JP2020094174A - Quantum dot, ink composition, and printed matter - Google Patents

Abstract

To provide: an ink composition that achieves excellent external quantum efficiency and further has excellent quantum dot dispersion stability and good inkjet discharging performance; and printed matter formed using the ink composition.SOLUTION: An ink composition comprises quantum dots (A) that are core-shell semiconductor fine particles surface-treated with a compound represented by a specific formula, and a solvent (B). Printed matter is formed using the ink composition.SELECTED DRAWING: None

Description

The present invention relates to a quantum dot exhibiting excellent external fluorescence quantum efficiency, an ink composition most suitable for an inkjet method, and a printed matter.

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 from 1 nanometer to several tens of nanometers in diameter, and is composed of about 10,000 atoms or less. The wavelength of the emitted fluorescence can be continuously controlled by the size of the particles, and sharp emission with highly symmetrical wavelength distribution of the fluorescence intensity can be obtained, which has recently attracted attention.
Quantum dots can adjust the fluorescence to a wavelength that easily penetrates the human body and can be delivered to any place in the body, so they are light emitting materials for bioimaging applications, wavelength conversion materials for solar cell applications without fear of fading, electronics and photonics applications. The development of light emitting materials or wavelength conversion materials has been studied.

When quantum dots are used as a wavelength conversion material, there is a problem that the light of the backlight is transmitted through the quantum dot layer, the light of the backlight is not sufficiently absorbed by the quantum dot layer, and the light is not sufficiently converted. In order to solve the above problems, a method of diffusing light by using scattering has been proposed. For example, in Patent Document 1, a light diffusion layer having scattering particles is provided in addition to a color conversion layer containing quantum dots. Is provided. In addition, Patent Document 2 describes a self-luminous resin composition having excellent sedimentation stability, which contains quantum dots using trioctylphosphine as a ligand and inorganic scattering particles.
On the other hand, a method of improving light absorption and light conversion by increasing the quantum dot concentration in the coating film has been proposed, and the ligand bound to the surface of the quantum dot is optimized to optimize the phase in the coating film or composition. It has been studied to improve the solubility.
For example, Patent Document 3 describes that a polyalkylene glycol chain is fixed to semiconductor ultrafine particles to achieve both hydrophilicity and nonspecific adsorption to a biological substance. In addition, Patent Document 4 describes an inkjet ink containing a quantum dot, an alumina-coated titanium oxide that is a light-scattering particle, and a polymer dispersant, which is excellent in sedimentation/separation suppression properties and ejection stability.

JP, 2017-161938, A JP, 2016-098375, A JP, 2002-121549, A JP, 2018-109141, A

However, in the method described in Patent Document 1, the light wavelength conversion efficiency can be improved by additionally providing the light diffusion layer, but the complexity of the display device itself increases, and there is a problem in terms of productivity, cost, and the like. Cause Further, in Patent Document 2, a trioctylphosphine ligand is used as a ligand, and when the concentration of quantum dots is increased, dispersion stability and inkjet ejection property are deteriorated, and optical properties cannot be improved.
Patent Document 3 has a problem that compatibility with water can be obtained by designing a ligand, but compatibility with a solvent cannot be obtained. Further, Patent Document 3 does not disclose the external conversion efficiency of the coating film.
Further, in Patent Document 4, a ligand having a long-chain alkyleneoxy group is used, and similarly to Patent Document 2, when the concentration of quantum dots is increased, dispersion stability and inkjet ejection property are deteriorated and optical properties are improved. I can't.

That is, an object of the present invention is to provide a quantum dot exhibiting excellent external fluorescence quantum efficiency, and an ink composition including the quantum dot, which has excellent external fluorescence quantum efficiency and excellent inkjet stability and excellent inkjet stability. And to provide printed matter.

The present invention relates to the following [1] to [10] inventions.

[1] Quantum dots (A), which are semiconductor fine particles surface-treated with a compound represented by the following general formula (1).
General formula (1)

[In the general formula (1),
X: Direct bond, or divalent linking group having a molecular weight of 150 or less Y: Methylene group, methine group, or tetra-substituted carbon atom Q: Sulfanyl group, alkylsulfanyl group, or monovalent heterocyclic group R containing a sulfur atom ¹ : Direct bond, imino group (NR ³ ), oxygen atom, or CH ₂ O
R ² : hydrogen atom, alkyl group, amino group (NR ⁴ R ⁵ ), or alkoxy group (OR ⁶ ).
R ^{3 to} R ⁵ : each independently, an alkyl group or a hydrogen atom R ⁶ : an alkyl group m: an integer of 1 to 3]

[2] The quantum dot (A) according to [1], wherein the semiconductor fine particles are a compound semiconductor.

[3] The quantum dot (A) according to [1] or [2], wherein the semiconductor fine particles are core-shell type, and the shell surface is treated with the compound represented by the general formula (1).

[4] The quantum dot (A) according to any one of [1] to [3], wherein in the general formula (1), R ¹ is an oxygen atom and R ² is an alkyl group.

[5] The quantum dot (A) according to any one of [1] to [4], wherein the divalent linking group represented by X in the general formula (1) has a molecular weight of 110 or less.

[6] An ink composition containing the quantum dots (A) according to any one of [1] to [5] and a solvent (B).

[7] An ink composition containing the quantum dots (A) according to any one of [1] to [5] and a binder component (C).

[8] The ink composition according to [7], further including light scattering particles (D).

[9] The ink composition according to any one of [6] to [8], which is used in an inkjet method.

[10] A printed matter formed using the ink composition according to any one of [6] to [8].

According to the present invention, a quantum dot exhibiting excellent external fluorescence quantum efficiency, and an ink composition and a printed matter having excellent external fluorescence quantum efficiency including the quantum dot and excellent inkjet stability and excellent dispersion stability. Can be provided.

<Quantum dot (A)>
The quantum dots (A) of the present invention are semiconductor fine particles surface-treated with a compound represented by the following general formula (1). "Surface-treated" means having the compound on at least a part of the surface of the semiconductor fine particles, and such a compound existing on the surface of the semiconductor fine particles is also referred to as a ligand.
Hereinafter, the present invention will be described in detail. Unless otherwise specified, "parts" and "%" mean "parts by mass" and "mass %".

[Semiconductor particles]
The semiconductor fine particles are semiconductors mainly containing an inorganic substance, and may have a single composition, a core-shell type, or a plurality of layers of three or more layers.
The semiconductor is a group of elements represented by Group 1 element, Group 2 element, Group 10 element, Group 11 element, Group 12 element, Group 13 element, Group 14 element, Group 15 element, Group 16 element and Group 17 element of the periodic table. It is a semiconductor made of a compound containing at least two or more elements selected from More preferably, the compound semiconductor is H, K, Rb, Cs, Cu, Ag, Zn, Cd, Hg, B, Al, Ga, In, Tl, C, Si, Ge, Sn, N, A semiconductor composed of a compound containing at least two elements selected from the group of elements represented by P, As, Sb, Pb, O, S, Se, Te, F, Cl, Br and I, and specifically CuCl , CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, MgTe, GaAs, GaP, GaSb, GaN, HgS, HgSe, HgTe, InAs, InP, InSb, InN, AlAs, AlP, AlSb, AlS, PbS, PbSe, Ge. _{, Si, CuInS 2, AgInS 2} , Si, Ge, Pb, InGaP, CH 3 NH 3 PbF 3, CH 3 NH 3 PbCl 3, CH 3 NH 3 PbBr 3, CH 3 NH 3 PbI 3, CsPbF 3, CsPbCl 3 , CsPbBr ₃ , CsPbI ₃ , RbPbF ₃ , RbPbCl ₃ , RbPbBr ₃ , RbPbI ₃ , KPbF ₃ , KPbCl ₃ , KPbBr ₃ , KPbI _{3 and the} like.
More preferably, H, K, Rb, Cs, Cu, Ag, Zn, B, Al, Ga, In, C, Si, Ge, Sn, N, P, O, S, Te, Cl, Br and I are used. It is a semiconductor made of a compound containing at least two elements selected from the group of elements shown.
For the purpose of emitting visible light, a semiconductor containing In as a constituent element is more preferable because of its 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 component different from that of the semiconductor forming the core. By making the shell a semiconductor with a large band gap, 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 efficiency of light emission and the stability of the fluorescence characteristics of the semiconductor quantum dots are improved, which is preferable.

The average particle size of the semiconductor fine particles including the core and the shell is preferably 0.5 nm to 100 nm, and the particle size that allows desired color development can be selected. In the case of the core-shell type, one semiconductor particle may contain a plurality of shell particles. The average particle size of the semiconductor fine particles and the average particle size of the core-shell type core having a single semiconductor composition are preferably 0.5 nm to 10 nm. An average particle size of 0.5 nm or more is preferable in terms of synthesis, and an average particle size of 10 nm or less is preferable because the quantum confinement effect is improved and desired fluorescence is easily obtained.
The average particle size of the quantum dots having a ligand on the surface is preferably 2 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 another shape.

The average particle size mentioned here is a value obtained by observing the quantum dots with a transmission electron microscope, measuring 30 sizes at random, and adopting the average value thereof. The particle size of the quantum dots was determined by specifying the semiconductor material portion of the quantum dots and using a scanning transmission electron microscope accompanied by energy dispersive X-ray analysis to obtain an image due to the difference in electron density between the ligand and the semiconductor particles. It can be measured from light and dark.

[Compound represented by the general formula (1)]
The quantum dot (A) of the present invention has a compound represented by the following general formula (1) as a ligand on the surface of semiconductor fine particles.

General formula (1)

[In the general formula (1),
X: Direct bond, or divalent linking group having a molecular weight of 150 or less Y: Methylene group, methine group, or tetra-substituted carbon atom Q: Sulfanyl group, alkylsulfanyl group, or monovalent heterocyclic group R containing a sulfur atom ¹ : Direct bond, imino group (—NR ³ ), oxygen atom, or CH ₂ O
R ^2: a hydrogen atom, an alkyl group, an amino group ^{(-NR 4 R} 5), or an alkoxy group ^(-OR 6)
R ^{3 to} R ⁵ : each independently, an alkyl group or a hydrogen atom R ⁶ : an alkyl group m: an integer of 1 to 3]

The substituent of the general formula (1) will be described.
The divalent linking group having a molecular weight of 150 or less in X is not particularly limited, but is preferably at least one group selected from the group consisting of an alkylene group and an oxyalkylene group, and an alkylene group and an oxyalkylene group are included. It may be a combination of groups. The molecular weight of the divalent linking group is preferably 130 or less, more preferably 110 or less.

Examples of the alkylene group include a methylene group, an ethylene group, a hexylene group, a dodecylene group or an ether.
A linear alkylene group such as icosylene may be mentioned, and the alkylene group may be substituted with an alkyl group having 1 to 3 carbon atoms, or a part of hydrogen may be removed to form a double bond. It may be a ring. An alkylene group having 1 to 6 carbon atoms is preferable, and an alkylene group having 1 to 3 carbon atoms is more preferable.

Examples of the oxyalkylene group include an oxymethylene group, an oxyethylene group, an oxyhexylene oxide group, an oxidedecylene group, a linear oxyalkylene group such as an oxyeicosylene group, and the like, but an alkyl group having 1 to 3 carbon atoms. May be substituted with, a part of hydrogen may be removed to form a double bond, or a ring may be formed. An oxyalkylene group having 1 to 5 carbon atoms is preferable, and an oxyalkylene group having 1 to 3 carbon atoms is more preferable.

Examples of the alkyl group in R ^{2 to} R ^{6 and} the alkyl group in the alkylsulfanyl group for Q include linear alkyl groups such as a methyl group, an ethyl group and a hexyl group, and the alkyl group has 1 to 3 carbon atoms. May be substituted with an alkyl group of, a part of hydrogen may be removed to form a double bond, or a ring may be formed. The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group.

Examples of the monovalent heterocyclic group containing a sulfur atom of Q include a thienyl group, a tetrahydrothienyl group, a cyanyl group, a thiazolyl group and a thiazinyl group. These may be substituted with an alkyl group having 1 to 6 carbon atoms. More preferably, it is a thienyl group or a thianyl group.

