JP7030276B2 - Semiconductor fine particle compositions and quantum dots, coating liquids and ink compositions containing them, inkjet inks, and coatings and printed materials using them, wavelength conversion films, color filters, light emitting elements - Google Patents

Description

The present invention relates to semiconductor fine particle compositions and quantum dots, coating liquids and ink compositions containing them, inkjet inks, coating materials and printed materials using them, wavelength conversion films, color filters, and light emitting elements.

Quantum dots, which are the main constituents of the present invention, are extremely small particles (dots) formed to confine electrons in a minute space in order to exhibit 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 or less atoms. In recent years, attention has been focused on the fact that the wavelength of the emitted fluorescence can be continuously controlled by the grain size and that sharp emission with high symmetry in the wavelength distribution of the fluorescence intensity can be obtained.
Quantum dots can be adjusted for fluorescence to a wavelength that easily penetrates the human body and can be delivered to any location in the body, so they are used for bioimaging as a light emitting material (Non-Patent Document 1), and as a wavelength conversion material without the risk of fading (solar cell applications). Patent Document 1), a clear light emitting material, and a wavelength conversion material are being studied for development in electronics and photonics applications (Patent Documents 2 and 3).

When developing for these applications, it is necessary to form fine patterns. A method of preparing a resist solution using a photosensitive material for pattern formation and irradiating it with light through a mask has been proposed (Patent Document 4). However, there are problems that the quantum dots are deteriorated when the photosensitive material or light is irradiated, and the quantum dots are also contained in the portion removed by development, and the utilization efficiency of the quantum dot material is poor.
The inkjet method is known as a method of not resisting. So far, quantum dot inks that can be used in the inkjet method have not been produced.

Further, as a problem of the quantum dot itself, in order to maximize the luminous efficiency (quantum yield) and obtain strong fluorescence emission, it is necessary to suppress the leakage of excitation energy to the outside as much as possible. Furthermore, when using quantum dots as a light emitting material for electroluminescent elements, it is necessary to recombine the positive and negative charges injected from the electrodes within (or near) the quantum dots to bring the quantum dots into an excited state. It is necessary to design that the electric charge can move smoothly, but the transfer of excitation energy is suppressed.
Here, as a method of promoting charge transfer, for example, a conjugated structure such as an aromatic ring is introduced on the outside of the quantum dot, and the design is such that the charge flows from the outside to the inside (Patent Document 5). However, in this method, on the contrary, there is a strong possibility that the excitation energy leaks from the inside to the outside, and it is difficult to sufficiently improve the quantum yield.

On the other hand, the inventors have previously attached a unique skeletal structure around the central skeletal structure, which is the light emitting site, in the organic electroluminescent element, instead of the host / dopant configuration that was common at the time. , A non-doped organic fluorescent material that can obtain highly efficient light emission has been developed (Patent Document 6).

Japanese Unexamined Patent Publication No. 2006-216560 Japanese Unexamined Patent Publication No. 2008-11254 Japanese Unexamined Patent Publication No. 2009-251129 Japanese Unexamined Patent Publication No. 2015-127733 Japanese Unexamined Patent Publication No. 2010-209141 Japanese Unexamined Patent Publication No. 10-251633

Kamitaka, "Semiconductor Quantum Dots, Their Synthesis Methods and Applications to Life Sciences", Production and Technology, Vol. 63, No. 2, 2011, p58-p65 Journal of the American chemical society 2007 129 15432-15433

An object of the present invention is to provide a coating liquid or an ink, particularly an ink that can be printed by an inkjet method, without impairing various characteristics of the semiconductor fine particle composition, particularly the fluorescence characteristics of quantum dots, and the use thereof is used. Further, it is an object of the present invention to provide a coated or printed matter having excellent characteristics and stability over time, more specifically, a wavelength conversion film, a color filter and a light emitting element having excellent fluorescence characteristics.

As a result of diligent studies to solve the above problems, the present inventor has used a compound having a specific structure as a coating material for quantum dots, so that the coating liquid and ink without impairing various properties such as quantum dots. In particular, it is possible to produce inks that can be printed by the inkjet method, and to provide the coated matter and printed matter using them, particularly the printed matter by the ink jet method, and the wavelength conversion film, color filter, and light emitting element using them. I found that there is.

That is, the present invention comprises semiconductor fine particles and a coating material that covers the surface of the particles, and the coating material has a structure represented by the following general formula (1), general formula (2), or general formula (3). The present invention relates to a semiconductor fine particle composition.

General formula (1)
Y- (Ar ¹ -X ¹ -Ar ⁴ ) _n

General formula (2)
Y- (Ar ¹ -X ¹ -Ar ² -X ² -Ar ⁴ ) _n

General formula (3)
Y- (Ar ¹ -X ¹ -Ar ² -X ² -Ar ³ -X ³ -Ar ⁴ ) _n

(However, in the general formulas (1), (2) and (3), Y is an adsorbing group that exerts an action of linking to the surface of semiconductor fine particles, and Ar ¹ to Ar ⁴ each independently have a substituent. It is also good, an aromatic ring group, a fused aromatic ring group, a heteroaromatic ring group, a fused heteroaromatic ring group, or a group having a structure in which 2 to 10 of the same or different two or more kinds of rings are linked, and Ar ¹ to each. Ar ³ is a divalent group and Ar ⁴ is a monovalent group. X ¹ to X ³ are independently alkyridine, alkylene, a divalent aliphatic ring group and a divalent complex aliphatic ring group, respectively. n is an integer of 1 or 2.)

The semiconductor fine particle composition according to claim 1, wherein Ar ¹ to Ar ⁴ are any of an aromatic ring group, a fused aromatic ring group, a heteroaromatic ring group, and a condensed heteroaromatic ring group, respectively. Regarding things.

Further, the present invention is characterized in that the semiconductor fine particle composition described above is characterized in that X ¹ to X ³ are disubstituted methylene groups which may independently bond with each other to form a ring. Regarding things.

The present invention also relates to the semiconductor fine particle composition, which is characterized in that the semiconductor fine particles are quantum dots.

The present invention also relates to the above-mentioned semiconductor fine particle composition, which further contains a solvent.

The present invention also relates to the above-mentioned semiconductor fine particle composition, which further contains a resin.

The present invention also relates to a coating liquid containing the semiconductor fine particle composition.

The present invention also relates to a coated product using the coating liquid.

The present invention also relates to an ink composition comprising the semiconductor fine particle composition.

The present invention also relates to an inkjet ink containing the ink composition.

The present invention also relates to a printed matter made by using the ink composition.

The present invention also relates to a wavelength conversion film formed on a substrate by using the coating liquid or the ink composition.

The present invention also relates to a color filter formed on a substrate by using the coating liquid or the ink composition.

The present invention also relates to a light emitting device in which the light emitting layer is formed by using the coating liquid or the ink composition.

INDUSTRIAL APPLICABILITY The present invention provides a coating liquid or an ink, particularly an ink that can be printed by an inkjet method, without impairing various characteristics of the semiconductor fine particle composition, particularly the fluorescence characteristics of quantum dots. Further, by using it, a coated or printed matter having excellent characteristics and stability over time, more specifically, a wavelength conversion film, a color filter and a light emitting element having excellent fluorescence characteristics are provided.

Hereinafter, the present invention will be described in detail.

