TWI656405B - Curable composition - Google Patents

Abstract

In the photolithography method, when a cured pattern is formed from a conventional curable composition, there is a problem that the residual film rate of the cured pattern after development is relatively low. The residual film rate is a value represented by the following formula (z).

Residual film ratio (%) = Td / Te × 100 (z) [In formula (z), Td is the film thickness of the hardened pattern, and Te is the film thickness of the composition layer after light irradiation]

The present invention relates to a curable composition containing a quantum dot, a polymerization initiator, and a polymerizable compound, wherein the polymerization initiator contains a member selected from the group consisting of an oxime compound, a fluorenyl phosphine compound, and A compound and at least one of the group formed by a biimidazole compound.

Description

Hardening composition

The present invention relates to a curable composition and a display device containing quantum dots.

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

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 10-186426

When the hardening composition described in Patent Document 1 forms a hardened pattern by a photolithography method, there is a problem that the residual film rate of the hardened pattern after development is low. Here, the hardened pattern refers to a person who forms a hardened film on a part of the substrate. The residual film rate is a value represented by the following formula (z).

Residual film rate (%) = Td / Te × 100 (z) [In formula (z), Td is the film thickness of the hardened pattern, and Te is the film thickness of the composition layer after light irradiation]

The present invention includes the following inventions.

[1] A curable composition containing a quantum dot, a polymerization initiator, and a polymerizable compound, wherein the polymerization initiator contains a member selected from the group consisting of an oxime compound, a fluorenyl phosphine compound, and A compound and at least one of the group formed by a biimidazole compound.

[2] The curable composition according to item [1], which is selected from the group consisting of an oxime compound, a fluorenylphosphine compound, and At least one of the group formed by the compound and the biimidazole compound is a compound having at least two aromatic rings in the molecule.

[3] The curable composition according to [1] or [2], wherein the polymerization initiator contains an oxime compound.

[4] The hardenable composition according to any one of [1] to [3], wherein the quantum dot contains a compound selected from a group 12 element and a group 16 element, a group 13 element and a group 15 element compound And at least one of the group formed by compounds of Group 14 elements and Group 16 elements.

[5] The curable composition according to any one of [1] to [4], which further contains a resin.

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

[7] A display device comprising 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 rate during development, and the quantum yield when the cured pattern emits light is excellent.

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

<Quantum dot (A)>

Quantum dots are semiconductor particles with a particle size of about 1 nm to 100 nm, and are particles that emit light by absorbing ultraviolet or visible light with a semiconductor band gap.

In terms of quantum dots, the chemical formulas include: CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, CdHgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe , CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeTe, HgZnSeP, HgZnSeP, HgZnSeP, HgZnSeP, HgZnSeP12, HgZnSeP, HgZnSeP, HgZnSeP, HgZnSeP, HgZnSeP, HgZnSeP, HgZnSeP, HgZnSeP, HgZnSeP, HgZnSeP, HgZnSeP, HgZnSeE, HgZnSeE, HgZnSeP, HgZnSeP, HgZnSe, HgZnSe, CdHgSe, CdHgSe, CdHgSe, CdHgSe, CdHgSe, CdHgSe, CdHgSe, CdHgSe, CdHgSe, CdHgSe, CdHgSe, HgZnSeP , GaAs, AlN, AlP, AlAs, InN, InP, InAs, GaNP, GaAs, GaPAs, AlNP, AlNAs, AlPAs, InNP, InNAs, InPAs, GaAlNP, GaAlNAs, GaAlPAs, GaInNP, GaInNAs, GaInPAs, InAlNP, InAlNAs, and InAlPAs Compounds such as Group 13 elements and Group 15 elements; Compounds such as PdS and PbSe Group 14 elements and Group 16 elements.

When the quantum dot contains S (sulfur atom) or Se (selenium atom), a quantum dot modified with a surface of a metal oxide or an organic substance may be used. Surface repaired by using The decorated quantum dots can prevent S or Se from being extracted due to the reactive components in the material forming the organic layer.

The quantum dots may be combined with the above-mentioned compounds to form a core-shell structure. Examples of such a combination include fine particles having a core of CdSe (cadmium selenide) and a shell of ZnS (zinc sulfide).

The energy state of a quantum dot depends on its size, so the emission wavelength can be freely selected by changing the particle size. For example, when the quantum dots are composed of only CdSe, the peak wavelengths of the fluorescence spectra when the particle diameters are 2.3 nm, 3.0 nm, 3.8 nm, and 4.6 nm are 528 nm, 570 nm, 592 nm, and 637 nm, respectively. In addition, the light emitted from the quantum dots has a narrow spectral width. By combining light having such a steep wave peak, the color gamut that can be displayed by the display device is enlarged. In addition, the quantum dots are highly responsive and can effectively utilize 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 may include two or more quantum dots that emit light of different wavelengths in combination. Examples of the light of the specific wavelength include red light, green light, and blue light.

The content ratio of the quantum dot (A) to the solid content is preferably 1 to 50% by mass, and more preferably 5 to 40% by mass. The solid content referred to in this specification refers to the total of the components of the hardenable composition excluding the solvent (E) and other solvents described later. The content of the solids in the composition can be measured by a known analysis method such as liquid chromatography or gas chromatography.

<Polymerizable Compound (B)>

The polymerizable compound (B) is a compound that can be polymerized by living radicals, acids, and the like generated by 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 preferred.

In this specification, "(meth) acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. Marks such as "(meth) acrylfluorenyl" and "(meth) acrylate" also have the same meaning.