The substituent Q in the general formula (1) is preferably a sulfanyl group, an alkylsulfanyl group, a thienyl group or a cyanyl group, and more preferably a sulfanyl group.

The number m of carbonyl groups is an integer of 1 to 3, but 1 or 2 is preferable, and 1 is more preferable. That is, Y is preferably a methylene group.

The carbonyl group is preferably present as an ester. That is, it is preferable that R ¹ is a direct bond and R ² is an alkoxy group, or R ¹ is an oxygen atom or CH ₂ O and R ² is an alkyl group, and more preferably R ¹ is an oxygen atom. And R ² is an alkyl group.

From the viewpoint of improving the content ratio of the quantum dots and ensuring compatibility, the compound represented by the general formula (1) preferably has a molecular weight of 80 to 400, more preferably 100 to 250.

Specific examples of the compound represented by the general formula (1) and other compounds are shown in Tables 1 to 3 below.

The quantum dot (A) may be surface-treated with another known ligand in addition to the compound represented by the general formula (1). Further, known quantum dots surface-treated with a known ligand other than the compound represented by the general formula (1) may be used in combination.

<Ink composition>
The quantum dot of the present invention can be made into an ink composition by further containing a solvent (B) and/or a binder component (C).

<Solvent (B)>
The solvent (B) is preferably an organic solvent, and when used as an inkjet ink, mainly from the viewpoint of solubility in a binder component described below, swelling action on a printer member in contact with ink, viscosity, and drying property at a nozzle, You can choose the best one.
The organic solvent preferably contains at least one selected from the group consisting of alcohol solvents, glycol solvents, ester solvents and ketone solvents. These may be used alone or in combination of two or more.

Examples of alcohol solvents include hexanol, heptanol, octanol, nonanol, decanol, undecanol, cyclohexanol, benzyl alcohol, and amyl alcohol.

Examples of the glycol solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, methoxymethoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol. Monobutyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol isopropyl ether, propylene glycol Mention may be made of monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 1-butoxyethoxypropanol, 1-methoxy-2-propylacetate and the like.

Examples of the ester solvent include ethyl lactate, propane lactate, butyl lactate and the like.

Examples of the ketone solvent include cyclohexanone, ethyl amyl ketone, diacetone alcohol, diisobutyl ketone, isophorone, methylcyclohexanone, acetophenone and the like.

The solvent (B) is a solvent (S-1) or a solvent (S-2) represented by the following general formula from the viewpoints of viscosity, ink drying property at a nozzle, solubility with respect to contained components, and swelling action with respect to apparatus members. And at least one selected from the group consisting of solvents (S-3) having two or more acetate structures, and having a boiling point of 120° C. to 260° C. at 760 mmHg, preferably 170° C. or higher. ..
Solvent (S-1):
^{_{R 18 - (O-C 2}} H 4) m -O-C (= O) -CH 3
[In the general formula, R ¹⁸ is an alkyl group having 1 to 8 carbon atoms, C ₂ H ₄ is a linear or branched ethylene chain, and 1≦m≦3. ]
Solvent (S-2):
^{_{R 19 - (O-C 3}} H 6) p -O-C (= O) -CH 3
[In the general formula, R ¹⁹ is an alkyl group having 1 to 8 carbon atoms, C ₃ H ₆ is a linear or branched propylene chain, and 1≦p≦3. ]

Specific examples of the solvents (S-1) to (S-3) include propylene glycol methyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol diacetate, 1, Examples thereof include 3-butylene glycol diacetate, 1,6-hexanediol diacetate, and triacetin, but are not limited thereto. Among them, propylene glycol methyl ether acetate or diethylene glycol monobutyl ether acetate is preferable from the viewpoint of ejection stability.

In addition, it is preferable that the content of the organic solvent having a boiling point of 170° C. or higher at 760 mmHg is 60% by mass or more with respect to the total amount of the solvent (B) from the viewpoints of ejection stability and ink drying property in the nozzle.

The SP value of the solvent (B) is preferably 8 to 13. The SP value in the present invention can be calculated by the Fedors estimation method which is calculated from the molecular structure.

<Binder component (C)>
A resin (C1) or a polymerizable compound (C2) can be used as the binder component (C).

[Resin (C1)]
As the resin, it is possible to use either a thermosetting resin or a thermoplastic resin, for example, petroleum resin, maleic acid resin, nitrocellulose, cellulose acetate butyrate, cyclized rubber, chlorinated rubber, alkyd resin, acrylic resin, Polyester resin, amino resin, vinyl resin, butyral resin, linear olefin resin, aromatic polyether resin, polyimide resin, fluorene polycarbonate resin, fluorene polyester resin, polycarbonate resin, polyamide (aramid) resin, polyarylate resin, polysulfone resin, Examples include polyether sulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate (PEN) resin, fluorinated aromatic polymer resin, epoxy resin, allyl ester curable resin, silsesquioxane UV curable resin, and the like. ..
The resin can be appropriately selected depending on the coating, printing method and substrate. Among them, acrylic resin is preferable from the viewpoint of affinity with the treating agent.

Specific examples of the resin include BR-50, BR-52, MB-2539, BR-60, BR-64, BR-73, BR-75, MB-2389, BR-80, BR- manufactured by Mitsubishi Rayon Co., Ltd. 82, BR-83, BR-84, BR-85, BR-87, BR-88, BR-90, BR-95, BR-96, BR-100, BR-101, BR-102, BR-105, BR-106, BR-107, BR-108, BR-110, BR-113, MB-2660, MB-2952, MB-3012, MB-3015, MB-7033, BR-115, MB-2478, BR- 116, BR-117, BR-118, BR-122, ER-502, A-11, A-12, A-14, A-21, B-38, B-60, B manufactured by Wilber-Ellis. -64, B-66, B-72, B-82, B-44, B-48N, B-67, B-99N, DM-55, BASF JONCRYL67, JONCRYL678, JONCRYL586, JONCRYL611, JONCRYL680, JONCRYL682. , JONCRYL683, JONCRYL690, JONCRYL819, JONCRYL JDX-C3000, JONCRYL JDX-C3080, Nissin Chemical Industry Solvain Resin CL, CNL, C5R, TA3, TA5R, Wacker Vinyl Resins E15/45, H14/36, H14/36. /43, E15/45M, E15/40M, Arakawa Chemical Co., Ltd. Superester 75, Ester gum HP, Malquid 33, Yasuhara YS Polystar T80, Mitsui Chemicals Hiretts HRT200X, Sartomer SMA2625P, Toyobo. Manufactured byron series, DIC manufactured polylite series, Ube Industries manufactured polyester polyol series, Tosoh manufactured Nippon Poland series, ADEKA manufactured Adeka New Ace series, Adeka polyether series, AGC made Exenol series, Daiichi Kogyo Seiyaku Poly Hardener, DK Flex, DK Polyol, Hard Master, Sanyo Kasei Prime Pole Series, Taisei Fine Chemicals 6000 Series, Mitsubishi Chemical jER828, jER825, jER834, jER1001, jER1002, jER1009, jER1010, jER806, jER807, jER4005P. , JER4007P, jER4010P, jER1256, jER152, Examples include jER154, jER157S70, 1031S, Kaneka Zemlac, and the like.
The above resins may be used alone or in combination of two or more.

The weight average molecular weight (Mw) of the resin is preferably 1,000 to 50,000, and particularly preferably 3,000 to 45,000 in order to stably eject the ink composition from the inkjet head. When the mass average molecular weight is 1,000 or more, the resistance of the printed matter to the coating film is sufficient, and when the mass average molecular weight is 50,000 or less, clogging of the inkjet head is less likely to occur and the ejection properties are good. The mass average molecular weight Mw can be determined as a styrene-equivalent molecular weight by gel permeation chromatography.

[Curing agent]
When the binder component (B) contains a resin, a curing agent may be used together. When a curing agent is used in combination, the curing agent is included in the binder component.
Examples of the curing agent include those that react with functional groups in the resin to form crosslinks between molecules, and include, for example, amine compounds, isocyanate compounds, polyol compounds, carboxylic acid compounds, acrylate monomers, carbodiimide compounds, and epoxy compounds. One or more compounds selected from the group consisting of an oxetane compound, a phenol compound, a benzoxazine compound, and a silane coupling agent can be used.

Further, as the cross-linking system to be formed, an amino group-epoxy cross-linking system, a urethane bond cross-linking system, an alkoxysilane cross-linking system, an ester group cross-linking system, or a composite cross-linking system in which two or more kinds thereof are combined is preferably used.

Specific examples of the amino group-epoxy cross-linking system include a combination of a bifunctional or higher amine compound and a bifunctional or higher epoxy compound, for example, an epoxy resin and a bifunctional or higher amine compound. Specific examples of the urethane bond crosslinking system include a combination of a polyol compound and a polyisocyanate compound, for example, a polyol resin and a difunctional or higher functional isocyanate compound. Specific examples of the alkoxysilane crosslinking system include a moisture curing system of an alkoxysilyl group pendant acrylic resin. Specific examples of the ester group crosslinking system include a combination of a carboxyl group pendant acrylic compound or a carboxyl group pendant polyester and a bifunctional or higher functional epoxy compound. For example, an epoxy resin and a bifunctional or higher functional carboxyl group pendant compound may be used. Can be mentioned.

Examples of the bifunctional or higher amine compound include chain aliphatic polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenediamine or diethylaminopropylamine; N-aminoethylpiperazine and di(4-amino-3). -Methylcyclohexyl) methane, Araldit HY-964, menthenediamine, isophoronediamine, S Cure211, S Cure212, di(4-aminocyclohexyl)methane, or 1,3-aminomethylenecyclohexane; Aliphatic aromatic amines such as xylylenediamine, xylylenediamine trimer, xylylenediamine derivative, and xylylene derivative; aromatic amines such as melamine, benzoguanamine, metaphenylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone; These can be used alone or in combination of two or more.

Examples of commercially available isocyanate compounds include Barnock series manufactured by DIC, Takenate series manufactured by Mitsui Chemicals, Coronate series manufactured by Tosoh, and Millionate series.

Examples of the carboxyl group pendant acrylic compound include a copolymer of (meth)acrylic acid and a (meth)acrylic monomer copolymerizable with (meth)acrylic acid.
Examples of the pendant carboxyl group polyester include an addition reaction product of a compound having two acid anhydride groups and a diol. Examples of the compound having two acid anhydride groups include ethylene glycol bisanhydrotrimellitate, glycerin bisanhydrotrimellitate monoacetate, benzophenone tetracarboxylic acid dianhydride, pyromellitic anhydride, 4, 4'-biphthalic anhydride and the like, and examples of the diol include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, neopentyl glycol, cyclohexanediol, cyclopentanediol, and the like. It can be synthesized according to the polyester synthesis method.

[Polymerizable compound (C2)]
As the polymerizable compound, a polymerizable monomer that is polymerized by irradiation with light or heat can be used, and a photopolymerizable monomer is preferable. The photopolymerizable monomer that can be used is not particularly limited, and may be a photoradical polymerizable monomer or a photocationic polymerizable monomer, and a monofunctional monomer and a polyfunctional monomer may be used alone or in combination. Good.

(Photo radical polymerizable monomer)
Specific examples of the photo-radical polymerizable monomer include benzyl (meth)acrylate, (ethoxy (or propoxy)-modified) 2-phenoxyethyl (meth)acrylate, dicyclopentenyl (oxyethyl) (meth)acrylate and phenoxy as monofunctional monomers. Diethylene glycol (meth)acrylate, 2-methoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, 2-ethoxyethyl (meth)acrylate, ethoxyethoxyethyl (meth)acrylate, methoxydipropylene glycol (meth)acrylate, Dipropylene glycol (meth)acrylate, β-carboxyl ethyl (meth)acrylate, trimethylolpropane formal (meth)acrylate, isoamyl (meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth) ) Acrylate, dicyclopentanyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 1,4-cyclohexanedimethanol (meth)acrylate, 2 -Hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, acrylamide (meth)acrylate, acryloylmorpholine, N-vinylcaprolactam, N-vinylpyrrolidone, N-vinylformamide, N-acryloyloxyethyl hexahydrophthalimide, ester acrylates, (meth)acrylic acid esters of methylolated melamine, epoxy (meth)acrylates, methyl (meth)acrylates, ethyl (meth)acrylates, various acrylic acid esters such as urethane acrylates, and Methacrylic acid ester, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinylformamide, acrylonitrile and the like can be mentioned.

