JP6666843B2 - Curable composition - Google Patents

Description

  The present invention relates to a curable composition including a quantum dot and a display device.

  Patent Document 1 describes a curable composition comprising semiconductor ultrafine particles (quantum dots), a solvent, and a polymerizable monomer.

JP-A-10-186426

When a cured pattern is formed from the curable composition described in Patent Document 1 by a photolithographic method, there is a problem that the residual film ratio of the cured pattern after development is low. Here, the cured pattern means a cured film formed on a part of the substrate. Further, the residual film ratio refers to a value represented by the following equation (z).
Remaining film ratio (%) = Td / Te × 100 (z)
[In the formula (z), Td represents the thickness of the cured pattern, and Te represents the thickness of the composition layer after light irradiation. ]

The present invention includes the following inventions.
[1] A curable composition comprising a quantum dot, a polymerization initiator and a polymerizable compound, wherein the polymerization initiator is at least one selected from the group consisting of an oxime compound, an acylphosphine compound, a triazine compound and a biimidazole compound. A curable composition comprising:
[2] The curable composition according to [1], wherein at least one selected from the group consisting of an oxime compound, an acylphosphine compound, a triazine compound, and a biimidazole compound is a compound having at least two aromatic rings in a molecule.
[3] The curable composition according to [1] or [2], wherein the polymerization initiator contains an oxime compound.
[4] The quantum dot includes at least one selected from the group consisting of a compound of a group 12 element and a group 16 element, a compound of a group 13 element and a group 15 element, and a compound of a group 14 element and a group 16 element. The curable composition according to any one of [1] to [3].
[5] The curable composition according to any one of [1] to [4], further including a resin.
[6] A cured film formed from the curable composition according to any one of [1] to [5].
[7] A display device including the cured film according to [6].

  According to the curable composition of the present invention, a cured pattern can be obtained with a high residual film ratio during development, and the cured pattern has an excellent quantum yield when light is emitted.

  The curable composition of the present invention contains a quantum dot (A), a polymerizable compound (B), and a polymerization initiator (C).

<Quantum dot (A)>
Quantum dots are semiconductor fine particles having a particle diameter of about 1 nm to 100 nm, and emit light by absorbing ultraviolet light or visible light using a semiconductor band gap.
Each of the quantum dots has a chemical formula of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, CdHgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeC, HgSeSe, HgSeSe, HgSeCZnSe CdZgSe, CdHgSeTe, CdHgZeSe, HdZgSe, HdZgSe, CdHgSe, CdHgSe, CdHgSe, CdHgZeSe, HdZgSe, HdZgSe, HdZgSe, HdZgSe, HdZgSe, HdZgSe, HdZgSe, HdZgSe, HdZgSe, HdZnSe , AlN, AlP, AlAs, InN, InP, InAs, GaNP, GaNAs, GaPA , AlNP, AlNAs, AlPAs, InNP, InNAs, InPAs, GaAlNP, GaAlNAs, GaAlPAs, GaInNP, GaInNAs, GaInPAs, InAlNP, InAlNAs, InAlPAs and other Group 13 elements; compounds of Group 14 such as PdS and PbSe And a compound of an element and a Group 16 element.
When the quantum dot contains S (sulfur atom) or Se (selenium atom), a quantum dot surface-modified with a metal oxide or an organic substance may be used. By using the surface-modified quantum dots, it is possible to prevent S or Se from being extracted by a reaction component in the material forming the organic layer.
The quantum dots may form a core-shell structure by combining the above compounds. Examples of such a combination include fine particles whose core is CdSe (cadmium selenide) and whose shell is ZnS (zinc sulfide).

Since the energy state of a quantum dot depends on its size, the emission wavelength can be freely selected by changing the particle diameter. For example, in the case of a quantum dot composed of only CdSe, the peak wavelength of the fluorescence spectrum when the particle diameter is 2.3 nm, 3.0 nm, 3.8 nm, and 4.6 nm is 528 nm, 570 nm, 592 nm, and 637 nm, respectively. It is. In addition, the light emitted from the quantum dot has a narrow spectral width, and by combining light having such a steep peak, the color gamut that can be displayed by the display device is expanded. Furthermore, quantum dots have high responsiveness and can efficiently use light emitted from a light source.
The curable composition of the present invention may contain only quantum dots that emit light of a specific wavelength by light emitted from a light source, or contain a combination of two or more types of quantum dots that emit light of different wavelengths. May be. Examples of the light having the specific wavelength include red light, green light, and blue light.

  The content of the quantum dots (A) is preferably from 1 to 50% by mass, more preferably from 5 to 40% by mass, based on the solid content. The solid content as referred to in the present specification means the total of the curable composition components excluding the solvent (E) described below and other solvents. The solid content in the composition can be measured by a known analytical means such as liquid chromatography or gas chromatography.

<Polymerizable compound (B)>
The polymerizable compound (B) is a compound that can be polymerized by an active radical, an acid, or the like generated from a polymerization initiator (C) described later. Examples of such a compound include a compound having an ethylenically unsaturated bond, and a (meth) acrylate compound is preferable.
In addition, in this specification, "(meth) acrylic acid" represents at least one kind selected from the group consisting of acrylic acid and methacrylic acid. Notations such as “(meth) acryloyl” and “(meth) acrylate” have the same meaning.

Among them, the polymerizable compound (B) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. As such a polymerizable compound, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( (Meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, 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 Is mentioned.
The weight average molecular weight of the polymerizable compound (B) is preferably from 150 to 2,900, more preferably from 250 to 1,500.

