KR20170048530A - Curable composition - Google Patents

Abstract

When a cured pattern is formed from a conventional curable composition by a photolithographic method, there is a problem that the residual film ratio of the cured pattern after development is low. The residual film ratio refers to a value represented by the following formula (z).
Residual film ratio (%) = Td / Te x 100 (z)
[In the formula (z), Td represents the film thickness of the cured pattern, and Te represents the film thickness of the composition layer after light irradiation.
A quantum dot, a polymerization initiator, a polymerizable compound, and a thiol compound. Wherein the thiol compound is a thiol compound having two or more sulfanyl groups in the molecule.

Description

{CURABLE COMPOSITION}

The present invention relates to a curable composition comprising 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.

Japanese Patent Application Laid-Open No. 10-186426

There is a problem that when the cured pattern is formed by the photolithographic method with the curable composition described in Patent Document 1, 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. The term "residual film ratio" refers to a value represented by the following equation (z).

Residual film ratio (%) = Td / Te x 100 (z)

[In the formula (z), Td represents the film thickness of the cured pattern, and Te represents the film 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, a polymerizable compound and a thiol compound.

[2] The curable composition according to [1], wherein the thiol compound is a thiol compound having two or more sulfanyl groups in the molecule.

[3] The method according to [1] or [2], wherein the quantum dot comprises 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 [2].

[4] The curable composition according to any one of [1] to [3], which further comprises a resin.

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

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

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

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

<Quantum dots (A)>

The quantum dot is a semiconductor fine particle having a particle diameter of about 1 nm to 100 nm and is a fine particle which absorbs ultraviolet light or visible light and emits light by using a band gap of a semiconductor.

As the quantum dots, CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe A compound of a group 12 element and a group 16 element such as CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe and HgZnSTe; GaN, GaP, GaAs, AlN, AlP, AlAs, InN, InP, InAs, GaNP, GaNAs, GaPAs, AlNP, AlNAs, AlPAs, InNP, InNAs, InPAs, GaAlNP, GaAlNAs, GaAlPAs, GaInNP, GaInNAs, GaInPAs, A compound of a Group 13 element and a Group 15 element such as InAlNAs and InAlPAs; PdS and PbSe, and the like.

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 the reaction component in the material for forming the organic layer.

Further, the quantum dots may form a core shell structure by combining the above-described compounds.

Examples of such a combination include fine particles in which the core is CdSe (cadmium selenide) and the shell is ZnS (zinc sulfide).

Since the energy state of the quantum dots depends on the size thereof, it is possible to freely select the emission wavelength by changing the particle diameter. For example, in the case of quantum dots 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. Further, the emitted light from the quantum dots has a narrow spectral width, and the displayable color gamut of the display device is enlarged by combining light having such a sharp peak. In addition, the quantum dot has high responsiveness, so that light emitted from the light source can be utilized efficiently.

The curable composition of the present invention may contain only quantum dots which emit light of a specific wavelength by the light emitted from the light source or may contain two or more kinds of quantum dots which emit light of different wavelengths. 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 1 to 50% by mass, more preferably 5 to 40% by mass, based on the solid content. As used herein, the solid content means the sum of components of the curable composition excluding the solvent (F) and other solvents to be described later. The content of the solid content in the composition can be measured by a known analytical means such as liquid chromatography or gas chromatography.

&Lt; 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) to be described later. As such a compound, for example, a compound having an ethylenic unsaturated bond, and the like, and preferably a (meth) acrylic acid ester compound.

In the present specification, "(meth) acrylic acid" means at least one kind selected from the group consisting of acrylic acid and methacrylic acid. The expressions 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 ethylenic unsaturated bonds. Examples of such a polymerizable compound include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) (Meth) acrylate, tetrapentaerythritol hexa (meth) acrylate, tripentaerythritol octa (metha) acrylate, tripentaerythritol hepta Ethylene glycol-modified pentaerythritol tetra (meth) acrylate, ethylene glycol-modified dipentaerythritol hexa (metha) acrylate, propylene glycol-modified pentaerythritol tetra (meth) acrylate, Acrylate, propylene glycol-modified dipentaerythritol hexa (meth) acrylate Caprolactone-modified pentaerythritol tetra (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate.

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

The content of the polymerizable compound (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 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.

&Lt; Polymerization initiator (C) >

The polymerization initiator (C) is not particularly limited as far as it is a compound capable of generating an active radical, an acid or the like by the action of light or heat and capable of initiating polymerization reaction, and a known polymerization initiator can be used.

Examples of the polymerization initiator that generates an active radical include alkylphenone compounds, O-acyloxime compounds, imidazole compounds, triazine compounds, and acylphosphine oxide compounds.