Further, as the photo-radical polymerizable polyfunctional monomer, dimethylol tricyclodecane di(meth)acrylate, (ethoxy(or propoxy))bisphenol A di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, ( Poly)ethylene glycol di(meth)acrylate, (ethoxy (or propoxy)ated) 1,6-hexanediol di(meth)acrylate, (ethoxy (or propoxy)ated) neopentyl glycol di(meth)acrylate, hydroxypivalic acid Neopentyl glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, (neopentyl glycol modified) trimethylolpropane di(meth)acrylate, tripropylene glycol di(meth)acrylate, dicyclopentanyl di(meth) Acrylate, pentaerythritol tri(or tetra)(meth)acrylate, trimethylolpropane tri(or tetra)(meth)acrylate, tetramethylolmethane tri(or tetra)(meth)acrylate, dipentaerythritol hexa(meth)acrylate, glycerin Examples thereof include di(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, tricyclodecanyl (meth)acrylate, hydroxyethyl vinyl ether, pentaerythritol trivinyl ether and the like.

(Photo-cationic polymerizable monomer)
Specific examples of the cationic photopolymerizable monomer include glycidyl methacrylate, 2-ethylhexyl oxetane, 3-hydroxymethyl-3-methyloxetane, 3-hydroxymethyl-3-ethyloxetane, and 3-hydroxymethyl-3 as monofunctional monomers. -Propyl oxetane, 3-hydroxymethyl-3-normal butyl oxetane, 3-hydroxymethyl-3-phenyl oxetane, 3-hydroxymethyl-3-benzyl oxetane, 3-hydroxyethyl-3-methyl oxetane, 3-hydroxyethyl- 3-ethyloxetane, 3-hydroxyethyl-3-propyloxetane, 3-hydroxyethyl-3-phenyloxetane, 3-hydroxypropyl-3-ethyloxetane, 3-hydroxypropyl-3-propyloxetane, 3-hydroxypropyl- Examples thereof include 3-phenyloxetane and 3-hydroxybutyl-3-methyloxetane.

Further, as the cationic photopolymerizable polyfunctional monomer, bisphenol A type epoxy compound, bisphenol F type epoxy compound, phenol novolac type epoxy compound, trimethylolpropane glycidyl ether, neopentyl glycol diglycidyl ether, 1,2-epoxy- 4-vinylcyclohexane, 1-methyl-4-(2-methyloxiranyl)-7-oxabicyclo[4.1.0]heptane, xylylenebisoxetane, 3-ethyl-3{[(3-ethyl Oxetane-3-yl)methoxy]methyl}oxetane and the like can be mentioned.

The content of the polymerizable compound (C2) is preferably 5 to 80% by mass based on the total solid content of the ink composition from the viewpoint of curability.

[Polymerization initiator]
When the binder component (B) contains a polymerizable compound, it is preferable to use a polymerization initiator together. Examples of the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator, and one kind may be used alone or two or more kinds may be mixed at an arbitrary ratio as necessary. When the polymerization initiator is used in combination, the polymerization initiator is regarded as the binder component.

When the binder component (B) contains a photopolymerizable compound, it is preferable to use a photopolymerization initiator together. The photopolymerization initiator may be a photoradical polymerization initiator or a photocationic polymerization initiator, and the type thereof is not limited. By including the photopolymerization initiator, the ink layer formed from the ink composition can be cured by irradiation with ultraviolet rays.

(Photo-radical polymerization initiator)
As the photo radical polymerization initiator, 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]- Acetophenone compounds such as 1-[4-(4-morpholinyl)phenyl]-1-butanone or 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one; benzoin; Benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyldimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4. Benzophenone compounds such as'-methyldiphenyl sulfide or 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2, A thioxanthone compound such as 4-diisopropylthioxanthone or 2,4-diethylthioxanthone; 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'-methoxystyryl)-6-triazine and other triazine compounds; 1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-be Oxime oxime)], or oxime ester compounds such as ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime); Phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinones such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone System compounds; borate compounds; carbazole compounds; imidazole compounds; or titanocene compounds.

Examples of commercially available acetophenone compounds include "Omnirad 907" (2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one) manufactured by IGM Resins BV. Omnirad 369" (2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone), "Omnirad 379" 2-benzyl-2. -Dimethylamino-1-(4-morpholinophenyl)-butan-1-one and the like can be mentioned.
Moreover, as a commercial item of a phosphine-type compound, "Omnirad 819" (bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide) made by IGM Resins BV., "Omnirad TPO H" (2,4 , 6-trimethylbenzoyldiphenylphosphine oxide) and the like.

(Photocationic polymerization initiator)
As the cationic photopolymerization initiator, diphenyliodonium hexafluorophosphate, iodonium salt such as 4-isopropyl-4′-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate, tri-p-tolylsulfonium hexafluorophosphate, triphenyl Examples thereof include sulfonium salts such as sulfonium tetrafluoroborate.

Commercially available iodonium salt compounds include "WPI-113" (bis[4-(alkylC10-C13)phenyl]iodonium hexafluorophosphate) manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., "WPI-116" (bis [4-(Alkyl C10-C13)phenyl]iodonium hexafluoroantimonate), "WPI-169" (bis[4-tert-butylphenyl]iodonium bisperfluorobutanesulfonylimide), "WPI-170" bis[4- Tert-butylphenyl]iodonium hexafluorophosphate), “WPI-124” (bis[4-(alkylC10-C13)phenyl]iodonium tetrakispentafluorophenylborate) and the like.
Examples of commercially available sulfonium salt compounds include CPI-100P (triarylsulfonium hexafluorophosphate), CPI-101A (triarylsulfonium hexafluoroantimonate), CPI-310BP (triarylsulfonium tetrakispenta) manufactured by San-Apro Ltd. Fluorophenyl borate), "Irgacure 290" (tetrakispentafluorophenyl borate) manufactured by BASF Corporation, and the like.

The photopolymerization initiators may be used singly or as a mixture of two or more kinds at an arbitrary ratio as needed.

Examples of the thermal polymerization initiator include a thermal radical polymerization initiator, a thermal cationic polymerization initiator, a thermal anionic polymerization initiator, or a mixture thereof.

Examples of thermal radical polymerization initiators include peroxides and azo compounds, and polymeric azo initiators composed of polymeric azo compounds can also be used.
Examples of the polymeric azo initiator include those having a structure in which a plurality of units such as polyalkylene oxide and polydimethylsiloxane are bonded via an azo group. Examples of the polymer azo initiator having a structure in which a plurality of units such as polyalkylene oxide are bonded via the azo group include, for example, a polycondensate of 4,4′-azobis(4-cyanopentanoic acid) and polyalkylene glycol. And polycondensation products of 4,4′-azobis(4-cyanopentanoic acid) and polydimethylsiloxane having a terminal amino group.
Examples of peroxides include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxy ester, diacyl peroxide, and peroxydicarbonate.

Examples of commercially available thermal radical polymerization initiators include Perbutyl O, Perhexyl O, Perbutyl PV (all manufactured by NOF CORPORATION), V-30, V-501, V-601, VPE-0201, VPE-0401, VPE-0601 (all manufactured by Wako Pure Chemical Industries, Ltd.) and the like can be mentioned.

Examples of the thermal cationic polymerization initiator include various onium salts such as quaternary ammonium salt, phosphonium salt and sulfonium salt. Examples of commercially available thermal cationic polymerization initiators include Adeka Opton CP-66, Adeka Opton CP-77 (all manufactured by ADEKA), Sun-Aid SI-60L, Sun-Aid SI-80L, and Sun-Aid SI-100L (all are Sanshin). Chemical Industry Co., Ltd., CI series (Nippon Soda Co., Ltd.) and the like.

<Light scattering particles (D)>
The ink composition of the present invention may contain light scattering particles (D). The light absorption of the quantum dots can be increased by scattering the light in the light conversion layer by the light scattering particles (D). Examples of the light scattering particles include inorganic light scattering particles (D1) and organic light scattering particles (D2).

<Inorganic light scattering particles (D1)>
Metal oxide particles can be preferably used as the inorganic light scattering particles (D1).
Examples of the metal oxide particles include titanium oxide (TiO ₂ ), zirconium oxide (ZrO ₂ ), cerium oxide (CeO ₂ ), hafnium oxide (HfO ₂ ), niobium pentoxide (Nb ₂ O ₅ ), tantalum pentoxide. (Ta ₂ O ₅ ), indium oxide (In ₂ O ₂ ), tin oxide (Sn ₂ O ₂ ), indium tin oxide (ITO), and at least one material selected from the group consisting of zinc oxide (ZnO). Particles consisting of Among them, particles of titanium oxide (TiO ₂ ), zirconium oxide (ZrO ₂ ), and zinc oxide (ZnO) are preferable, and titanium oxide (TiO ₂ ) particles are preferable from the viewpoint of translucency, dispersibility, weather resistance, and light resistance. Particularly preferred.

The titanium oxide is not particularly limited, and titanium oxide (TiO ₂ ) surface-treated in advance may be used. By performing the surface treatment, it is possible to stabilize dispersion and improve weather resistance. Any known surface treatment method and surface treatment agent can be used.

Specific examples of titanium oxide include "Taipec CR-50, 50-2, 57, 80, 90, 93, 95, 953, 97, 60, 60-2, 63, 67, 58, 58- manufactured by Ishihara Sangyo Kaisha, Ltd. 2,85" "Taipaque R-820, 830, 930, 550, 630, 680, 670, 580, 780, 780-2, 850, 855" "Taipaque A-100, 220" "Taipaque W-10" "Taipaque" PF-740, 744" "TTO-55(A), 55(B), 55(C), 55(D), 55(S), 55(N), 51(A), 51(C)" " "TTO-S-1, 2" "TTO-M-1, 2", manufactured by Teika "Titanics JR-301, 403, 405, 600A, 605, 600E, 603, 805, 806, 701, 800, 808". "Titanics JA-1, C, 3, 4, 5", "Titanics MT-01, 10EX, 05, 100S, 100TV, 100Z, 150EX, 150W, 100AQ, 100WP, 100SA, 100HD, 300HD, 500HD, 500B. , 500SA, 500SAS, 600B, 600SA, 700B, 700HD, MTY-02, 110M3S, 700BS, JMT-150IB, 150AO, 150FI, 150ANO", DuPont "Ty Pure R-900, 902, 960, 706, 931" and the like. Is mentioned.

From the viewpoint of redispersibility of the ink composition, it is preferable that there is no strong aggregation between the metal oxide fine particles. Therefore, the average primary particle diameter of the metal oxide fine particles is preferably 100 nm or less, more preferably 30 nm or more and 100 nm or less. Within the above range, aggregation between particles can be prevented and an ink composition having excellent redispersibility can be provided.

<Organic light scattering particles (D2)>
The organic light scattering particles (D2) are fine particles made of an organic component, and the shape thereof is not particularly limited, but it is preferably spherical from the viewpoint of the light scattering effect of a backlight or the like. By using the spherical organic light-scattering particles, the backlight is scattered and the quantum dots (A) are sufficiently excited, so that the luminous efficiency of the printed matter obtained from the ink composition can be further enhanced.

Examples of the organic fine particles include silicone fine particles, melamine resin fine particles, melamine-benzoguanamine resin fine particles, acrylic resin fine particles (for example, polymethylmethacrylate fine particles (hereinafter referred to as PMMA fine particles), and acrylic-styrene copolymer weight. Examples thereof include coalescing particles, polycarbonate particles, polyethylene particles, polystyrene particles, benzoguanamine resin particles, etc. These may be used alone or in combination of two or more kinds.

Specific examples of the silicone-based fine particles include KMP-594, KMP-597, KMP-598, KMP-600, KMP-601, KMP-602 (manufactured by Shin-Etsu Chemical Co., Ltd.), Trefil E-506S, EP-9215 ( Toray Dow Corning Co., Ltd.) and the like.