Among them, the polymerizable compound (B) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such a polymerizable compound include trimethylolpropane tri (meth) acrylate, neopentaerythritol tri (meth) acrylate, neopentaerythritol tetra (meth) acrylate, and dineopentyl. Tetraol penta (meth) acrylate, dinepentaerythritol hexa (meth) acrylate, trinepentaerythritol octa (meth) acrylate, trinepentaerythritol hepta (meth) acrylate, tetra Neopentaerythritol deca (meth) acrylate, tetranepentaerythritol nona (meth) acrylate, ginseng (2- (meth) propenyloxyethyl) isotricyanate, ethylene diethylene glycol Alcohol modification neopentaerythritol tetra (meth) acrylate, ethylene glycol modification dipentaerythritol hexa (meth) acrylate, propylene glycol modification neopentaerythritol tetra (meth) acrylate, propylene glycol modification Dipentaerythritol hexa (meth) acrylate, caprolactone modified neopentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, and the like.

The weight-average molecular weight of the polymerizable compound (B) is preferably 150 to 2,900, and more preferably 250 to 1,500.

The content ratio of the polymerizable compound (B) to the solid content is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and 17 to 55 mass% is even better. When the content rate of the polymerizable compound (B) is within the aforementioned range, the residual film rate 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 can start a polymerization reaction by generating an active radical, an acid, or the like by the action of light or heat, and contains a compound selected from the group consisting of an oxime compound, a biimidazole compound, and At least one of the group formed by a compound and a fluorenylphosphine compound. Among them, an oxime compound is preferred. When such a polymerization initiator is used, the residual film rate of a hardened pattern becomes high.

In addition, the above-mentioned oxime compound, biimidazole compound, The compound and the fluorenylphosphine compound tend to have a higher degree of polymerization during the production of a cured film, and are therefore preferably compounds having at least two aromatic rings in the molecule.

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 benzene ring, a pyridine ring, a pyrimidine ring, and a tricyclic ring; Rings such as 6-membered rings, and these condensed rings.

The oxime compound is preferably an O-fluorenyl oxime compound, and is a compound having a partial structure represented by formula (d1). In the following, * indicates a bond.

Examples of the oxime compound include N-benzylideneoxy-1- (4-phenylthiophenyl) butane-1-one-2-imine and N-benzylideneoxy- 1- (4-phenylthiophenyl) octane-1-one-2-imine, N-benzyloxy -1- (4-phenylthiophenyl) -3-cyclopentylpropane-1-one-2-imine, N-ethoxyl-1- [9-ethyl-6- (2- Methylbenzyl) -9H-carbazol-3-yl] ethane-1-imine, N-ethoxy-1--1- [9-ethyl-6- {2-methyl-4- (3,3-Dimethyl-2,4-dioxolylmethyloxy) benzylidene} -9H-carbazol-3-yl] ethane-1-imine, N-ethyl Phenoxy-1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzene Formamyloxy-1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-one-2- Imines; compounds described in Japanese Patent Laid-Open No. 2011-132215, International Publication No. 2008/78678, International Publication No. 2008/78686, International Publication No. 2012/132558, and the like. Commercial products such as Irgacure OXE01, OXE02 (above, manufactured by BASF), and N-1919 (made by ADEKA) can also be used.

Among them, the oxime compound is selected from the group consisting of N-benzyloxy-1- (4-phenylthiophenyl) butane-1-one-2-imine, and N-benzyloxy- 1- (4-phenylthiophenyl) octane-1-one-2-imine, N-benzyloxy-1- (4-phenylthiophenyl) -3-cyclopentyl Propane-1-one-2-imine and N-ethoxyl-1- [9-ethyl-6- (2-methylbenzyl) -9H-carbazol-3-yl] ethyl At least one of the groups formed by alkane-1-imines is preferred, and N-benzyloxy-1- (4-phenylthiophenyl) octan-1-one-2- Imine and / or N-ethoxyl-1- [9-ethyl-6- (2-methylbenzyl) -9H-carbazol-3-yl] ethane-1-imine more good.

The biimidazole compound is, for example, a compound represented by 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 phenyl, tolyl, xylyl, ethylphenyl, and naphthyl, and phenyl is preferred.

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 preferred. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and a methoxy group is preferred.

Examples of the biimidazole compound include, for example, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2-chlorobenzene). ) -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'-tetrakis (alkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetrakis (bis (Alkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (trialkoxyphenyl) biimidazole, 4,4', An imidazole compound in which a phenyl group at the 5,5'-position is substituted with an alkoxycarbonyl group and the like. These compounds are described in, for example, Japanese Patent Laid-Open No. 06-75372, Japanese Patent Laid-Open No. 06-75373, Japanese Patent Laid-Open No. 48-38403, Japanese Patent Laid-Open No. 62-174204, and Japanese Patent Laid-Open No. 7- No. 10913 and the like. Among them, a compound represented by the following formula or a mixture thereof is preferred.

Aforementioned three Compounds include, for example, 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-tris , 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-tri , 2,4-bis (trichloromethyl) -6-piperyl-1,3,5-tri , 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) vinyl] -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) vinyl] -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) vinyl] -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) vinyl] -1,3,5-tris Wait. Among them, 2,4-bis (trichloromethyl) -6-piperyl-1,3,5-tris Better.

Examples of the fluorenylphosphine compound include bis (2,4,6-trimethylbenzylfluorenyl) -phenylphosphine oxide and (2,4,6-trimethylbenzylfluorenyl) diphenyl Phosphine oxide, etc.

These polymerization initiators may be used singly or in combination of two or more polymerization initiators. When two or more polymerization initiators are used in combination, it can be used with the above-mentioned oxime compound, biimidazole compound, A combination of a known polymerization initiator other than the compound and the phosphonium phosphine compound.

