenylene, 1, 3-phenylene, 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 and the like.
Examples of the alkyl group having 1 to 8 carbon atoms in Y include a linear or branched alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, and an octyl group.
Examples of the monomer represented by the formula (a 1) include mono [ (meth) acryloyloxyalkyl ] esters of dicarboxylic acids such as mono [2- (meth) acryloyloxyethyl ] succinate and mono [2- (meth) acryloyloxyethyl ] phthalate. From the viewpoint of dispersibility of the ligand-containing semiconductor particles (A) in an organic solvent, a monomer represented by the equation (a 1) of mono [ (meth) acryloyloxyalkyl ] ester of a dicarboxylic acid is advantageous.
In order to introduce a carboxyl group and/or a carboxylic anhydride group directly bonded to the molecular main chain into the resin, (a) may be (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, maleic anhydride, 3,4,5, 6-tetrahydrophthalic acid, 3,4,5, 6-tetrahydrophthalic anhydride, or the like. From the viewpoint of copolymerization reactivity and 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 ]:
the resin (B-1 a) has 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;
the resin composition comprises a resin (B-1B) and a resin (B-2), wherein the resin (B-1B) has at least one carboxyl group and a carboxylic anhydride group, and the carboxyl group and the carboxylic anhydride group are all bonded to the molecular main chain via a linking group; the resin (B-2) has at least one carboxyl group and a carboxylic anhydride group, and all of the carboxyl group and the carboxylic anhydride group are directly bonded to the molecular main chain.
Satisfying any one or both of [ i ] and [ ii ] contributes to improving the dispersibility of the ligand-containing semiconductor particles (a) in the curable resin composition and also contributes to improving the pattern formability of the curable resin composition.
In [ i ], the resin (B) may contain only the resin (B-1 a), may contain the resin (B-1 a) and the resin (B-1B), and may contain the resin (B-1 a) and the resin (B-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-1 a).
Among the acid values shown in the resin (B), the acid value X based on the carboxyl group and/or carboxylic acid anhydride group directly bonded to the molecular main chain and the acid value Y based on the carboxyl group and/or carboxylic acid anhydride group bonded to the molecular main chain via a linking group a Ratio of (A) to (B) of a For example, (0 mg-KOH/g or more and 150mg-KOH/g or less)/(20 mg-KOH/g or more and 150mg-KOH/g or less), preferably (40 mg-KOH/g or more and 100mg-KOH/g or less)/(40 mg-KOH/g or more and 120mg-KOH/g or less), more preferably (40 mg-KOH/g or more and 80mg-KOH/g or less)/(60 mg-KOH/g or more and 90 mg-KO/g or more)H/g or less).
Ratio X/Y a When the content is within the above range, the dispersibility of the resin (B) and the developability (developing speed and pattern formability) of the curable resin composition can be improved.
The acid value of the resin (B) is, for example, from 20mg-KOH/g to 200mg-KOH/g, preferably from 40mg-KOH/g to 170mg-KOH/g, and more preferably from 60mg-KOH/g to 150 mg-KOH/g. Within the above range, both developability and high dispersibility can be achieved.
The acid value is a value measured as the amount (mg) of potassium hydroxide required for neutralizing 1g of the resin, and can be determined by titration using an aqueous potassium hydroxide solution, for example.
The acid value of the solution of the resin (B) is preferably 5 to 180mg-KOH/g, more preferably 10 to 100mg-KOH/g, still more preferably 12 to 50 mg-KOH/g.
The acid value of the solution is a value measured as the amount (mg) of potassium hydroxide required for neutralizing 1g of the solution, and can be determined by titration using an aqueous potassium hydroxide solution, for example.
The solution acid value is a value measured by dissolving the resin (B) in a predetermined solvent, and the concentration is, for example, 10 mass% to 50 mass%. When the acid value of the solution is within the above range, 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 3000 to 100000, more preferably 5000 to 50000, and still more preferably 5000 to 30000. When the molecular weight is within the above range, the unexposed portion has high solubility in a developer, and the residual film ratio or hardness of the obtained pattern tends 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, more preferably 1.2 to 4.
The content of the resin (B) is preferably 5 to 70 mass%, more preferably 10 to 65 mass%, and still more preferably 15 to 60 mass% in 100 mass% of the solid content of the curable resin composition. When the content of the resin (B) is within the above range, the solubility of the unexposed portion to the developer tends to be high.
[3] polymerizable Compound (C)
The polymerizable compound (C) is not particularly limited as long as it is a compound which can be polymerized by irradiation with light or the like via an active radical or the like generated from the polymerization initiator (D), and examples thereof include compounds 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 3 or more ethylenically unsaturated bonds. Specific examples of the photopolymerizable compound having 3 or more ethylenically unsaturated bonds include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol 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, and the like.