Specific examples of the melamine-based resin fine particles include Eposter SS, Eposter S, Eposter FS, Eposter S6, Eposter S12 (manufactured by Nippon Shokubai Co., Ltd.) and the like.
Specific examples of the melamine-benzoguanamine-based resin fine particles include Eposter M30 (manufactured by Nippon Shokubai Co., Ltd.).

Specific examples of the acrylic resin fine particles include Eposter MA1002, Eposter MA1004, Eposter MA1006, Eposter MA1010 (manufactured by Nippon Shokubai Co., Ltd.), Tough FH-S005, Tough FH-S008, Tough FH-S010, Tough FH-S015, Tough Tick. FH-S020 (manufactured by Toyobo Co., Ltd.), Chemisnow MX-80H3wT, MX-150, MX-180TA, MX-300, MX-500, MX-1000, MX-1500H, MX-2000, MX-3000 (Souken Chemical Co., Ltd.) Company-made) etc.

Specific examples of the acryl-styrene copolymer fine particles include Eposter MA2003 (manufactured by Nippon Shokubai Co., Ltd.), FS-102, FS-201, FS-301, MG-451, MG-351, (Nippon Paint Industrial Coating). Su Co., Ltd.) and the like.

Specific examples of the polycarbonate-based fine particles include the fine particles described in JP-A-2014-125495, the fine particles obtained by the production method described in JP-A-2011-26471, and the fine particles obtained by the method described in JP-A-2001-213970. Etc.

Specific examples of the polyethylene-based fine particles include Miperon XM-220, XM221U (manufactured by Mitsui Chemicals, Inc.), Flow Beads LE-1080 (manufactured by Sumitomo Seika Chemicals, Ltd.) and the like.
Specific examples of the polystyrene-based fine particles include Chemisnow SX-130H, SX-350H, SX-500H (manufactured by Soken Kagaku Co., Ltd.).

Specific examples of the benzoguanamine-based resin fine particles include Eposter MS, Eposter M05, and Eposter L15 (manufactured by Nippon Shokubai Co., Ltd.).

Further, as the organic light-scattering particles (D2), acrylic resin fine particles containing a fluorine substituent can be used. Examples of such fluorine-substituted group-containing acrylic resin particles include fluorine-substituted group-containing polymethylmethacrylate-based particles, fluorine-substituted group-containing acrylic-styrene copolymer particles, fluorine-containing group-containing polycarbonate-based particles, and polyvinyl fluoride particles. Etc. The inclusion of fluorine prevents aggregation between particles and facilitates redispersibility after once settling. Further, by containing a fluorine group, the refractive index can be made lower than that of the binder component containing the quantum dots (A), and the luminous efficiency can be further improved in combination with the scattering effect, which is preferable.

The average particle diameter of the organic light scattering particles (D2) is not particularly limited, but is preferably 100 nm or more and 1000 nm or less. Within the above range, a sufficient scattering effect can be exhibited. Further, even if the scattering intensity (haze value) is small, the scattering angle is wide, so that scattering effective for total reflection can be obtained, and the scattering effect inside the coating film is enhanced, so that the light efficiency is improved, which is preferable. The average particle size and particle size distribution of the organic light scattering particles (D2) can be adjusted by the synthesis conditions such as polymerization temperature and polymerization composition.

The light scattering particles (D) are preferably used as a dispersion from the viewpoint of suppressing sedimentation in the ink composition. The dispersion can be obtained by dispersing with a dispersant suitable for the surface state of the light scattering particles (D). The average particle size and particle size distribution of the light scattering particles (D) can be adjusted by changing the conditions such as a disperser, a dispersion medium, a dispersion time, or a dispersant.
As the disperser, a paint conditioner (manufactured by Red Devil Co.), a ball mill, a sand mill (“Dyno Mill” manufactured by Shinmaru Enterprises Co., Ltd.), an attritor, a pearl mill (“DCP mill” manufactured by Eirich, etc.), a co-ball mill, a homomixer, Homogenizer ("Clearmix" manufactured by M Technique Co., Ltd.), wet jet mill ("Genus PY" manufactured by Genus, "Nanomizer" manufactured by Nanomizer), microbead mill ("Super Apec Mill" manufactured by Kotobuki Industries Co., Ltd.) "Ultra apek mill") can be used. When using a medium for the dispersing machine, it is preferable to use glass beads, zirconia beads, alumina beads, magnetic beads, polystyrene beads, or the like. Dispersion may be performed stepwise by using two or more types of dispersers or two or more types of media having different sizes.

The content of the light scattering particles (D) is preferably 2 to 20% by mass, more preferably 5 to 12.5% by mass, based on the total amount of the ink composition of the present invention. It is preferable that the amount is 5% by mass or more, since a sufficient scattering effect is obtained and high luminous efficiency is obtained. When the content is 12.5% by mass or less, aggregation of the light scattering particles is suppressed, haze of the coating film surface does not increase, and high luminous efficiency is obtained, which is preferable.

The ink composition may include both inorganic light scattering particles (D1) and organic light scattering particles (D2). In that case, the ratio ((D2)/(D1)) of the organic light-scattering particles (D2) to the inorganic light-scattering particles (D1) is preferably 0.2 or more and less than 4.5. It is more preferably 0.5 or more and less than 4.0, and particularly preferably 0.5 or more and less than 1.0. By setting the content in the above range, it is possible to provide an ink composition which is excellent in redispersibility even when it is settled while suppressing the settling of aggregates. Further, it is possible to maintain a high external quantum efficiency for a printed matter formed from the ink composition.

In the present specification, the “average particle size” and the “particle size” are different from the average primary particle size, and are the dispersed particle size in the ink composition that takes into account the particle size of secondary particles due to aggregation. is there. These can be measured by an optical microscope or obtained by a dynamic light scattering method. Here, the reason for distinguishing from the average primary particle diameter is that even if the scattering particles having the same average primary particle diameter are used, the average particle diameter depends on the dispersion state of the light scattering particles (D) in the ink composition. And the particle size distribution may be different. "Average particle size" is the value of the dispersed particle size in 50% by volume of the measurement sample, and the content of particles having a particle size of 600 nm or more is the volume% of the particle size of 600 nm or more in the dispersed particle size of the measurement sample. Is. These can be measured by "Nanotrack UPA" manufactured by Nikkiso Co., Ltd. by the dynamic light scattering method.

<Other ingredients>
The ink composition of the present invention is particularly suitable for use as an inkjet ink in an inkjet system. Other components such as a polymerization inhibitor, a sensitizer and an additive can be added to the ink composition from the viewpoint of physical properties required for printed matter and storage stability. These may be used alone or in combination of two or more.

[Polymerization inhibitor]
The ink composition may contain a polymerization inhibitor in order to enhance storage stability. Examples of the polymerization inhibitor include 4-methoxyphenol, hydroquinone, methylhydroquinone, t-butylhydroquinone, 2,5-t-butyl-4-methylphenol, phenothiazine, and aluminum salt of N-nitrosophenylhydroxylamine. Be done. The content of the polymerization inhibitor is preferably 0.01 to 0.1% by mass based on the total solid content of the ink composition, from the viewpoint of enhancing the stability while maintaining the curability.

(Sensitizer)
The ink composition may contain a sensitizer. Examples of the sensitizer include chalcone derivatives, unsaturated ketones represented by dibenzalacetone, etc., 1,2-diketone derivatives represented by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives. , Polymethine dyes such as xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonole derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivative, azurenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative , Naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrylium derivative, tetraphyrin derivative, annulene derivative, spiropyran derivative, spirooxazine derivative, thiospiropyran derivative, metal arene complex, organic ruthenium complex, or Michler's ketone derivative, α-acyloxy ester , Acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3′, or 4,4′. -Tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-diethylaminobenzophenone and the like can be mentioned. These sensitizers may be used alone or in a mixture of two or more at an arbitrary ratio, if necessary.

In addition, the ink composition of the present invention may contain additives such as a surface conditioner, a leveling agent, an ultraviolet absorber and an antioxidant, if necessary, in order to enhance printability and printed matter resistance.

The content of the other component depends on the desired quantum dot concentration, but is preferably 0 to 100 parts by mass with respect to 1 part by mass of the quantum dot. If it exceeds 100 parts by mass, the quantum dot content becomes low, and sufficient fluorescence intensity may not be obtained.

The ink composition of the present invention has a pore size of 5 μm or less, preferably 3 μm or less, after dispersion and/or after all components are blended, in order to suppress the generation of foreign matter due to the aggregation of particles in the formed coating film and to maintain smoothness. It is preferable to filter with the following filters.

When the ink composition of the present invention is used in the inkjet method, the viscosity of the inkjet ink at 25° C. is preferably 2 to 100 mPa·s, more preferably 2 to 40 mPa·s, and particularly preferably 4 to 20 mPa·s. Is. Within this viscosity range, stable ejection characteristics can be exhibited even from a head having a normal frequency of 4 to 10 KHz to a high frequency head of 10 to 50 KHz. When the viscosity is 2 mPa·s or more, the ejection followability is not deteriorated in the high frequency head, which is preferable. When it is 100 mPa·s or less, the ejection property is good and the ejection stability is excellent, which is preferable.

When the ink composition is used in an inkjet method, the surface tension of the inkjet ink is preferably 20 to 40 mN/m, more preferably 24 to 35 mN/m. When it is 20 mN/m or more, the ink can form droplets, and when it is 40 mN/m or less, the ink can be stably ejected from the head.

Further, it is preferable that the ink composition has an electric conductivity of 10 μS/cm or less in a piezo head and does not cause electrical corrosion inside the head. Further, in the continuous type, it is necessary to adjust the electric conductivity by the electrolyte, and in this case, it is preferable to adjust the electric conductivity to 0.5 mS/cm or more.

<Printed matter>
The printed matter of the present invention has a printing layer containing quantum dots formed from an ink composition on a substrate, and the printing layer is preferably formed by an inkjet printing method. When a printed matter is formed by an inkjet method, the ink composition of the present invention is supplied to a printer head of an inkjet recording type printer, and the inkjet ink is ejected from the printer head onto a substrate. Then, a step of drying the solvent contained in the inkjet ink, or through a step of polymerizing the polymerizable compound contained in the inkjet ink by irradiating with active energy rays such as ultraviolet rays or electron beams, on the substrate, An ink layer (printing layer) can be formed.

The step of drying the solvent is not limited as long as the solvent can be removed, and may be air drying. The drying temperature is preferably 40° C. or higher and 180° C. or lower, and the drying time may be 1 minute or longer, 10 minutes or longer, and 120 minutes or shorter. By setting the temperature range or the drying time within the above range, it is possible to obtain a strong coating film in which the solvent is sufficiently dried.

Moreover, when irradiating with ultraviolet rays as a light source of active energy rays, for example, a high pressure mercury lamp, a metal halide lamp, a low pressure mercury lamp, an ultrahigh pressure mercury lamp, an ultraviolet laser, an LED, or sunlight can be used. The exposure dose may be 100 mJ/cm ² or more and 2000 mJcm ² or less. By setting the light source in the exposure range, a sufficiently strong ink layer can be obtained.

The inkjet method is not particularly limited, and known methods such as a charge control method for discharging ink by using electrostatic attraction, a drop-on-demand method (pressure pulse method) using vibration pressure of a piezo element, and an electric signal are used. To an acoustic beam and irradiate the ink to radiate the ink to eject the ink using radiation pressure, and a thermal ink jet (Bubble Jet (registered trademark)) that heats the ink to form bubbles and uses the generated pressure. Any method may be used.

The inkjet head used in the inkjet method may be an on-demand system or a continuous system. Further, as the discharge method, an electro-mechanical conversion method (eg, single cavity type, double cavity type, bender type, piston type, share mode type, shared wall type, etc.), electric-heat conversion method (eg: thermal inkjet) Type, bubble jet (registered trademark) type, etc., electrostatic attraction type (eg electrolytic control type, slit jet type etc.), discharge type (eg spark jet type etc.), etc. However, any ejection method may be used. The ink nozzles and the like used for recording by the inkjet method are not particularly limited and can be appropriately selected according to the purpose.

The amount of ink droplets ejected from the inkjet head is preferably 0.2 to 20 picoliters (pL), and 1 to 15 picoliters (pL), from the viewpoint that the drying load reducing effect is great and the image quality is improved. Is more preferable.

