JP2018120134A - Quantum dot and quantum dot-containing composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a quantum dot containing a semiconductor fine particle, wherein the quantum dot has improved fluorescence yield; when the quantum dot is used for coloring, coating or printing of a molding, it can maintain the fluorescence properties; and it has high resistance, and provide a composition containing the quantum dot.SOLUTION: Treating a semiconductor fine particle with a specific surface treatment agent makes it possible to obtain a quantum dot having excellent fluorescence properties and high resistance, and a composition containing the quantum dot.SELECTED DRAWING: None

Description

  The present invention relates to a quantum dot and a composition containing the quantum dot.

Quantum dots are extremely small particles (dots) formed to confine electrons in a minute space in order to develop unique optical properties according to quantum mechanics. The size of one quantum dot is 1 nanometer to several tens of nanometers in diameter, and is composed of about 10,000 atoms or less. In recent years, attention has been attracted to the fact that the wavelength of emitted fluorescence can be continuously controlled by the size of the grains, and that sharp light emission with a highly symmetrical wavelength distribution of fluorescence intensity can be obtained.
Quantum dots can adjust fluorescence to a wavelength that easily passes through the human body, and can be delivered to any place in the body. Therefore, quantum dots can be used for bioimaging as a luminescent material (Non-Patent Document 1), and for solar cells as a wavelength conversion material that does not fear discoloration ( Patent document 1), development of electronics and photonics applications (patent documents 2 and 3) as clear light-emitting materials and wavelength conversion materials has been studied.

A characteristic required when developing for these applications is the quantum yield of fluorescence.
In order to improve the fluorescence yield, Non-Patent Document 2 discloses an example in which semiconductor fine particles are coated with semiconductor fine particles made of In-P with myristic acid which is an organic aliphatic carboxylic acid.

However, since it is difficult to apply and print quantum dots alone, a diluent such as a solvent or a monomer is used. However, it is difficult to carry out while maintaining the fluorescence characteristics during molding, application, and printing. It has been a problem that the decrease in the level is greatly reduced. Although there is a method of enclosing the entire quantum dot-containing shaped article with a barrier agent in order to suppress a decrease in quantum efficiency, there is a drawback that workability is lowered.

JP 2006-216560 A JP 2008-112154 A JP 2009-251129 A

Shintaka, “Semiconductor quantum dots, their synthesis and application to life science,” Production and Technology, Vol. 63, No. 2, 2011, p58-p65 Journal of the American chemical society 2007 129 15432-15433

  The object of the present invention is to improve the fluorescence yield of quantum dots and to provide highly resistant quantum dots and quantum dots that can maintain fluorescence characteristics when colored, coated, and printed on a molded article using quantum dots. It is to provide a composition containing.

  As a result of intensive studies to solve the above problems, the present inventor has found that by using semiconductor fine particles surface-treated with a treatment agent having a specific structure, quantum efficiency can be improved and tolerance can be improved. It was.

  That is, the present invention relates to a quantum dot containing semiconductor fine particles, wherein the semiconductor fine particles are surface-treated with a treating agent containing a compound having a pyridine structure.

Further, the present invention relates to the quantum dot, wherein the semiconductor fine particle is a compound semiconductor.

Further, the present invention relates to the quantum dot, wherein the semiconductor fine particle is a core-shell type.

Moreover, it is related with the quantum dot containing composition characterized by including the said quantum dot and a solvent.

Further, the present invention relates to the quantum dot-containing composition, further comprising a photopolymerizable monomer.

According to the first to third aspects of the present invention, a highly reliable quantum dot including a semiconductor quantum dot and having excellent fluorescence characteristics is provided.
Moreover, according to the 4th-5th aspect of this invention, the quantum dot composition which is excellent in the fluorescence characteristic with the favorable workability | operativity using diluents, such as a solvent and a monomer, and has high reliability is provided.

Hereinafter, the present invention will be described in detail.
The quantum dot of the present invention is characterized by containing semiconductor fine particles surface-treated with a treating agent containing a compound having a pyridine structure.