The curable resin composition may contain 1 or more polymerizable compounds (C). The content of the polymerizable compound (C) is preferably 20 to 150 parts by mass, and more preferably 80 to 120 parts by mass, relative to 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 an active radical, an acid, or the like by the action of light or heat to initiate polymerization, and a known polymerization initiator can be used.
Examples of the polymerization initiator (D) include: oxime compounds such as O-acyloxime compounds, phenylalkylketone compounds, bisimidazole compounds, triazine compounds, acylphosphine oxide compounds, and the like. In view of sensitivity, pattern formability, and the like, 2 or more polymerization initiators (D) may be used in combination. The polymerization initiator (D) preferably contains an oxime compound such as an O-acyloxime compound in order to facilitate precise production of a pattern shape having sensitivity and a desired line width.
The O-acyloxime compound is a compound having a structure represented by the formula (d). The bond sites are denoted as follows.
Figure BDA0001580089800000161
As the O-acyloxime compound, there may be mentioned: 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-cyclopentylpropane-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-dioxopentylmethyloxy) benzoyl } -9H-carbazol-3-yl ] ethane-1-imine, N-acetoxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylpropane-1-imine, N-acetoxy-1- [4- (2-hydroxyethyloxy) phenylthiophenyl ] propan-1-one-2-imine, N-acetoxy-1- [4- (1-methyl-2-methoxyethoxy) -2-methylphenyl ] -1- (9-ethyl-6-nitro-9H-carbazol-3-yl) methane-1-imine and the like. Commercially available products such as Irgacure (registered trademark) OXE01, irgacure OXE02, irgacure OXE03 (manufactured by BASF Co., ltd.), N-1919, NCI-930, and NCI-831 (manufactured by ADEKA Co., ltd.) can be used. These O-acyloxime compounds are advantageous in improving the lithographic performance.
The phenylalkylketone compound is a compound having a structure represented by formula (d 4) or formula (d 5). In these structures, the benzene ring may have a substituent.
Figure BDA0001580089800000162
Examples of the compound having the structure represented by the formula (d 4) include: 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-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, and the like. Commercially available products such as Irgacure (registered trademark) 369, irgacure 907, and Irgacure 379 (all manufactured by BASF) can be used.
The compounds having the structure represented by the formula (d 5) are exemplified by: 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomers of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α -diethoxyacetophenone, benzyl dimethyl ketal, and the like.
From the viewpoint of sensitivity, the phenylalkylketone compound is preferably a compound having a structure represented by the formula (d 4).
Examples of bisimidazole compounds include: 2,2' -bis (2-chlorophenyl) -4,4',5,5' -tetraphenylbisimidazole, 2,2' -bis (2,3-dichlorophenyl) -4,4',5,5' -tetraphenylbisimidazole (see Japanese patent laid-open No. 6-75372, japanese patent laid-open No. 6-75373, etc.), 2,2' -bis (2-chlorophenyl) -4,4',5,5' -tetrakis (alkoxyphenyl) bisimidazole, 2,2' -bis (2-chlorophenyl) -4,4',5,5' -tetrakis (dialkoxyphenyl) bisimidazole, 2,2' -bis (2-chlorophenyl) -4,4',5,5' -tetrakis (trialkoxyphenyl) bisimidazole (see Japanese patent laid-open No. 48-38403, japanese patent laid-open No. 62-174204, etc.), imidazole compounds in which the phenyl group at the 4,4',5,5' -position is substituted with an alkoxycarbonyl group (see Japanese patent laid-open No. 7-10913, etc.). Among them, compounds represented by the following formula or a mixture thereof is preferable.
Figure BDA0001580089800000171
Examples of 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) vinyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (3, 4-dimethoxyphenyl) vinyl ] -1,3, 5-triazine and the like.
The acylphosphine oxide compounds may be exemplified by: 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; benzophenone compounds such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 ' -methyldiphenyl sulfide, 3', 4' -tetrakis (t-butylperoxycarbonyl) benzophenone, and 2,4, 6-trimethylbenzophenone; quinone compounds such as 9, 10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone, etc.; 10-butyl-2-chloroacridone, dibenzoyl, methyl phenylglyoxylate, titanocene compounds and the like. These are preferably used in combination with the polymerization initiation aid (D1) (particularly, an amine compound) described later.
The polymerization initiator (D) preferably contains at least 1 polymerization initiator selected from the group consisting of a phenylalkyl ketone compound, a triazine compound, an acylphosphine oxide compound, an O-acyloxime compound and a bisimidazole compound, and more preferably contains an O-acyloxime compound.