The combination of two or more polymerization initiators may be a combination of the same compounds having different structures, or a combination of different compounds. When the same kind of compound is combined, it is a group of oxime compounds. The combination is more preferable, and the combination of the O-fluorenyl oxime compound and the compound having a partial structure represented by formula (d1) is more preferable. Examples of such a combination include N-benzyloxy-1- (4-phenylthiophenyl) octan-1-one-2-imine and N-ethoxyl-1 -A combination of [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl] ethane-1-imine. At this time, N-benzyloxy-1- (4-phenylthiophenyl) octane-1-one-2-imine and N-acetoxy-1- [9-ethyl The compounding ratio of -6- (2-methylbenzyl) -9H-carbazol-3-yl] ethane-1-imine is preferably 10:90 to 90:10, and 30: 70 to 70:30 is more preferable, and 30:70 to 50:50 is more preferable.

Combinations of different compounds include oxime compounds and biimidazole compounds, oxime compounds and Compounds, oxime compounds and fluorenylphosphine compounds, biimidazole compounds and Compounds, biimidazole compounds and fluorenylphosphine compounds, three A combination of a compound and a phosphonium phosphine compound, and the like.

Examples of known polymerization initiators include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, ortho-benzyl benzoic acid methyl ester Ester, 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetrakis (third butylperoxycarbonyl) di Benzophenone compounds such as benzophenone, 2,4,6-trimethylbenzophenone and 4,4'-bis (diethylamino) benzophenone; 9,10-phenanthrenequinone, 2 -Quinone compounds such as ethyl anthraquinone and fluorenone; 10-butyl-2-chloroacridone, benzil, methyl phenylglyoxylate, titanocene compounds, and the like.

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

<Polymerization starter (C1)>

If necessary, a polymerization initiator (C1) may be used together. The polymerization initiation aid (C1) is a compound or a sensitizer for promoting the polymerization of a polymerizable compound that is polymerized by a polymerization initiator. When a polymerization initiator (C1) is contained, it is usually used in combination with a polymerization initiator. Examples of the polymerization initiation aid (C1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- Isoamyl dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethyl-p-toluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 4,4 Of these, '-bis (ethylmethylamino) benzophenone is preferred, and 4,4'-bis (diethylamino) benzophenone is preferred. Commercial products such as EAB-F (Hodogaya Chemical Industry Co., Ltd.) can also be used.

As the aforementioned alkoxyanthracene compound, 9,10-di Methoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 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 , 1-chloro-4-propoxythioxanthone, etc.

Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, and dimethylphenylthio Acetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthalene Thioglycolic acid, N-naphthylglycine, naphthyloxyacetic acid, and the like.

When the polymerization initiation aid (C1) is contained, the content of the polymerization initiation aid (C1) is preferably from 0.1 to 300 parts by mass, and from 0.1 to 200 parts by mass based on 100 parts by mass of the polymerizable compound (B). Better. When the curable composition contains a resin (D) described later, the content of the polymerization initiator (C1) is 0.1 to 30 parts by mass based on 100 parts by mass of the total amount of the resin (D) and the polymerizable compound (B). It is preferably, and more preferably 1 to 20 parts by mass. When the content of the polymerization initiator (C1) is within this range, there is a tendency that a cured film can 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 aforementioned components.

<Resin (D)>

The resin (D) is preferably an alkali-soluble resin. In the case of resin (D), List: For example, the following resins [K1] to [K4].

Resin [K1]: at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (a) (hereinafter also referred to as "(a)"), copolymerizable with (a) Resin and resin [K2] obtained by copolymerizing monomer (c) (but different from (a). Hereinafter also referred to as "(c)"): The copolymer of (a) and (c) is used Resin and resin [K3] formed by reacting a cyclic ether structure having 2 to 4 carbon atoms with an ethylenically unsaturated monomer (b) (hereinafter also referred to as "(b)"): in (b) and (c) Resin and resin [K4] formed by reacting (a) in the copolymer (represented by reacting (a) in the copolymer of (b) and (c), and then reacting carboxylic anhydride Resin.

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-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2, Unsaturated dicarboxylic acids such as 3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexenedicarboxylic 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] hept-2-ene, 5- Carboxyl-6-ethylbicyclo [2.2.1] hept-2-ene and other bicyclic unsaturated compounds containing carboxyl groups; Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, Unsaturated dicarboxylic acid such as 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride Acid anhydrides; poly [2- (meth) acrylfluorenyloxyethyl] succinate, mono [2- (meth) acrylfluorenyloxyethyl] phthalate, and more Unsaturated mono [(meth) acryloxyalkyl] esters of carboxylic acids; such as unsaturated acrylic esters of α- (hydroxymethyl) acrylic acid containing hydroxyl and carboxyl groups in the same molecule.

Among these, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferable from the viewpoint of copolymerization reactivity or the viewpoint of the solubility of the obtained resin to an alkali aqueous solution.

As for (b), for example, a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an ethylene oxide ring, an oxetane ring, and a tetrahydrofuran ring) and ethylene Monounsaturated monomers. (b) A monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth) acrylfluorenyloxy group is preferred.

Examples of (b) include glycidyl (meth) acrylate, beta-methylglycidyl (meth) acrylate, beta-ethylglycidyl (meth) acrylate, and epoxy Propyl vinyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-ethylene Phenylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (cyclo (Oxypropoxymethyl) styrene, 2,4-bis (glycidoxymethyl) styrene Ene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-ginsyl (glycidoxymethyl) Based) styrene, 2,3,5-gins (glycidoxymethyl) styrene, 2,3,6-gins (glycidyloxymethyl) styrene, 3,4,5-g (Glycidoxymethyl) styrene, 2,4,6-ginsyl (glycidoxymethyl) styrene and other monomers having an ethylene oxide ring and ethylenically unsaturated bonds; 3-methyl 3-methylpropenyloxymethyloxetane, 3-methyl-3-propenyloxymethyloxetane, 3-ethyl-3-methacrylidine Methyloxymethyloxetane, 3-ethyl-3-propenyloxymethyloxetane, 3-methyl-3-methacryloxyethyloxane Butane, 3-methyl-3-propenyloxyethyloxetane, 3-ethyl-3-methylpropenyloxyethyloxetane, 3-ethyl- 3-propenyloxyethyloxetane and other monomers having an oxetane ring and an ethylenically unsaturated bond; tetrahydrofuran methyl acrylate (for example, VISCOAT V # 150, Osaka Organic Chemical Industry Co., Ltd. )), Tetrahydrofuran methyl methacrylate Tetrahydrofuran ring and having an ethylene bond of the unsaturated monomer.