<Semiconductor fine particles>
The semiconductor fine particle of the present invention is a semiconductor containing an inorganic substance as a component, and may be a single composition, a core-shell type, or a plurality of three or more layers.
The semiconductor of the present invention is at least two or more selected from the group consisting of group 2 elements, group 10 elements, group 11 elements, group 12 elements, group 13 elements, group 14 elements, group 15 elements and group 16 elements It is a semiconductor which consists of a compound containing these elements.
More preferably, it is a compound semiconductor. The compound semiconductor is at least two selected from the element group represented by Zn, Cd, B, Al, Ga, In, C, Si, Ge, Sn, N, P, As, Sb, Pb, S, Se, and Te. It is a semiconductor which consists of a compound containing these elements.
More preferably, it is selected from the group of elements represented by Zn, B, Al, Ga, In, C, Si, Ge, Sn, N, P, S, and Te, excluding elements that are of concern for human safety. It is a semiconductor made of a compound containing at least two kinds of elements.
For applications that emit visible light, a semiconductor containing In as a constituent element is more preferable because of the narrow band gap.

  The core-shell type semiconductor fine particles have a structure in which the core structure is covered with a semiconductor having a different component from the semiconductor forming the core. By using a semiconductor having a large bunt gap on the outside, excitons (electron-hole pairs) generated by photoexcitation are confined in the core. As a result, the probability of non-radiative transition on the surface of the semiconductor fine particles is reduced, and the quantum yield of light emission and the stability of the fluorescence characteristics of the semiconductor quantum dots are improved.

  The average particle size of the semiconductor fine particles of the present invention is preferably from 0.5 nm to 100 nm, and a particle size capable of obtaining a desired color can be selected. In the case of the core-shell type, one semiconductor fine particle may contain a plurality of shell fine particles. In the case of a single semiconductor composition, the average particle size of the semiconductor fine particles and the average particle size of the core-shell type core are preferably 0.5 nm to 10 nm. Synthesis with an average particle size of less than 0.5 nm is difficult, and if it exceeds 10 nm, the quantum confinement effect cannot be obtained and the desired fluorescence cannot be obtained.

The quantum dots of the present invention preferably have an average particle size of 3 nm to 1 μm.
The shape of the quantum dots is not limited to a spherical shape, and may be a rod shape, a disk shape, or other shapes.

<Treatment agent>
The quantum dots of the present invention are obtained by subjecting semiconductor fine particles to a surface treatment with the above-mentioned treatment agent. As a surface treatment method, for example, by adding during the synthesis of semiconductor fine particles, the treatment agent is chemically adsorbed in advance. A method for producing treated semiconductor fine particles, a method in which the treatment agent is chemically adsorbed on the surface of the semiconductor fine particles by stirring the semiconductor fine particles and the treatment agent in a solvent, and the surface treatment is performed. An example is a method of producing semiconductor fine particles that have been chemically adsorbed and surface-treated when semiconductor fine particles are re-dispersed in a solvent containing a treating agent after roughly removing.

The treatment agent of the present invention is characterized by containing a compound having a pyridine structure. The compound having a pyridine structure refers to a compound having a pyridine moiety and a substituent moiety.
The substitution position on the pyridine moiety may be any of ortho-position, meta-position and para-position as seen from nitrogen, or may be bipyridine.
Examples of the substituent include an optionally substituted alkyl group, ketone group, ether group, and amino group.
Examples of the optionally substituted alkyl group include linear alkyl groups such as methyl, ethyl, hexyl, dodecyl, eicosyl, branched alkyl groups such as 2-ethylhexyl, and cyclic alkyl groups such as 3-cyclohexylpropyl group. . Like the ethenyl group, it may contain multiple CC multiple bond sites and may be substituted with an aromatic ring such as a hydroxyl group, an amino group, a ketone group, an ester group or a phenyl group.
Examples of the ketone group that may be substituted include an acetyl group and an acetylbutyl group. The ketone group may form an imide, amide group or ester group.
Examples of the ether group that may be substituted include an ether group containing ether oxygen in the main chain such as an ethyl ether group, a butyl ether group, and a 2-methoxyethyl ether group, and a branched portion such as a 2-methoxy-hexyl group containing ether oxygen. And ether groups. The ether group may form an ester group.
Examples of the amino group which may be substituted include secondary amines such as amino group and ethylamino group, tertiary amines such as 4-di-isopropylamino group and cyclohexylamine, diamines such as diethylaminopropyl group, and dimethylaminoethyl. It may be a triamine such as an aminoethylamino group, may be substituted with a ketone group, and may contain a cyclic structure.