The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 25 parts by mass, and still 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). When the content of the polymerization initiator (D) is within the above range, the exposure time tends to be shortened due to high sensitivity, and therefore, the productivity of a cured film such as a wavelength conversion film tends to be improved.
[5] polymerization initiation aid (D1)
The curable resin composition may contain a polymerization initiator (D1). The polymerization initiation assistant (D1) is a compound for promoting the polymerization of the polymerizable compound (C) which initiates the polymerization by the polymerization initiator (D), or a sensitizer. When the polymerization initiator aid (D1) is contained, it is used in combination with the polymerization initiator (D).
Examples of the polymerization initiation aid (D1) include: amine compounds, alkoxyanthracene compounds, thioxanthone compounds, carboxylic acid compounds, and the like. Among them, a thioxanthone compound is preferable. The polymerization initiator (D1) may be used in combination of 2 or more.
Examples of the amine compound include: triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N-dimethyl-p-toluidine, 4' -bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4' -bis (diethylamino) benzophenone, 4' -bis (ethylmethylamino) benzophenone, and the like, and among them, 4' -bis (diethylamino) benzophenone is preferable. Commercially available products such as EAB-F (manufactured by Baotu chemical industries, ltd.) can be used.
Examples of the alkoxyanthracene compound 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, and the like.
Examples of thioxanthone compounds include: 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.
Examples of the 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 and the like.
The content of the polymerization initiation aid (D1) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiation aid (D1) is within the above range, the productivity of a cured film such as a wavelength conversion film can be further improved
[6] solvent (E)
Curable resin composition the curable resin composition preferably contains 1 or more kinds of solvents (E). Examples of the solvent (E) include an ester solvent (a solvent containing-C (= O) -O-), an ether solvent other than the ester solvent (a solvent containing-O-), an ether ester solvent (a solvent containing-C (= O) -O-and-O-), a ketone solvent other than the ester solvent (a solvent containing-C (= O) -), an alcohol solvent, an aromatic hydrocarbon solvent, an amide solvent, and dimethyl sulfoxide.
The ester solvent may be exemplified by: methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexyl acetate, 2-methylcyclohexyl acetate, cyclohexyl propionate, cis-3, 5-trimethylcyclohexyl acetate, 4-tert-butylcyclohexyl acetate, cyclohexyl butyrate, isopropyl cyclohexanecarboxylate, gamma-butyrolactone, and the like.
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 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 methylethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, methylanisole, methoxycyclohexane, and the like.
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, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, and the like.
Examples of ketone solvents include: 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-methyl-2-pentanone, cyclopentanone, 2-acetylcyclopentanone, cyclohexanone, 2-acetylcyclohexanone, isophorone, and the like.
Alcohol solvents may be listed: methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerol, and the like. Aromatic hydrocarbon solvents include: benzene, toluene, xylene, mesitylene, and the like. Examples of the amide solvent include: n, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, and the like.
The solvent (E) preferably contains at least 1 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 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, cyclohexanol, benzene, toluene, xylene, and mesitylene, and more preferably contains at least 1 selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate, cyclohexyl acetate, methoxycyclohexane, isopropyl cyclohexanecarboxylate, cyclopentanone, cyclohexanone, and cyclohexanol from the viewpoint of coatability and drying property.
The solvent (E) preferably contains a solvent (E-a) having at least 1 of an alicyclic hydrocarbon group (a non-aromatic cyclic hydrocarbon group) and an ether bond (-O-), an ester bond (-C (= O) -O-), and a ketone bond (-C (= O) -), from the viewpoint of dispersibility of the ligand-containing semiconductor particles (a) and the resin (B) in the curable resin composition.
The solvent (E) may be composed of the solvent (E-a) alone or may be a mixture of the solvent (E-a) with another solvent. In the case of a mixture, the solvent (E-a) is preferably contained in an amount of 20 mass% or more, more preferably 30 mass% or more, and still more preferably 40 mass% or more, from the viewpoint of dispersibility of the ligand semiconductor particles (a) and the resin (B) in the curable resin composition.
As the solvent (E-a), there may be mentioned: cyclohexyl acetate, 2-methylcyclohexyl acetate, cyclohexyl propionate, cis-3, 5-trimethylcyclohexyl acetate, 4-tert-butylcyclohexyl acetate, cyclohexyl butyrate, isopropyl cyclohexanecarboxylate, methoxycyclohexane, cyclopentanone, 2-acetylcyclopentanone, cyclohexanone, 2-acetylcyclohexanone, and the like.