[Base material]
The base material constituting the printed matter of the present invention is not particularly limited, but is a plastic base material such as polycarbonate, hard vinyl chloride, soft vinyl chloride, polystyrene, foam polystyrene, PMMA, polypropylene, polyethylene, PET, or a mixture or modified product thereof, high-quality paper, Examples include paper base materials such as art paper, coated paper, cast coated paper, and synthetic paper, glass, metal base materials such as stainless steel, and wood.

<Color filter>
The ink composition of the present invention can be used to form a color filter that absorbs incident light in a wavelength-selective manner and transmits or reflects light of a part of wavelength, and the color filter is a color liquid crystal display device. Besides, it can be used for manufacturing a color solid-state imaging device, an organic EL display device, a quantum dot display device, electronic paper, and the like. In particular, when the inkjet method is selected, it is possible to print a required amount in a required place and suppress consumption of quantum dots and the like, which is preferable.
The color filter includes a red filter segment, a green filter segment, and a blue filter segment, and may further include a magenta color filter segment, a cyan color filter segment, and a yellow filter segment, and at least one filter segment, It may be formed from the ink composition of the present invention.

When a color filter is manufactured using the ink composition of the present invention, a black matrix may be formed in advance before forming the filter segment on the transparent substrate or the reflective substrate. As the black matrix, chromium, a chromium/chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light shielding agent is dispersed is used, but the black matrix is not limited thereto. It is also possible to previously form a thin film transistor (TFT) on the above transparent substrate or reflective substrate, and then form the filter segment. Further, an overcoat film, a transparent conductive film, or the like may be formed on the color filter of the present invention, if necessary.

<Light wavelength conversion layer>
A layer formed by drying an organic solvent after coating/printing with the ink composition of the present invention or a layer formed of a cured film formed by irradiation with ultraviolet rays can be used as a light wavelength conversion layer. The light wavelength conversion layer is capable of converting the excitation light into fluorescence on the long wavelength side and emitting it, and there is no particular limitation as long as the relationship between the excitation light wavelength and the emission fluorescence wavelength can be maintained, and examples include blue and ultraviolet light. Can be used as excitation light to obtain green or red fluorescence, or ultraviolet light or visible light can be used as excitation light to obtain fluorescence in the near-infrared region.
The thickness of the light wavelength conversion layer is preferably 1 to 500 μm, more preferably 1 to 50 μm, and further preferably 1 to 10 μm. When the thickness is 1 μm or more, a high wavelength conversion effect can be obtained, which is preferable. Further, when the thickness is 500 μm or less, the light source unit can be made thin when incorporated in the light source unit, which is preferable.

<Light wavelength conversion member>
The light wavelength conversion layer described above can be used as a light wavelength conversion member.
The light wavelength conversion member is a member in which the above-mentioned light wavelength conversion layer is formed on at least one surface of a specific base material. The base material is not particularly limited, but includes polycarbonate, hard vinyl chloride, soft vinyl chloride, polystyrene, foam polystyrene, PMMA, polypropylene, polyethylene, plastic base materials such as PET, and mixed or modified products thereof, fine paper, art paper, coated paper, Examples include paper base materials such as cast-coated paper and glass, metal base materials such as stainless steel.
Although the base material used is selected depending on the application, a plastic base material or a mixture or modified product thereof is preferable from the viewpoint of durability as long as it is a prepaid card or a traffic card. In addition to the plastic base material, a paper base material is preferable as long as it is a one-dimensional bar code, a two-dimensional bar code, or a QR code (registered trademark) (matrix type two-dimensional code) as an information recording medium. If it is a color filter for wavelength conversion, a transparent substrate is preferable.

<Light emitting element>
The layer formed using the ink composition of the present invention can be used as a light emitting layer in a light emitting device. The light emitting element has a substrate, a cathode and an anode provided on the substrate, a light emitting layer is provided between both electrodes, and a charge transport layer is provided on at least one of the cathode and the anode. Further, due to the property of the light emitting device, at least one of the anode and the cathode is transparent.
As a mode of stacking the light emitting element, a mode in which a hole transport layer, a light emitting layer, and an electron transport layer are sequentially stacked from the anode side is preferable. Further, a charge blocking layer or the like may be provided between the hole transport layer and the light emitting layer or between the light emitting layer and the electron transport layer. A hole injection layer may be provided between the anode and the hole transport layer, and an electron injection layer may be provided between the cathode and the electron transport layer. The light emitting layer may be a single layer, or the light emitting layer may be divided into a first light emitting layer, a second light emitting layer, a third light emitting layer, and the like. Further, each layer may be divided into a plurality of secondary layers.

As the substrate, for example, a substrate used for a known organic EL element can be used. The substrate may be a resin film or a gas barrier film, and may be, for example, JP2004-136466A, JP2004-148566A, JP2005-246716A, JP2005-262529A. The gas barrier film described in 1 above can also be preferably used.
The thickness of the substrate is not particularly limited, but is preferably 30 μm to 700 μm, more preferably 40 μm to 200 μm, and further preferably 50 μm to 150 μm. Further, in any case, the haze is preferably 3% or less, more preferably 2% or less, still more preferably 1% or less, and the total light transmittance is preferably 70% or more, more preferably 80% or more, further preferably 90%. That is all.

[anode]
The anode is generally required to have a function as an electrode for supplying holes to the organic compound or inorganic compound layer, and there is no particular limitation on the shape, structure, size or the like, and the application and purpose of the light emitting device. According to the above, it can be appropriately selected from known electrode materials. As mentioned above, the anode is usually provided as a transparent anode. The transparent anode is described in detail in “New Development of Transparent Electrode Film” supervised by Yutaka Sawada, published by CMC (1999). When a plastic substrate having low heat resistance is used as the substrate, ITO, IZO or IGZO is used, and a transparent anode formed at a low temperature of 150° C. or lower is preferable.

[cathode]
The cathode usually has a function as an electrode for injecting electrons into an organic compound or an inorganic compound layer, and there is no particular limitation on its shape, structure, size, etc. Accordingly, it can be appropriately selected from known electrode materials.
Examples of the material forming the cathode include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof. Specific examples include Group 2 metals (eg, Mg, Ca, etc.), gold, silver, lead, aluminum, lithium-aluminum alloys, magnesium-silver alloys, rare earth metals such as indium, ytterbium, and the like. These may be used singly, but from the viewpoint of achieving both stability and electron injectability, two or more may be preferably used in combination.

Among these, as a material forming the cathode, a material mainly containing aluminum is preferable. The material mainly containing aluminum means aluminum alone or an alloy of aluminum and 0.01 to 100 mass% of an alkali metal or a Group 2 metal (for example, lithium-aluminum alloy, magnesium-aluminum alloy, etc.). The material of the cathode is described in detail in JP-A-2-15595 and JP-A-5-121172. In addition, a dielectric layer made of an alkali metal or Group 2 metal fluoride, oxide or the like may be inserted between the cathode and the organic compound or inorganic compound layer to a thickness of 0.1 to 5 nm. This dielectric layer can also be regarded as a kind of electron injection layer.

The thickness of the cathode can be appropriately selected depending on the material forming the cathode and cannot be specified unconditionally, but is usually about 10 nm to 5 μm, preferably 50 nm to 1 μm. Further, the cathode may be transparent or opaque. The transparent cathode can be formed by forming a thin film of the cathode material to a thickness of 1 to 10 nm and further stacking a transparent conductive material such as ITO, IZO or IGZO.

[Light emitting layer]
The light-emitting layer receives holes from the anode, the hole injection layer or the hole transport layer and receives electrons from the cathode, the electron injection layer or the electron transport layer when an electric field is applied, and recombines the holes with the electrons. Is a layer having a function of providing and emitting light. The light emitting layer may be composed of only quantum dots, or may be composed of a mixed layer of quantum dots and a host material. The light emitting material may further contain a fluorescent light emitting material or a phosphorescent light emitting material, and the dopant may be one kind or two or more kinds. The host material is preferably a charge transport material. The host material may be one kind or two or more kinds, and examples thereof include a configuration in which an electron transporting host material and a hole transporting host material are mixed. Further, the light emitting layer may contain a material which has no charge transporting property and does not emit light. Further, the light emitting layer may be one layer or two or more layers, and each layer may emit light of different emission colors.

Examples of the fluorescent material include, for example, benzoxazole derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimide derivatives, coumarin derivatives, condensed aromatics. Compound, perinone derivative, oxadiazole derivative, oxazine derivative, aldazine derivative, pyraridine derivative, cyclopentadiene derivative, bisstyrylanthracene derivative, quinacridone derivative, pyrrolopyridine derivative, thiadiazolopyridine derivative, cyclopentadiene derivative, styrylamine derivative, di Ketopyrrolopyrrole derivatives, aromatic dimethylidin compounds, various metal complexes represented by 8-quinolinol derivative metal complexes and pyrromethene derivative metal complexes, polymer compounds such as polythiophene, polyphenylene, polyphenylene vinylene, compounds such as organic silane derivatives, etc. Is mentioned.

Examples of the phosphorescent material include a complex containing a transition metal atom or a lanthanoid atom. The transition metal atom is not particularly limited, but preferably includes ruthenium, rhodium, palladium, tungsten, rhenium, osmium, iridium, and platinum, and more preferably rhenium, iridium, and platinum.
Examples of the lanthanoid atom include lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutecium. Among these lanthanoid atoms, neodymium, europium, and gadolinium are preferable.

Examples of the ligand of the complex include G.I. Wilkinson et al., Comprehensive Coordination Chemistry, Pergamon Press Co., 1987, H. Yersin, "Photochemistry and Co., Ltd., Organisms, Vol. The ligands and the like described in Fusasha Publishing Co., Ltd., 1982 are mentioned.

Examples of the host material contained in the light emitting layer include those having a carbazole skeleton, those having a diarylamine skeleton, those having a pyridine skeleton, those having a pyrazine skeleton, those having a triazine skeleton, and arylsilane skeletons. The materials that are included, and the materials exemplified in the later-described hole injection layer, hole transport layer, electron injection layer, and electron transport layer are mentioned.

[Hole injection layer, hole transport layer]
The hole injection layer and the hole transport layer are layers having a function of receiving holes from the anode or the anode side and transporting them to the cathode side. It may be an organic compound or an inorganic compound as long as it has the above-mentioned function, and may be a low molecular compound, a high molecular compound or a metal oxide. Specifically, the hole injection layer and the hole transport layer include carbazole derivative, triphenylamine derivative, triazole derivative, oxazole derivative, oxadiazole derivative, imidazole derivative, polyarylalkane derivative, pyrazoline derivative, pyrazolone derivative, and phenylene. Diamine derivative, arylamine derivative, amino-substituted chalcone derivative, styrylanthracene derivative, fluorenone derivative, hydrazone derivative, stilbene derivative, silazane derivative, aromatic tertiary amine compound, styrylamine compound, aromatic dimethylidyne compound, porphyrin compound, Phthalocyanine compounds, low-molecular compounds such as organic silane derivatives, carbon compounds such as carbon and fullerene, inorganic compounds composed of metal oxides such as vanadium pentoxide and molybdenum trioxide, polyvinylcarbazole, polypyrrole, poly(3,4-ethylene) It is preferably a layer containing a polymer compound such as dioxythiophene)-poly(styrene sulfonic acid) (PEDOT-PSS).

[Electron injection layer, electron transport layer]
The electron injection layer and the electron transport layer are layers having a function of receiving electrons from the cathode or the cathode side and transporting them to the anode side. The electron injection layer, the electron transport layer, specifically, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, Aromatic ring tetracarboxylic acid anhydrides such as carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, naphthalene and perylene, phthalocyanine derivatives, metal complexes of 8-quinolinol derivatives, metal phthalocyanines, benzoxazoles and benzothiazoles as ligands Containing various metal complexes represented by the following metal complexes, low molecular weight compounds such as organic silane derivatives, metal oxides such as zinc oxide (ZnO) and titanium oxide (TiO2), and organic or inorganic compounds doped with alkali metals. It is preferably a layer.