Although the specific example of a processing agent is shown below, it is not limited.

The solvent that the composition of the present invention may contain is a dispersion of the colorant in the resin, and the coating of the colored composition of the present invention on a substrate such as a glass substrate so that the dry film thickness becomes a desired film thickness. Used to make it easier to do.
As a solvent,
Toluene, 1,2,3-trichloropropane, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3, 5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1 -Butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methyl Lupyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, P-chlorotoluene, P-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, water, methanol, ethanol, Isopropyl alcohol, tertiary tertiary butanol, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene Glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol Recall monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether Acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl Ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene Glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol Le, methyl isobutyl ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.
These solvents can be used singly or in combination of two or more at any ratio as required.

When the composition containing the quantum dots of the present invention is applied and patterned by ultraviolet irradiation and photolithography, a photosensitive material, a monomer, and an oligomer are added, and a positive resist or negative resist is added. Type resist. These can be used alone or in admixture of two or more.
Examples of the photosensitive substance that may be contained in the composition of the present invention include a photopolymerization initiator, a photoacid generator, and a photobase generator. A photosensitive substance can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 Acetophenone compounds such as-[4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or ben Benzoin compounds such as rudimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, or 3,3 ′, 4 Benzophenone compounds such as 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, etc. 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -S-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- ( 4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- (4 Triazine compounds such as' -methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], or O Oxime ester compounds such as (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide Or phosphine compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds Or a titanocene compound or the like is used.
Examples of the photoacid generator include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium 2- (adamantan-1-ylcarbonyloxy) -1,1,3,3,3-pentafluoropropane-1-sulfonate, and triphenyl. Sulfonium norbornane sultone-2-yloxycarbonyldifluoromethanesulfonate, triphenylsulfonium piperidin-1-ylsulfonyl-1,1,2,2,3,3-hexafluoropropane-1-sulfonate, triphenylsulfonium adamantane-1- Iroxycarbonyldifluoromethanesulfonate, 4-cyclohexylphenyldiphenylsulfonium camphorsulfonate, 4-methanesulfonylphenyldiphenylsulfonium nonafluoro- sulfonium salts such as n-butanesulfonate;
1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (6-n-butoxynaphthalen-1-yl) tetrahydrothiophenium 2-bicyclo [2.2.1] Tetrahydrothiophenium salts such as hept-2-yl-1,1,2,2-tetrafluoroethane-1-sulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium camphorsulfonate;
N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene And N-sulfonyloxyimide compounds such as -2,3-dicarboximide.

  The photopolymerization initiator and / or photoacid generator is a resin component contained in the photocurable adhesive (from the saturated alicyclic epoxy ester compound of the present invention and other active energy polymerizable compounds contained as necessary). The resin component is preferably 0.01 to 20 parts per 100 parts. If it is less than 0.01 part, curing is insufficient, and if it is more than 20 parts, coloring from the photoacid generator and other physical properties are reduced.

Examples of the photobase generator include 4- (methylthiobenzoyl) -1-methyl-1-morpholinoethane, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, 2-benzyl-2-dimethylamino- Heterocyclic group-containing photobase generators such as 1- (4-morpholinophenyl) -butanone, N- (2-nitrobenzyloxycarbonyl) pyrrolidine, 1- (anthraquinone-2-yl) ethylimidazole carboxylate, 2-nitro Benzylcyclohexyl carbamate, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, bis [[(2-nitrobenzyl) oxy] carbonyl] hexane-1,6-diamine, triphenylmethanol, o-carbamoylhydroxyl Amide, o-carbamoylo Shim, hexaamminecobalt (III) tris (triphenylmethyl borate) and the like.

<Sensitizer>
Furthermore, the coloring composition for a color filter of the present invention can contain a sensitizer.
Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 ', or 4,4'-tetra (t-butylperoxycarbonyl) benzopheno And 4,4′-diethylaminobenzophenone.
These sensitizers can be used singly or in combination of two or more at any ratio as necessary.

<Photopolymerizable monomer>
The photopolymerizable monomer used in the present invention includes monomers or oligomers that are cured by ultraviolet rays or heat to form a resin, and these can be used alone or in combination of two or more.