The content of the solvent (E) in 100% by mass of the curable resin composition is preferably 60% by mass or more and 95% by mass or less, and more preferably 65% by mass or more and 92% by mass or less. In other words, the solid content of the curable resin composition is preferably 5 mass% to 40 mass%, more preferably 8 mass% to 35 mass%. When the content of the solvent (E) is within the above range, the coating property of the curable resin composition and the flatness at the time of coating tend to be good, and the light emission characteristics of a cured film such as a wavelength conversion film tend to be good.
[ 7 ] leveling agent (F)
The curable resin composition may contain 1 or more leveling agents (F). Examples of the leveling agent (F) include: silicone surfactants, fluorine surfactants, silicone surfactants having fluorine atoms, and the like. These may have a polymerizable group in a side chain.
Examples of the silicone surfactant include: surfactants having siloxane bonds in the molecule, and the like. Specifically, the silicone resin composition includes DORPOSE DC3PA, DORPOSE SH7PA, DORPOSE DC11PA, DORPOSE SH21PA, DORPOSE SH28PA, DORPOSE SH29PA, DORPOSE SH30PA, DORPOSE SH8400 (trade name, manufactured by DORPOSE KANNING 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 Mitsui Kagaku Kogyo Co., ltd.), and the like.
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-TOP EF303, F-TOP EF351, F-TOP EF352 (manufactured by Mitsubishi Material electronics Co., ltd.), surflon (registered trademark) S381, surflon S382, surflon SC101, surflon SC105 (manufactured by Asahi Nitro (Co., ltd.) and E5844 (manufactured by Daiki chemical research Co., ltd.) can be mentioned.
Examples of the silicone surfactant having a fluorine atom include: and surfactants having siloxane bonds and fluorocarbon chains in the molecule. Specifically, megafac (registered trademark) R08, megafac BL20, megafac F475, megafac F477, and Megafac F443 (manufactured by DIC corporation) may be mentioned.
The content of the leveling agent (F) in 100% by mass of the curable resin composition is usually 0.001% by mass or more and 0.2% by mass or less, preferably 0.002% by mass or more and 0.1% by mass or less, and more preferably 0.005% by mass or more and 0.05% by mass or less.
[ 8 ] antioxidant (G)
The curable resin composition may contain an antioxidant (G) from the viewpoint of improving heat resistance and light resistance of the curable resin composition. The antioxidant (G) is not particularly limited as long as it is an industrially commonly used antioxidant, and a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, and the like can be used. The antioxidant (G) may be used in combination of 2 or more.
Examples of the phenolic antioxidant include: \\124522360\\124941248363 (registered trademark) 1010 (Irganox 1010: pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], manufactured by BASF (strain), 12452609412483\\12463124731076; octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, BASF (strain), 1245212523609412483124124731330 (Irganox 1330, 3',3", 5',5" -hexa-tert-butyl-a, a ' Manufactured by BASF), 1245212523601249412483\ (124631520L (Irganox 1520L:4, 6-bis (octylthiomethyl) o-cresol, manufactured by BASF (strain), \1245212523, (124) 1249412463124633125 (Irganox 3125, manufactured by BASF (strain)), \124521252312460565 (Irganox 565): 2, 4-bis (n-octylthio) -6- (4-hydroxy-3 ',5' -di-tert-butylanilino) -1,3, 5-triazine, manufactured by BASF (strain), 12450591247312412579 (registered trademark) AO-80 (1245012487\\124731250212580: 3, 9-bis (2- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1, 1-dimethylethyl) -2,4,8, 10-tetraoxaspiro (5, 5) undecane, manufactured by ADEKA, 124731251125211247012512512520 (registered trademark), 1251211247012512512542, 12412542 GA-80, 124125112520 (sumizier, manufactured by Sumilizer chemie strain), 241241241245046, 24509473.
Examples of the phosphorus-containing antioxidant include: 1245223601250112473 (available from the group consisting of (R.sub.v. Pat. No. 2, 5) and (R.sub.v. No. 2, 5) of the groups described in (R.sub.v. No. 2, 4-di-t-butylphenyl) via a series of groups described by the following general methods (described in patent publication No. 5) by the following general methods (patent publication No. 2, 5) and (No. 2) by the general methods of the invention, described by the general methods cited therein, wherein (R.sub.v. No. 2,1245) is incorporated by reference, by the patent No. 2,1251241245.
Examples of the sulfur-based antioxidant include: dialkyl thiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl thiodipropionate and distearyl thiodipropionate, and β -alkylmercaptopropionate compounds of polyhydric alcohols such as tetrakis [ methylene (3-dodecylthio) propionate ] methane.
[9 ] other ingredients
The curable resin composition may further contain 1 or 2 or more kinds of fillers, polymer compounds other than the resin (B), adhesion promoters, ultraviolet absorbers, anti-coagulation agents, organic acids, organic amine compounds, thiol compounds, curing agents, light scattering agents, and other additives, as necessary.