As the alkylphenone compound, an aminoalkylphenone compound is preferable. Specific examples of the alkylphenone compound include diethoxyacetophenone, 2-methyl-1- (4-methylsulfanylphenyl) -2-morpholinopropane-1-one, 2- 2- (4-methylphenylmethyl) butan-1-one, 2-hydroxy-2- Methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) Hexyl phenyl ketone, and oligomers of 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one. Methyl-1- (4-methylsulfanylphenyl) -2-morpholinopropane-1-one, 2-dimethylamino-1- (4-morpholinophenyl) 1-on. Irgacure 369, 907 (manufactured by Chiba, Japan) or the like may be used.

The O-acyloxime compound may be a compound having a partial structure represented by formula (d1). Herein, * denotes a combined hand.

Examples of the oxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy- 2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan- Yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3 -Dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethan- 1-imine, N- acetoxy- 1- [ Benzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropan- 1-imine, N-benzoyloxy- -Yl] -3-cyclopentylpropan-1-one-2-imine; The compounds disclosed in Japanese Patent Application Laid-Open Nos. H11-132215, 2008/78678, 2008/78686, and 2012/132558. Commercially available products such as Irgacure (registered trademark) OXE01, OXE02 (manufactured by BASF) and N-1919 (manufactured by ADEKA) may be used.

Among them, the oxime compound is preferably selected from the group consisting of N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy- 2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine.

The non-imidazole 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 a phenyl group, a toluyl group, a xylyl group, an ethylphenyl group and a naphthyl group, and preferably a phenyl group.

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 preferably a chlorine atom. 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, preferably a methoxy group.

Examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis Phenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4' Tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'- Tetra (alkoxyphenyl) imidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, a phenyl group in the 4,4'5,5'- position is bonded to a carboalkoxy group And an imidazole compound substituted by a halogen atom. These compounds are disclosed, for example, in JP-A-06-75372, JP-A-06-75373, JP-A-48-38403, JP-A-62-174204 Japanese Patent Application Laid-Open No. 7-10913, and the like. Among them, a compound represented by the following formula or a mixture thereof is preferable.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4 Bis (trichloromethyl) -6- [2- (5-methylfuran-1-yl) 2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- Triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- Dimethyl-2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine, and the like. Among them, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine is preferable.

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

Other 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'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert- butylperoxycarbonyl) benzophenone Benzophenone compounds such as 2,4,6-trimethylbenzophenone and 4,4'-bis (diethylamino) benzophenone; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethyl anthraquinone, camphorquinone, etc .; Butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds.

In order to improve the reaction efficiency at the time of forming the cured film, it is preferable that the polymerization initiator (C) contains an O-acyloxime compound.

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

&Lt; Polymerization initiator (C1) >

If necessary, the polymerization initiator (C1) may be used in combination. The polymerization initiator (C1) is a compound or a sensitizer used for promoting polymerization of the polymerizable compound initiated polymerization by the polymerization initiator. When the polymerization initiator (C1) is contained, usually the polymerization initiator (C ). Examples of the polymerization initiator (C1) include an amine compound, an alkoxyanthracene compound, a thioxanthone compound, and a carboxylic acid compound.

When the polymerization initiator (C1) is contained, the content of the polymerization initiator (C1) is preferably 0.1 to 300 parts by mass, more preferably 0.1 to 200 parts by mass, per 100 parts by mass of the polymerizable compound (B) Mass part. When the curable composition contains the resin (E) described later, the content of the polymerization initiator (C1) is preferably 0.1 to 30 mass parts per 100 mass parts of the total amount of the resin (E) and the polymerizable compound (B) More preferably 1 to 20 parts by mass. When the amount of the polymerization initiator (C1) is within this range, there is a tendency that a cured film can be formed with higher sensitivity.

&Lt; Thiol compound (D) >

The curable composition of the present invention comprises a thiol compound (D). The thiol compound (D) is a compound having a sulfanyl group (-SH) in the molecule. Since the thiol compound has a sensitizing effect, the curable composition containing it tends to be hardened.