From (b) (b), which has high reactivity during the production of resins [K2] to [K4], and is less likely to remain unreacted, (b) is based on the presence of an ethylene oxide ring and an ethylenically unsaturated bond. Monomers are preferred.

Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, second butyl (meth) acrylate, and (meth) Tertiary butyl acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, (meth) acrylic acid Cyclopentyl, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl ester (the Common names in the technical field: dicyclopentane (meth) acrylate or tricyclodecyl (meth) acrylate), tricyclo [meth) acrylate [5.2.1.0 ^2,6 ] decene-8-yl ester (Common names in this technical field: dicyclopentenyl (meth) acrylate), dicyclopentyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantane (meth) acrylate Alkyl esters, allyl (meth) acrylates, propargyl (meth) acrylates, phenyl (meth) acrylates, naphthyl (meth) acrylates, (meth) benzyl (meth) acrylates, etc. Acrylates; 2-hydroxyethyl (meth) acrylate, 2-hydroxy (meth) acrylate (Meth) acrylic esters containing hydroxyl groups such as propyl esters; dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconic acid; bicyclic [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-bis (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-dimethoxy Bicyclo [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 Ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxy Carbonylcarbonyl bicyclo [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 (third butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1 ] Hept-2-ene and other bicyclic unsaturated compounds; N-phenyl-cis-butene-diimide, N-cyclohexyl-cis-butene-diimide, N-benzyl-cis-butene-diimide, N-succinimide-3-cis-butenediimide benzoate, N-succinimide-4-cis-butenediimide butyrate, N-succinimide -6-cis-butene-diimidehexanoate, N-succinimide-imino-3-maleimide-imide-propionate, N- (9-acridyl) cis-butene-diimide Derivatives such as amines such as amines; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, 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.

From the viewpoint of copolymerization reactivity and heat resistance, among them, styrene, vinyltoluene, N-phenylcis-butenedifluoreneimine, N-cyclohexylcisbutenedifluoreneimine, N-benzyl cis butene diamidine, bicyclo [2.2.1] hept-2-ene and the like are preferred.

In the resin [K1], based on the total structural units constituting the resin [K1], the ratio of the structural unit derived from each monomer is based on the structural unit derived from (a) being 2 to 70 mol% and derived from (c). The structural unit is preferably 30 to 98 mol%. Meanwhile, 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 within the above range, the storage stability of the curable composition, the developability when a cured pattern is formed, and the solvent resistance of the obtained cured pattern tend to be excellent.

Resin [K1], for example, refer to the article "Polymer Synthetic "Experimental method" (by Otsu Takayuki Publishing House Chemical Co., Ltd., 1st edition, first brush, issued March 1, 1972) and the references described in this document.

Specific examples include: putting a predetermined amount of (a) and (c), a polymerization initiator, and a solvent into a reaction container, for example, by replacing oxygen with nitrogen to deoxidize the surrounding ambient gas, and heating while stirring and Method of insulation. The polymerization initiator and solvent used here are not particularly limited, and can be used by ordinary users in this field. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) Or organic peroxides (benzylidene peroxide, etc.). The solvent may be any one that dissolves each monomer, and examples of the solvent (E) that can be included in the curable composition of the present invention include solvents described below.

The obtained copolymer may be used directly after the reaction, a concentrated or diluted solution, or a method such as re-precipitation to take out the solid (powder). In particular, since the solvent during the polymerization can be used directly in the preparation of the curable composition of the present invention by using the solvent (E) described later, the curable composition of the present invention can be simplified. Of manufacturing steps.

Resin [K2] can be obtained by copolymerizing (a) and (c), and adding a cyclic ether having 2 to 4 carbon atoms in (b) to a carboxylic acid and / or from (a) Carboxylic anhydride.

First, the copolymers (a) and (c) are produced in the same manner as described in the method for producing the resin [K1]. At this time, the ratio from the individual structural units, The ratio is preferably the same as that listed in the resin [K1].

Next, the carboxylic acid and / or carboxylic anhydride derived from (a) in the aforementioned copolymer is subjected to an addition reaction of a cyclic ether having 2 to 4 carbon atoms in (b).

Next, after the production of the copolymers (a) and (c), the ambient gas in the flask is replaced with nitrogen to air, and the reaction between (b), the carboxylic acid or carboxylic anhydride and the cyclic ether is reacted. Catalysts (such as ginsyl (dimethylaminomethyl) phenol) and polymerization inhibitors (such as hydroquinone) are placed in flasks and reacted at, for example, 60 to 130 ° C for 1 to 10 hours to produce resins [K2 ].

Relative to (a) 100 mol, the amount of (b) used is preferably 5 to 80 mol, and more preferably 10 to 75 mol. By setting it within this range, the storage stability of the hardenable composition, the developability of the hardened pattern, and the balance of the solvent resistance, heat resistance, mechanical strength, and sensitivity of the obtained hardened pattern become good. tendency.

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

The reaction conditions such as the production method, reaction temperature, and time can be appropriately adjusted in consideration of the amount of heat generated by the production equipment or polymerization. In addition, similar to the polymerization conditions, the production method or the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.