Examples of the filler include: glass, silica, alumina, and the like. Examples of the polymer compound other than the resin (B) include: polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, and the like.
Examples of the adhesion promoter include: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane.
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 compounds such as 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5-hexyloxyphenol; and the like. Examples of the anti-coagulating agent include sodium polyacrylate and the like.
Examples of the curing agent include: a compound capable of crosslinking the resin (B) by reacting with the carboxyl group in the resin (B) by heating, a compound capable of homopolymerizing and curing, and the like. Examples thereof include epoxy compounds and oxetane compounds.
Examples of the light scattering agent include: metal or metal oxide particles, glass particles, and the like. Examples of the metal oxides include: tiO 2 2 、SiO 2 、BaTiO 3 ZnO, etc.
Examples of the light scattering agent include particles of metal oxides, and TiO is more preferable 2 、SiO 2 And so on.
The particle diameter of the light scattering agent is, for example, about 0.03 μm to 20 μm, preferably about 0.05 μm to 1 μm, and more preferably about 0.05 μm to 300 nm. The content of the light scattering agent is usually 0.001 mass% or more and 50 mass% or less, preferably 1 mass% or more and 40 mass% or less, and more preferably 5 mass% or more and 30 mass% or less in 100 mass% of the curable resin composition.
< method for producing 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 needed.
The ligand-containing semiconductor particles (a) are preferably subjected to the following treatment: a semiconductor particle having an organic ligand coordinated thereto is prepared or prepared, and then subjected to a ligand reduction treatment for reducing the amount of the organic ligand coordinated to the semiconductor particle, so that the L/P mass ratio is 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 may be performed by extracting the organic ligand coordinated to the semiconductor particles with an appropriate solvent. The solvents for extraction include: ethanol, methanol, and the like. The extraction conditions were as follows: the dispersion containing the ligand semiconductor particles (a) is dropped into a solvent for extraction to precipitate the dispersion, and then the precipitate is separated by a centrifugal separator to remove a supernatant, and the supernatant is redispersed in a predetermined solvent (hexane, toluene, chloroform, etc.).
< cured film, patterned cured film, wavelength conversion film, and display device >
The cured film can be obtained by curing a film (layer) composed of the curable resin composition. At this time, patterning may be performed by a method such as a photolithography method, an inkjet method, a printing method, or the like, thereby obtaining a patterned cured film. The cured film or the patterned cured film may be suitable as a wavelength conversion film (wavelength conversion filter) that emits light of a wavelength different from that of the incident light. The wavelength conversion film is suitable for display devices such as liquid crystal display devices and organic EL devices. The pattern forming method is preferably photolithography. The photolithography method is a method in which a curable resin composition is applied to a substrate, dried to form a curable resin composition layer, and the curable resin composition layer is exposed to light through a photomask and developed.
As the substrate, a glass plate such as quartz glass, borosilicate glass, aluminosilicate glass, soda lime glass having a silica coating layer on the surface thereof, a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate, a substrate such as silicon, or a substrate having a thin film of aluminum, silver/copper/palladium alloy formed on the substrate, or the like can be used.
The formation of the cured film patterned by the photolithography can be performed by a known or customary apparatus or conditions. For example, the following can be made. First, a curable resin composition is applied onto a substrate, and volatile components such as a solvent are removed by heat drying (prebaking) and/or drying under reduced pressure, followed by drying, thereby obtaining a curable resin composition layer. Examples of the coating method include spin coating, slit and spin coating.
The temperature at the time of heating and drying is preferably 30 ℃ to 120 ℃ and more preferably 50 ℃ to 110 ℃. The heating time is preferably 10 seconds to 10 minutes, more preferably 30 seconds to 5 minutes. When the drying is carried out under reduced pressure, it is preferably carried out under a pressure of 50Pa to 150Pa, and at a temperature of 20 ℃ to 25 ℃. The thickness of the curable resin composition layer is not particularly limited, and may be appropriately selected according to the 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 may be used. As the light source for exposure, a light source emitting light having a wavelength of 250nm to 450nm is preferable. For example, light of less than 350nm may be cut by a filter for cutting the wavelength region, or light of about 436nm, about 408nm, or about 365nm may be selectively extracted by a band-pass filter for extracting the wavelength region. Examples of the light source include: mercury lamps, light emitting diodes, metal halides, etc., halogen lamps, etc.
Since parallel light can be uniformly irradiated onto the entire exposure surface, or the correct positions of the photomask and the substrate on which the curable resin composition layer is formed can be aligned, an exposure apparatus such as a mask aligner or a step and repeat apparatus is preferably used for the exposure.