  The content of the polymerizable compound (B) is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass, and still more preferably from 17 to 55% by mass, based on the solid content. When the content of the polymerizable compound (B) is within the above range, the residual film ratio of the cured pattern and the chemical resistance of the cured pattern tend to be further improved.

<Polymerization initiator (C)>
The polymerization initiator (C) is a compound that generates an active radical, an acid or the like by the action of light or heat and can initiate a polymerization reaction, and is a group consisting of an oxime compound, a biimidazole compound, a triazine compound, and an acylphosphine compound. At least one selected from the group consisting of: Especially, it is preferable to contain an oxime compound. When these polymerization initiators are used, the residual film ratio of the cured pattern increases.
Further, the oxime compound, biimidazole compound, triazine compound and acylphosphine compound are compounds having at least two aromatic rings in the molecule because the degree of polymerization at the time of producing a cured film tends to be higher. Preferably, there is.
Examples of the aromatic ring include a five-membered ring such as a furan ring, a pyrrole ring, an imidazole ring, a thiophene ring and a thiazole ring; a six-membered ring such as a benzene ring, a pyridine ring, a pyrimidine ring and a triazine ring; and a condensed ring thereof. Can be

The oxime compound is preferably an O-acyl oxime compound and a compound having a partial structure represented by the formula (d1). Hereinafter, * represents a bond.

Examples of the oxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-. On-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2- Methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-di) Oxacyclopentanylmethyloxy) 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-cyclopentylpropan-1-one-2-imine; described in JP-A-2011-132215, WO 2008/78678, WO 2008/78686, and WO 2012/132558. And the like. Commercial products such as Irgacure OXE01, OXE02 (all manufactured by BASF) and N-1919 (ADEKA) may be used.
Above all, oxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-. 2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine and N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) At least one member selected from the group consisting of) -9H-carbazol-3-yl] ethane-1-imine; N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine; // N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carba Lumpur-3-yl] ethan-1-imine is more preferable.

［式（ｄ５）中、Ｒ^５１〜Ｒ^５６は、置換基を有してもよい炭素数６〜１０のアリール基を表す。］The biimidazole compound is, for example, a compound represented by the formula (d5).

[In the formula (d5), R ^{51 to} R ⁵⁶ represent an aryl group having 6 to 10 carbon atoms which may have a substituent. ]

Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a toluyl group, a xylyl group, an ethylphenyl group, and a naphthyl group, and a phenyl group is preferable.
Examples of the substituent include a halogen atom and an alkoxy group having 1 to 4 carbon atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom is preferable. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and the like, and a methoxy group is preferable.

Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4, 4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,3-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2, 2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxy Phenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (dialkoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4, 4 ', 5,5'-tetra (trialkoxy) (Ciphenyl) biimidazole, and imidazole compounds in which the phenyl group at the 4,4'5,5'-position is substituted by a carboalkoxy group. These compounds are described in, for example, JP-A-06-75372, JP-A-06-75373, JP-B-48-38403, JP-A-62-174204, and JP-A-7-10913. Have been. Among them, a compound represented by the following formula or a mixture thereof is preferable.

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 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-methoxy (Styryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4 -Bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino- 2-methylpheni ) Ethenyl] -1,3,5-triazine, such as 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine. Among them, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine is preferred.

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

  The above-mentioned polymerization initiators may be used alone, or two or more polymerization initiators may be used in combination. When two or more polymerization initiators are used in combination, they may be combined with known polymerization initiators other than the above-mentioned oxime compounds, biimidazole compounds, triazine compounds, and acylphosphine compounds.

  As a combination of two or more polymerization initiators, the same kind of compounds having different structures may be combined, or different kinds of compounds may be combined. When compounds of the same type are combined, a combination of oxime compounds is preferred, and a combination of O-acyl oxime compounds having a partial structure represented by the formula (d1) is more preferred. Examples of such combinations include N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine and N-acetoxy-1- [9-ethyl-6- (2-methyl Benzoyl) -9H-carbazol-3-yl] ethane-1-imine. In this case, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine and N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole The compounding ratio of [-3-yl] ethane-1-imine is preferably from 10:90 to 90:10, more preferably from 30:70 to 70:30, and from 30:70 to 50:50. It is more preferred that there be.

  As a combination of different compounds, oxime compounds and biimidazole compounds, oxime compounds and triazine compounds, oxime compounds and acylphosphine compounds, biimidazole compounds and triazine compounds, biimidazole compounds and acylphosphine compounds, triazine compounds and acylphosphine compounds Combinations and the like can be mentioned.

  Known polymerization initiators include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 ′ Benzophenone compounds such as -methyldiphenyl sulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone and 4,4'-bis (diethylamino) benzophenone; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, Jae compounds and the like.

  The content of the polymerization initiator (C) is preferably from 0.1 to 300 parts by mass, more preferably from 0.1 to 200 parts by mass, based on 100 parts by mass of the polymerizable compound (B). When the curable composition contains the resin (D) described below, the content of the polymerization initiator (C) is preferably based on 100 parts by mass of the total amount of the resin (D) and the polymerizable compound (B) described later. Is 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass. When the content of the polymerization initiator (C) is within the above range, the sensitivity is increased and the exposure time tends to be shortened, so that the productivity of the cured film is improved.

<Polymerization initiation aid (C1)>
If necessary, a polymerization initiator (C1) may be used in combination. The polymerization initiation aid (C1) is a compound or a sensitizer used to promote the polymerization of the polymerizable compound whose polymerization has been initiated by the polymerization initiator. When it contains a polymerization initiator (C1), it is usually used in combination with a polymerization initiator. Examples of the polymerization initiator (C1) include an amine compound, an alkoxyanthracene compound, a thioxanthone compound, and a carboxylic acid compound.

  Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (Ethylmethylamino) benzophenone and the like can be mentioned, and among them, 4,4′-bis (diethylamino) benzophenone is preferable. A commercially available product such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) may be used.

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

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

  As the carboxylic acid compound, phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, Examples include N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

  When the polymerization initiator (C1) is included, the content of the polymerization initiator (C1) is preferably 0.1 to 300 parts by mass, more preferably 100 parts by mass of the polymerizable compound (B). Is 0.1 to 200 parts by mass. When the curable composition contains the resin (D) described below, the content of the polymerization initiator (C) is preferably 0 based on 100 parts by mass of the total amount of the resin (D) and the polymerizable compound (B). 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass. When the amount of the polymerization initiator (C1) is within this range, a cured film tends to be formed with higher sensitivity.

  The curable composition of the present invention preferably contains a resin (D), a solvent (E), and / or a leveling agent (F) in addition to the above components.

<Resin (D)>
The resin (D) is preferably an alkali-soluble resin. Examples of the resin (D) include the following resins [K1] to [K4].
Resin [K1]: Copolymerizable with at least one (a) (hereinafter sometimes referred to as “(a)”) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and (a) A resin obtained by copolymerizing a monomer (c) (however, different from (a); hereinafter sometimes referred to as “(c)”);
Resin [K2]: a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond in a copolymer of (a) and (c) (hereinafter referred to as “(b)”) In some cases) reacted resin,
Resin [K3]: a resin obtained by reacting (a) with a copolymer of (b) and (c),
Resin [K4]: A resin obtained by reacting (a) with a copolymer of (b) and (c) and further reacting with a carboxylic anhydride.

Examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m- and p-vinylbenzoic acid;
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 Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] Bicyclo unsaturated compounds containing a carboxy group such as hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- Unsaturated dicarboxylic acid anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride;
Unsaturated mono [(meth) acryloyloxyalkyl] esters of di- or higher-valent polycarboxylic acids such as mono [2- (meth) acryloyloxyethyl] succinate and mono [2- (meth) acryloyloxyethyl] phthalate Kind;
Examples include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.
Among these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferred from the viewpoint of copolymerization reactivity and the solubility of the obtained resin in an aqueous alkali solution.

  (B) is, for example, a monomer having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. is there. (B) is preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth) acryloyloxy group.

(B) includes glycidyl (meth) acrylate, β-methyl glycidyl (meth) acrylate, β-ethyl glycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinyl Benzyl 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 (glycidyl) Monomers having an oxirane ring such as oxymethyl) styrene and an ethylenically unsaturated bond; 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3- Methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacryloyloxyethyloxetane, 3 -Ethyl-3-acrylo Monomers having an oxetane ring such as ruoxyethyloxetane and an ethylenically unsaturated bond; tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofuryl such as tetrahydrofurfuryl methacrylate Examples include a monomer having a ring and an ethylenically unsaturated bond.
(B) has high reactivity during the production of the resins [K2] to [K4], and unreacted (b) hardly remains. Therefore, (b) includes an oxirane ring and an ethylenically unsaturated bond. Are preferred.

Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 2-ethylhexyl (meth). Acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate (common name in the art: dicyclopentanyl (meth) acrylate or tricyclodecyl (meth) acrylate), tricyclo [5.2.1.0 ^{2, 6} ] decene-8-yl (meth) a Acrylate (common name in the art: dicyclopentenyl (meth) acrylate), dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) ) (Meth) acrylates such as acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, and benzyl (meth) acrylate;
Hydroxy 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] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2 .1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2′-hydroxyethyl) bicyclo [2.2. 1] Hept-2-ene, 5,6-dimethoxybicyclo [2.2 1] Hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5 -Hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [ 2.2.1] Hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5 , 6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene and 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene Bicyclo unsaturated compounds;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 Dicarbonylimide derivatives such as -maleimidopropionate, N- (9-acridinyl) maleimide;
Styrene, α-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, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferred from the viewpoint of copolymerization reactivity and heat resistance. preferable.

In the resin [K1], the ratio of the structural units derived from each monomer is such that the structural units derived from (a) are 2 to 70 mol% based on all structural units constituting the resin [K1]. And the structural unit derived from (c) is preferably 30 to 98 mol%. It is more preferable that the structural unit derived from (a) is 10 to 70 mol% and the structural unit derived from (c) is 30 to 90 mol%.
When the ratio of the structural unit of the resin [K1] is in the above range, the storage stability of the curable composition, the developability when forming a cured pattern, and the solvent resistance of the obtained cured pattern tend to be excellent. is there.

  The resin [K1] can be obtained, for example, by the method described in the document "Experimental Method for Polymer Synthesis" (published by Takayuki Otsu, published by Kagaku Dojin, 1st Edition, 1st edition, March 1, 1972) and the literature. And can be produced with reference to the references described in the above.

  Specifically, a predetermined amount of each of (a) and (c), a polymerization initiator and a solvent are put in a reaction vessel, and the atmosphere is deoxygenated by replacing oxygen with nitrogen. There is a method of keeping the temperature. The polymerization initiator and the solvent used here are not particularly limited, and those usually used in the art can be used. For example, as a polymerization initiator, an azo compound (eg, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile)) or an organic peroxide (eg, benzoyl peroxide) is used. Is mentioned. Any solvent may be used as long as it dissolves each monomer, and examples of the solvent (E) that may be contained in the curable composition of the present invention include the solvents described below.