[Hole blocking layer]
The hole blocking layer is a layer having a function of preventing holes transported from the anode side to the light emitting layer from passing through to the cathode side. In the present invention, a hole blocking layer can be provided as an organic compound layer adjacent to the light emitting layer on the cathode side. The electron transport layer/electron injection layer may also have the function of the hole blocking layer.
Examples of organic compounds forming the hole blocking layer include aluminum complexes such as BAlq, triazole derivatives, and phenanthroline derivatives such as BCP. Further, a layer having a function of preventing electrons transported from the cathode side to the light emitting layer from passing through to the anode side can be provided at a position adjacent to the light emitting layer on the anode side. The hole transport layer/hole injection layer may also have this function.

<Light emitting device>
Further, the light wavelength conversion member and the light emitting element can be combined and used as a light emitting device. In the light emitting device, at least one of the light wavelength converting layer of the light wavelength converting member and the light emitting layer of the light emitting element may be formed using the ink composition of the present invention.
The light wavelength conversion member converts excitation light into fluorescence on the long wavelength side and emits it. For example, it converts blue or ultraviolet light into green or red fluorescence, or converts ultraviolet light or visible light into near-red light. It can be converted into fluorescence in the outer region. The light wavelength conversion member is not particularly limited as long as it maintains the relationship between the excitation light wavelength and the emission fluorescence wavelength, and an optimum one can be appropriately selected.
As a light source of a conventionally known light emitting element, a semiconductor light emitting element such as a light emitting diode (LED) or a semiconductor laser (LD); organic electroluminescence (organic EL); or quantum dot can be used. ..

Hereinafter, the present invention will be described in more detail by way of examples, but the following examples do not limit the scope of rights of the present invention. In the examples, "part" means "part by mass" and "%" means "% by mass". The mass average molecular weight was measured by GPC and calculated in terms of polystyrene.

<Synthesis of Compound (Quantum Dot Treatment Agent) Represented by General Formula (1)>
(Synthesis of Compound 1)
In a Dean-Stark apparatus, 2 parts of acetic acid, 1 part of 2-mercaptoethanol, 0.05 part of concentrated sulfuric acid and 20 parts of toluene were heated under reflux for 3 hours. After adding 40 parts of ethyl acetate, the reaction mixture was washed twice with 20 parts of water and finally with 20 parts of saturated aqueous sodium hydrogen carbonate solution. The organic layer was dried over magnesium sulfate, magnesium sulfate was filtered off, and then the organic solvent was distilled off under reduced pressure to obtain Compound 1 shown in Table 1. The yield was 70%.

(Synthesis of Compound 2)
In a Dean-Stark apparatus, 2 parts of acetic acid, 2-(2-(2-mercaptoethoxy)ethoxy)ethanol, 0.05 part of concentrated sulfuric acid, and 20 parts of toluene were heated under reflux for 3 hours. After adding 40 parts of ethyl acetate, the reaction mixture was washed twice with 20 parts of water and finally with 20 parts of saturated aqueous sodium hydrogen carbonate solution. The organic layer was dried over magnesium sulfate, the magnesium sulfate was filtered off, and the organic solvent was distilled off under reduced pressure to obtain Compound 2 shown in Table 1. The yield was 80%.

(Synthesis of Compound 3)
In a Dean-Stark apparatus, 2 parts of acetic acid, 6-mercapto-1-hexanol, 0.05 parts of concentrated sulfuric acid, and 20 parts of toluene were heated under reflux for 3 hours. After adding 40 parts of ethyl acetate, the reaction mixture was washed twice with 20 parts of water and finally with 20 parts of saturated aqueous sodium hydrogen carbonate solution. The organic layer was dried over magnesium sulfate, the magnesium sulfate was filtered off, and the organic solvent was distilled off under reduced pressure to obtain Compound 3 shown in Table 1. The yield was 86%.

(Synthesis of Compound 4)
2-(2-(2-Mercaptoethoxy)ethoxy)ethanol (1 part) and dimethyl carbonate (6 parts) were refluxed for 24 hours in the presence of potassium carbonate (1 part). After the potassium carbonate was filtered off, the mixture was evaporated under reduced pressure to give compound 4 shown in Table 1. The yield was 88%.

(Synthesis of Compound 5)
1 part of mercaptopropionic acid, 10 parts of methanol and 0.05 part of concentrated sulfuric acid were heated under reflux for 3 hours. The reaction mixture was evaporated under reduced pressure to remove methanol, 40 parts of ethyl acetate was added, the reaction mixture was washed twice with 20 parts of water, and finally with 20 parts of saturated aqueous sodium hydrogen carbonate solution. The organic layer was dried over magnesium sulfate, the magnesium sulfate was filtered off, and the organic solvent was distilled off under reduced pressure to obtain compound 5 shown in Table 1. The yield was 77%.

(Synthesis of Compound 6)
1 part of 3,3-diethoxy-1-propanol, 1 part of paratoluenesulfonic acid chloride and 1.5 parts of pyridine were reacted in 20 parts of tetrahydrofuran at room temperature for 24 hours. After tetrahydrofuran was distilled off under reduced pressure, 20 parts of ethyl acetate was added, and the mixture was washed twice with 20 parts of saturated aqueous sodium hydrogen carbonate solution. The organic layer was dried over magnesium sulfate, magnesium sulfate was filtered off, and the organic layer was evaporated under reduced pressure. Next, under a nitrogen atmosphere, 15 parts of ethanol, 1 part of water, and 2 parts of thiourea were added to the obtained mixture, and the mixture was heated under reflux for 3 hours, 20 parts of 10% sodium hydroxide was added, and the mixture was heated under reflux for 3 hours. After ethanol was distilled off under reduced pressure, 10 parts of water was added, hydrochloric acid was added until pH=2, and the mixture was stirred at room temperature for 2 hours. After adjusting the pH to 5 to 6 with sodium hydrogen carbonate, 20 parts of ethyl acetate was added, and the organic layer was washed twice with 10 parts of water. The organic layer was dried over magnesium sulfate, magnesium sulfate was filtered off, and the organic layer was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate 1:n-hexane 9) to obtain compound 6 shown in Table 1. The yield was 59%.

(Synthesis of Compound 7)
4-Hydroxy-2-butanone (1 part), paratoluenesulfonic acid chloride (1 part) and pyridine (1.5 parts) were reacted in tetrahydrofuran (20 parts) at room temperature for 24 hours. After tetrahydrofuran was distilled off under reduced pressure, 20 parts of ethyl acetate was added, and the mixture was washed twice with 20 parts of saturated aqueous sodium hydrogen carbonate solution. The organic layer was dried over magnesium sulfate, magnesium sulfate was filtered off, and the organic layer was evaporated under reduced pressure. Next, under a nitrogen atmosphere, 15 parts of ethanol, 1 part of water, and 2 parts of thiourea were added to the obtained mixture, and the mixture was heated under reflux for 3 hours, 20 parts of 10% sodium hydroxide was added, and the mixture was heated under reflux for 3 hours. After ethanol was distilled off under reduced pressure, 10 parts of water was added, hydrochloric acid was added until pH=2, and the mixture was stirred at room temperature for 2 hours. After adjusting the pH to 5 to 6 with sodium hydrogen carbonate, 20 parts of ethyl acetate was added, and the organic layer was washed twice with 10 parts of water. The organic layer was dried over magnesium sulfate, magnesium sulfate was filtered off, and the organic layer was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate 1:n-hexane 9) to obtain compound 7 shown in Table 1. The yield was 47%.

(Synthesis of Compound 8)
After dissolving 6 parts of 6-mercaptohexanoic acid, 1 part of N,N-diisopropylcarbodiimide and 0.05 parts of 4-dimethylaminopyridine in 20 parts of dichloromethane and stirring, 1.1 parts of propylamine was added, and at room temperature. The reaction was carried out for 24 hours. After evaporating the solvent under reduced pressure, the mixture was dissolved in 20 parts of ethyl acetate, washed 3 times with 10 parts of 5% hydrochloric acid, and then once with 10 parts of saturated aqueous sodium hydrogen carbonate solution. The organic layer was dried over magnesium sulfate, magnesium sulfate was filtered off, and the organic layer was distilled off under reduced pressure to obtain compound 8 shown in Table 1. The yield was 70%.

(Synthesis of Compound 9)
After dissolving 1 part of acetic acid, 1 part of N,N-diisopropylcarbodiimide and 0.05 part of 4-dimethylaminopyridine in 20 parts of dichloromethane and stirring, 1.1 parts of cysteamine was added and reacted at room temperature for 24 hours. .. After evaporating the solvent under reduced pressure, the mixture was dissolved in 20 parts of ethyl acetate, washed 3 times with 10 parts of 5% hydrochloric acid, and then once with 10 parts of saturated aqueous sodium hydrogen carbonate solution. The organic layer was dried over magnesium sulfate, magnesium sulfate was filtered off, and the organic layer was distilled off under reduced pressure to obtain Compound 9 shown in Table 1. The yield was 70%.

(Synthesis of Compound 10)
0.85 parts of cysteamine was dissolved in 10 parts of N,N-dimethylformamide, 0.78 parts of ethylisocyanate was added at 0° C., and the mixture was reacted at room temperature for 24 hours. After removing N,N-dimethylformamide under reduced pressure, 10 parts of ethyl acetate was added to the mixture, and the mixture was washed twice with 10 parts of water. The organic layer was dried over magnesium sulfate, magnesium sulfate was filtered off, and the organic layer was distilled off under reduced pressure to obtain Compound 10 shown in Table 1. The yield was 55%.

(Synthesis of Compound 11)
Under a nitrogen atmosphere, 1 part of acetylacetonate was dissolved in 10 parts of tetrahydrofuran, and 1.6 parts of potassium carbonate was added. Next, 1 part of 3-chloro-1-propanethiol was dissolved in 3 parts of tetrahydrofuran and added dropwise over 1 hour. After stirring at room temperature for 24 hours, tetrahydrofuran was distilled off under reduced pressure and the residue was dissolved in 20 parts of ethyl acetate. The mixture was washed once with 20 parts of 5% dilute hydrochloric acid and then with a saturated aqueous sodium hydrogen carbonate solution. After drying the organic layer with magnesium sulfate, magnesium sulfate was filtered off, and the organic layer was distilled off under reduced pressure to obtain Compound 11 shown in Table 2. The yield was 67%.

(Synthesis of Compound 12)
Under a nitrogen atmosphere, 10 parts of dimethyl malonate was dissolved in 100 parts of tetrahydrofuran, cooled to 0° C., and then 3 parts of 60% sodium hydride was added little by little. Next, 2 parts of 3-chloro-1-propanethiol was dissolved in 20 parts of tetrahydrofuran and added dropwise over 1 hour. After stirring at room temperature for 24 hours, the solvent was distilled off under reduced pressure, 100 parts of ethyl acetate was added, and an aqueous ammonium chloride solution was added dropwise to make the aqueous layer weakly acidic. The organic layer was washed 3 times with 100 parts of water, dried over magnesium sulfate, the magnesium sulfate was filtered off, and the organic layer was distilled off under reduced pressure to obtain Compound 12 shown in Table 2. The yield was 56%.

(Synthesis of Compound 13)
In a Dean-Stark apparatus, 5 parts of acetic acid, 1 part of 1-thioglycerol, 0.05 part of concentrated sulfuric acid and 30 parts of toluene were heated under reflux for 3 hours. After toluene was distilled off under reduced pressure, 40 parts of ethyl acetate was added, and the reaction mixture was washed twice with 20 parts of water and finally with 20 parts of a saturated aqueous sodium hydrogen carbonate solution. The organic layer was dried over magnesium sulfate, magnesium sulfate was filtered off, and then the organic solvent was distilled off under reduced pressure to obtain Compound 13 shown in Table 2. The yield was 62%.

(Synthesis of Compound 14)
In a Dean-Stark apparatus, 5 parts of acetic acid, 1 part of 3-thiophene methanol, 0.05 parts of concentrated sulfuric acid and 30 parts of toluene were heated under reflux for 3 hours. After toluene was distilled off under reduced pressure, 40 parts of ethyl acetate was added, and the reaction mixture was washed twice with 20 parts of water and finally with 20 parts of a saturated aqueous sodium hydrogen carbonate solution. The organic layer was dried over magnesium sulfate, the magnesium sulfate was filtered off, and the organic solvent was distilled off under reduced pressure to obtain Compound 14 shown in Table 2. The yield was 77%.