Examples of the compound having one sulfanyl group in the molecule include 2-sulfanyloxazole, 2-sulfanylthiazole, 2-sulfanylbenzimidazole, 2-sulfanylbenzothiazole, 2-sulfanylpyridine-3-ol, 2-sulfanylpyridine-N-oxide, 4-amino-6-hydroxy-2-sulfanylpyrimidine Amino-2-sulfanylpyrimidine, 6-amino-5-nitroso-2-uracil, 4,5-diamino-6- Hydroxy-2-sulfanylpyrimidine, 4,6-diamino-2-sulfanylpyrimidine, 2,4-diamino-6-sulfanylpyrimidine, 4,6-dihydroxy- 4-hydroxy-2-sulfanyl-6-methylpyrimidine, 4-hydroxy-2-sulfanyl-6-propylpyrimidine, 2- 4-methylpyrimidine, 2-sulfanylpyrimidine, 2-uracil, 3,4,5,6-tetrahydropyrimidine-2-thiol, 4,5-diphenylimidazole- , 2-sulfanyl 2-sulfanyl-1-methylimidazole, 4-amino-3-hydrazino-5-sulfanyl-1,2,4-triazole, 3-amino- Methyl-4H-1,2,4-triazole-3-thiol, 3-sulfanyl 1H- Amino-5-sulfanyl-1,3,4-thiadiazole, 5-amino-1,3,4-thiadiazole-2-thiol, (Furan-2-yl) methanethiol, 2-sulfanyl-5-thiazolidone, 2-sulfanylthiazoline, 2-sulfanyl- (3H) -quinazolinone, 1-phenyl-1H-tetrazole-5-thiol, 2-quinolinethiol, 2-sulfanyl-5-methylbenzimidazole, 2-sulfanyl- , 6-amino-2-sulfanylbenzothiazole, 5-chloro-2-sulfanylbenzothiazole, 6-ethoxy-2-sulfanylbenzothiazole, 4-amino-6-sulfanylpyrazolo [2,4-d] pyridine, 2-sulfanylnaphthoic acid, 2-amino-6-purin thiol , 6-sulfanyl purine, 4-sulfanyl-1H-pyrazolo [2,4-d] pyrimidine and the like.

Examples of the compound having two or more sulfanyl groups in the molecule include hexane dithiol, decanediol, 1,4-bis (methylsulfanyl) benzene, butanediol bis (3-sulfanylpropionate), butanediol bis (3-sulfanyl acetate), trimethylolpropane tris (3-sulfanyl acetate), butanediol bis (3-sulfanyl propionate), trimethylolpropane tris (3-sulfanyl acetate), pentaerythritol tetrakis (3-sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl acetate), trishydroxyethyl tris (3-sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl butyrate), 1,4-bis (3-sulfanylbutyloxy) butane, dipentaerythritol hexakis Pentaerythritol hexakis (3-sulfanyl acetate ), Dipentaerythritol hexakis (3-sulfanylbutylate), and the like.

As the thiol compound, a compound having two or more sulfanyl groups in the molecule is preferable, and a compound having three or more is more preferable. When a thiol compound is used, the residual film ratio of the cured pattern becomes high.

The content of the thiol compound (D) is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the total amount of the resin (E) and the polymerizable compound (B). When the content of the thiol compound (D) is within this range, the sensitivity of polymerization at the time of forming a cured pattern becomes higher and the residual film ratio of the cured pattern after development tends to be higher.

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

&Lt; Resin (E) >

The resin (E) is preferably an alkali-soluble resin. Examples of the resin (E) include the following resins [K1] to [K4].

(A) (hereinafter, sometimes referred to as "(a)") selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride; a monomer (c) copolymerizable with (a) (Which is different from (a), hereinafter sometimes referred to as "(c)")

Resin [K2]: A monomer (b) (hereinafter referred to as "(b)") having a cyclic ether structure and an ethylenic unsaturated bond having 2 to 4 carbon atoms in the copolymer of (a) Lt; / RTI &gt;

Resin [K3]: a resin obtained by reacting (a) a copolymer of (b) and (c)

Resin [K4]: Resin (a) is reacted with the copolymer of (b) and (c) and further reacted with carboxylic acid anhydride.

(a) include, for example, 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, 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- 5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept- [2.2.1] hept-2-ene, and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene; Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride , Unsaturated dicarboxylic anhydrides such as dimethyl tetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hept-2-eno anhydride; (Meth) acryloyloxyalkyl] unsaturated monocarboxylic acid mono [2- (meth) acryloyloxyethyl] phthalic acid mono [2- (meth) acryloyloxyethyl] Esters; and unsaturated acrylates containing a hydroxyl group and a carboxyl group in the same molecule, such as? - (hydroxymethyl) acrylic acid.

Of these, acrylic acid, methacrylic acid and maleic anhydride are preferable from the viewpoint of copolymerization reactivity and the solubility of the resulting resin in an aqueous alkali solution.

(b) is, for example, a monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenic unsaturated bond. Examples of the cyclic ether structure having 2 to 4 carbon atoms include oxirane ring, oxetane ring, tetrahydrofuran ring and the like, and one type may be used, or a plurality of types may be used in combination. (b) is preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth) acryloyloxy group.

(meth) acrylate,? -ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-methylglycidyl (meth) acrylate, Vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether,? -Methyl-o-vinyl benzyl glycidyl ether,? -Methyl- methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5- Styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) Styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (glycidyloxymethyl) A monomer having an oxirane ring and an ethylenic unsaturated bond; Methyl-3-acryloyloxymethyl oxetane, 3-ethyl-3-methacryloyloxymethyl oxetane, 3-ethyl-3- Acryloyloxyethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl- Cetane, 3-ethyl-3-acryloyloxyethyloxetane, and other oxetane rings and an ethylenically unsaturated bond; (For example, "Viscot V # 150" manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofuran ring such as tetrahydrofurfuryl methacrylate, and a monomer having an ethylenic unsaturated bond .