  The obtained copolymer may be used as it is after the reaction, may be used as a concentrated or diluted solution, or may be taken out as a solid (powder) by a method such as reprecipitation. A thing may be used. In particular, by using the solvent (E) described below as a solvent for the polymerization, the solution after the reaction can be used as it is for the preparation of the curable composition of the present invention. The production process of the composition can be simplified.

The resin [K2] obtains a copolymer of (a) and (c), and converts the cyclic ether having 2 to 4 carbon atoms of (b) into a carboxylic acid and / or carboxylic anhydride derived from (a). It can be manufactured by adding it to a product.
First, a 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 the structural units derived from each is the same as that of the resin [K1].

Next, the carboxylic acid and / or carboxylic anhydride derived from (a) in the copolymer is subjected to an addition reaction with a cyclic ether having 2 to 4 carbon atoms of (b).
Subsequent to the production of the copolymer of (a) and (c), the atmosphere in the flask was replaced with air from nitrogen, and (b) a reaction catalyst for the reaction between the carboxylic acid or carboxylic anhydride and the cyclic ether (for example, Production of resin [K2] by placing tris (dimethylaminomethyl) phenol and the like and a polymerization inhibitor (for example, hydroquinone) in a flask and reacting at 60 to 130 ° C. for 1 to 10 hours, for example. Can be.

  (B) is preferably used in an amount of 5 to 80 mol, more preferably 10 to 75 mol, per 100 mol of (a). By setting the content within this range, the storage stability of the curable composition, the developability when forming a cured pattern, and the balance of solvent resistance, heat resistance, mechanical strength and sensitivity of the obtained cured pattern are improved. Tend.

  The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total of (a), (b) and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total of (a), (b) and (c).

  The reaction conditions such as the charging method, the reaction temperature and the time can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by polymerization, and the like. As in the case of the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.

  As the resin [K3], as a first step, a copolymer of (b) and (c) is obtained in the same manner as in the method for producing the resin [K1] described above. Similarly to the above, the obtained copolymer may be used as it is after the reaction, as a concentrated or diluted solution, or as a solid (powder) by a method such as reprecipitation. You may use what was taken out as.

  The ratio of the structural units derived from (b) and (c) is such that the structural unit derived from (b) is 5 to 95 moles with respect to the total number of moles of all the structural units constituting the copolymer. %, And the structural unit derived from (c) is preferably 5 to 95 mol%. More preferably, the structural unit derived from (b) is 10 to 90 mol%, and the structural unit derived from (c) is 10 to 90 mol%.

Further, the carboxylic acid or carboxylic anhydride of (a) is added to the cyclic ether derived from (b) of the copolymer of (b) and (c) under the same conditions as in the method for producing the resin [K2]. The resin [K3] can be obtained by subjecting the product to an addition reaction.
The amount of (a) used to react with the copolymer is preferably 5 to 80 mol per 100 mol of (b).

The resin [K4] is a resin obtained by further reacting a carboxylic anhydride with the resin [K3].
A carboxylic anhydride is added to a hydroxy group generated by the reaction between the cyclic ether and the carboxylic acid or carboxylic anhydride.
Examples of the carboxylic anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1 , 2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride and the like. The amount of the carboxylic anhydride to be used is preferably 0.5 to 1 mol per 1 mol of the (a) used.

Specific examples of the resin (D) include resins [K1] such as benzyl (meth) acrylate / (meth) acrylic acid copolymer and styrene / (meth) acrylic acid copolymer; benzyl (meth) acrylate / ( A resin obtained by adding glycidyl (meth) acrylate to a (meth) acrylic acid copolymer; a resin obtained by adding glycidyl (meth) acrylate to a tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer; Resin [K2] such as a resin obtained by adding glycidyl (meth) acrylate to a cyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer; tricyclodecyl (meth) acrylate / glycidyl (meth) A resin obtained by reacting (meth) acrylic acid with an acrylate copolymer, tricyclodecyl ( (T) a resin [K3] such as a resin obtained by reacting (meth) acrylic acid with a copolymer of acrylate / styrene / glycidyl (meth) acrylate; a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate And resin [K4] such as a resin obtained by further reacting a resin obtained by reacting (meth) acrylic acid with tetrahydrophthalic anhydride.
Among them, the resin (D) preferably contains at least one selected from the group consisting of a resin [K2], a resin [K3] and a resin [K4].

The weight average molecular weight in terms of polystyrene of the resin (D) is preferably from 3,000 to 100,000, more preferably from 5,000 to 50,000, and still more preferably from 5,000 to 30,000. . When the molecular weight is within the above range, the hardness of the cured film is improved, the residual ratio of the cured pattern is high, the solubility of the unexposed portion in the composition layer in the developing solution is good, and the resolution of the cured pattern is improved. Tend to.
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (D) is preferably from 1.1 to 6, and more preferably from 1.2 to 4.

  The acid value of the resin (D) is preferably from 50 to 170 mg-KOH / g, more preferably from 60 to 150 mg-KOH / g, and still more preferably from 70 to 135 mg-KOH / g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (D), and can be determined, for example, by titration using an aqueous solution of potassium hydroxide.

  The content of the resin (D) is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass, and still more preferably from 17 to 55% by mass, based on the total amount of the solid components. When the content of the resin (D) is within the above range, the resolution of the cured pattern and the residual film ratio of the cured pattern tend to be further improved.