<Semiconductor fine particle composition and quantum dots>
The quantum dots constituting the main constituent of the present invention are compositions composed of specific semiconductor fine particles, and the semiconductor fine particles are semiconductors containing an inorganic substance as a component. Generally, a single composition or a core-shell type may be used. It may be a plurality of layers or more.
The semiconductor of the present invention is a single element selected from the group of elements represented by Group 2 elements, Group 10 elements, Group 11 elements, Group 12 elements, Group 13 elements, Group 14 elements, Group 15 elements and Group 16 elements, or 2 It is a semiconductor made of a compound containing more than one kind of element. Of the above, a compound semiconductor is preferable. The compound semiconductor is at least two kinds selected from the element group represented by Zn, Cd, B, Al, Ga, In, C, Si, Ge, Sn, N, P, As, Sb, Pb, S, Se and Te. It is a semiconductor composed of a compound containing the above elements.
More preferably, it is selected from the group of elements represented by Zn, B, Al, Ga, In, C, Si, Ge, Sn, N, P, S and Te, excluding the elements that may be safe for humans. It is a semiconductor composed of a compound containing at least two kinds of elements. For applications that emit visible light, semiconductors containing In as a constituent element are more preferable because of the narrow bandgap.
More specifically, as the material, Group IV of the Periodic Table of carbon (C) (atypical carbon, graphite, graphene, carbon nanotubes, diamonds, etc.), silicon (Si), germanium (Ge), tin (Sn), etc. Single element, Periodic table group V element such as phosphorus (P) (black phosphorus), single element of periodic table VI element such as selenium (Se), tellurium (Te), tin oxide (IV) boron nitride (BN), boron phosphide (BP), boron arsenide (BAs), aluminum nitride (AlN), aluminum phosphide (AlP), aluminum arsenide (AlAs), aluminum antimonized (AlSb), gallium nitride (GaN), phosphorus. Periodic Table III of Periodic Table III of gallium oxide (GaP), gallium arsenide (GaAs), gallium antimonized (GaSb), indium nitride (InN), indium phosphate (InP), indium arsenide (InAs), indium antimonized (InSb), etc. Compounds of Group Elements and Group V Elements of the Periodic Table Aluminum (Al ₂ S ₃ ), Aluminum Serene (Al ₂ Se ₃ ), Gallium Sulfide (Ga ₂ S ₃ ), Gallium Selenium (Ga Se, Ga ₂ Se ₃ ) ) Gallium tellalide (GaTe, Ga ₂ Te ₃ ), indium oxide (In ₂ O ₃ ), indium sulfide (In ₂ S ₃ , In S), indium selenium (In ₂ Se ₃ ), indium tellurate (In ₂ Te) ₃ ) Compounds of Group III elements of the Periodic Table and Group VI of the Periodic Table, zinc oxide (ZnO), zinc sulfide (ZnS), zinc selenium (ZnSe), zinc telluride (ZnTe), cadmium oxide (ZnTe) Group II elements of the Periodic Table such as CdO), cadmium sulfide (CdS), cadmium selenium (CdSe), cadmium tellurized (CdTe), mercury sulfide (HgS), mercury selenium (HgSe), mercury tellurized (HgTe), etc. And a compound of the Group VI element of the Periodic Table, a compound of the Group I element of the Periodic Table and the Group VI element of the Periodic Table such as copper (I) (Cu _2O ), copper chloride (I) (CuCl), odor. Compounds of Group I elements of the Periodic Table and Group VII elements of the Periodic Table such as copper (I) (CuBr), copper (I) (CuI), silver chloride (AgCl), silver bromide (AgBr), etc. However, if necessary, two or more of these may be used in combination. These semiconductors may contain elements other than the constituent elements. For example, taking Group III-V as an example, an alloy system such as INGaP or INGaN may be used. Further, semiconductor fine particles doped with rare earth elements or transition metal elements are also used in the above materials. For example, ZnS: Mn, ZnS: Tb, ZnS: Ce, LaPO ₄ : Ce and the like can be mentioned.
Among them, silicon (Si), germanium (Ge), gallium nitride (GaN), gallium sulfide (GaP), gallium sulfide (GaAs), indium nitride (InN), indium sulfide (InP), indium sulfide (InAs), Gallium selenide (GaSe, Ga ₂ Se ₃ ), indium sulfide (In ₂ S ₃ , InS), zinc oxide (ZnO), zinc sulfide (ZnS), zinc selenium (ZnSe), zinc tellurate (ZnTe), oxidation. Alloys such as cadmium (CdO), cadmium sulfide (CdS), cadmium selenide (CdSe), cadmium telluride (CdTe), InGaP, InGaN, etc. are preferably used, and in particular, indium phosphate (InP) and cadmium selenide are preferably used. (CdSe), zinc sulfide (ZnS), and zinc selenium (ZnSe) are particularly preferably used.

Further, as the material of the semiconductor fine particles, perovskite crystals can also be preferably used. The perovskite crystal suitable as the quantum dot of the present invention has a composition represented by the following general formula (2) and has a three-dimensional crystal structure.
General formula (2)
ABZ ₃
In formula (2), A is a monovalent cation of at least one amine compound selected from methylammonium (CH ₃ NH ₂ ) and formamidinium (NH ₂ CHNH), or rubidium (CH 3 NH 2). It is a monovalent cation of at least one alkali metal element selected from Rb), cesium (Ce), and franchium (Fr), and B is at least one selected from lead (Pb) and tin (Sn). It is a divalent cation of a metal element, where Z is a monovalent anion of at least one halogen element selected from iodine (I), bromine (Br), and chlorine (Cl).

The core / shell type semiconductor fine particles preferably used in the present invention have a structure in which the core structure is coated with a semiconductor component different from the semiconductor component forming the core. When the outside is a semiconductor with a large bunt gap, excitons (electron-hole pairs) generated by energy excitation such as light are confined in the core. As a result, the probability of non-radiative transition on the surface of the semiconductor fine particles is reduced, and the quantum yield of light emission and the stability of the fluorescence characteristics of the semiconductor quantum dots are improved. When used as quantum dots, suitable combinations of materials satisfying the above conditions include CdSe / ZnS, CdSe / ZnSe, CdS / ZnS, CdSe / CdS, CdTe / CdS, InP / ZnS, PbSe / PbS, and the like. Examples thereof include GaP / ZnS, Si / ZnS, InN / GaN, InP / CdSSe, InP / ZnSeTe, InGaP / ZnSe, InGaP / ZnS, Si / AlP, InP / ZnSTe, InGaP / ZnSTe, and InGaP / ZnSSe.
Further, ZnS, CdS, ZnSe and the like are often used as the shell component of the fine particles. Among them, when the core component of the fine particles is a semiconductor fine particle containing In as a constituent element, ZnS has no element toxicity and is used as a quantum dot. It is particularly excellent in characteristics such as exciton confinement, and is preferably used.

The average particle size of the inorganic material portion of the semiconductor fine particles of the present invention is preferably 0.5 nm to 100 nm, and a particle size that gives desired characteristics can be selected. In the case of the core / shell type, a plurality of shell fine particles may be contained in one semiconductor fine particle. The average particle size of the semiconductor fine particles in the case of a single semiconductor composition and the average particle size of the core / shell type core are preferably 0.5 nm to 10 nm. It is difficult to synthesize an average particle size of less than 0.5 nm, and in the case of quantum dots, if it exceeds 10 nm, the quantum confinement effect cannot be obtained and the desired fluorescence cannot be obtained. The feature of quantum dots is that the fluorescence wavelength can be arbitrarily changed by changing the core particle size even if the same material is used, and the particle size is set according to the desired fluorescence wavelength. The average thickness of the shell corresponds to the difference between the particle radius of the inorganic material part and the core particle radius. In the case of quantum dots, it is difficult to excite the core depending on the excitation method. Further, the average particle size of the entire fine particles including the coating material is preferably 2 nm to 1 μm. The shape of the semiconductor fine particles is not limited to a spherical shape, and may be a rod shape, a disk shape, or any other shape.

When the semiconductor fine particles of the present invention are quantum dots, the quantum dots in the coating liquid or ink have a plurality of types of quantum dots having different particle sizes in order to obtain a plurality of emission peaks, such as red and green. Can be mixed and used, and the ratio can be freely selected within the range of the content in the ink in total.

<Coating material>
The semiconductor fine particles of the present invention can be used by exposing the inorganic material portion, but they are necessary for making fine particles, stability when used as a coating liquid or ink, coating, printability, and coating. It is preferably coated with an organic substance in order to exhibit characteristics when it is in the final form as a printed matter or printed matter and to improve environmental resistance such as stability over time. These organic substances are often referred to as coating materials or protective materials, and are often referred to as treatment agents for the surface of fine particles, especially in the case of quantum dots, or ligands or ligands in the case of quantum dots.