Resin [K3], the first stage is the same as the method for producing the above-mentioned resin [K1], and copolymers (b) and (c) are obtained. Same as above, obtained The copolymer can be directly used as a solution after the reaction, a concentrated or diluted solution, or a method such as reprecipitation to take out a solid (powder).

The ratio of the structural units derived from (b) and (c) to the total molar number of all the structural units constituting the aforementioned copolymer is such that the structural units derived from (b) are 5 to 95 mole%, and The structural unit derived from (c) is preferably 5 to 95 mole%. Meanwhile, it is more preferable that the structural unit derived from (b) is 10 to 90 mol%, and the structural unit derived from (c) is more preferably 10 to 90 mol%.

In addition, the carboxylic acid of (a) can be obtained from the cyclic ether derived from (b) in the copolymers of (b) and (c) under the same conditions as the method for producing the resin [K2]. Or a carboxylic anhydride addition reaction to obtain a resin [K3].

The amount of (a) to be reacted in the copolymer described above is preferably 5 to 80 moles relative to (b) 100 moles.

The resin [K4] is a resin in which the carboxylic anhydride is reacted in the resin [K3]. Among the hydroxyl groups generated by the reaction of a cyclic ether with a carboxylic acid or a carboxylic acid anhydride, a carboxylic acid addition reaction is performed.

Examples of the carboxylic acid anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6 -Tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] heptane- 2-ene anhydride and the like. The amount of carboxylic anhydride used is preferably 0.5 to 1 mole relative to the amount of 1 mole used in (a).

Specific examples of the resin (D) include (meth) propylene Resins such as benzyl acid / (meth) acrylic acid copolymers, styrene / (meth) acrylic acid copolymers [K1]; in benzyl (meth) acrylic acid / (meth) acrylic acid copolymers Resin to which glycidyl (meth) acrylate is added, and tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer to which glycidyl (meth) acrylate is added Resins, resins with tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymers, and resins with propylene oxide (meth) acrylate added [K2 ]; A resin obtained by reacting (meth) acrylic acid in a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate, and tricyclodecyl (meth) acrylate / Resin and other resins made by reacting (meth) acrylic acid in copolymers of styrene / glycidyl (meth) acrylate [K3]; Tricyclodecyl (meth) acrylate / (meth) acrylic acid Among the resins obtained by reacting (meth) acrylic acid in the copolymer of propylene oxide ester, resins such as resin obtained by reacting tetrahydrophthalic anhydride [K4] and the like.

Among them, the resin (D) preferably contains at least one selected from the group consisting of the resin [K2], the resin [K3], and the resin [K4].

The weight average molecular weight of the resin (D) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 5,000 to 30,000. When the molecular weight is within the aforementioned range, the hardness of the cured film is increased, the residual film rate of the cured pattern is increased, and the solubility of the unexposed portion in the composition layer to the developing solution is good. Therefore, the resolution of the cured pattern is improved. tendency.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (D) is preferably 1.1 to 6, and more preferably 1.2 to 4.

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

The content of the resin (D) with respect to the total solid content is preferably 7 to 65% by mass, more preferably 13 to 65% by mass, and even more preferably 17 to 55% by mass. When the content of the resin (D) is within the aforementioned range, the resolution of the cured pattern and the residual film rate of the cured pattern tend to be further increased.

<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 this field can be used. Examples include: ester solvents (solvents containing -COO- and -O-free), ether solvents (solvents containing -O- and -COO-free), and ether ester solvents (containing- COO- and -O- solvents), ketone solvents (solvents containing -CO-, no -COO- in the molecule), alcohol solvents (containing OH in the molecule, -O-, -CO- and -COO- Solvents), aromatic hydrocarbon solvents, amidine solvents, dimethyl sulfene and the like.

Examples of the ester solvent include methyl lactate, ethyl lactate, n-butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, Isoamyl acetate, n-butyl propionate, isopropyl butyrate, ethyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, ethyl acetate, ethyl acetate醯 Ethyl acetate, cyclohexane Alcohol 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, and 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-methylbutane Alcohol, tetrahydrofuran, tetrahydropyran, 1,4-di Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenyl ether and Methyl anisole and so on.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and 3-methoxy Methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxy Ethyl propionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropanoic acid ethyl ester, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether ethyl Acid esters, 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 Wait.

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

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

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

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

In terms of solvents, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone or toluene is preferred.

The content of the solvent (E) with respect to the total amount of the curable composition is preferably 70 to 95% by mass, and more preferably 75 to 92% by mass. In other words, the solid content of the curable composition is preferably 5 to 30% by mass, and 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 coating tends to be better, and at the same time, a cured film having an appropriate film thickness tends to be easily formed.

<Leveling agent (F)>

Examples of the leveling agent (F) include a polysiloxane-based surfactant, a fluorine-based surfactant, and a polysiloxane-based surfactant having a fluorine atom. These may have a polymerizable group in a side chain.

Examples of the polysiloxane-based surfactant include a surfactant having a siloxane bond in the molecule. Specifically, Toray Silicone DC3PA, SH7PA of the same name, DC11PA of the same name, SH21PA of the same name, SH28PA of the same name, SH29PA of the same name, SH30PA of the same name, SH8400 of the same name (product Name: Toray Dow Corning (stock system); KP321, KP322, KP323, KP324, KP326, KP340, KP341 (Shinyue Chemical Industry (stock) system); TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan LLC).

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain in the molecule. Specific examples include Fluorad (registered trademark) FC430, same name FC431 (made by Sumitomo 3M (stock)); Megafac (registered trademark) F142D, same name F171, same name F172, same name F173, same name F177, same name F183, same name F554, same name R30, the same name RS-718-K (in DIC), Eftop (registered trademark) EF301, EF303, EF351, EF352 (Mitsubishi Materials Electronics Corporation), Surflon (registered trademark) S381, the same name S382, the same name SC101, the same name SC105 (made by Asahi Glass) and E5844 (made by Daikin Fine Chemical Research Institute).