(Synthesis of Compound 15)
In a Dean-Stark apparatus, 5 parts of acetic acid, 1 part of 2-thiophene methanol, 0.05 parts of concentrated sulfuric acid, and 30 parts of toluene were heated under reflux for 3 hours. After toluene was distilled off under reduced pressure, 40 parts of ethyl acetate was added, and the reaction mixture was washed twice with 20 parts of water and finally with 20 parts of a saturated aqueous sodium hydrogen carbonate solution. The organic layer was dried over magnesium sulfate, the magnesium sulfate was filtered off, and the organic solvent was distilled off under reduced pressure to obtain Compound 15 shown in Table 2. The yield was 74%.

(Synthesis of Compound 16)
In a Dean-Stark apparatus, 5 parts of acetic acid, 1 part of tetrahydro-2H-pyran-4-ol, 0.05 parts of concentrated sulfuric acid and 30 parts of toluene were heated under reflux for 3 hours. After toluene was distilled off under reduced pressure, 40 parts of ethyl acetate was added, and the reaction mixture was washed twice with 20 parts of water and finally with 20 parts of a saturated aqueous sodium hydrogen carbonate solution. The organic layer was dried over magnesium sulfate, the magnesium sulfate was filtered off, and the organic solvent was distilled off under reduced pressure to obtain Compound 16 shown in Table 2. The yield was 81%.

(Synthesis of Compound 18)
After dissolving 1 part of acetic acid, 1 part of N,N-diisopropylcarbodiimide and 0.05 part of 4-dimethylaminopyridine in 20 parts of dichloromethane and stirring, 1.6 parts of 3-methylthiopropylamine were added, and the mixture was allowed to stand at room temperature for 24 hours. Reacted for hours. After evaporating the solvent under reduced pressure, the mixture was dissolved in 20 parts of ethyl acetate, washed 3 times with 10 parts of 5% hydrochloric acid, and then once with 10 parts of saturated aqueous sodium hydrogen carbonate solution. The organic layer was dried over magnesium sulfate, magnesium sulfate was filtered off, and the organic layer was distilled off under reduced pressure to obtain Compound 18 shown in Table 2. The yield was 72%.

<Manufacture of quantum dots>
[Comparative Example 1] (quantum dot QD-0)
0.55 parts of anhydrous zinc acetate, 7.0 parts of dodecanethiol (Compound 0), and 5.0 parts of oleylamine were dissolved by heating to prepare an additive solution. Separately, 0.22 parts of indium chloride and 8.25 parts of octylamine were placed in a reaction vessel and heated to 165° C. while bubbling nitrogen. After the indium chloride was dissolved, 0.86 part of diethylaminophosphine was injected in a short time, and the temperature was controlled at 165° C. for 20 minutes. Then, it cooled rapidly and it cooled at 40 degreeC. After pouring the above-mentioned addition liquid and heating at 240° C. for 2 hours, it was allowed to cool to room temperature. After allowing to cool, it was purified by a reprecipitation method using hexane and ethanol. The precipitate was collected and dried under reduced pressure to obtain a quantum dot QD-0 in which core-shell type semiconductor fine particles having a core of InP and a shell of ZnS were surface-treated with dodecanethiol (Compound 0).

[Example 1] (quantum dot QD-1)
The quantum dots QD-0 were dispersed in toluene to a solid content concentration of 1%. A toluene solution of 5% Compound 1 in the same amount as the diluted solution was added, and the mixture was stirred for 12 hours. Purification was performed by a reprecipitation method using toluene and hexane. The precipitate was collected and dried under reduced pressure to obtain quantum dot QD-1 surface-treated with Compound 1.

[Examples 2 to 18] [Comparative examples 2 to 6] (quantum dots QD-2 to 23)
Quantum dots QD-2 to 23 were prepared in the same manner as QD-1, except that the compounds 2 to 22 shown in Table 4 were used as the surface treatment agent.

<Production of binder component (C) resin>
(Resin solution 1)
70.0 parts of xylene was charged into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer in a separable 4-neck flask, the temperature was raised to 80° C., and the inside of the reaction vessel was replaced with nitrogen, and then a dropping tube A mixture of 18.0 parts of n-butyl methacrylate, 12.0 parts of methyl methacrylate, and 0.4 parts of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a solution of an acrylic resin having a mass average molecular weight (Mw) of 26,000. After cooling to room temperature, about 2 parts of the resin solution was sampled, heated and dried at 180° C. for 20 minutes to measure the solid content concentration, and the resin solution synthesized above was adjusted so that the solid content concentration was 10% by mass. Was added to obtain a resin solution 1 of acrylic resin.

(Resin solution 2)
70.0 parts of xylene was charged into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer in a separable 4-neck flask, the temperature was raised to 80° C., and the inside of the reaction vessel was replaced with nitrogen, and then a dropping tube A mixture of 14.0 parts of n-butyl methacrylate, 10.0 parts of methyl methacrylate, 6.0 parts of styrene, and 0.4 parts of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a solution of an acrylic resin having a mass average molecular weight (Mw) of 26,000. After cooling to room temperature, about 2 parts of the resin solution was sampled, heated and dried at 180° C. for 20 minutes to measure the solid content concentration, and the resin solution synthesized above was adjusted so that the solid content concentration was 10% by mass. Was added to obtain a resin solution 2 of acrylic resin.

(Resin solution 3)
Polyvinyl butyral resin (“S-REC BL-S” manufactured by Sekisui Chemical Co., Ltd.) was dissolved in toluene so that the solid content concentration was 10% to obtain a resin solution 3.

(Resin solution 4)
200 parts of norbornene, 50 parts of cyclopentene, 180 parts of 1-hexene and 750 parts of toluene were placed in a reaction vessel purged with nitrogen and heated to 60°C. This was modified with 0.62 parts of a toluene solution of triethylaluminum (1.5 mol/l) and tert-C ₄ H ₅ OH/CH ₃ OH (tert-C ₄ H ₉ OH/CH ₃ OH/W=0. 0.35/0.3/1; molar ratio) of 3.7 parts of WCl ₆ solution (concentration 0.05 mol/l) was added, and the mixture was heated and stirred at 80° C. for 3 hours to perform ring-opening polymerization reaction and hydrogenation reaction. Then, the solid content concentration was adjusted to 10% with trimethylbenzene to obtain a resin solution 4.

<Production of light scattering particle (D) dispersion>
(Metal oxide fine particle dispersion liquid (D1-1))
In 60 parts of ethylene glycol monobutyl ether acetate, 20 parts of MT700B (manufactured by Teika Co., Ltd., fine particle titanium oxide, average primary particle size 80 nm) and 20 parts of BYK-2155 (manufactured by Big Chemie Co., Ltd.) were blended, and glass beads (particles were used. (Diameter: 850 to 1180 μm) was added, and dispersion treatment was performed for 2 hours using a paint conditioner to obtain a metal oxide fine particle dispersion liquid (D1-1).
The average particle diameter of the metal oxide fine particles in the obtained metal oxide fine particle dispersion liquid (D1-1) was 85 nm.

(Metal oxide fine particle dispersion (D1-2))
A metal oxide fine particle dispersion liquid (D1) was obtained in the same manner as the metal oxide fine particle dispersion liquid (D1-1), except that MT700B was changed to MT600B (manufactured by TAYCA CORPORATION, fine particle titanium oxide, average primary particle diameter 50 nm). -2) was obtained.
The average particle diameter of the metal oxide fine particles in the obtained metal oxide fine particle dispersion liquid (D1-2) was 48 nm.

(Metal oxide fine particle dispersion liquid (D1-3))
A metal oxide was prepared in the same manner as the metal oxide fine particle dispersion liquid (D1-1), except that the MT700B was changed to MT600SA (manufactured by TAYCA CORPORATION, Si, Al treatment, fine particle titanium oxide, average primary particle diameter 50 nm). A fine particle dispersion (D1-3) was obtained.
The average particle diameter of the metal oxide fine particles in the obtained metal oxide fine particle dispersion liquid (D1-3) was 49 nm.

(Organic fine particle dispersion (D2-1))
Under a nitrogen atmosphere, 50 parts of trifluoroethylmethacrylate, 40 parts of methyl methacrylate, 5 parts of allyl methacrylate and 5 parts of isobornyl methacrylate are added to 560 parts of water, stirred, and heated to 80° C. An aqueous solution prepared by dissolving 0.167 parts of 2-azobis(2-amidinopropane)dihydrochloride in a very small amount of water was added all at once, and polymerization was carried out at 80° C. for 8 hours. After the polymerization, ethylene glycol monobutyl ether was added, and water was removed by stripping to adjust the solid content to 20% by mass to obtain an organic fine particle dispersion liquid (D2-1) which is a fluorine atom-containing acrylic resin fine particle.
The average particle diameter of the organic fine particles in the obtained organic fine particle dispersion liquid (D2-1) was 280 nm.

(Organic fine particle dispersion (D2-2-4))
Organic fine particles, which are acrylic resin fine particles containing fluorine atoms, were prepared in the same manner as in the organic fine particle dispersion liquid (D2-1), except that the solvent composition and the monomer composition were changed to the compositions and blending amounts (parts) shown in Table 5. A dispersion liquid (D2-2-4) was obtained. Table 5 shows the average particle size of the obtained organic fine particle dispersion liquid.

(Organic fine particle dispersion (D2-5))
In 80 parts of ethylene glycol monobutyl ether acetate, 16.0 parts of Eposter S (manufactured by Nippon Shokubai Co., Ltd., melamine-formaldehyde condensate, average particle size 200 nm) and 4.0 parts of BYK-111 (manufactured by Big Chemie Co., Ltd.) Glass beads (particle diameter: 850-1180 μm) were added and dispersed for 2 hours using a paint conditioner to obtain an organic fine particle dispersion liquid (D2-5) which was melamine resin fine particles.
The average particle diameter of the organic fine particles in the obtained organic fine particle dispersion liquid (D2-5) was 175 nm.

(Organic fine particle dispersion (D2-6))
An melamine resin fine particle organic material was obtained in the same manner as the organic fine particle dispersion liquid (D2-5) except that the eposter S was changed to an eposter FS (Nippon Shokubai Co., Ltd., melamine-formaldehyde condensate, average particle diameter 200 nm). A fine particle dispersion liquid (D2-6) was obtained.
The average particle diameter of the organic fine particles in the obtained organic fine particle dispersion liquid (D2-6) was 173 nm.

(Organic fine particle dispersion (D2-7))
Crosslinked acrylic resin fine particles were prepared in the same manner as the organic fine particle dispersion liquid (D2-5) except that the Eposter S was changed to MX-80H3wTM (crosslinked acrylic monodisperse particles manufactured by Soken Chemical Co., Ltd., average particle size 800 nm). An organic fine particle dispersion liquid (D2-7) was obtained.
The average particle size of the organic fine particles in the obtained organic fine particle dispersion liquid (D2-7) was 732 nm.

(Organic fine particle dispersion (D2-8))
Organic fine particle dispersion except that Eposter S was changed to MX-80H3wTM (manufactured by Soken Chemical Industry Co., Ltd., crosslinked acrylic monodisperse particles, average particle diameter 800 nm) and BYK-111 was changed to BYK-2155 (manufactured by Big Chemie Co., Ltd.). In the same manner as in (D2-5), an organic fine particle dispersion liquid (D2-8) which is a crosslinked acrylic resin fine particle was obtained.
The average particle size of the organic fine particles in the obtained organic fine particle dispersion liquid (D2-6) was 673 nm.

<Preparation of ink composition>
[Example 101]
(Ink composition 1)
25 parts of the quantum dots (QD-1) and 146.5 parts of the resin solution 14 were weighed and 28.5 parts of diethylene glycol monobutyl ether acetate were added to a container which can be sealed. Then, the mixture was sealed and stirred, and filtered using a membrane filter having a pore size of 1 μm to obtain an ink composition 1.

[Examples 102 to 121, Comparative Examples 101 to 105]
(Ink composition 2 to 21, 0, 57 to 60)
Ink compositions 2 to 21 and 0, in the same manner as the ink composition 1, except that the quantum dots, the resin solution, and the solvent were weighed in the order shown in Table 6 and Table 7 in a container that can be sealed. 57-60 were prepared. Further, in Comparative Examples 101 to 105, the amount of the solvent in which 25 parts of the quantum dots were completely dispersed was added.