The coating material in the present invention is characterized by having a structure represented by the general formula (1), the general formula (2), or the general formula (3).
General formula (1)
Y- (Ar ¹ -X ¹ -Ar ⁴ ) _n

General formula (2)
Y- (Ar ¹ -X ¹ -Ar ² -X ² -Ar ⁴ ) _n

General formula (3)
Y- (Ar ¹ -X ¹ -Ar ² -X ² -Ar ³ -X ³ -Ar ⁴ ) _n

(However, in the general formulas (1), (2) and (3), Y is an adsorbing group that exerts an action of linking to the surface of semiconductor fine particles, and Ar ¹ to Ar ⁴ each independently have a substituent. It is also good, an aromatic ring group, a fused aromatic ring group, a heteroaromatic ring group, a fused heteroaromatic ring group, or a group having a structure in which 2 to 10 of the same or different two or more kinds of rings are linked, and Ar ¹ to each. Ar ³ is a divalent group and Ar ⁴ is a monovalent group. X ¹ to X ³ are independently alkyridine, alkylene, a divalent aliphatic ring group and a divalent complex aliphatic ring group, respectively. n is an integer of 1 or 2.)
The most important feature of this compound is ((Ar ¹ -X ¹ -Ar ⁴ )), (Ar ¹ -X ¹ -Ar ² -X ² -Ar ⁴ ), or (Ar ¹ -X ¹ -Ar ² -X). The portion of ² -Ar ³ -X ³ -Ar ⁴ ) (hereinafter, this portion is referred to as Q group) is composed of an aromatic ring group, a fused aromatic ring group, a heteroaromatic ring group, and a condensed heteroarominal ring group. More than one conjugated ring (or a partial structure in which several of them are connected) is connected in a non-conjugated structure. As a result, the excitation energy in the semiconductor fine particles is suppressed from leaking to the outside, and the quantum efficiency is improved. Further, when used for an electroluminescent element, it contributes to an improvement in luminous efficiency and a decrease in drive voltage. The details of this reason are unknown, but due to charge hopping, the non-conjugated structure blocks the path of energy transfer propagating in π-conjugation, but maintains the overlap of intermolecular and intramolecular exciton rings. It is presumed that the movement of holes and electrons occurs, and excitons are likely to be generated by charge recombination in the vicinity of quantum dots, especially when used in an electric field light emitting element.

Specific examples of Ar ¹ to Ar ⁴ of the present invention include benzene, toluene, xylene, ethylbenzene, naphthalene, anthracene, phenanthrene, fluorene, pyrene, chrysen, naphthacene, perylene, azulene, fluorenone, anthracinone, dibenzosverenone and tetracyano. A group consisting of a substituted or unsubstituted aromatic ring or fused aromatic ring such as quinodimethane, or furan, thiophene, pyrrole, pyridine, pyron, oxazole, pyrazine, oxadiazole, triazole, thiadiazol, indol, quinoline, isoquinoline, Consists of substituted or unsubstituted heteroaromatic rings or fused heteroaromatic rings such as carbazole, aclysine, thioxanthone, coumarin, acridone, diphenylene sulfone, quinoxalin, benzothiazole, phenazine, phenanthroline, phenothiazine, quinacridone, flavanthrone, and indanslon. It is the basis. Furthermore, biphenyl, terphenyl, binaphthyl, bifluorenylidene, bipyridine, biquinolin, flavon, phenyltriazine, bisbenzothiazole, bithiophene, phenylbenzotriazole, phenylbenzimidazole, phenylaclydin, bis (benzoxazolyl) thiophene, Bis (phenyloxazolyl) benzene, biphenylylphenyloxadiazole, diphenylbenzoquinone, diphenylisobenzofuran, diphenylpyridine, stilben, dibenzyl, diphenylmethane, bis (phenylisopropyl) benzene, diphenylfluorene, diphenylhexafluoropropane, dibenzylnaphthyl Ketone, dibenzylidenecyclohexanone, distyrylnaphthalene, (phenylethyl) benzylnaphthalene, diphenyl ether, methyldiphenylamine, benzophenone, phenylbenzoate, diphenylurea, diphenylsulfide, diphenylsulfone, diphenoxybiphenyl, bis (phenoxyphenyl) sulfone, bis ( Phenoxyphenyl) A group having a skeleton in which two or more ring structure units of the same type or different types such as propane, diphenoxybenzene, ethylene glycol diphenyl ether, neopentyl glycol diphenyl ether, dipicorylamine, and dipyridylamine are linked. Of these, a group consisting of the compounds listed as the substituted or unsubstituted aromatic ring, condensed aromatic ring, heteroaromatic ring, and condensed heteroaromatic ring in the first half of the example is preferable.

Specific examples of X ¹ to X ³ of the present invention consist of substituted or unsaturated chain hydrocarbons such as an alkylidene group such as methylene, ethylidene, propyridene and butylidene, and an alkylene group such as ethylene, propylene and butylene. Divalent groups, saturated or partially unsaturated aliphatic rings such as cyclopentane, cyclohexane, cyclohexene, 4-methylcyclohexane, cycloheptane, tetrahydrofuran, tetradrothiophene, pyrrolin, pyrrolidine, imidazoline, imidazolidine, pyrazoline, Examples thereof include a divalent group consisting of a saturated or partially unsaturated complex aliphatic ring such as pyrazolidine, piperidine, piherazine, morpholin, dihydrooxazole, dihydrothiazole, and indolin. Furthermore, when all the sp3 carbons on the ring such as inden, fluorene, phenalene, 2H-pyrrole, pyran, 4H-chromen, and xanthene are substituted to form a quaternary carbon group, methylene having a substituent of the present invention is used. included. Of these, a disubstituted methylene group in which two conjugated rings such as 2,2-propanol, 1,1-cyclohexylidene, and 9,9-fluorenylidene are linked by the same carbon atom is particularly preferable. The reason why these are preferable is that the substituent is twisted by the sp3 carbon of the methylene group, so that it is difficult to take an orderly structure as a whole such as the orientation and lamination of the conjugated ring, and the dispersed state is maintained when the coating liquid or ink is used. It is easy to maintain, and deterioration of the film state due to crystallization or the like can be suppressed when it is made into a coated or printed matter.

Table 1 specifically exemplifies typical examples of the structures (Q groups) described in the above description, but the present invention is not limited to these representative examples.

The adsorption group Y to the semiconductor fine particles of the present invention is the same as the terminal portion of the treatment agent at the time of synthesizing the semiconductor fine particles described later, and is an organic hydroxide, an organic acid, an organic amine, a sulfur-containing organic substance, a phosphorus-containing organic substance, and the like. Examples thereof include a heteroatom-containing carbon chain having these partial structures and an unshared electron pair, a chelate ligand composed of a heterocycle and the like. Specific examples of Y in the present invention include -OH, -C (= O) OH, -C (= O) O-, -C (= O) CH ₂ (O =) C-, and -C (=). O) O (O =) C-, -NH ₂ , = NH, -PH ₂ , = PH, -P (= O) H ₂ , = P (= O) H, -P (= O) (OH) ₂ , = P (= O) (OH), -P (= O) (OH) O-, -SH, -SS-, -S (= O) ₂ (OH), = S (= O) ₂ , -S (= O) ₂ O- and so on. Here,-at the left end or the right end of each composition formula indicates that it is bound to one Q group, and = at the left end indicates that it is bound to two Q groups. (= O) or (O =) indicates an oxygen atom having a double bond with the element on the = side. (OH) indicates a hydroxyl group bonded to the leftmost atom. Here, in the adsorption to the semiconductor fine particles, those having a hydrogen atom bonded to the hetero atom generally desorb the hydrogen atom and form an ionic bond or a covalent bond with the metal constituting the fine particles. Heteroatoms that do not have a hydrogen atom are adsorbed by donating their unshared electron pair to a metal atom. Further, when a plurality of binding or adsorbing sites are present in the molecule, the molecule is more strongly adsorbed and is less likely to be detached.

The adsorption group Y of the present invention has one or two Q groups of the present invention depending on the valence. Depending on the type of adsorption group Y, it is possible to have three or more Q groups, but if the Q group is bulky and covers the entire adsorption group, it cannot approach the semiconductor fine particles, or it can be adsorbed. Even if there is, there is a high possibility that the required number of coating materials cannot be attached on the fine particles due to the interference between the Q groups between the plurality of coating materials. Therefore, in the present invention, the number of Q groups contained in one molecule of the coating material is preferably 1 or 2. Other than the Q group of the present invention, such as a part of the sites to which the Q group should be attached in the present invention and the hydrocarbon chain in which the hydrogen atom at the adsorption base is generally used in a treatment agent for synthesizing semiconductor fine particles described later. It may be substituted with a substituent of.

Hereinafter, representative examples of the covering materials (general formulas (1) to (3)) of the present invention are specifically exemplified in Table 2, but the present invention is not limited to these representative examples.

In the synthesis of the coating material (general formulas (1) to (3)) of the present invention, the Q group structure is modified with the adsorbent group Y according to the structure, and the Q group is bonded at the non-conjugated bond portion of the Q group. It can be appropriately carried out by a method such as adding the other to the compound having one attached, or a combination thereof. For example, compound B-6 in Table 3 can be synthesized by substituting an amine for a precursor having a substituent of bromine. Further, 4-α-cumylphenol and compounds B-2 and B-3 in Table 3 are commercially available as reagents and industrial raw materials, and can be used as they are as the coating material of the present invention or the present invention. It can be used as a raw material for another compound that serves as a coating material.