Examples of the photopolymerizable monomer include methyl methacrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, cyclohexyl methacrylate, β-carboxyethyl methacrylate, polyethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, triethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, 1,6-hexanediol di Glycidyl ether dimethacrylate, bisphenol A diglycidyl ether dimethacrylate, neopentyl grease Diglycidyl ether dimethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentamethacrylate, tricyclodecanyl methacrylate, ester acrylate, methylolated melamine methacrylate, epoxy methacrylate, urethane acrylate, etc. Acrylic acid ester and methacrylic acid ester, acrylic acid, methacrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, methacrylamide, N-hydroxymethylmethacrylamide, N-vinylformamide, acrylonitrile However, it is not necessarily limited to these.
These photopolymerizable compounds can be used singly or in combination of two or more at any ratio as required.

<Method for producing acrylic resin solution>
(Adjustment of acrylic resin solution 1)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), A mixture of 0.4 part of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight (Mw) of 26000. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Propylene glycol monoethyl was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Acrylic resin solution 1 was prepared by adding ether acetate.

(Adjustment of acrylic resin solution 2)
A separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirring device was charged with 370 parts of cyclohexanone, heated to 80 ° C., and the atmosphere in the flask was replaced with nitrogen. 18 parts of milphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2,2′-azobisisobutyronitrile 2.0 Part of the mixture was added dropwise over 2 hours. After dropping, the reaction was further carried out at 100 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour. Next, the inside of the container is replaced with air, and 0.5 part of trisdimethylaminophenol and 0.1 part of hydroquinone are put into 9.3 parts of acrylic acid (100% of glycidyl group) and the container is placed at 120 ° C. The reaction was continued for 6 hours, and when the acid value of the solid content reached 0.5, the reaction was terminated to obtain an acrylic resin solution. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl group) and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain a solution of an acrylic resin having a weight average molecular weight (Mw) of 19000. Obtained. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Then, an acrylic resin solution 2 which is an active energy ray curable resin was prepared.

(Adjustment of acrylic resin solution 3)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. Further, a mixture of 14.8 parts of n-butyl methacrylate, 14.8 parts of methyl methacrylate and 0.4 parts of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight (Mw) of 22000. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Propylene glycol monoethyl was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Acrylic resin solution 3 was prepared by adding ether acetate.

<Synthesis of quantum dots>
QD: InP / ZnS core-shell quantum dots were synthesized as follows according to the description in the technical literature “Inorganic Chemistry 2016, (17), pp 838-8386”.

[Example 1]
Synthesis of Quantum Dot QD-1 0.29 g of indium acetate, 0.28 g of zinc octoate, 1.00 g of stearic acid, and 20 ml of 1-octadecene were placed in a 25 ml flask and heated to 100 ° C. Then, it depressurizingly distilled at the temperature. The inside of the flask was viewed with argon gas and heated to 300 ° C. Separately, the solution was poured into 5 ml of hexane of 0.25 g of tris (trimethylsilyl) phosphine prepared in a glow box without water, reacted at 280 ° C. for 9 minutes, and rapidly cooled. 3.2 ml of this solution, 10 ml of 1-octadecene and 2.5 ml of oleylamine were placed in a flask and stirred for 15 minutes, and then 0.93 g of zinc dibenzyldithiocarbamate was added. The inside of the reaction flask was replaced with argon, the temperature was raised to 170 ° C. in 45 minutes, and the temperature was kept at 170 ° C. for 2 hours. After cooling, acetone was added and separated by centrifugal sedimentation. The precipitated paste was dispersed in toluene, 0.8 g of the ligand 1 shown in Table 1 was added as a treating agent, and the mixture was stirred at room temperature for 24 hours, concentrated under reduced pressure, then added with acetone, and separated by centrifugal sedimentation. Again, it was dispersed in toluene to obtain a 10% toluene solution of QD-1.

[Examples 2 to 19 and Comparative Example 1]
(Quantum dots QD-2 to 20)
A 10% toluene solution of quantum dots QD-2 to 20 was synthesized in the same manner as in Example 1 except that the type of treatment agent was changed. Table 1 shows the types of treatment agents used in the synthesis of the quantum dots QD-2 to 20.

The structures of ligands 1-19 in Table 1 are shown in Table 2.

<Negative resist>
[Example 20]
Preparation of QD negative resist 1 A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare QD resist 1.