Example 122
(Ink composition 22)
46.5 parts of the resin solution 1, 25 parts of the quantum dots (QD-1), 16 parts of the metal oxide fine particle dispersion liquid (D1-1), and 12.5 parts of diethylene glycol monobutyl ether acetate were weighed in a container that can be sealed. .. Then, the mixture was sealed and stirred, and filtered using a membrane filter having a pore size of 1 μm to obtain an ink composition 22.

[Examples 123 to 140]
(Ink compositions 23-40)
An ink composition similar to that of the ink composition 22 except that the resin composition, the quantum dots, the metal oxide fine particle dispersion liquid, and the organic fine particle dispersion liquid were weighed in this order in a container that can be sealed with the composition shown in Table 6. Products 23 to 40 were prepared.

[Example 141]
(Ink composition 41)
In a container that can be sealed, 65 parts of diethyl acrylamide, 25 parts of a polymerizable compound, quantum dots (QD-2), 7.5 parts of Omnirad 907 (IGM Resins BV photopolymerization initiator), Kayacure DETX-S. 2.5 parts (photopolymerization initiator manufactured by Nippon Kayaku Co., Ltd.) was weighed. Then, the ink composition 41 was obtained by sealing and stirring, and then filtering using a membrane filter having a pore size of 1 μm.

[Examples 142 and 143]
(Ink composition 42, 43)
An ink composition 42, 43 was prepared in the same manner as the ink composition 41 except that the polymerizable compound, the quantum dots, the Omnirad 907, and the Kayacure DETX-S were weighed in the compounding composition shown in Table 6 in an airtight container. Was prepared.

[Example 144]
(Ink composition 44)
In a container that can be sealed, 40 parts of diethyl acrylamide, 25 parts of quantum dots (QD-2), 7.5 parts of Omnirad 907, 2.5 parts of Kayacure DETX-S, 25 parts of metal oxide fine particle dispersion liquid (D1-1). Was weighed. After that, the ink composition 44 was sealed and stirred, and filtered using a membrane filter having a pore size of 1 μm to obtain an ink composition 44.

[Examples 145 to 153, Comparative Examples 107 to 110]
(Ink composition 45-53, 62-65)
Except for measuring the polymerizable compound, quantum dots, Omnirad 907, Kayacure DETX-S, metal oxide fine particle dispersion liquid, and organic fine particle dispersion liquid in this order in a container that can be sealed with the composition shown in Table 6 and Table 7. Ink compositions 45 to 53 and 62 to 65 were prepared in the same manner as the ink composition 44.

[Example 154]
(Ink composition 54)
In a container that can be sealed, 25 parts of quantum dots (QD-2), 5 parts of jER1001 (manufactured by Mitsubishi Chemical Co., epoxy resin), 1 part of laccamide TD-984 (solvent polyamidoamine amine curing agent manufactured by DIC), 53 parts of toluene and 16 parts of the metal oxide fine particle dispersion liquid (D1-1) were weighed. Then, the ink was sealed and stirred, and filtered using a membrane filter having a pore size of 1 μm to obtain an ink composition 54.

[Example 155, Comparative Example 111]
(Ink composition 55, 66)
Quantum dots, a resin, a curing agent, a solvent, and a metal oxide fine particle dispersion liquid were weighed in a container that can be sealed with the compounding compositions shown in Tables 6 and 7. Then, the mixture was sealed and stirred, and filtered using a membrane filter having a pore size of 1 μm to obtain ink compositions 55 and 66.

[Example 156]
(Ink composition 56)
25 parts of quantum dots (QD-2) and 75 parts of diethylene glycol monobutyl ether acetate were added to the container which can be sealed. Then, the ink was sealed and stirred, and filtered using a membrane filter having a pore size of 1 μm to obtain an ink composition 56.

The abbreviations in Tables 6 and 7 are shown below.
DBCA: Diethylene glycol monobutyl ether acetate (boiling point 247°C, SP value 8.9, corresponding to solvent (S-1))
PGMAc: Propylene glycol methyl ether acetate (boiling point 147°C, SP value 8.7, corresponding to solvent (S-2))
MEK: methyl methyl ketone DEAA: diethyl acrylamide DPGDA: dipropylene glycol diacrylate jER1001: epoxy resin manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 450 to 500, number average molecular weight 900
Byron 200: Toyobo Co., Ltd. polyester resin, glass transition temperature 67° C., number average molecular weight 17,000
TD-984: Solvent-free polyamidoamine type amine type curing agent "Laccamide TD-984" manufactured by DIC, amine value 285 to 315 mgKOH/g
D110N: "Takenate D-110N" manufactured by Mitsui Chemicals, Inc., a trimethylolpropane modified product of xylylene diisocyanate initiator 1: IGM Resins BV photopolymerization initiator "Omnirad907", α-aminoalkylphenone initiator 2 : Nippon Kayaku Co., Ltd. photopolymerization initiator "Kayacure DETX-S", 2,4-diethylthioxanthone

<Evaluation of ink composition>
The following evaluation was implemented about the obtained ink composition. The results are shown in Table 8.

[Excitation light transmittance]
The ink composition containing no polymerizable compound was applied to a transparent film (polyester film Lumirror 75S10 manufactured by Toray Industries, Inc.) so as to have a film thickness of 6.0 μm after drying using a bar coater, and under a 100° C. environment. Dried. The ink composition containing the polymerizable compound was applied to a transparent film (polyester film Lumirror 75S10 manufactured by Toray Industries, Inc.) so that the film thickness after drying was 6.0 μm using a bar coater, and the applied film was nitrogen. Using an LED irradiator installed in the replaced glove box, an integrated light amount of 500 mJ/cm ² (UVA conversion) was applied to cure.
The excitation light transmittance of the obtained film was measured using QE-2000 manufactured by Otsuka Electronics Co., Ltd., and evaluated according to the following criteria. The excitation wavelength was 450 nm.
A: Less than 10% (good)
○: 10% or more and less than 20% (usable)
Δ: 20% or more and less than 30% (unusable)
X: 30% or more (defective)

[External quantum efficiency]
The ink composition containing no polymerizable compound was applied to a transparent film (polyester film Lumirror 75S10 manufactured by Toray Industries, Inc.) so as to have a film thickness of 6.0 μm after drying using a bar coater, and under a 100° C. environment. Dried. The ink composition containing the polymerizable compound was applied to a transparent film (polyester film Lumirror 75S10 manufactured by Toray Industries, Inc.) so that the film thickness after drying was 6.0 μm using a bar coater, and the applied film was nitrogen. Using an LED irradiator installed in the replaced glove box, an integrated light amount of 500 mJ/cm ² (UVA conversion) was applied to cure.
The external quantum efficiency (EQE) of the obtained film was measured using QE-2000 manufactured by Otsuka Electronics Co., Ltd., and evaluated according to the following criteria. The excitation wavelength was 450 nm, and the fluorescence wavelength integration range was 500 nm to 800 nm.
◎: 20% or more (very good)
○: 15% or more and less than 20% (good)
△: 10% or more and less than 15% (usable)
X: less than 10% (cannot be used)

[Dispersion stability]
The viscosity of the obtained ink composition at 25° C. was measured immediately after the ink composition was prepared and after the aging at 25° C. for 48 hours using a viscometer Viscomate VM-10A-L (manufactured by SEKONIC). The rate of change in viscosity was calculated and evaluated according to the following criteria.
◯: Viscosity change rate is less than ±5% (good)
Δ: Viscosity change rate is ±5% or more and less than ±10% (unusable)
X: Viscosity change rate is ±10% or more (poor)

[IJ printing test]
Using the obtained ink composition, IJ printing test was conducted under the following conditions. The obtained printed matter and the ejection status were evaluated according to the following criteria.
The ink composition containing the polymerizable compound was cured by irradiation with an integrated light amount of 500 mJ/cm ² (UVA conversion) using an LED irradiator installed in a nitrogen-substituted glove box instead of drying after printing. .. The ink composition containing a curing agent was aged at 40° C. for 3 days instead of being dried after printing to be cured.
(Printing conditions)
Printing machine DimatixMaterialsPrinter
Cartridge 10 Dimatix Materials Cartridges, 10 pL
Print pattern Lattice pattern with 1 mm spacing Substrate cover glass/Matsunami Glass Industry substrate temperature 30°C
Drying after printing 40℃ 20 minutes (evaluation standard)
◯: Discharged according to the print pattern (good)
×: Nozzle clogging occurred (defective)

[IJ continuous dischargeability]
Using the obtained ink composition, IJ continuous ejection was performed in the same manner as in the above printing test. The discharge condition was visually confirmed and evaluated according to the following criteria.
(Evaluation criteria)
◯: Continuous discharge possible time is 30 minutes or more (good)
Δ: Continuous dischargeable time is 10 minutes or more and less than 30 minutes (usable)
×: Continuous discharge possible time is less than 10 minutes (unusable)

A coating film using the ink composition of the present invention containing quantum dots, which are semiconductor fine particles surface-treated with a specific ligand compound, has low excitation light transmittance, high external quantum efficiency (EQE), and dispersion. It was excellent in stability. Further, it has a good IJ ejection property, and it was shown to be useful for an inkjet ink.
In each of the examples, the excitation light transmittance was low and excellent. This is because the ligand compounds 1 to 18 used in the examples have a carbonyl structure at the end of the molecular chain, which enhances the affinity between the solvent and the quantum dots, and the excitation light transmittance is increased to a suitable level. It is considered that the quantum dots were dispersed.
Examples 101 to 103, 113 to 115 including quantum dots surface-treated with a ligand compound (compounds 1 to 3 and 13 to 15) having an acetoxy terminal in which R ¹ is an oxygen atom and R ² is an alkyl group are , The external quantum efficiency was superior to other ligand compounds.
In Examples 122 to 140 and 144 to 155 in which the metal oxide fine particles were used in combination, the metal oxide fine particles functioned as a scatterer, and thus the excitation light transmission was further reduced. In addition, the external quantum efficiency is also improved with the combined use of the metal oxide fine particles, and it is considered that this is because the paths through which the scattered light is absorbed by the quantum dots are increased.
In addition, Examples 122 to 124, 129 to 140, 144 to 153 which are surface-treated with a compound having an acetoxy terminal in which R ¹ is an oxygen atom and R ² is an alkyl group are external quantum. The efficiency was especially good. It is speculated that this is because the ligand compound having an acetoxy terminal has the ability to stably disperse the quantum dots even in the presence of light scattering particles.

Claims (10)

A quantum dot (A), which is semiconductor fine particles surface-treated with a compound represented by the following general formula (1).
General formula (1)
[In the general formula (1),
X: Direct bond, or divalent linking group having a molecular weight of 150 or less Y: Methylene group, methine group, or tetra-substituted carbon atom Q: Sulfanyl group, alkylsulfanyl group, or monovalent heterocyclic group R containing a sulfur atom ¹ : Direct bond, imino group (NR ³ ), oxygen atom, or CH ₂ O
R ² : hydrogen atom, alkyl group, amino group (NR ⁴ R ⁵ ), or alkoxy group (OR ⁶ ).
R ^{3 to} R ⁵ : each independently, an alkyl group or a hydrogen atom R ⁶ : an alkyl group m: an integer of 1 to 3] The quantum dot (A) according to claim 1, wherein the semiconductor fine particles are a compound semiconductor. The quantum dot (A) according to claim 1 or 2, wherein the semiconductor fine particles are a core-shell type, and the shell surface is treated with the compound represented by the general formula (1). In the general formula (1), the quantum dot (A) according to any one of claims 1 to 3, wherein R ¹ is an oxygen atom and R ² is an alkyl group. The quantum dot (A) according to any one of claims 1 to 4, wherein the divalent linking group represented by X in the general formula (1) has a molecular weight of 110 or less. An ink composition comprising the quantum dots (A) according to any one of claims 1 to 5 and a solvent (B). An ink composition comprising the quantum dots (A) according to any one of claims 1 to 5 and a binder component (C). The ink composition according to claim 7, further comprising light scattering particles (D). The ink composition according to claim 6, which is used in an inkjet method. A printed matter formed using the ink composition according to claim 6.