<Solvent (E)>
The solvent (E) is not particularly limited as long as it dissolves the polymerizable compound (B), the polymerization initiator (C) and the resin (D), and a solvent generally used in the art can be used. For example, an ester solvent (a solvent containing -COO- in the molecule but not containing -O-), an ether solvent (a solvent containing -O- in the molecule but not containing -COO-), and an ether ester solvent (a solvent containing -COO- in the molecule) , A solvent containing -COO- and -O-), a ketone solvent (a solvent containing -CO- in the molecule and not containing -COO-), an alcohol solvent (containing OH in the molecule, -O-,- Solvents that do not contain CO— and —COO—), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

  Examples of the ester solvent include methyl lactate, ethyl lactate, n-butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, and isopropyl butyrate. , Ethyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate and γ-butyrolactone.

  Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and 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, diethyl Glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, and the like phenetol and methyl anisole.

  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, and 3-ethoxy. Ethyl propionate, 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 monoethyl ether acetate and diethylene glycol monobutyl ether acetate.

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

  Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

  Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene and mesitylene.

  Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone.

  As a solvent, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone Or toluene is preferred.

  The content of the solvent (E) is preferably from 70 to 95% by mass, more preferably from 75 to 92% by mass, based on the total amount of the curable composition. In other words, the solid content of the curable composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass. When the content of the solvent (E) is within the above range, the flatness of the composition layer at the time of application tends to be better, and a cured film having an appropriate thickness tends to be easily formed.

<Leveling agent (F)>
Examples of the leveling agent (F) include a silicone-based surfactant, a fluorine-based surfactant, and a silicone-based surfactant having a fluorine atom. These may have a polymerizable group in the side chain.
Examples of the silicone-based surfactant include a surfactant having a siloxane bond in a molecule. Specifically, Toray silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade name: manufactured by Dow Corning Toray Co., Ltd.), KP321, KP322, KP323, KP324 , KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan GK). .

  Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain in a molecule. Specifically, Florado (registered trademark) FC430 and FC431 (manufactured by Sumitomo 3M Limited), Megafac (registered trademark) F142D, F171, F172, F173, F177, F183, F554, and F554 R30, RS-718-K (manufactured by DIC Corporation), EFTOP (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals, Inc.), Surflon (registered trademark) S381, S382, SC101 and SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.).

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

  The content of the leveling agent (F) is preferably from 0.001% by mass to 0.2% by mass, and more preferably from 0.002% by mass to 0.1% by mass, based on the total amount of the curable composition. The content is more preferably 0.01% by mass or more and 0.05% by mass or less. When the content of the leveling agent (F) is within the above range, the flatness of the cured film can be further improved.

  Incidentally, the curable composition of the present invention, if necessary, fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, and other additives known in the art. May be further included.

<Curing film>
The cured film of the present invention can be obtained by applying the curable composition of the present invention to a substrate and curing the composition by the action of light or heat. The cured film of the present invention may be formed on the entire surface of the substrate, or may be formed on a part of the substrate (that is, a cured pattern). Examples of a method for forming a cured film on a part of the substrate include a photolithographic method, an inkjet method, and a printing method. Among them, the photolithographic method is preferred. The photolithographic method is a method in which a curable composition of the present invention is applied to a substrate, dried as necessary to form a composition layer, and the composition layer is exposed through a photomask, and developed. is there.
As a method of forming a cured film on the entire surface of the substrate, a curable composition of the present invention is applied to a substrate, and dried if necessary to form a composition layer, and the composition layer is heated and / or heated. A method of exposing the entire surface of the material layer.

  As the substrate, quartz glass, borosilicate glass, alumina silicate glass, a glass plate such as soda lime glass having a silica-coated surface, a resin plate of polycarbonate, polymethyl methacrylate, polyethylene terephthalate, etc., siliconcon, on the substrate On which aluminum, silver, a silver / copper / palladium alloy thin film or the like is formed.

The formation of the cured pattern by the photolithographic method can be performed by a known or commonly used device or condition. For example, it can be manufactured as follows.
First, the curable composition is applied on a substrate, and dried by heating (prebaking) and / or drying under reduced pressure to remove volatile components such as a solvent, thereby obtaining a composition layer. Examples of the coating method include a spin coating method, a slit coating method, a slit and spin coating method, and the like.
The temperature in the case of performing heat drying is preferably 30 to 120 ° C, more preferably 50 to 110 ° C. The heating time is preferably from 10 seconds to 60 minutes, more preferably from 30 seconds to 30 minutes.
When performing drying under reduced pressure, it is preferable to perform drying under a pressure of 50 to 150 Pa in a temperature range of 20 to 25 ° C.
The thickness of the composition layer is not particularly limited, and may be appropriately selected according to the thickness of the target cured pattern.

Next, the composition layer is exposed through a photomask for forming a target cured pattern. The pattern on the photomask is not particularly limited.
As a light source used for exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferable. For example, light having a wavelength of about 436 nm, about 408 nm, or about 365 nm may be selectively extracted from the light having the wavelength according to the absorption wavelength of the polymerization initiator using a bandpass filter. Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp and the like can be mentioned.
An exposure apparatus such as a mask aligner and a stepper is used in order to uniformly irradiate the entire exposure surface with parallel rays or to perform accurate alignment between the photomask and the substrate on which the composition layer is formed. Is preferred. The exposed composition layer is cured by polymerizing a polymerizable compound or the like contained in the composition layer.

By developing the exposed composition layer by contacting it with a developing solution, the unexposed portions of the composition layer are dissolved and removed in the developing solution to obtain a cured pattern. Examples of the developer include an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, and tetramethylammonium hydroxide, and an organic solvent. The concentration of the alkaline compound in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Examples of the organic solvent include those similar to the solvent (E) described above. Further, the developer may contain a surfactant.
The developing method may be any of a paddle method, a dipping method and a spray method. Further, the substrate may be inclined at an arbitrary angle during development.