(b) has a high reactivity at the time of production of the resins [K2] to [K4] and the unreacted portion (b) desirable.

(meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert- (Meth) acrylate, cyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, (Meth) acrylate, dicyclopentanyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl Decyl (meth) acrylate), tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate (dicyclopentenyl (meth) acrylate in the state of the art), dicyclopentanyloxy Ethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate Sites, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) (meth) acrylic acid esters such as acrylate;

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

Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate;

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

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

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

Of these, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide and bicyclo [2.2.1] hept-2- ene are preferred from the viewpoint of copolymerization reactivity and heat resistance Do.

The proportion of the structural unit derived from each monomer in the resin [K1] is preferably from 2 to 70 mol% based on the entire structural unit constituting the resin (K1), the structural unit derived from the structural unit (a) (c) is preferably 30 to 98 mol%. , More preferably 10 to 70 mol% of the structural unit derived from (a) and 30 to 90 mol% of the structural unit derived from (c).

When the ratio of the structural unit of the resin [K1] is within the above range, there is a tendency that the storage stability of the curable composition, the developability in forming the cured pattern, and the solvent resistance of the obtained cured pattern are excellent.

The resin [K1] can be synthesized by a method described in, for example, "Experimental Method of Polymer Synthesis" (published by the Chemical Society of Japan, 1st Edition, 1st Edition, March 1, 1972, Can be prepared by reference to the literature.

Specifically, a predetermined amount of the components (a) and (c), a polymerization initiator and a solvent are placed in a reaction vessel, for example, by replacing oxygen by nitrogen, thereby obtaining a deoxidized atmosphere, . The polymerization initiator and the solvent to be used herein are not particularly limited and those generally used in the art can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutylonitrile, 2,2'-azobis (2,4-dimethylvaleronitrile) and the like) and organic peroxides such as benzoyl peroxide As the solvent, any solvent may be used as long as it dissolves the respective monomers. As the solvent (F) which may be contained in the curable composition of the present invention, there may be mentioned a solvent described later.

As the obtained copolymer, the solution after the reaction may be used as it is, or a concentrated or diluted solution may be used, or it may be taken out as a solid (powder) by a method such as re-precipitation. Particularly, since the solution after the reaction can be used as it is for preparing the curable composition of the present invention, the process for producing the curable composition of the present invention can be simplified by using the solvent (F) described later as the solvent in the polymerization .

Resin [K2] is obtained by obtaining a copolymer of (a) and (c) and adding a cyclic ether having 2 to 4 carbon atoms in (b) to a carboxylic acid and / or carboxylic anhydride derived from (a) can do.

First, the copolymer of (a) and (c) is prepared in the same manner as the method described as the method for producing the resin [K1]. In this case, the proportion of the structural units derived from each of them is preferably the same as that of the resin [K1].

Subsequently, a cyclic ether having 2 to 4 carbon atoms of (b) is allowed to react with a part of the carboxylic acid and / or carboxylic anhydride derived from (a) in the copolymer.

Subsequent to the preparation of the copolymer of (a) and (c), the atmosphere in the flask is replaced by air from nitrogen, (b) a reaction catalyst of reaction between carboxylic acid or carboxylic anhydride and cyclic ether, (K2) can be prepared, for example, by reacting at 60 to 130 占 폚 for 1 to 10 hours with a polymerization inhibitor (e.g., hydroquinone) or the like in a flask.

(b) is preferably 5 to 80 moles, more preferably 10 to 75 moles, per 100 moles of (a). By setting this range, there is a tendency that the balance between the storage stability of the curable composition, the developability in forming a cured pattern, and the solvent resistance, heat resistance, mechanical strength and sensitivity of the resulting cured pattern are improved.

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

The reaction conditions such as the feeding method, the reaction temperature and the time can be appropriately adjusted in consideration of the production equipment or the amount of heat generated by polymerization. Also, in the same manner as the polymerization conditions, the method of charging and the reaction temperature can be appropriately adjusted in consideration of the production facility or the amount of heat generated by polymerization.

The resin [K3] is a first step, and the copolymer of (b) and (c) is obtained in the same manner as the resin [K1] described above. As in the case of the above, the solution after the reaction may be used as it is, or a concentrated or diluted solution may be used as the obtained copolymer, or it may be taken out as a solid (powder) by a method such as re-precipitation.

the proportion of the structural units derived from (b) and (c) is in the range of 5 to 95 mol% based on the total moles of the total structural units constituting the copolymer, (c) ) Is preferably 5 to 95 mol%. It is more preferable that the structural unit derived from (b) is 10 to 90 mol%, and the structural unit derived from (c) is 10 to 90 mol%.