The coating material of the present invention can be used as a treatment agent during the synthesis of semiconductor fine particles, but due to differences in properties, the synthesis may not be successful or the coating material itself may be deteriorated during the synthesis. .. Therefore, it is preferable to use a general treatment agent at the time of synthesis and later replace it with the coating material of the present invention.

The organic substance that can be used as a treatment agent for the synthesis of the semiconductor fine particles of the present invention has a strong polarity or an unshared electron pair that adsorbs to the metal portion of the inorganic semiconductor fine particles, and further, a carbon chain or an aromatic ring is linked. It is an organic substance having a partial structure having a high affinity with a solvent or a resin used as a coating liquid or an ink by having a structure, a polyalkylene glycol structure, or the like. Such organic substances are generally well known as dispersants for organic and inorganic pigments and inorganic compound materials, and surfactants and emulsifiers used in detergents and emulsion formation. These compounds can also be used in the invention. Further, a compound having a partial structure used as a ligand of a metal complex, particularly a compound having a chelate ligand structure having two or more coordination bonds with a metal, is adsorbed on the metal portion of the semiconductor fine particles. It is easy to use and difficult to remove, so it can be used. In particular, the organic substance that can be used as a treatment agent in the present invention is preferably an organic substance having an alkyl group having 8 or more carbon atoms as a partial structure, which has a high boiling point and can be expected to interact with an alkyl chain portion. Further, it is better to have a polar group in order to strengthen the action on the semiconductor fine particles, and examples of the organic substances that can be treated include organic acids, organic amines, sulfur-containing organic substances, and phosphorus-containing organic substances.

As the organic acid, a compound having a carboxylic acid at the terminal can be used, an aromatic ring and an ether group can be contained, and a plurality of carboxylic acids may be contained in the molecule. Specific examples include benzoic acid, biphenylcarboxylic acid, butylbenzoic acid, hexylbenzoic acid, cyclohexylbenzoic acid, naphthalenecarboxylic acid, hexanoic acid, heptanic acid, octanoic acid, ethylhexanoic acid, hexenoic acid, octenoic acid, citronellic acid, and sverin. Acids, ethylene glycol bis (4-carboxyphenyl) ether, (2-butoxyethoxy) acetic acid and the like can be mentioned.
The organic acid having an alkyl group having 8 or more carbon atoms as a partial structure is a compound having an alkyl group having 8 or more carbon atoms among the organic acids, and specifically, nonanoic acid, decanoic acid, lauric acid, and myristine. Examples thereof include acids, palmitic acid, stearic acid, trichosanoic acid, lignoseric acid, oleic acid, eicosazienoic acid, linolenic acid, sebacic acid, (2-octyloxy) acetic acid and the like.

As the organic amine, a compound having an amino group at the terminal can be used, and examples thereof include aromatic ring n-butylamine, iso-butylamine, tert-butylamine, n-hexylamine, n-heptylamine, and cyclohexylamine.
As an organic amine having an alkyl group having 8 or more carbon atoms as a partial structure,
Examples thereof include octylamine, dodecaamine, heptadecane-9-amine, N, N-dimethyl-n-octylamine and the like.

Examples of sulfur-containing organic substances include thiols and disulfides.
Thiols include allyl mercaptan, 1,3-benzenedimethanethiol, 2-amino-5-mercapto-1,3,4-thiadiazol, 3-amino-5-mercapto-1,2,4-triazolebutanethiol. , N-hexanethiol, n-heptanethiol, and the like.
Examples of sulfur-containing organic substances of thiols having an alkyl group having 8 or more carbon atoms as a partial structure include dodecanethiol, 1-docosanthiol, tert-dodecyl mercaptan and the like.
Examples of disulfides include bis (4-chloro-2-nitrophenyl) disulfide, hexyl sulfide, 3,3', 5,5'-tetrachlorodiphenyl disulfide and the like.
Examples of the sulfur-containing organic substances of sulfides having an alkyl group having 8 or more carbon atoms as a partial structure include dodecyl disulfide, octadecyl disulfide, and dodecyl octadecyl disulfide.

Examples of phosphorus-containing organic substances include butyl phosphate, hexyl phosphate, diisopropyl phosphate, mono-2-ethylhexyl phosphonate (2-ethylhexyl), propylphosphonic acid, hexylphosphonic acid, methyl hexylphosphonate, and hexyl isopropylphosphonate. can give.
Examples of the phosphorus-containing organic substance having an alkyl group having 8 or more carbon atoms as a partial structure include octyl phosphate, didodecyl phosphate, dodecyl phosphate, dodecylphosphonic acid, dodecyl hexylphosphonate, decylphosphonic acid, and isopropyl decylphosphonate. Be done.

As a method for synthesizing the semiconductor fine particles of the present invention, generally known methods such as a method for producing in glass, a method for synthesizing in an aqueous solution, and a method for synthesizing in an organic solvent can be used. In particular, regarding InP / ZnS core-shell type quantum dots, technical documents "Journal of American Chemical Society. 2007, 129, 15432-15433", "Journal of American Chemical Society. 2016, 138, 5923-59", "Journal of American Chemical Society. 2016, 138, 5923-59" Regarding quantum dots, the technical document "Journal of American Chemical Society. 2009, 131, 5691-5697", the technical document "Chemistry of Chemicals. 2009, 21,242-2249", and the technical document "Journal of the American Chemical Society" for Si quantum dots. It can be synthesized by referring to the method described in "2010, 132, 248-253".

To replace the surface-treated semiconductor fine particle composition with the treatment agent used at the time of synthesis with the coating material of the present invention, the surface-treated semiconductor fine particle composition and the coating material of the present invention are mixed and stirred in a solvent or the surface. The treated semiconductor fine particle composition can be roughly removed by centrifugal sedimentation or the like, and then the semiconductor fine particles are redispersed in the solvent containing the coating material of the present invention. As a result, by surface-treating a coating material having a high affinity with a desired solvent or resin suitable for the coating liquid or ink, the final form of the desired coated or printed matter can be obtained, as described above. , A semiconductor fine particle composition, particularly a composition having very high characteristics as a quantum dot, can be suitably used in the final form. The coating material of the present invention and the above-mentioned general synthetic treatment agent may be used in combination as a coating material at the time of synthesis, coating liquid, or ink.

<Solvent and resin, additives>
The solvent used in the present invention includes toluene, 1,2,3-trichloropropane, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, and 2-methyl. -1,3-Propanediol, 3,5,5-trimethyl-2-cyclohexene-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol , 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene , N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o- Dichlorobenzene, P-chlorotoluene, P-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, water, methanol, ethanol, isopropyl alcohol, tershal tarshalbutanol, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, Ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotarsial butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol Monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclo Hexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glyco Lumethyl Ether Acetate, Dipropylene Glycol Monoethyl Ether, Dipropylene Glycol Monobutyl Ether, Dipropylene Glycol Monopropyl Ether, Dipropylene Glycol Monomethyl Ether, Diacetone Alcohol, Triacetin, Tripropylene Glycol Monobutyl Ether, Tripropylene Glycol Monomethyl Ether, Propylene Glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propio Nate, benzyl alcohol, methylisobutylketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester and the like can be mentioned.
Of these, in order to print by the inkjet method, it is necessary to use a solvent having a boiling point of 120 ° C. or higher at normal pressure in order to prevent drying at the ejection head. An example of a solvent having a boiling point of 120 ° C. or higher at normal pressure is given. 1,4-Butanediol (228 ° C), 1,3-Butanediol (208 ° C), 2-ethyl-1-hexanol (185 ° C), benzyl alcohol (205 ° C), diisobutylketone (168 ° C), cyclohexanone (18 ° C) 156 ° C), diacetone alcohol (168 ° C), butyl acetate (121 ° C), methoxybutyl acetate (171 ° C), cellosolve acetate (156 ° C), propylene glycol monomethyl ether acetate (146 ° C), amyl acetate (130 ° C). , Methyl lactate (145 ° C), ethyl lactate (154 ° C), butyl lactate (188 ° C), ethylene glycol monomethyl ether acetate (145 ° C), ethylene glycol monomethyl ether (125 ° C), ethylene glycol monoethyl ether (134 ° C), Ethylene glycol monobutyl ether (171 ° C), ethylene glycol (197 ° C), propylene glycol (187 ° C), propylene glycol monomethyl ether (121 ° C), methoxymethylbutanol (173 ° C), diethylene glycol dimethyl ether (162 ° C), ethylene glycol diethyl. Ether (121 ° C), perchloroethylene (121 ° C), dichlorobenzene (180 ° C), N-methyl-2-pyrrolidone (202 ° C), dimethylformamide (153 ° C), ethyl 3-ethoxypropionate (170 ° C) , Gamma-butyrolactone (203 ° C.), dimethylsulfoxyside (189 ° C.) and the like.
From the viewpoint of solubility, a hydrocarbon-based solvent having a boiling point of 120 ° C. or higher at normal pressure is preferable, and an aromatic hydrocarbon-based solvent having a boiling point of 120 ° C. or higher at normal pressure is particularly preferable.