Examples of the polysiloxane-based 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, the same name as BL20, the same name as F475, the same name as F477, and the same name as F443 (made by DIC).

The content of the leveling agent (F) with respect to the total amount of the hardenable composition is 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 0.01% by mass or more and 0.05% by mass or less The following is better. When the content of the leveling agent (F) is within the aforementioned range, the flatness of the cured film can be made better.

The curable composition of the present invention may further contain additives known in the technical field, such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, and chain transfer agents, as necessary. .

<Hardened 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 it 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 (ie, a cured pattern). Examples of a method for forming a cured film on a part of the substrate include a photolithography method, an inkjet method, and a printing method. Among them, photolithography is preferred. The photolithography method is a method in which the curable composition of the present invention is coated on a substrate, and if necessary, dried to form a composition layer, and the composition layer is exposed through a photomask to develop.

A method of forming a cured film on the entire surface of the substrate includes coating the substrate with the curable composition of the present invention, drying it as necessary to form a composition layer, heating the composition layer, and / or applying the composition to the composition. Layer full exposure method.

Examples of the substrate include glass plates such as quartz glass, borosilicate glass, alumina silicate glass, and soda lime glass coated with silicon dioxide, or polycarbonate, polymethyl methacrylate, and poly Resin plates, such as ethylene terephthalate, are made of polysiloxane, aluminum, silver, silver / copper / palladium alloy films, and the like formed on the substrate.

Forming a hardened pattern by photolithography, known or commonly used Device or conditions. For example, it can be produced as follows.

First, a curable composition is coated on a substrate, and volatile components such as a solvent are removed by heating (pre-baking) and / or drying under reduced pressure to obtain 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 for heating and drying is preferably 30 to 120 ° C, and more preferably 50 to 110 ° C. The heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.

When drying under reduced pressure, it is preferable to carry out under a pressure of 50 to 150 Pa and a temperature range of 20 to 25 ° C.

The film thickness of the composition layer is not particularly limited as long as it is appropriately selected in accordance with the film thickness of the target curing pattern.

Next, the composition layer is exposed through a mask for forming a target hardened pattern. The pattern on the photomask is not particularly limited.

The light source used in the exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, the light of this wavelength can be combined with the absorption wavelength of the polymerization initiator to selectively extract light near 436 nm, 408 nm, or 365 nm by a band-pass filter. Specific examples include a mercury lamp, a light-emitting diode, a metal halide lamp, and a halogen lamp.

In order to illuminate parallel light uniformly on the entire exposure surface, or to accurately position the mask and the substrate on which the composition layer has been formed, an exposure device such as a mask aligner and a stepper is used. Better. The exposed composition layer is hardened by polymerizing a polymerizable compound or the like contained in the composition layer.

The exposed composition layer is brought into contact with the developing solution for development, and the unexposed portion of the composition layer is dissolved in the developing solution and removed to obtain a hardened pattern. Examples of the developing solution include an aqueous solution or an organic solvent of a basic compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide. The concentration of the basic compound in the aqueous solution is preferably 0.01 to 10% by mass, and more preferably 0.03 to 5% by mass. Examples of the organic solvent include the same as those of the above-mentioned solvent (E). The developing solution may contain a surfactant.

The development method may be any of a puddle method, a dipping method, and a spray method. In addition, the substrate can be tilted at any angle during development.

It is preferable to further heat (post-bake) the hardened pattern obtained from the development. The heating temperature is preferably 150 to 250 ° C, and more preferably 160 to 235 ° C. The heating time is preferably 1 to 120 minutes, and more preferably 10 to 60 minutes. By heating after development, the unreacted polymerizable compound and the like contained in the hardened pattern can be polymerized, so that a hardened pattern having better 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 different wavelength from the irradiated light. In the curable composition used when forming the cured film of the present invention, the wavelength of light emitted can be selected by selecting the component or particle size of the quantum dots contained in the curable composition.

Since the cured film of the present invention has the function of converting the wavelength of the irradiated light as described above, it can be used as a color conversion layer of a display device. Examples of such a display device include, for example, Japanese Patent Application Laid-Open No. 2006-309219 The display devices described in Japanese Patent Application Publication No. 2006-310303, Japanese Patent Application Publication No. 2013-15812, Japanese Patent Application Publication No. 2009-251129, and Japanese Patent Application Publication No. 2014-2363 are disclosed.

The curable composition of the present invention can obtain a cured pattern with a high residual film rate during development and has excellent quantum yield when the cured pattern emits light. Therefore, it is useful as a color conversion layer for a display device, especially for a liquid crystal display device. Color conversion layer.

[Example]

Hereinafter, the present invention will be described in more detail with reference to examples.

"%" And "part" in the examples are mass% and mass parts, unless otherwise specified.

Synthesis Example 1

In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and an air pipe, 100 parts of propylene glycol monomethyl ether acetate was added, and the temperature was raised to 120 ° C. while stirring instead of nitrogen. Next, in a monomer mixture formed of 40 parts of benzyl methacrylate and 20 parts of methacrylic acid, 1 part of a polymerization initiator 2,2'-couple was added to 100 parts of the monomer mixture. Azobis (2,4-dimethylvaleronitrile), and 1 part of the polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) has been added, it takes 2 hours from The dropping funnel was dropped into a flask and stirred at 120 ° C for 2 hours to obtain a copolymer solution. Next, the inside of the flask was replaced with air, 10 parts of propylene methacrylate, 0.44 parts of triphenylphosphine, and 0.08 parts of methylhydroquinone were put into the copolymer solution, and the reaction was continued at 120 ° C. When the solid content acid value becomes 130 KOHmg / g, the reaction is terminated. To this, 80 parts of propylene glycol monomethyl ether acetate was added, thereby obtaining 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.