The carboxylic acid or carboxylic acid anhydride of (a) is added to the cyclic ether derived from (b) of the copolymer of (b) and (c) under the same conditions as the method of producing the resin [K2] , Whereby resin [K3] can be obtained.

The amount of (a) to be reacted with the copolymer is preferably 5 to 80 moles per 100 moles of (b).

The resin [K4] is a resin obtained by further reacting the resin [K3] with a carboxylic acid anhydride.

The carboxylic acid anhydride is subjected to addition reaction to the hydroxyl group generated by the reaction of the cyclic ether and the carboxylic acid or the carboxylic acid anhydride.

Examples of the carboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6 -Tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo [2.2.1] hept-2-eno anhydride. The amount of the carboxylic acid anhydride to be used is preferably 0.5 to 1 mole based on 1 mole of the amount of (a).

Specific examples of the resin (E) include resins [K1] such as benzyl (meth) acrylate / (meth) acrylic acid copolymer and styrene / (meth) acrylic acid copolymer; A resin obtained by adding glycidyl (meth) acrylate to a benzyl (meth) acrylate / (meth) acrylic acid copolymer, a resin obtained by adding glycidyl (meth) acrylate to a tricyclodecyl (meth) acrylate / styrene / (K2) such as a resin obtained by adding glycidyl (meth) acrylate to a tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer; A resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid, a resin obtained by reacting tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) A resin [K3] such as a resin obtained by reacting (meth) acrylic acid with a copolymer; A resin [K4] such as a resin obtained by reacting a (meth) acrylic acid with a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate in addition to tetrahydrophthalic anhydride have.

Among them, it is preferable that the resin (E) includes at least one kind selected from the group consisting of resin [K2], resin [K3] and resin [K4].

The weight average molecular weight of the resin (E) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 30,000. When the molecular weight is within the above range, the hardness of the cured film is improved, the residual film ratio of the cured pattern is high, the solubility of the unexposed portion in the developer in the composition layer is good, and the resolution of the cured pattern tends to be improved.

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

The acid value of the resin (E) 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. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the resin (E), and can be determined by, for example, titration using an aqueous potassium hydroxide solution.

The content of the resin (E) 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 solid content. When the content of the resin (E) 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.

&Lt; Solvent (F) >

The solvent (F) is not particularly limited as long as it dissolves the polymerizable compound (B), the polymerization initiator (C), the thiol compound (D) and the resin (E), and a solvent commonly used in the art can be used. For example, an ester solvent (a solvent containing -COO- in the molecule and containing no -O-), an ether solvent (a solvent containing -O- and no -COO- in the molecule), an ether ester (Solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule and not including -COO-), alcohol solvent (containing OH in the molecule, O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethylsulfoxide 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-pentyl formate, isopentyl acetate, n-butyl propionate, Butyl acetate, methyl isobutyrate, ethyl isobutyrate, ethyl isobutyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetone 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 Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, And the like.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate , Ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, Methyl propionate, methyl propionate, methyl 2-ethoxy-2-methyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono Propyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether Teracetate and diethylene glycol monobutyl ether acetate, and the like.

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

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

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

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

As the 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-methyl-2-pentanone or toluene is preferred.

The content of the solvent (F) is preferably 70 to 95% by mass, and more preferably 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, and more preferably 8 to 25% by mass. When the content of the solvent (F) is within the above range, the flatness of the composition layer at the time of coating tends to be better, and a cured film having an appropriate film thickness tends to be easily formed.

&Lt; Leveling agent (G) >

Examples of the leveling agent (G) include a silicone surfactant, a fluorinated surfactant, and a silicon surfactant having a fluorine atom. These may have a polymerizable group in the side chain.

Examples of the silicone surfactant include a surfactant having a siloxane bond in the molecule. Specifically, TORAY Silicon DC3PA, copper SH7PA, copper DC11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, copper SH8400 (trade name; manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP340, KP341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan Joint- .

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain in the molecule. Concretely, fluororads (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Ltd.), Megapack (registered trademark) F142D, copper F171, copper F172, copper F173, copper F177, copper F183, copper F554, (Trade name) manufactured by Mitsubishi Materials Electronics Co., Ltd.), RS-718-K (manufactured by DIC Corporation), Eftop EF301, EF303, EF351 and EF352 S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Research Institute).

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

The content of the leveling agent (G) is preferably 0.001 mass% or more and 0.2 mass% or less, preferably 0.002 mass% or more and 0.1 mass% or less, more preferably 0.01 mass% or more and 0.05 mass or less, % Or less. When the content of the leveling agent (G) is within the above range, the flatness of the cured film can be further improved.

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

<Cured 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 on a part of the substrate (i.e., a curing 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, a photolithographic method is preferable. The photolithography method is a method in which the curable composition of the present invention is applied to a substrate, dried as necessary to form a composition layer, and exposed and developed through the photomask.