  It is preferable to further heat (post-bake) the cured pattern obtained by development. The heating temperature is preferably from 150 to 250 ° C, more preferably from 160 to 235 ° C. The heating time is preferably from 1 to 120 minutes, more preferably from 10 to 60 minutes. By heating after development, polymerization of unreacted polymerizable compounds and the like contained in the cured pattern can be advanced, so that a cured pattern having more excellent chemical resistance can be obtained.

By irradiating the cured film with ultraviolet light or visible light, the cured film of the present invention emits light having a wavelength different from the irradiation light. In the curable composition used for forming the cured film of the present invention, the wavelength of emitted light can be selected by selecting the components and particle diameter of the quantum dots contained in the curable composition.
Since the cured film of the present invention has a function of converting the wavelength of irradiation light as described above, it can be used as a color conversion layer of a display device. As such a display device, for example, JP-A-2006-309219, JP-A-2006-310303, JP-A-2013-15812, JP-A-2009-251129, JP-A-2014-2363 and the like And a display device described in (1).

  The curable composition of the present invention can obtain a cured pattern with a high residual film ratio during development, and further, since the cured pattern has an excellent quantum yield when light is emitted, a display device, in particular, a liquid crystal display device It is useful as a color conversion layer.

Hereinafter, the present invention will be described in more detail with reference to examples.
"%" And "parts" in the examples are% by mass and parts by mass unless otherwise specified.

Synthesis Example 1
100 parts of propylene glycol monomethyl ether acetate was placed in a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, and the mixture was stirred while being purged with nitrogen, and heated to 120 ° C. Next, a monomer mixture consisting of 40 parts of benzyl methacrylate and 20 parts of methacrylic acid was added with 1 part of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) to 100 parts of the monomer mixture, and a dropping funnel was added. After that, the mixture was dropped into the flask over 2 hours, and further stirred at 120 ° C. for 2 hours to obtain a copolymer solution. Next, the inside of the flask was replaced with air, and 10 parts of glycidyl methacrylate, 0.44 part of triphenylphosphine and 0.08 part of methylhydroquinone were added to the above copolymer solution, and the reaction was further continued at 120 ° C. to obtain a solid acid. The reaction was terminated when the value reached 130 KOHmg / g. 80 parts of propylene glycol monomethyl ether acetate was added thereto to obtain a resin D1 solution having a solid content of 30%. The weight average molecular weight of the resin D1 was 3.0 × 10 ⁴ .

The weight average molecular weight (Mw) of the resin was measured by the GPC method under the following conditions.
Apparatus: K2479 (manufactured by Shimadzu Corporation)
Column: SHIMADZU Shim-pack GPC-80M
Column temperature; 40 ° C
Solvent; tetrahydrofuran Flow rate: 1.0 mL / min
Detector; RI
Standard material for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

<Preparation of curable composition>
The following were used for preparation of the curable composition.
(A) Quantum dot CZ520: Quantum dot manufactured by NN-LABS, 10% toluene dispersion, core-shell type (core: CdSe, shell: ZnS).
CZ620: quantum dots manufactured by NN-LABS, 10% toluene dispersion, core-shell type (core: CdSe, shell: ZnS).
(B) Polymerizable compound KAYARAD (registered trademark) DPHA: dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd.
(C) Polymerization initiator Irgacure (registered trademark) OXE 01: an oxime compound manufactured by BASF, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine.
B-CIM: a biimidazole compound manufactured by Hodogaya Chemical Co., Ltd., 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole.
Irgacure (registered trademark) OXE 02: an oxime compound manufactured by BASF, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine.
Irgacure (registered trademark) 819: an acylphosphine compound manufactured by BASF, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.
Triazine PP: a triazine compound manufactured by Panchim, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine.
(C1) Polymerization initiation assistant EAB-F: 4,4'-bis (diethylamino) benzophenone manufactured by Hodogaya Chemical Industry Co., Ltd.
(F) Leveling agent Toray Silicone SH8400: a product of Dow Corning Toray Co., Ltd., a polyether-modified silicone oil.

[Example 1]
(A) 240 parts of quantum dot "CZ520" and "TO-1382" (monoesterified product of dipentaerythritol pentaacrylate and succinic acid, dipentaerythritol hexaacrylate and dipentaerythritol penta made by Toagosei Co., Ltd.) (A mixture of acrylates) was mixed, and the quantum dots were sufficiently dispersed by a bead mill to prepare a quantum dot dispersion liquid. Next, (B) 40 parts of the polymerizable compound “KAYARAD DPHA”, (C) 8 parts of the polymerization initiator “Irgacure OXE 01”, (D) 60 parts of the resin D1 as a resin (in terms of solid content), (E) As a solvent, 654 parts of propylene glycol monomethyl ether acetate and 0.1 part of (F) a leveling agent “Toray Silicone SH8400” were mixed to obtain a curable composition.

[Example 2]
(A) 240 parts of quantum dot “CZ520” and 24 parts of “TO-1382” manufactured by Toagosei Co., Ltd. were mixed, and the quantum dots were sufficiently dispersed by a bead mill to prepare a quantum dot dispersion liquid. Then, (B) 40 parts of the polymerizable compound “KAYARAD DPHA”, (C) 7 parts of the polymerization initiator “B-CIM”, (C1) 1 part of the polymerization initiation auxiliary agent “EAB-F”, (D) A curable composition obtained by mixing 60 parts of resin D1 as resin (in terms of solid content), 654 parts of propylene glycol monomethyl ether acetate as solvent (E) and 0.1 part of (F) leveling agent “Toray Silicone SH8400”. I got something.