Hydrocarbon solvents having a boiling point of 120 ° C or higher at normal pressure include octane (125 ° C), decane (174 ° C), 1-decene (171 ° C), decahydronaphthalene (191 ° C), and butylcyclohexane (180 ° C). , 2,3, -Dimethylheptane (140 ° C.) and the like.
Examples of the aromatic hydrocarbon solvent having a boiling point of 120 ° C. or higher at normal pressure include xylene (138 ° C.), mesitylene (164 ° C.), methylnaphthalene (245 ° C.), tert-butylbenzene (168 ° C.), and n-butylbenzene. (183 ° C) and the like.

Further, the inkjet ink of the present invention can also contain a solvent having a boiling point of less than 120 ° C. Solvents contained include methanol, ethanol, isopropyl alcohol, normal propyl alcohol, butanol, isobutanol, tertiary butanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, methyl acetate, normal propyl acetate, isopropyl acetate, 1,4. -Dioxane, methyl tertiary butyl ether, isopropyl ether), ethylene glycol dimethyl ether, methylene chloride, trichloroethylene, fluorocarbon, bromopropane, chloroform, tetrahydrofuran, dimethyl carbonate, diethyl carbonate, acetonitrile, 1,3-dioxolane and the like.
Solvents having a boiling point of less than 120 ° C. are preferably mixed within the range of 0 to 60% of the volatile content. If the content is higher than this, the ink dries quickly and it becomes difficult to eject the ink jet.

Examples of the resin include petroleum-based resin, maleic acid resin, nitrocellulose, cellulose acetate butyrate, cyclized rubber, rubber chloride, alkyd resin, acrylic resin, polyester resin, amino resin, vinyl resin, butyral resin and the like. It can be selected in a timely manner depending on the coating, printing method and base material. Further, as the resin that may be contained, a linear olefin resin, an aromatic polyether resin, a polyimide resin, a fluorene polycarbonate resin, a fluorene polyester resin, a polycarbonate resin, a polyamide (aramid) resin, and a polyarylate Resins, polysulfone resins, polyether sulfone resins, polyparaphenylene resins, polyamideimide resins, polyethylene naphthalate (PEN) resins, fluorinated aromatic polymer resins, (modified) acrylic resins, epoxy Examples thereof include based resins, allyl ester-based curable resins and silsesquioxane-based ultraviolet curable resins.

A surfactant may be added to the coating liquid and the ink of the present invention for the purpose of adjusting the surface tension and ensuring the wettability of the ink on the printing substrate. In the present invention, any cationic, anionic, amphoteric, or nonionic surfactant can be used.
Examples of the cationic surfactant include fatty acid amine salts, aliphatic quaternary ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, and imidazolinium salts.

Anionic surfactants include fatty acid soaps, N-acyl-N-methylglycine salts, N-acyl-N-methyl-β-alanine salts, N-acylglutamates, acylated peptides, alkylsulfonates, etc. Alkylbenzene sulphonate, alkylnaphthalen sulphonate, dialkyl sulfosuccinic acid ester salt, alkyl sulfoacetate salt, α-olefin sulfonate, N-acylmethyl taurine, sulfated oil, higher alcohol sulfate ester salt, secondary higher alcohol Examples thereof include sulfate ester salts, alkyl ether sulfate salts, secondary higher alcohol ethoxysulfates, fatty acid alkylolamide sulfate ester salts, alkyl ether phosphate ester salts, and alkyl phosphate ester salts.
Examples of the amphoteric tenside include carboxybetaine type, sulfobetaine type, aminocarboxylate, and imidazolinium betaine.
Examples of the nonionic surfactant include polyoxyethylene secondary alcohol ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene sterol ether, polyoxyethylene lanolin derivative polyoxyethylene polypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, and poly. Oxyethylene castor oil, hardened castor oil, polyoxyethylene sorbitol fatty acid ester, polyethylene glycol fatty acid ester, fatty acid monoglyceride, polyglycerin fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester, sucrose fatty acid ester, fatty acid alkanolamide, polyoxyethylene Examples thereof include fatty acid amides, polyoxyethylene alkylamines, alkylamine oxides, acetylene glycols and acetylene alcohols.

Among the surfactants, it is preferable to use a surface tension adjusting agent in order to improve the wettability to the printing substrate, and specifically, acetylenediol-based, silicon-based, acrylic-based, and fluorine-based are preferable. .. The above-mentioned surfactant may be used alone or in combination of two or more.

As the coating liquid and ink of the present invention, various additives such as plasticizers, ultraviolet inhibitors, light stabilizers, antioxidants, and hydrolysis inhibitors can also be used.

<Printing method>
The coated matter and printed matter of the present invention can be obtained by forming or coating the coating liquid of the present invention on a substrate. Known wet film forming methods such as spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen printing method, It can be produced by using a coating method such as a flexo printing method, an offset printing method, an inkjet printing method, a capillary coating method, and a nozzle coating method.
Examples of the base material include a glass plate and a resin plate.

Of these, the inkjet printing method used in the present invention is a single-pass method in which inkjet ink is ejected to a recording medium only once for recording, and a method perpendicular to the transport direction of the recording medium between the maximum recording width of the recording medium. Any serial type method in which recording is performed while reciprocating scanning a short shuttle head in the direction may be adopted. Further, the inkjet recording device needs to include an inkjet head (ink ejection means) for ejecting inkjet ink and a drying step for drying the ink ejected from the inkjet head. When the ink is ejected from the inkjet head, the ejected ink lands on the printing substrate and an image is recorded, and the image is conveyed into the drying device as the printing substrate is conveyed, and the drying process is performed. ..

The inkjet method is not particularly limited, and is known as a known method, for example, a charge control method for ejecting ink by using an electrostatic attraction, a drop-on-demand method (pressure pulse method) using the vibration pressure of a piezo element, or an electric signal. An acoustic inkjet method that converts the ink into an acoustic beam and irradiates the ink to eject the ink using radiation pressure, and a thermal inkjet method that heats the ink to form bubbles and uses the generated pressure (Bubble Jet (registered trademark)). Any method may be used.

The inkjet head used in the inkjet method may be an on-demand method or a continuous method. Further, as the discharge method, an electric-mechanical conversion method (eg, single cavity type, double cavity type, bender type, piston type, shared mode type, shared wall type, etc.), an electric-heat conversion method (eg, thermal inkjet). Specific examples include molds, bubble jet (registered trademark) types, electrostatic suction methods (eg, electrolytic control type, slit jet type, etc.), and discharge methods (eg, spark jet type, etc.). However, any discharge method may be used. The ink nozzle or the like used when recording by the inkjet method is not particularly limited, and can be appropriately selected according to the purpose.

As for the amount of ink droplets ejected from the inkjet head, 0.2 to 20 picolitres (pL) are preferable from the viewpoint of greatly reducing the drying load and improving image quality, and 1 to 15 picolitres (pL). Is more preferable.

The wavelength conversion film and color filter, which are the final forms of the present invention, are used for absorbing light from a light source and extracting light of a desired wavelength by transmitted light that has not been absorbed or fluorescence emission generated by light absorption. Is. In particular, when quantum dots are used in the present invention, fluorescence emission with an excellent quantum yield will be used. The wavelength conversion film of the present invention is a coating or printing film obtained by applying the coating liquid or the ink composition of the present invention to a substrate and containing quantum dots emitting fluorescent colors of green and red. It is a planar member that converts blue light of a light source into white light mainly in a display panel or lighting, or adjusts pseudo-white light having an irregular color tone to a desired color tone.
Examples of the base material include a glass plate and a resin plate.

Further, the color filter of the present invention is a color filter obtained by forming at least one segment of a filter segment using the coating liquid or the ink composition of the present invention, and is particularly used for a liquid crystal display panel. Specifically, there are three or more kinds of fine striped filter segments having different hues arranged in parallel or crossed on the surface of a transparent substrate such as glass, or fine mosaic-like filter segments are arranged vertically and horizontally. It consists of those arranged in a certain arrangement. In the present invention, unlike the light absorption type color filter that extracts blue, green, and red light from a conventional white light source, green and red are extracted mainly by a blue LED or the like as a light source and a fluorescent filter. When quantum dots are used, energy loss is reduced because the fluorescence is extracted with high quantum yield instead of dimming due to light absorption, and the wavelength distribution is narrow and colors close to pure colors can be obtained, resulting in a highly efficient display. It can be manufactured.