As a method for forming a cured film on the entire surface of the substrate, there can be cited a method of applying the curable composition of the present invention to a substrate, drying it if necessary to form a composition layer, and heating the composition layer and / .

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

Formation of a cured pattern by the photolithographic method can be carried out by a known apparatus or condition. For example, it can be manufactured as follows.

First, the curable composition is applied on a substrate, and the composition is dried by heating (prebaking) and / or drying under reduced pressure to remove volatile components such as a solvent to obtain a composition layer. Examples of the application method include a spin coat method, a slit coat method, and a slit and spin coat method.

The temperature in the case of heat drying is preferably 30 to 120 ° C, more preferably 50 to 110 ° C. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.

In the case of performing the reduced-pressure drying, it is preferable that the drying is carried out at a temperature of 20 to 25 캜 under a pressure of 50 to 150 Pa.

The film thickness of the composition layer is not particularly limited and may be appropriately selected depending on the film thickness of the intended curing pattern.

Subsequently, the composition layer is exposed through a photomask for forming a target curing 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 of about 436 nm, about 408 nm, or around 365 nm may be selectively extracted from the light of the wavelength by the band-pass filter depending on the absorption wavelength of the polymerization initiator. Specific examples thereof include mercury lamps, light emitting diodes, metal halide lamps, and halogen lamps.

It is preferable to use an exposure apparatus such as a mask aligner and a stepper to uniformly irradiate the entire exposure surface with a parallel light beam or accurately align the photomask with the substrate on which the composition layer is formed. The exposed composition layer is cured by polymerizing a polymerizable compound or the like contained in the composition layer.

The exposed composition layer is brought into contact with a developing solution and developed, whereby the unexposed portion of the composition layer is 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, tetramethylammonium hydroxide, and organic solvents. The concentration of the alkaline compound in the aqueous solution is preferably 0.01 to 10% by mass, and more preferably 0.03 to 5% by mass. The organic solvent may be the same as the solvent (F) described above. Further, the developer may contain a surfactant.

The developing method may be any of paddle method, dipping method and spray method. Further, the substrate may be inclined at an arbitrary angle during development.

It is preferable to further heat (post-baking) the cured pattern obtained by the development. The heating temperature is preferably 150 to 250 占 폚, more preferably 160 to 235 占 폚. The heating time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes. By heating after development, the polymerization of the unreacted polymerizable compound or the like contained in the cured pattern can be promoted, so that a cured pattern having better chemical resistance can be obtained.

By irradiating ultraviolet light or visible light to the cured film, the cured film of the present invention emits light of a wavelength different from that of the irradiated light. In the curable composition used for forming the cured film of the present invention, the wavelength of the light emitted can be selected by selecting the components and particle diameters of the quantum dots contained in the curable composition.

Since the cured film of the present invention has a function of changing the wavelength of the 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, Japanese Laid-Open Patent Publication Nos. 2006-309219, 2006-310303, 2013-15812, 2009-251129, And a display device described in Japanese Patent Application Laid-Open No. 2014-2363.

The curable composition of the present invention can obtain a cured pattern at a high residual film ratio during development and the cured pattern has excellent quantum yield when light is emitted, .

Example

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

In the examples, &quot;% &quot; and &quot; part (s) &quot;

Synthesis Example 1

Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas introducing tube, 100 parts of propylene glycol monomethyl ether acetate was added and stirred while replacing nitrogen, and the temperature was raised to 120 ° C. Subsequently, 1 part of the polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was added to 100 parts of the monomer mixture in a monomer mixture composed of 40 parts of benzyl methacrylate and 20 parts of methacrylic acid, Was added dropwise from the funnel over 2 hours to the flask, and further stirred at 120 DEG C for 2 hours to obtain a copolymer solution. Next, 10 parts of glycidyl methacrylate, 0.44 part of triphenylphosphine, and 0.08 part of methylhydroquinone were added to the copolymer solution, and the reaction was continued at 120 ° C. to obtain a copolymer having a solid content of acid value of 130 KOH mg / g, the reaction was terminated. Thus, 80 parts of propylene glycol monomethyl ether acetate was added to obtain a resin E1 solution having a solid content of 30%. The weight average molecular weight of Resin E1 was 3.0 x 10 ⁴ .

The weight average molecular weight (Mw) of the resin was measured by the GPC method under the following conditions.

Device; K2479 (manufactured by Shimadzu Corporation)

column; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 ℃

menstruum; Tetrahydrofuran

Flow rate; 1.0 mL / min

Detector; RI

Calibration standards; 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 the preparation of the curable composition, respectively.

(A) Quantum dot

CZ520: quantum dot, 10% toluene dispersion, core shell type (core: CdSe, shell: ZnS) manufactured by NN-LABS.