The exposed curable resin composition layer is developed by contacting it with a developing solution, thereby forming a pattern of the curable resin composition layer on the substrate. By the development, the unexposed portion of the curable resin composition layer is dissolved in a developing solution and removed. The developer is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide. The concentration of these basic compounds in the aqueous solution is preferably 0.01 to 10 mass%, more preferably 0.03 to 5 mass%. The developer may further contain a surfactant. Examples of the developing method include: paddle stirring, dipping, spraying, and the like. Further, the substrate may be inclined at an arbitrary angle at the time of development. After development, washing with water is preferably performed.
Further, the pattern of the obtained curable resin composition layer is preferably subjected to post-baking. The temperature of the postbaking is preferably 60 ℃ to 250 ℃ and more preferably 110 ℃ to 240 ℃. The post-baking time is preferably 1 minute to 120 minutes, more preferably 10 minutes to 60 minutes. The cured film after post-baking has a film thickness of, for example, 1 μm to 10 μm, preferably 3 μm to 10 μm.
Examples
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 used are on a mass basis unless otherwise specified.
< production example 1-1: production of ligand-containing semiconductor particle (A) (-1 >)
(1) Preparing semiconductor quantum dots
As the semiconductor quantum dot, a core-shell type semiconductor quantum dot InP530 [ manufactured by NN-LABS corporation ] having an InP (core)/ZnS (1 st shell)/ZnS (2 nd shell) structure was used. Oleylamine is coordinated to the surface of the semiconductor quantum dot.
(2) Reduction of ligand treatment
Next, the ligand reduction treatment is performed on the semiconductor Quantum Dots (QDs) 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, and diluted. Subsequently, 30 parts by volume of ethanol was added to precipitate QD, and the resultant was centrifuged. The supernatant was removed and 3 volumes of hexane were added to redisperse the QDs. A total of 3 such treatments were performed (ethanol addition for precipitation → centrifugation → removal of supernatant → addition of hexane for redispersion). In the 3 rd redispersion, isopropyl cyclohexanecarboxylate (CHCI) was added instead of hexane so that the concentration of QD (containing an oleylamine ligand) was 20 mass%, thereby obtaining QD dispersion-a.
(3) Determination of the L/P Mass ratio
The obtained QD dispersion liquid-a was measured for L/P mass ratio [ mass ratio of organic ligand to semiconductor quantum dot; [ mass of organic ligand ]/[ mass of semiconductor quantum dot ].
30. Mu.L of the QD dispersion was weighed into an aluminum pot, and thermogravimetric measurement was carried out at a temperature range of 45 ℃ to 550 ℃ at a temperature rise rate of 5 ℃/min under a nitrogen stream using a thermogravimetric analyzer "TGDTA6200" (manufactured by Nippon Seiko Co., ltd.). The L/P mass ratio was determined by dividing the mass of the organic ligand by the mass of the semiconductor quantum dot, using the weight change of 170 ℃ to 550 ℃ as the CHCI volatilization completion temperature as the weight (mass) of the organic ligand, and the weight of the residue after completion of the measurement as the weight (mass) of the semiconductor quantum dot.
Production examples 1 to 2: production of ligand-containing semiconductor particle (A) (-2 >)
To 100 parts of QD dispersion liquid-a, 14.5 parts of oleic acid was added, CHCI was added so that the concentration of QD (containing oleylamine and oleic acid ligand) became 20 mass%, and then the mixture was stirred at 80 ℃ for 3 hours, thereby obtaining QD dispersion liquid-B. The same procedure as in (3) of production example 1-1 was repeated, and the L/P mass ratio of the QD dispersion-B obtained was measured.
Production examples 1 to 3: production of ligand-containing semiconductor particle (A) (-3)
To 100 parts of QD dispersion liquid-a obtained in production example 1-1, 49.0 parts of oleic acid was added, CHCI was added so that the concentration of QD (containing oleylamine and oleic acid ligand) was 20 mass%, and then the mixture was stirred at 80 ℃ for 3 hours, thereby obtaining QD dispersion liquid-C. The same procedure as in (3) of production example 1-1 was repeated, and the L/P mass ratio of the QD dispersion-C obtained was measured.
The summary of production examples 1-1 to 1-3 is shown in Table 1.