In general, a color filter is often manufactured by a resist method of patterning exposure and removing unnecessary parts in development after producing a solid thin film, and it cannot be applied to the fine particle composition of the present invention. Although it is possible, it is advantageous to apply the inkjet method in the present invention from the viewpoint of productivity due to the difference in the number of processes and low cost of no material loss in the developing process.

Further, a light emitting device having a light emitting layer formed by using a coating liquid or an ink composition, which is one of the final forms of the present invention, will be described in detail.

The light-emitting device in the present invention is generally referred to as an electroluminescent device, and is composed of an element in which a single-layer or multi-layered organic layer is formed between an anode and a cathode. Refers to an element consisting only of an electroluminescent layer between it and the cathode. On the other hand, the multi-layer electroluminescent element facilitates the injection of holes and electrons into the light emitting layer in addition to the light emitting layer, and facilitates the recombination of holes and electrons in the light emitting layer. It refers to a stack of a hole injection layer, a hole transport layer, a hole blocking layer, an electron injection layer, and the like. Further, an interconnect layer that exists adjacent to the light emitting layer between the light emitting layer and the anode and has a role of separating the light emitting layer and the anode or the light emitting layer from the hole injection layer or the hole transport layer. Layers may be inserted. Therefore, typical element configurations of the multilayer electro-emitting element are (1) anode / hole injection layer / light emitting layer / cathode, and (2) anode / hole injection layer / hole transport layer / light emitting layer / cathode. , (3) anode / hole injection layer / light emitting layer / electron injection layer / cathode, (4) anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode, (5) anode / positive Pore injection layer / light emitting layer / hole blocking layer / electron injection layer / cathode, (6) anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron injection layer / cathode, (7) Anodic / light emitting layer / hole blocking layer / electron injection layer / cathode, (8) anode / light emitting layer / electron injection layer / cathode (9) anode / hole injection layer / hole transport layer / interlayer layer / light emitting layer / Cathode, (10) Anodic / hole injection layer / interlayer layer / light emitting layer / electron injection layer / cathode, (11) anode / hole injection layer / hole transport layer / interlayer layer / light emitting layer / electron injection It is conceivable that the element configuration is laminated with a multi-layer configuration such as a layer / cathode.

Further, each of the above-mentioned layers may be formed by a layer structure of two or more layers, or several layers may be repeatedly laminated. As such an example, in recent years, for the purpose of improving the light extraction efficiency, an element configuration called "multi-photon emission" in which a part of the layers of the above-mentioned multi-layer electroluminescent element is multi-layered has been proposed. This is, for example, in an electroluminescent element composed of a glass substrate / anode / hole transport layer / electron transporting light emitting layer / electron injection layer / charge generating layer / light emitting unit / cathode. A method of laminating a plurality of layers of the portions can be mentioned.

For the hole injection layer, a hole injection material that exhibits an excellent hole injection effect on the light emitting layer and can form a hole injection layer having excellent adhesion to the anode interface and thin film forming property is used. Further, when such a material is laminated in multiple layers and a material having a high hole injection effect and a material having a high hole transport effect are laminated in multiple layers, the materials used for each are referred to as a hole injection material and a hole transport material. Sometimes. The material for an electroluminescent device of the present invention can be suitably used for both a hole injection material and a hole transport material. These hole injection materials and hole transport materials need to have a large hole mobility and a small ionization energy of usually 5.5 eV or less. As such a hole injection layer, a material that transports holes to the light emitting layer with a lower electric field strength is preferable, and further, when an electric field with a hole mobility of, for example, ¹⁰⁴ to ¹⁰⁶ V / cm is applied, at least. It is preferably ^10-6 cm ² / V · sec. The other hole injecting material and hole transporting material that can be mixed with the electroluminescent device material of the present invention are not particularly limited as long as they have the above-mentioned preferable properties. Any material can be selected and used from those commonly used as hole charge transport materials in transmission materials and known materials used for the hole injection layer of electroluminescent devices.

Specific examples of such hole injecting materials and hole transporting materials include triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, and arylamine derivatives. , Amino-substituted carcon derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilben derivatives, silazane derivatives, polysilane-based derivatives, aniline-based copolymers, conductive polymer oligomers (particularly thiophene oligomers), etc. can.

Of these, porphyrin compounds, aromatic tertiary amine compounds and styrylamine compounds can also be used as suitable ones. For example, 4,4'-bis (N- (1-naphthyl) -N-phenylamino) biphenyl having two fused aromatic rings in the molecule, or three triphenylamine units linked in a starburst type. Examples thereof include 4,4', 4 "-tris (N- (3-methylphenyl) -N-phenylamino) triphenylamine, etc., and copper phthalocyanine, hydrogen phthalocyanine, etc. as the hole injection material. Further, phthalocyanine derivatives can also be mentioned. In addition, inorganic compounds such as aromatic dimethylidene compounds, p-type Si and p-type SiC can also be used as hole injection materials and hole transport materials.

Further, materials that can be used for the hole injection layer include molybdenum oxide (MnO _x ), vanadium oxide (VO _x ), ruthenium oxide (RuO _x ), copper oxide (CuO _x ), tungsten oxide (WO _x ), and iridium oxide. Inorganic oxides such as (IrO _x ) can also be mentioned.

In order to form the hole injection layer described above, the above-mentioned compound is thinned by a known method such as a vacuum deposition method, a spin coating method, a casting method, or an LB method. The film thickness of the hole injection layer is not particularly limited, but is usually 5 nm to 5 μm.

Examples of the material used for the interlayer layer include polyvinylcarbazole and its derivatives, polyarylene derivatives having aromatic amines in the side chain or main chain, arylamine derivatives, and polymers containing aromatic amines such as triphenyldiamine derivatives. Further, as the film forming method of the interlayer layer, when a high molecular weight material is used, a method of forming a film from a solution is exemplified.

For the film formation of the interlayer layer from the solution, known wet film forming methods such as spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, etc. A coating method such as a dip coating method, a spray coating method, a screen printing method, a flexo printing method, an offset printing method, an inkjet printing method, a capillary coating method, or a nozzle coating method can be used.

The optimum value of the thickness of the interlayer layer differs depending on the material used, and it may be selected so that the drive voltage and the luminous efficiency are appropriate values. Usually, it is 1 nm to 1 μm, preferably 2 to 500 nm. More preferably, it is 5 to 200 nm.

On the other hand, as the electron injection layer, an electron injection material that exhibits an excellent electron injection effect on the light emitting layer and can form an electron injection layer having excellent adhesion to the cathode interface and thin film forming property is used. Examples of such electron-injected materials include metal complex compounds, nitrogen-containing five-membered ring derivatives, fluorenone derivatives, anthraquinodimethane derivatives, diphenoquinone derivatives, thiopyrandioxide derivatives, perylenetetracarboxylic acid derivatives, fleolenilidenemethane. Examples thereof include derivatives, anthron derivatives, silol derivatives, triarylphosphin oxide derivatives, polyquinolin and its derivatives, polyquinoxaline and its derivatives, polyfluorene and its derivatives, calcium acetylacetonate, sodium acetate and the like. Inorganic / organic composite materials in which a metal such as cesium is doped with vasophenanthroline, and the proceedings of the 50th Joint Lecture Meeting on Applied Physics, No. BCP, TPP, T5MPyTZ, etc. described on page 3, 1402, published in 2003 are also given as examples of electron injection materials, but they can form a thin film necessary for device fabrication, inject electrons from the cathode, and transport electrons. As long as it is a material, it is not particularly limited to these.