[Example 3]
(A) 240 parts of quantum dot “CZ520” and 24 parts of “TO-1382” manufactured by Toagosei Co., Ltd. were mixed, and the quantum dots were sufficiently dispersed by a bead mill to prepare a quantum dot dispersion liquid. Next, (B) 40 parts of the polymerizable compound “KAYARAD DPHA”, (C) 8 parts of the polymerization initiator “Irgacure 819”, (D) 60 parts of the resin D1 as the resin (in terms of solid content), (E) A curable composition was obtained by mixing 654 parts of propylene glycol monomethyl ether acetate as a solvent and 0.1 part of (F) a leveling agent “Toray Silicone SH8400”.

[Example 4]
(A) 240 parts of quantum dot “CZ520” and 24 parts of “TO-1382” manufactured by Toagosei Co., Ltd. were mixed, and the quantum dots were sufficiently dispersed by a bead mill to prepare a quantum dot dispersion liquid. Then, (B) 40 parts of the polymerizable compound “KAYARAD DPHA”, (C) 8 parts of the polymerization initiator “Triazine PP”, (D) 60 parts of resin D1 as resin (in terms of solid content), and (E) solvent As a result, 654 parts of propylene glycol monomethyl ether acetate and 0.1 part of (F) a leveling agent “Toray Silicone SH8400” were mixed to obtain a curable composition.

[Example 5]
(A) 270.7 parts of quantum dot "CZ620" and 24 parts of "TO-1382" manufactured by Toagosei Co., Ltd. were mixed, and the quantum dots were sufficiently dispersed by a bead mill to prepare a quantum dot dispersion liquid. . Next, (B) 40 parts of the polymerizable compound “KAYARAD DPHA”, (C) 8 parts of the polymerization initiator “Irgacure OXE 01”, (D) 60 parts of the resin D1 as a resin (in terms of solid content), (E) A curable composition was obtained by mixing 393 parts of propylene glycol monomethyl ether acetate as a solvent and 0.2 parts of (F) a leveling agent “Toray Silicone SH8400”.

[Example 6]
(C) A curable composition was obtained in the same manner as in Example 5, except that the blending amount of the polymerization initiator "Irgacure OXE 01" was changed to 10 parts.

[Example 7]
(C) A curable composition was obtained in the same manner as in Example 5, except that the blending amount of the polymerization initiator "Irgacure OXE 01" was changed to 12 parts.

Example 8
(C) A curable composition was obtained in the same manner as in Example 5, except that "Irgacure OXE 02" was used as the polymerization initiator.

[Example 9]
(C) A curable composition was obtained in the same manner as in Example 8, except that the amount of the polymerization initiator “Irgacure OXE 02” was changed to 10 parts.

[Example 10]
(C) A curable composition was obtained in the same manner as in Example 8, except that the blending amount of the polymerization initiator "Irgacure OXE 02" was changed to 12 parts.

[Example 11]
(C) A curable composition was obtained in the same manner as in Example 5, except that 12 parts of "Irgacure 819" was mixed as a polymerization initiator.

[Example 12]
(C) A curable composition was obtained in the same manner as in Example 5, except that 12 parts of "triazine PP" was mixed as a polymerization initiator.

[Example 13]
(C) A curable composition was obtained in the same manner as in Example 5, except that 3.6 parts of "Irgacure OXE 01" and 8.4 parts of "Irgacure OXE 02" were used as the polymerization initiator.

[Example 14]
(C) Curing was carried out in the same manner as in Example 13 except that the amount of the polymerization initiator “Irgacure OXE 01” was changed to 6.0 parts and the amount of the polymerization initiator “Irgacure OXE 02” was changed to 6.0 parts. The composition was obtained.

[Example 15]
(C) Curing was carried out in the same manner as in Example 13 except that the amount of the polymerization initiator “Irgacure OXE 01” was changed to 8.4 parts and the amount of the polymerization initiator “Irgacure OXE 02” was changed to 3.6 parts. The composition was obtained.

[Example 16]
(C) A curable composition was obtained in the same manner as in Example 13, except that 6.0 parts of "Irgacure OXE 01" and 6.0 parts of "Irgacure 819" were used as the polymerization initiator.

[Example 17]
(C) A curable composition was obtained in the same manner as in Example 13, except that 6.0 parts of "Irgacure OXE 01" and 6.0 parts of "Triazine PP" were used as the polymerization initiator.

[Example 18]
(C) A curable composition was obtained in the same manner as in Example 13, except that 6.0 parts of "Irgacure OXE 02" and 6.0 parts of "Irgacure 819" were used as the polymerization initiator.

[Example 19]
(C) A curable composition was obtained in the same manner as in Example 13, except that 6.0 parts of "Irgacure OXE 02" and 6.0 parts of "Triazine PP" were used as the polymerization initiator.

[Comparative Example 1]
(A) 220 parts of quantum dots “CZ520” and 22 parts of “DISPERBYK-180 (main component: alkylol ammonium salt of a copolymer containing an acid group)” manufactured by BYK Japan KK To sufficiently disperse the quantum dots to prepare a quantum dot dispersion. Then, (B) 100 parts of the polymerizable compound "KAYARAD DPHA", (E) 677 parts of propylene glycol monomethyl ether acetate as a solvent, and (F) 0.1 part of a leveling agent "Toray Silicone SH8400" are mixed. A curable composition was obtained.