[ TABLE 1]
Figure BDA0001580089800000271
Production example 2-1: preparation of a solution containing resin (B) < 1 >)
To a flask having a condenser and a stirrer, 100 parts of Propylene Glycol Monomethyl Ether Acetate (PGMEA) was added to conduct nitrogen substitution. While stirring at 70 ℃ and dropping 7.6 parts of methyl methacrylate (manufactured by Tokyo chemical Co., ltd.) and dicyclopentanyl methacrylate (Ri. RTM.) over 30 minutes at the same time5.6 parts of 12501124491252331632.7 parts of methacrylic acid (manufactured by Tokyo Kagaku Kogyo Co., ltd.) and 1- [2- (methacryloyloxy) ethyl succinate]A mixed solution of 6.4 parts of an ester (manufactured by Sigma Aldrich Japan contract Co., ltd.), 2.1 parts of 2,2' -azobis (2, 4-dimethylvaleronitrile) (manufactured by Wako pure chemical industries, ltd.), 1.4 parts by mass of pentaerythritol tetrakis (3-mercaptopropionate) [ PEMP ] (manufactured by SC organic chemical Co., ltd.), and 100 parts of PGMEA was polymerized at the temperature for 2 hours. After the reaction solution was slowly cooled to room temperature, the reaction solution was added dropwise to ethanol, and the precipitate was recovered by filtration and dried by a vacuum dryer at 40 ℃.20 parts of the obtained white powder was dissolved in a mixed solvent of 40 parts of PGMEA and 40 parts of CHCI to obtain a resin solution-a (resin concentration: 20 mass%). The weight average molecular weight of the obtained resin was 17000 (standard polystyrene equivalent value by gel permeation chromatography). Based on the amount of the charged material, the acid value of the obtained solid resin component was calculated to be X/Y a ＝80/70(mg-KOH/g)。
Production example 2-2: preparation of a solution containing resin (B) — 2 >
As the monomers, 14.3 parts of methyl methacrylate (manufactured by Tokyo chemical Co., ltd.) and 2.4 parts of methacrylic acid (manufactured by Tokyo chemical Co., ltd.) were used without using 1- [2- (methacryloyloxy) ethyl succinate]A resin solution-b (resin concentration: 20% by mass) was obtained in the same manner as in production example 2-1, except that the ester (Sigma Aldrich Japan contract Co., ltd.) was used. The weight average molecular weight of the obtained resin was 17000 (standard polystyrene equivalent value by gel permeation chromatography). Based on the amount of the charged material, the acid value of the solid resin component was calculated to be X/Y a ＝70/0(mg-KOH/g)。
Production examples 2 to 3: preparation of a solution containing resin (B) < 3 >
A resin solution-c (resin concentration: 20 mass%) was obtained in the same manner as in production example 2-1, except that 10.3 parts of methyl methacrylate (Tokyo chemical industry Co., ltd.) was used as the monomer and methacrylic acid (Tokyo chemical industry Co., ltd.) was not used. The weight average molecular weight of the obtained resin was 16000 (standard obtained by gel permeation chromatography)Quasi-polystyrene conversion). Based on the amount of the charged material, the acid value of the solid resin component was calculated to be X/Y a ＝0/70(mg-KOH/g)。
Production examples 2 to 4: preparation of a solution containing resin (B-4 >
According to Japanese patent JP2015-028139 publication [0191 ]]The resin solution was prepared, and PGMEA was added to obtain a resin solution-d having a resin concentration of 20% by mass. The acid value of the solid resin component was calculated to be X/Y based on the amount of the charged resin a ＝49/0(mg-KOH/g)。
< example 1 >
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 an antioxidant (G-1) at a concentration of 20% by mass were placed in a flask, and heated with stirring at 80 ℃ for 12 hours. After that, the mixture was cooled to room temperature to obtain a solution containing the QD and the resin.
Next, 3.75 parts of the polymerizable compound (C-1), 3.75 parts of the polymerizable compound (C-2), 0.20 part of the polymerization initiator (D-1), 0.75 part of the antioxidant (G-2), 0.25 part of a PGMEA solution containing the leveling agent (F-1) at a concentration of 10% by mass, and 8.50 parts of PGMEA were mixed. The obtained mixed solution was added to the solution containing the QD and the resin, and stirred and mixed to obtain a curable resin composition. The solid content concentration of the obtained curable resin composition was 25 mass%. The kinds of the blending components used in this example and the amounts thereof are shown in Table 2. In table 2, the unit of the amount used is part 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 to 4 and comparative examples 1 and 2 >
A curable resin composition was prepared in the same manner as in example 1, except that the kinds and the amounts of the QD dispersion, the resin solution, and other mixing components used were as shown in table 2. The solid content concentrations of the curable resin compositions obtained in examples 2 to 4 and comparative examples 1 to 2 were all 25 mass%. In the curable resin compositions obtained in examples 2 to 4 and comparative examples 1 and 2, it was confirmed by visual observation that the resin was uniformly dissolved and the QDs were uniformly dispersed.