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

(B) a polymerizable compound

KAYARAD (registered trademark) DPHA: dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.

(C) Polymerization initiator

Irgacure (registered trademark) 907: aminoalkylphenone manufactured by BASF, 2-methyl-1- (4-methylsulfanylphenyl) -2-morpholinopropane-1-one.

Irgacure (registered trademark) OXE01: an oxime compound manufactured by BASF, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine.

(D) Thiol compound

PEMP: manufactured by SC Organic Chemicals, pentaerythritol tetrakis (3-sulfanyl propionate)

(F) Leveling agent

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

[Example 1]

(A) 240 parts of a quantum dot "CZ520" and 24 parts of "DISPERBYK-180" (trade name: alkylol ammonium salt of a copolymer containing a main component and an acid group) produced by Big Chem Japan Co., Was sufficiently dispersed to prepare a quantum dot dispersion. Subsequently, 40 parts of (B) a polymerizable compound "KAYARAD DPHA", 8 parts of a polymerization initiator "Irgacure 907" as a polymerization initiator (C), 3 parts of a thiol compound "PEMP" 654 parts of E1 as a solvent (in terms of solid content), (F) 654 parts of propylene glycol monomethyl ether acetate as a solvent, and (G) 0.1 part of a leveling agent "Toray Silicone SH8400" were mixed to obtain a curable composition.

[Example 2]

(A) 240 parts of a quantum dot "CZ520", and "TO-1382" (a mixture of dipentaerythritol pentaacrylate and a monoester of succinic acid, dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate 24 parts) were mixed and the quantum dots were sufficiently dispersed by a bead mill to prepare a quantum dot dispersion. Subsequently, 40 parts of (B) a polymerizable compound "KAYARAD DPHA", 8 parts of a polymerization initiator "Irgacure 907" as a polymerization initiator (C), 3 parts of a thiol compound "PEMP" 654 parts of E1 as a solvent (in terms of solid content), (F) 654 parts of propylene glycol monomethyl ether acetate as a solvent, and (G) 0.1 part of a leveling agent "Toray Silicone SH8400" were mixed to obtain a curable composition.

[Example 3]

(A) 240 parts of a quantum dot "CZ620" and 24 parts of "DISPERBYK-180" manufactured by Big Chem Japan Co., Ltd. were mixed and the quantum dots were fully dispersed by a bead mill to prepare a quantum dot dispersion. Subsequently, 40 parts of (B) a polymerizable compound "KAYARAD DPHA", 8 parts of a polymerization initiator "Irgacure 907" as a polymerization initiator (C), 3 parts of a thiol compound "PEMP" 654 parts of E1 as a solid (in terms of solid content), (F) 654 parts of propylene glycol monomethyl ether acetate as a solvent, and (G) 0.1 part of a leveling agent "Toray Silicone SH8400" were mixed to obtain a curable composition.

[Example 4]

240 parts of (A) quantum dot " CZ620 "and 24 parts of" TO-1382 " manufactured by Toa Sekkeishi Kogyo Co., Ltd., and quantum dots were sufficiently dispersed by a bead mill to prepare a quantum dot dispersion. Subsequently, 40 parts of (B) a polymerizable compound "KAYARAD DPHA", 8 parts of a polymerization initiator "Irgacure 907" as a polymerization initiator (C), 3 parts of a thiol compound "PEMP" 654 parts of E1 as a solvent (in terms of solid content), (F) 654 parts of propylene glycol monomethyl ether acetate as a solvent, and (G) 0.1 part of a leveling agent "Toray Silicone SH8400" were mixed to obtain a curable composition.

[Example 5]

271.7 parts of (A) quantum dot "CZ620" and 24 parts of "TO-1382 " manufactured by Toa Synthetic Co., Ltd. were mixed and the quantum dots were fully dispersed by a bead mill to prepare a quantum dot dispersion. Then, 40 parts of the polymerizable compound (B) "KAYARAD DPHA", 10 parts of the polymerization initiator "Irgacure OXE01" as the polymerization initiator (C), 0.1 part of the thiol compound "PEMP" , 60 parts of E1 (in terms of solid content), 393.6 parts of propylene glycol monomethyl ether acetate as the (F) solvent, and 0.1 part of (G) leveling agent "Toray Silicone SH8400"

[Example 6]

And the amount of the (D) thiol compound "PEMP" was changed to 0.5 parts and the amount of the (F) solvent to 394.8 parts, respectively.

[Example 7]

Except that the amount of the quantum dot "CZ620" was changed to 272.7 parts (A), the amount of the thiol compound "PEMP" was changed to 1.0 parts, and the amount of the solvent (F) was changed to 396.3 parts, A composition was obtained.

[Example 8]

Except that the amount of the quantum dot "CZ620" in (A) was changed to 276.8 parts, the amount of the thiol compound "PEMP" was changed to 3.0 parts, and the amount of the (F) solvent was changed to 402.2 parts, A composition was obtained.