Among the electron-injected materials, preferred examples include a metal complex compound, a nitrogen-containing five-membered ring derivative, a silol derivative, and a triarylphosphine oxide derivative. As a preferable metal complex compound that can be used in the present invention, a metal complex of 8-hydroxyquinoline or a derivative thereof is suitable. Specific examples of the metal complex of 8-hydroxyquinoline or a derivative thereof include tris (8-hydroxyquinolinate) aluminum, tris (2-methyl-8-hydroxyquinolinate) aluminum, and tris (4-methyl-8-). Hydroxyquinolinate) Aluminum, Tris (5-Methyl-8-Hydroxyquinolinate) Aluminum, Tris (5-phenyl-8-Hydroxyquinolinate) Aluminum, Bis (8-Hydroxyquinolinate) (1-naphtholat) ) Aluminum, bis (8-hydroxyquinolinate) (2-naphtholat) Aluminum, bis (8-hydroxyquinolinate) (phenorate) aluminum, bis (8-hydroxyquinolinate) (4-cyano-1-naphtholate) ) Aluminum, bis (4-methyl-8-hydroxyquinolinate) (1-naphtholate) aluminum, bis (5-methyl-8-hydroxyquinolinate) (2-naphtholate) aluminum, bis (5-phenyl-8) -Hydroxyquinolinate) (phenorate) aluminum, bis (5-cyano-8-hydroxyquinolinate) (4-cyano-1-naphtholate) aluminum, bis (8-hydroxyquinolinate) chloroaluminum, bis (8) -Aluminum complex compounds such as hydroxyquinolinate (o-cresolate) aluminum, tris (8-hydroxyquinolinate) gallium, tris (2-methyl-8-hydroxyquinolinate) gallium, tris (4-methyl- 8-Hydroxyquinolinate) gallium, tris (5-methyl-8-hydroxyquinolinate) gallium, tris (2-methyl-5-phenyl-8-hydroxyquinolinate) gallium, bis (2-methyl-8) -Hydroxyquinolinate) (1-naphtholate) gallium, bis (2-methyl-8-hydroxyquinolinate) (2-naphtholate) gallium, bis (2-methyl-8-hydroxyquinolinate) (phenorate) gallium , Bis (2-methyl-8-hydroxyquinolinate) (4-cyano-1-naphtholate) gallium, bis (2,4-dimethyl-8-hydroxyquinolinate) (1-naphtholate) gallium, bis (2) , 5-Dimethyl-8-Hydroxyquinolinate) (2-naphtholate) gallium, bis (2-methyl-5-phenyl-8-hydroxyquinolinate) (phenorate) gallium, bis (2-methyl-5- Cyano-8-hydroxyquinolinate) (4-cyano-1-naphtholate) gallium, bis (2-methyl-8-hydroxyquinolinate) chlorogallium, bis (2-methyl-8-hydroxyquinolinate) ( In addition to gallium complex compounds such as o-cresolate gallium, 8-hydroxyquinolinate lithium, bis (8-hydroxyquinolinate) copper, bis (8-hydroxyquinolinate) manganese, bis (10-hydroxybenzo [h] ] Kinolinate) Metal complex compounds such as berylium, bis (8-hydroxyquinolinate) zinc, and bis (10-hydroxybenzo [h] quinolinate) zinc can be mentioned.

Among the electron-injected materials that can be used in the present invention, preferred examples of the nitrogen-containing five-membered ring derivative include an oxadiazole derivative, a thiazole derivative, an oxadiazole derivative, a thiadiazole derivative, and a triazole derivative. , 5-bis (1-phenyl) -1,3,4-oxadiazole, 2,5-bis (1-phenyl) -1,3,4-thiazole, 2,5-bis (1-phenyl) -1, 3,4-Oxadiazole, 2- (4'-tert-butylphenyl) -5- (4 "-biphenyl) 1,3,4-oxadiazole, 2,5-bis (1-naphthyl) -1 , 3,4-Oxadiazole, 1,4-bis [2- (5-phenyloxadiazolyl)] benzene, 1,4-bis [2- (5-phenyloxadiazolyl) -4-tert-butyl Benzene], 2- (4'-tert-butylphenyl) -5- (4 "-biphenyl) -1,3,4-thiadiazole, 2,5-bis (1-naphthyl) -1,3,4-thiadiazole , 1,4-Bis [2- (5-phenylthiazolyl)] benzene, 2- (4'-tert-butylphenyl) -5- (4 "-biphenyl) -1,3,4-triazole, 2 , 5-Bis (1-naphthyl) -1,3,4-triazole, 1,4-bis [2- (5-phenyltriazolyl)] benzene and the like can be mentioned.

Further, examples of the material that can be used for the electron injection layer include inorganic oxides such as zinc oxide (ZnO) and titanium oxide (TiO ₂ ).

Further, as the hole blocking layer, a hole blocking material that can prevent holes that have passed through the light emitting layer from reaching the electron injection layer and can form a layer having excellent thin film forming properties is used. Examples of such hole blocking materials include aluminum complex compounds such as bis (8-hydroxyquinolinate) (4-phenylphenolate) aluminum and bis (2-methyl-8-hydroxyquinolinate) ( Examples thereof include gallium complex compounds such as 4-phenylphenolate) gallium and nitrogen-containing condensed aromatic compounds such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP).

As the light emitting layer of the electroluminescent element of the present invention, one having the following functions is suitable.
Injection function; A function that can inject holes from the anode or hole injection layer when an electric field is applied, and can inject electrons from the cathode or electron injection layer. Transport function; Function to move by the force of light emission function; A function to provide a field for recombination of electrons and holes and connect this to light emission. Also, the transport capacity expressed by the mobility of holes and electrons may be large or small.

The light emitting layer formed by using the coating liquid or the ink composition of the present invention can be preferably used. In order to obtain a light emitting layer formed by using the coating liquid or ink composition of the present invention, the light emitting layer is formed by combining the coating liquid or ink composition of the present invention with other light emitting compounds. Can be done.

As a compound exhibiting blue to green light emission that may be added to the coating liquid or ink composition of the present invention in order to obtain a light emitting layer formed by using the coating liquid or ink composition of the present invention. Can be used as a fluorescent whitening agent such as benzothiazole-based, benzimidazole-based, benzoxazole-based, metal chelated oxynoid compound, and styrylbenzene-based compound.

Examples of the metal chelated oxinoid compound include 8-hydroxyquinoline-based metal complexes such as tris (8-quinolinol) aluminum and dilithium epintridione as suitable compounds.

Further, as the styrylbenzene compound, for example, a distyrylpyrazine derivative can also be used as a material for the light emitting layer. In addition, a polyphenyl compound may be added to the coating liquid or ink composition of the present invention.

Further, in addition to the above-mentioned fluorescent whitening agent, metal chelated oxynoid compound, styrylbenzene compound and the like, for example, 12-phthaloperinone, 1,4-diphenyl-1,3-butadiene, 1,1,4,4-tetraphenyl -1,3-butadiene, naphthalimide derivative, perylene derivative, oxadiazole derivative, aldazine derivative, pyrazirin derivative, cyclopentadiene derivative, pyrolopyrrole derivative, styrylamine derivative, coumarin compound, polymer compound, 9,9', Examples thereof include 10,10'-tetraphenyl-2,2'-biantrasen, PPV (polyparaphenylene vinylene) derivatives, polyfluorene derivatives and their copolymers. Further, with phenolic ligands such as bis (2-methyl-8-quinolinolate) (para-phenylphenolate) aluminum (III) and bis (2-methyl-8-quinolinolate) (1-naphtholate) aluminum (III), Examples thereof include metal complexes having a substituted 8-quinolinolate ligand at the same time.

The light emitting layer for obtaining white light emission is not particularly limited, but the following can be used. An electroluminescent laminated structure that defines the energy level of each layer and emits light by using tunnel injection (European Patent No. 0390551).
Similarly, an element using tunnel injection and a white light emitting element is described as an example (Japanese Patent Laid-Open No. 3-230584). A light emitting layer having a two-layer structure is described (Japanese Patent Laid-Open No. 2-220390 and JP-A-2-216790). A light emitting layer is divided into a plurality of layers and each is composed of a material having a different emission wavelength (Japanese Patent Laid-Open No. 4-51491). A structure in which a blue light emitter (fluorescence peak 380 to 480 nm) and a green light emitter (480 to 580 nm) are laminated and further contained a red phosphor (Japanese Patent Laid-Open No. 6-207170). A structure in which the blue light emitting layer contains a blue fluorescent dye, the green light emitting layer has a region containing a red fluorescent dye, and further contains a green phosphor (Japanese Unexamined Patent Publication No. 7-142169).

Further, as the material used for the anode of the electric field light emitting element of the present invention, a metal having a large work function (4 eV or more), an electrically conductive compound, or a mixture thereof is preferably used as an electrode material. Specific examples of such an electrode material include metals such as Au and conductive materials such as CuI, ITO, SnO ₂ , and ZnO. In order to form this anode, these electrode materials can be formed into a thin film by a method such as a thin film deposition method or a sputtering method. When the light emitted from the light emitting layer is taken out from the anode, it is desirable that the anode has a property that the transmittance of the anode with respect to the light emitted is larger than 10%. Further, the sheet resistance of the anode is preferably several hundred Ω / □ or less. Further, the film thickness of the anode is usually selected in the range of 10 nm to 1 μm, preferably 10 to 200 nm, although it depends on the material.