< example 5 >
25 parts of QD dispersion liquid-A, 11.4 parts of resin solution-a, 34.1 parts of resin solution-b, and 1.50 parts of PGMEA solution containing 20 mass% antioxidant (G-1) were placed in a flask, heated at 80 ℃ with stirring for 12 hours, and then allowed to cool to room temperature, thereby obtaining a solution containing QD and resin.
Next, 3.05 parts of a polymerizable compound (C-1), 3.05 parts of a polymerizable compound (C-2), 0.15 part of a polymerization initiator (D-1), 0.60 part of an antioxidant (G-2), 0.25 part of a PGMEA solution containing a leveling agent (F-1) at a concentration of 10% by mass, 5.15 parts of a light scattering agent, and 16.0 parts of PGMEA were mixed. The obtained mixed solution was added to the QD-and-resin-containing solution, and stirred and mixed to obtain a curable resin composition. The solid content concentration of the obtained curable resin composition was 25 mass%. The kinds of the blending components used in the present example and the amounts thereof are shown in Table 2. Visual observation confirmed that the resin was uniformly dissolved and the QDs were uniformly dispersed in the obtained curable resin composition.
[ TABLE 2]
Figure BDA0001580089800000291
The details of the mixed components shown in table 2 are as follows.
[1] A polymerizable compound (C-1): propoxylated pentaerythritol triacrylate ("NK ESTER ATM-4PL" manufactured by Ninghamu chemical Co., ltd.)
[2] A polymerizable compound (C-2): pentaerythritol triacrylate (NK ESTER A-TMM-3LM-N, manufactured by Ningkomura chemical industries, ltd.),
[3] polymerization initiator (D-1): o-acyloxime polymerization initiator "NCI-930" manufactured by ADEKA, inc.),
[4] solvent (E-1): PGMEA, a,
[5] leveling agent (F-1): polyether-modified silicone oil leveling agent "Dongli silicone SH8400" manufactured by Dongli silicone corporation,
[6] antioxidant (G-1): a hindered phenol type antioxidant "124508759, manufactured by ADEKA corporation, 12473124791250260"
[ 7 ] antioxidant (G-2): a phenol phosphorus antioxidant manufactured by sumitomo chemical corporation "\12473125121\\1245270 (registered trademark) GP"
[ 8 ] light scattering agent: a titanium oxide particle dispersion "SF WHITEGC4134" (titanium oxide particle concentration: 73 mass%) manufactured by Shanyang dye Co., ltd.
[ evaluation test ]
(1) Pattern formability
0.45mL of the curable resin composition was dropped onto a glass substrate, spin-coated at 150rpm for 20 seconds, and then dried (pre-baked) at 100 ℃ for 3 minutes to form a curable resin composition layer. Next, a photomask having a line and space pattern with a line width of 50 μm was used at 40mJ/cm in an atmospheric gas atmosphere 2 Pattern exposure was performed with the exposure amount (365 nm standard). The distance between the substrate and the photomask was 120 μm. The pattern-exposed curable resin composition layer was immersed in an aqueous developer having a potassium hydroxide concentration of 0.04 mass% at 23 ℃ for 70 seconds, washed with water, and post-baked at 230 ℃ for 20 minutes in an oven to obtain a patterned cured film. The cured film has a film thickness of 5 to 6 μm.
1 point of a line (line having a mask width of 50 μm) of the patterned cured film was observed using a Laser Microscope (3D Measuring Laser Microscope olsz0, manufactured by olympus corporation), and the pattern formability was evaluated based on the following evaluation criteria. The results are shown in Table 2.
A: the line width is in the range of [ mask width (50 μm) -2 μm ] or more [ mask width (50 μm) +3 μm ] or less;
b: the line width is in the range of [ mask width (50 μm) -6 μm ] or more, less than [ mask width (50 μm) -2 μm ], or more than [ mask width (50 μm) +3 μm ], or less than [ mask width (50 μm) +10 μm ];
c: the line width is less than [ mask width (50 μm) -6 μm ], or greater than [ mask width (50 μm) +10 μm ];
d: there are places where development is insufficient, that is, places where adjacent lines are connected, or there is insufficient development adhesion and the lines are peeled off.
(2) Luminous intensity
A cured film was formed on the glass substrate in the same manner as in the evaluation test of the "pattern formability" described above, except that the photomask was not used. The cured film-coated glass substrate was placed on a blue backlight, and the light emission intensity was measured using a total luminous FLUX measuring device "CSTM-OP-RADIANT-FLUX" manufactured by ocean optics. The emission intensity of the cured film of example 5 was 9 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);
Figure FDA0003878099010000011
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.
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