[Example 9]

Was prepared in the same manner as in Example 5, except that the amount of the quantum dot "CZ620" was changed to 291.2 parts (A), the amount of the thiol compound "PEMP" was changed to 10.0 parts, and the amount of the solvent (F) was changed to 423.1 parts, A composition was obtained.

[Example 10]

Except that the amount of the quantum dot "CZ620" was changed to 311.7 parts (A), the amount of the thiol compound "PEMP" was changed to 20.0 parts, and the amount of the (F) solvent was changed to 452.9 parts, respectively. A composition was obtained.

[Comparative Example]

220 parts of (A) quantum dot " CZ520 "and 22 parts of" DISPERBYK-180 "manufactured by Big Chem Japan Co., Ltd. were sufficiently mixed to disperse quantum dots by a bead mill. Subsequently, 100 parts of (B) the polymerizable compound "KAYARAD DPHA", (F) 677 parts of propylene glycol monomethyl ether acetate as a solvent, and (G) 0.1 part of a leveling agent "TORAYI SAN SH8400" .

&Lt; Preparation of cured film &

The curable composition was applied on a glass substrate (Eagle 2000; Corning) having a size of 5 cm on both sides by spin coating, and then pre-baked at 100 ° C for 1 minute to obtain a composition layer. After cooling, the entire surface of the composition layer was irradiated with light at an exposure dose of 150 mJ / cm ² (365 nm standard) using an exposure machine (TME-150RSK, manufactured by Topcon Co., Ltd.) in an air atmosphere. After light irradiation, the substrate was immersed in an aqueous developing solution (an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide) at 23 DEG C for 60 seconds, washed with water and then postbaked in an oven at 200 DEG C for 10 minutes To obtain a cured film.

&Lt; Measurement of film thickness &

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

<Measurement of quantum yield ratio>

To the quantum dot dispersion used in the preparation of the curable composition, toluene was added so that the absorbance at a wavelength of 450 nm became 0.4 to prepare a diluted dispersion. The quantum yield of each of the diluted dispersion and the cured film obtained above was measured by a fluorescence quantum yield measuring apparatus (C9920-02G; manufactured by Hamamatsu Photonics K.K.) at an excitation wavelength of 450 nm. The quantum yield ratio was calculated from the measured quantum yield by the following equation (y). In the formula (y), Qf represents the quantum yield of the cured film, and Qs represents the quantum yield of the quantum dot diluted dispersion.

Quantum yield ratio = Qf / Qs x 100 (y)

&Lt; Observation of luminescent color &

The resulting cured film was irradiated with a UV lamp having a wavelength of 350 nm under a dark room to observe the luminescent color of the cured film visually.

&Lt; Evaluation of residual film ratio &

The curable composition was applied on a glass substrate (Eagle 2000; Corning) having a size of 5 cm on both sides by spin coating, and then pre-baked at 100 ° C for 1 minute to obtain a composition layer. After cooling down, the space between the substrate on which the composition layer was formed and the quartz glass photomask was set to 100 mu m and the surface of the quartz glass photomask was irradiated with light of 80 mJ / cm &lt; 2 &gt; ² &lt; / RTI &gt; (365 nm standard). As the photomask, a 100 μm line and space pattern was formed. The film thickness of the composition layer after light irradiation was measured by a film thickness measuring device (DEKTAK3; manufactured by Japan Vacuum Technology Co., Ltd.).

Subsequently, the substrate on which the composition layer after irradiation with light was formed was immersed in an aqueous developing solution (aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide) at 23 캜 for 60 seconds to develop and wash it 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 Japan Vacuum Technology Co., Ltd.).

The residual film ratios of the cured patterns were determined by the equation (z). When the residual film ratio is 90% or more, it can be judged that the sensitivity of the curable composition is good. In the formula (z), Td represents the film thickness of the cured pattern, and Te represents the film thickness of the composition layer after light irradiation.

Residual film ratio (%) = Td / Te x 100 (z)

Further, in the curable composition of the comparative example, since the composition layer after light irradiation was completely dissolved in the developer, no cured pattern was obtained on the substrate, and thus 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 at a high residual film ratio at the time of development, and the cured pattern has excellent quantum yield when light is emitted.

Claims (6)

A quantum dot, a polymerization initiator, a polymerizable compound, and a thiol compound. The method according to claim 1,
Wherein the thiol compound is a thiol compound having two or more sulfanyl groups in the molecule. 3. The method according to claim 1 or 2,
Wherein the quantum dot comprises 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 group 14 element and a group 16 element. 4. The method according to any one of claims 1 to 3,
Further comprising a resin. A cured film formed from the curable composition according to any one of claims 1 to 4. A display device comprising the cured film according to claim 5.