QD-1 10% toluene solution: 0.60 part acrylic resin solution 1: 9.66 parts propylene glycol monomethyl ether acetate (PGMAC): 24.1 parts acrylic resin solution 2: 3.22 parts photopolymerizable monomer ( "Aronix M-402" manufactured by Toagosei Co., Ltd.): 0.86 parts dipentaerythritol hexaacrylate photopolymerization initiator ("OXE-02" manufactured by Ciba Japan): 0.70 parts Etanone, 1- [9-ethyl -6- (2-Methylbenzoyl) -9H-carbazol-3-yl]-, 1- (o-acetyloxime)

[Examples 21-39 and Comparative Example 2]
QD negative resists 2 to 20 were prepared in the same manner as in Example 20 except that the type of quantum dots was changed. Table 3 shows the types of quantum dots used in the preparation of the QD negative resists 2 to 20.

<Evaluation of QD negative resist>
The obtained QD resist was applied with a spin coater so as to have a dry film thickness of 1 μm to prepare a coated substrate. After application, it was pre-dried in a hot air oven at 70 ° C. for 5 minutes. After performing ultraviolet exposure at 50 mj / square cm, the substrate was dipped in an alkaline developer of 0.04% KOH aqueous solution for 2 minutes, washed with pure water, dried and subjected to alkali development. Then, after heating in an oven at 220 ° C. for 20 minutes, it was allowed to cool and post-baked.
The fluorescence quantum yield after preliminary drying (pre-baking), ultraviolet exposure, alkali development, and post-baking was measured with an external quantum efficiency measuring device (C9920 manufactured by Hamamatsu Photonics Co., Ltd.).
Compared with the fluorescence quantum yield after pre-baking, it is preferable that the change is small, 80% or more 5, 79-60% 4, 59-40% 3, 39-20% 2, 2, less than 19% 1 is summarized in Table 3.

When the processing agent of this invention was used, it was shown that there is little quantum yield fall compared with the processing agent which does not have a pyridine structure. Although the effect mechanism of the treatment agent has not been clarified, it is presumed that the sterically small pyridine nitrogen lone pair acted favorably on the QD surface.

<Positive resist>
[Example 40]
Preparation of QD positive resist 21 A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare a QD resist 21.

QD-1 10% toluene solution: 0.60 parts Acrylic resin solution 3: 13.7 parts Toluene: 24.1 parts Photoacid generator (manufactured by PAI-101 Midori Chemical Co., Ltd.): 0.70 parts 2- (4 -Methylphenylsulfonyloxyimino)-(4-methoxyphenyl) acetonitrile

[Examples 41 to 58 and Comparative Example 3]
QD negative resists 22 to 39 were prepared in the same manner as in Example 40 except that the type of quantum dots was changed. Table 4 shows the types of quantum dots used in the production of the QD positive resists 21-40.

[Evaluation of QD positive resist]
The obtained QD positive resist was applied with a spin coater so as to have a dry film thickness of 1 μm to prepare a coated substrate. After application, it was pre-dried in a hot air oven at 70 ° C. for 5 minutes. The substrate was immersed in an alkaline developer of 0.04% KOH aqueous solution for 2 minutes, washed with pure water, dried and subjected to alkali development. Then, after heating in an oven at 220 ° C. for 20 minutes, it was allowed to cool and post-baked.
The fluorescence quantum yield after preliminary drying (pre-baking), ultraviolet exposure, alkali development, and post-baking was measured with an external quantum efficiency measuring device (C9920 manufactured by Hamamatsu Photonics Co., Ltd.).
Compared with the fluorescence quantum yield after pre-baking, it is preferable that the change is small, 80% or more 5, 79-60% 4, 59-40% 3, 39-20% 2, 2, less than 19% 1 is summarized in Table 4.

Similar to the negative resist, the effect of the treatment agent of the present invention was shown.

Claims (5)

A quantum dot comprising semiconductor fine particles, wherein the semiconductor fine particles are surface-treated with a treatment agent containing a compound having a pyridine structure. 2. The quantum dot according to claim 1, wherein the semiconductor fine particle is a compound semiconductor. 3. The quantum dot according to claim 1, wherein the semiconductor fine particles are of a core / shell type. A quantum dot-containing composition comprising the quantum dot according to claim 1 and a solvent. Furthermore, a photopolymerizable monomer is contained, The quantum dot content composition according to claim 4 characterized by things.