<Preparation of cured film>
The curable composition was applied on a 5 cm square glass substrate (Eagle 2000, manufactured by Corning) by spin coating, and then prebaked at 100 ° C. for 1 minute to obtain a composition layer. After cooling, the entire surface of the composition layer was irradiated with light using an exposure machine (TME-150RSK; manufactured by Topcon Corporation) at an exposure amount of 150 mJ / cm ² (based on 365 nm) in an air atmosphere. After light irradiation, it is immersed in an aqueous developer (an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide) at 23 ° C for 60 seconds, washed with water, and then placed in an oven at 200 ° C for 10 minutes. Post-baking was performed to obtain a cured film.

<Film thickness measurement>
The thickness of the obtained cured film was measured by a film thickness measuring device (DEKTAK3, manufactured by Nippon Vacuum Engineering Co., Ltd.).

<Measurement of quantum yield ratio>
Toluene was added to the quantum dot dispersion used in the preparation of the curable composition so that the absorbance at a wavelength of 450 nm became 0.4 to prepare a diluted dispersion. With respect to the diluted dispersion and the cured film obtained above, the quantum yield at an excitation wavelength of 450 nm was measured using a fluorescence quantum yield measuring device (C9920-02G, manufactured by Hamamatsu Photonics KK).
The quantum yield ratio was calculated from the measured quantum yield by the following equation (y).
Quantum yield ratio = Qf / Qs × 100 (y)
[In the formula (y), Qf represents the quantum yield of the cured film, and Qs represents the quantum yield of the diluted quantum dot dispersion. ]

<Emission color observation>
The obtained cured film was irradiated with a UV lamp having a wavelength of 350 nm in a dark room, and the emission color of the cured film was visually observed.

<Evaluation of residual film ratio>
The curable composition was applied on a 5 cm square glass substrate (Eagle 2000, manufactured by Corning) by spin coating, and then prebaked at 100 ° C. for 1 minute to obtain a composition layer. After cooling, the distance between the substrate on which the composition layer was formed and the quartz glass photomask was set to 100 μm, and an exposure machine (TME-150RSK, manufactured by Topcon Corporation) was used to pass through the photomask under an air atmosphere. The composition layer was irradiated with light at an exposure amount of 80 mJ / cm ² (based on 365 nm). A photomask on which a 100 μm line and space pattern was formed was used. The film thickness of the composition layer after light irradiation was measured by a film thickness measuring device (DEKTAK3, manufactured by Japan Vacuum Engineering Co., Ltd.).
Next, the substrate on which the composition layer after light irradiation is formed is immersed in an aqueous developer (an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide) at 23 ° C. for 60 seconds. The resultant was developed and washed with water to obtain a cured pattern. The film thickness of the obtained cured pattern was measured by a film thickness measuring device (DEKTAK3, manufactured by Nippon Vacuum Engineering Co., Ltd.).
The residual film ratio of the cured pattern was determined by equation (z). If the residual film ratio is 90% or more, it can be determined that the sensitivity of the curable composition is good.
Remaining film ratio (%) = Td / Te × 100 (z)
[In the formula (z), Td represents the thickness of the cured pattern, and Te represents the thickness of the composition layer after light irradiation. ]

  In the curable composition of the comparative example, the composition layer after light irradiation was completely dissolved in the developer, and a cured pattern was not obtained on the substrate, so that the quantum yield ratio and the emission color could not be observed. .

  According to the curable composition of the present invention, a cured pattern can be obtained with a high residual film ratio during development, and the cured pattern has an excellent quantum yield when light is emitted.

Claims (7)

A quantum dot, a curable composition comprising a polymerization initiator and a polymerizable compound, wherein the polymerization initiator comprises at least one selected from the group consisting of an oxime compound, an acylphosphine compound, a triazine compound and a biimidazole compound,
Further, a curable composition comprising a leveling agent and an alkali-soluble resin, wherein the alkali-soluble resin comprises at least one selected from the group consisting of the following resins [K2] to [K4].
Resin [K2]: In the copolymer of (a) and (c), the carboxylic acid and / or carboxylic anhydride derived from (a) is added to cyclic ether having 2 to 4 carbon atoms of (b). With addition reaction.
However, (a) is at least one member selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and (c) is different from (a) and is a copolymerizable monomer with (a). (B) is a monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond.
Resin [K3]: Addition reaction of carboxylic acid and / or carboxylic anhydride contained in (a) to cyclic ether derived from (b) contained in a copolymer of (b) and (c). Resin.
Resin [K4]: Addition reaction of carboxylic acid and / or carboxylic anhydride contained in (a) to cyclic ether derived from (b) contained in a copolymer of (b) and (c). And a resin obtained by addition reaction with a carboxylic anhydride.   The curable composition according to claim 1, wherein at least one selected from the group consisting of an oxime compound, an acylphosphine compound, a triazine compound, and a biimidazole compound is a compound having at least two aromatic rings in a molecule.   The curable composition according to claim 1, wherein the polymerization initiator contains an oxime compound.   The quantum dot includes at least one selected from the group consisting of a compound of a Group 12 element and a Group 16 element, a compound of a Group 13 element and a Group 15 element, and a compound of a Group 14 element and a Group 16 element. 3. The curable composition according to any one of 3.   The curable composition according to any one of claims 1 to 4, wherein the content of the quantum dots is 1% by mass or more and 50% by mass or less based on the solid content.   A cured film formed from the curable composition according to claim 1.   A display device comprising the cured film according to claim 6.