Installation; K2479 (made by Shimadzu Corporation)

Column; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 ℃

Solvent; tetrahydrofuran

Flow rate; 1.0mL / min

Detector; R1

Calibration reference materials; TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (made by TOSOH)

<Preparation of hardening composition>

In the preparation of the curable composition, each of the following was used.

(A) Quantum dot

CZ520: Quantum dots made by NN-LABS, 10% toluene dispersion, core-shell type (core: CdSe, shell: ZnS).

CZ620: Quantum dots made by NN-LABS, 10% toluene dispersion, core-shell type (core: CdSe, shell: ZnS).

(B) Polymerizable compound

KAYARAD (registered trademark) DPHA: Nippon Kayaku Co., Ltd., Erxin Pentaerythritol hexaacrylate.

(C) Polymerization initiator

Irgacure (registered trademark) OXE 01: an oxime compound manufactured by BASF, N-benzyloxy-1- (4-phenylthiophenyl) 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'-diamine Imidazole.

Irgacure (registered trademark) OXE 02: an oxime compound manufactured by BASF, N-ethoxyl-1- [9-ethyl-6- (2-methylbenzyl) -9H-carbazole-3- Group] ethane-1-imine.

Irgacure (registered trademark) 819: a fluorenylphosphine compound manufactured by BASF, bis (2,4,6-trimethylbenzylfluorenyl) -phenylphosphine oxide.

Triazine PP: Panchim (Part 3) Compound, 2,4-bis (trichloromethyl) -6-piperyl-1,3,5-tris .

(C1) Polymerization initiation aid

EAB-F: 4,4'-bis (diethylamino) benzophenone manufactured by Hodogaya Chemical Industry Co., Ltd.

(F) Leveling agent

Toray Silicone SH8400: a product of Toray Dow Corning Co., Ltd., a polyether modified silicone oil.

[Example 1]

240 parts of (A) quantum dot "CZ520" and 24 parts of "TO-1382" (a mono-esterified product of dipentaerythritol pentaacrylate and succinic acid, and dipentaerythritol) Hexaacrylate and dipivalate tetrapentaacrylate A mixture) is mixed, and the quantum dots are sufficiently dispersed by a bead mill to prepare a quantum dot dispersion. Next, 40 parts of (B) the polymerizable compound "KAYARAD DPHA", 8 parts of (C) the polymerization initiator "Irgacure OXE 01", 60 parts of (D) resin resin D1 (equivalent solid content), 654 Parts of (E) solvent of propylene glycol monomethyl ether acetate and 0.1 part of (F) leveling agent "Toray Silicone SH8400" were mixed to obtain a hardenable composition.

[Example 2]

240 parts of (A) quantum dots "CZ520" and 24 parts of "TO-1382" manufactured by Toa Kosei Co., Ltd. were mixed, and the quantum dots were sufficiently dispersed by a bead mill to prepare a quantum dot dispersion. Next, 40 parts (B) of the polymerizable compound "KAYARAD DPHA", 7 parts (C) of the polymerization initiator "B-CIM", 1 part (C1) of the polymerization initiator "EAB-F", 60 parts of the resin D1 (equivalent solid content) of the (D) resin, 654 parts of the propylene glycol monomethyl ether acetate of the (E) solvent, and 0.1 part of the (F) leveling agent "Toray Silicone SH8400" were mixed and hardened. Sexual composition.

[Example 3]

240 parts of (A) quantum dots "CZ520" and 24 parts of "TO-1382" manufactured by Toa Kosei Co., Ltd. were mixed, and the quantum dots were sufficiently dispersed by a bead mill to prepare a quantum dot dispersion. Next, 40 parts of (B) the polymerizable compound "KAYARAD DPHA", 8 parts of (C) the polymerization initiator "Irgacure 819", 60 parts of the resin D1 of the resin (D) (converted solid content), and 654 parts (E) solvent of propylene glycol monomethyl ether acetate and 0.1 part of (F) leveling agent "Toray Silicone SH8400 "was mixed to obtain a hardening composition.

[Example 4]

240 parts of (A) quantum dots "CZ520" and 24 parts of "TO-1382" manufactured by Toa Kosei Co., Ltd. were mixed, and the quantum dots were sufficiently dispersed by a bead mill to prepare a quantum dot dispersion. Next, 40 parts of (B) the polymerizable compound "KAYARAD DPHA", 8 parts of (C) the polymerization initiator "Triazine PP", 60 parts of the resin D1 of the resin (D) (equivalent solid content), and 654 parts (E) solvent of propylene glycol monomethyl ether acetate and 0.1 part of (F) leveling agent "Toray Silicone SH8400" were mixed to obtain a hardenable composition.

[Example 5]

270.7 parts of (A) quantum dot "CZ620" and 24 parts of "TO-1382" manufactured by Toa Kosei Co., Ltd. were mixed, and the quantum dots were sufficiently dispersed by a bead mill to prepare a quantum dot dispersion. Next, 40 parts of (B) the polymerizable compound "KAYARAD DPHA", 8 parts of (C) the polymerization initiator "Irgacure OXE 01", 60 parts of the resin (D) resin D1 (converted solid content), 393 Parts of (E) solvent of propylene glycol monomethyl ether acetate and 0.2 parts of (F) leveling agent "Toray Silicone SH8400" were mixed to obtain a hardenable composition.

[Example 6]

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

[Example 7]

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

[Example 8]

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

[Example 9]

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

[Example 10]

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

[Example 11]

A hardening composition was obtained in the same manner as in Example 5 except that 12 parts of "Irgacure 819" was mixed as the (C) polymerization initiator.

[Example 12]

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

[Example 13]

A hardening 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 (C) polymerization initiator.

[Example 14]

A hardening composition was obtained in the same manner as in Example 13 except that the blending amount of the (C) polymerization initiator "Irgacure OXE 01" was changed to 6.0 parts and the blending amount of "Irgacure OXE 02" was changed to 6.0 parts.

[Example 15]

A hardening composition was obtained in the same manner as in Example 13 except that the blending amount of the (C) polymerization initiator "Irgacure OXE 01" was changed to 8.4 parts and the blending amount of "Irgacure OXE 02" was changed to 3.6 parts.

[Example 16]

A hardening 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 (C) polymerization initiator.

[Example 17]

A hardening 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 (C) polymerization initiator.

[Example 18]

A hardening 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 (C) polymerization initiator.

[Example 19]

A hardening 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 (C) polymerization initiator.

[Comparative Example 1]

220 parts (A) of the quantum dot "CZ520" and 22 parts of "DISPERBYK-180 (main component: alkylol ammonium salt) of an acid group-containing copolymer, manufactured by BYK Chemie Japan ) ", And the quantum dots are sufficiently dispersed by a bead mill to prepare a quantum dot dispersion. Next, 100 parts of (B) the polymerizable compound "KAYARAD DPHA", 677 parts of the (E) solvent of propylene glycol monomethyl ether acetate, and 0.1 part of the (F) leveling agent "Toray Silicone SH8400" were mixed to obtain Hardening composition.

<Production of hardened film>

After the curable composition was applied to a 5 cm square glass substrate (Eagle 2000, manufactured by Corning) by a spin coating method, a composition layer was obtained by pre-baking at 100 ° C for 1 minute. After being allowed to cool, the entire surface of the composition layer was irradiated with light at an exposure amount (based on 365 nm) of 150 mJ / cm ² in an atmospheric environment using an exposure machine (TME-150RSK; manufactured by Topcon). After light irradiation, it was immersed in an aqueous developing solution (aqueous solution containing 0.12% of nonionic surfactant and 0.04% potassium hydroxide solution) at 23 ° C for 60 seconds, and then washed in water at 200 ° C in an oven. After post-baking for 10 minutes, a cured film was thereby obtained.

<Measurement of film thickness>

The film thickness of the obtained cured film was measured with a film thickness measuring device (DEKTAK3, manufactured by Japan Vacuum Technology Co., Ltd.).

<Determination of Quantum Yield Ratio>

To the quantum dot dispersion liquid used for the preparation of the curable composition, toluene was added so that the absorbance at a wavelength of 450 nm was 0.4 to prepare a diluted dispersion liquid. Using a fluorescence quantum yield measurement device (C9920-02G, manufactured by Hamamatsu Photonics Co., Ltd.), the quantum yield at an excitation wavelength of 450 nm was measured on the diluted dispersion and the obtained cured film, respectively.

From the measured quantum yield, the quantum yield ratio is calculated by the following formula (y).

Quantum yield ratio = Qf / Qs × 100 (y) [In formula (y), Qf is the quantum yield of the cured film, and Qs is the quantum yield of the quantum dot dilution dispersion]

<Observation of luminous color>

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

<Residual film rate evaluation>

After the curable composition was applied to a 5 cm square glass substrate (Eagle 2000, manufactured by Corning) by a spin coating method, a composition layer was obtained by pre-baking at 100 ° C for 1 minute. After allowing to cool, the distance between the substrate on which the composition layer was formed and the mask made of quartz glass was set to 100 μm, and an exposure machine (TME-150RSK, manufactured by Topcon Corporation) was used to expose the light through the atmosphere in the atmosphere. The cover was irradiated with light at an exposure amount (based on a 365 nm) of 80 mJ / cm ² on the composition layer. The photomask uses a 100 μm line and space pattern. The film thickness of the composition layer after light irradiation was measured with a film thickness measuring device (DEKTAK3, manufactured by Japan Vacuum Technology Co., Ltd.).

Next, the substrate on which the composition layer was formed after light irradiation was immersed in an aqueous imaging solution (an aqueous solution containing 0.12% of a nonionic surfactant and an 0.04% potassium hydroxide solution) at 23 ° C. for 60 seconds to develop an image. After washing, a hardened pattern is obtained. The film thickness of the obtained hardened pattern was measured with a film thickness measuring device (DEKTAK3, manufactured by Japan Vacuum Technology Co., Ltd.).

The residual film rate of the hardened pattern was obtained from the formula (z). As long as the residual film rate is 90% or more, it can be judged that the sensitivity of the curable composition is good.

Residual film rate (%) = Td / Te × 100 (z) [In formula (z), Td is the film thickness of the hardened pattern, and Te is the film thickness of the composition layer after light irradiation]

Further, in the curable composition of the comparative example, the composition layer after light irradiation was completely dissolved in the developing solution, and a cured pattern could not be obtained on the substrate. Therefore, the quantum yield ratio and luminous color could not be observed.

[Industrial availability]

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

Claims (6)

A hardening composition containing quantum dots, a polymerization initiator and a polymerizable compound, wherein the polymerization initiator contains: a combination selected from the group consisting of an oxime compound and an acylphosphine compound, an oxime compound

At least one of the combination of compounds. The hardening composition as described in item 1 of the patent application scope, wherein the oxime compound, the acetylphosphine compound and the three

The compound is a compound having at least two aromatic rings in the molecule. The hardenable composition as described in item 1 or 2 of the patent application, wherein the quantum dot contains a compound selected from Group 12 elements and Group 16 elements, Group 13 elements and Group 15 elements, and Group 14 elements and 16 At least one of the group formed by the compound of the group element. The curable composition as described in item 1 or 2 of the patent application scope further contains resin. A cured film formed from the curable composition as described in any one of claims 1 to 4. A display device containing the cured film described in item 5 of the patent application.