Further, as the material used for the cathode of the electric field light emitting element of the present invention, a metal having a small work function (4 eV or less), an alloy, an electrically conductive compound, or a mixture thereof is used as an electrode material. Specific examples of such an electrode material include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / silver alloy, aluminum / aluminum oxide, aluminum / lithium alloy, indium, rare earth metal and the like. This cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. Here, when the light emitted from the light emitting layer is taken out from the cathode, the transmittance of the cathode with respect to the light emitted is preferably larger than 10%. The sheet resistance of the cathode is preferably several hundred Ω / □ or less, and the film thickness is usually 10 nm to 1 μm, preferably 50 to 200 nm.

Regarding the method for producing the electroluminescent device of the present invention, an anode, a light emitting layer, a hole injection layer if necessary, and an electron injection layer if necessary are formed by the above materials and methods, and finally a cathode is formed. do it. Further, the electroluminescent device can be manufactured from the cathode to the anode in the reverse order of the above.

This electroluminescent device is manufactured on a translucent substrate. This translucent substrate is a substrate that supports an electroluminescent element, and its translucency is preferably such that the transmittance of light in the visible region of 400 to 700 nm is 50% or more, preferably 90% or more. It is preferable to use a smoother substrate.

These substrates are not particularly limited as long as they have mechanical and thermal strength and are transparent, but for example, a glass plate, a synthetic resin plate, or the like is preferably used. Examples of the glass plate include plates formed of soda lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, quartz and the like. Examples of the synthetic resin plate include a plate such as a polycarbonate resin, an acrylic resin, a polyethylene terephthalate resin, a polyether sulfide resin, and a polysulfon resin.

As a method for forming each layer excluding the light emitting layer of the electric field light emitting element of the present invention, a dry film forming method such as vacuum deposition, electron beam irradiation, sputtering, plasma, ion plating, spin coating, dipping, flow coating and the like can be used. Any method of the wet film forming method can be applied. In addition, special table 2002-534782 and S.A. T. Lee, et al. , Proceedings of SID'02, p. The LITI (Laser Induced Thermal Imaging) method described in 784 (2002), printing (offset printing, flexographic printing, gravure printing, screen printing), inkjet printing, and the like can also be applied.

The organic layer excluding the polymer material is particularly preferably a molecular deposition film. Here, the molecular deposition film is a thin film deposited and formed from a material compound in a gas phase state, or a film solidified and formed from a material compound in a solution state or a liquid phase state, and is usually this molecular deposition film. Can be classified from the thin film (molecular cumulative film) formed by the LB method by the difference in aggregate structure, higher-order structure, and the functional difference caused by the difference. Further, as disclosed in Japanese Patent Application Laid-Open No. 57-57181, a binder such as a resin and a material compound are dissolved in a solvent to form a solution, which is then thinned by a spin coating method or the like. , An organic layer can be formed. The film thickness of each layer is not particularly limited, but if the film thickness is too thick, a large applied voltage is required to obtain a constant light output, resulting in inefficiency. On the contrary, if the film thickness is too thin, pinholes, etc. Is generated, and it becomes difficult to obtain sufficient emission brightness even when an electric field is applied. Therefore, the film thickness of each layer is preferably in the range of 1 nm to 1 μm, but more preferably in the range of 10 nm to 0.2 μm.

Further, in order to improve the stability of the electroluminescent element with respect to temperature, humidity, atmosphere and the like, a protective layer may be provided on the surface of the element, or the entire element may be coated or sealed with a resin or the like. In particular, when coating or sealing the entire element, a photocurable resin that is cured by light is preferably used.

The current applied to the electroluminescent device of the present invention is usually direct current, but pulse current or alternating current may be used. The current value and voltage value are not particularly limited as long as they do not destroy the element, but considering the power consumption and life of the element, it is desirable to efficiently emit light with as little electric energy as possible.

The method for driving the electroluminescent element of the present invention can be driven not only by the passive matrix method but also by the active matrix method. Further, as a method of extracting light from the electroluminescent element of the present invention, it can be applied not only to a method of bottom emission in which light is extracted from the anode side but also to a method of top emission in which light is extracted from the cathode side. These methods and techniques are described in Junji Kido, "All about electroluminescence", Nihon Jitsugyo Publishing Co., Ltd. (published in 2003).

The main method of the full colorization method of the electroluminescent element of the present invention includes a three-color painting method, a color conversion method, and a color filter method. Examples of the three-color painting method include a vapor deposition method using a shadow mask, an inkjet method, and a printing method. In addition, special table 2002-534782 and S.A. T. Lee, et al. , Proceedings of SID'02, p. The laser thermal transfer method described in 784 (2002) (also referred to as Laser Induced Thermo Imaging, LITI method) can also be used. The color conversion method is a method of converting from blue to green and red having a longer wavelength than blue through a color conversion (CCM) layer in which a fluorescent dye is dispersed by using a light emitting layer that emits blue light. The color filter method uses an electroluminescent element that emits white light to extract light of the three primary colors through a color filter for liquid crystal. In addition to these three primary colors, some white light is extracted as it is and used for light emission. As a result, the luminous efficiency of the entire element can be increased.

Further, the electroluminescent device of the present invention may adopt a microcavity structure. This is because the electric field light emitting element has a structure in which a light emitting layer is sandwiched between an anode and a cathode, and the emitted light causes multiple interference between the anode and the cathode, but the reflectance and transmittance of the anode and the cathode are transmitted. It is a technology that positively utilizes the multiple interference effect and controls the emission wavelength extracted from the element by appropriately selecting the optical characteristics such as the rate and the film thickness of the organic layer sandwiched between them. .. This also makes it possible to improve the emission chromaticity. For the mechanism of this multiple interference effect, refer to J.M. AM-LCD Digital Papers by Yamada et al., OD-2, p. 77-80 (2002).

As described above, the electroluminescent device using the light emitting layer formed by using the coating liquid or the ink composition of the present invention can obtain long-term light emission with a low driving voltage. Therefore, this electric field light emitting element can be used as a flat panel display such as a wall-mounted television or various flat light emitters, as well as a light source such as a copier or a printer, a light source such as a liquid crystal display or an instrument, a display board, an indicator light or the like. Can be applied.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not particularly limited to the examples. In the examples, "parts" and "%" represent "parts by weight" and "% by weight".

<Semiconductor fine particle (quantum dot) dispersion liquid synthesis / preparation>
QD: InP / ZnS core-shell quantum dots were synthesized as follows according to the description of the technical document "Inorganic Chemistry 2016, (17), pp883-18386".
0.22 parts of indium chloride and 8.25 parts of octylamine were placed in a reaction vessel and heated to 180 ° C. while performing nitrogen bubbling. After indium chloride was dissolved, 0.86 part of diethylaminophosphine was injected in a short time and controlled at 180 ° C. for 20 minutes. Then, it was rapidly cooled to 40 ° C. Separately, an additive solution prepared by heating and dissolving 0.55 parts of acetic anhydride and 15.0 parts of compound B-6 in Table 2 was injected, heated at 220 ° C. for 5 hours, and then allowed to cool to room temperature. After allowing to cool, purification was carried out by a reprecipitation method using hexane and ethanol. Further, using toluene, the solid content concentration was adjusted to 10%, and a quantum dot dispersion liquid QD-1 surface-coated with B-6 was obtained.

0.22 parts of indium chloride and 8.25 parts of octylamine were placed in a reaction vessel and heated to 165 ° C. while performing nitrogen bubbling. After indium chloride was dissolved, 0.86 part of diethylaminophosphine was injected in a short time and controlled at 165 ° C. for 20 minutes. Then, it was rapidly cooled to 40 ° C. Separately, an additive solution prepared by heating and dissolving 0.55 parts of acetic anhydride, 7.0 parts of dodecanethiol and 5.0 parts of oleylamine was injected, heated at 240 ° C. for 2 hours, and then allowed to cool to room temperature. After allowing to cool, purification was carried out by a reprecipitation method using hexane and ethanol. Further, using toluene, the solid content concentration was adjusted to 10%, and a quantum dot dispersion liquid QD-2 surface-coated with dodecanethiol (C-1) was obtained.

This dispersion QD-2 was further diluted with toluene to a solid content concentration of 1%. A 5% toluene solution of compound B-3 in Table 2 was prepared, added in the same amount, and stirred for 12 hours. Purification was performed by the reprecipitation method using hexane and ethanol. A quantum dot dispersion QD-3 was obtained, which was prepared to have a solid content concentration of 10% using trimethylbenzene and surface-coated with compound B-3.

As shown in Table 3, the compounds B-3, which are the surface coating treatment agents for the dispersion liquid QD-3, are compounded in Table 2, B-2, B-4, B-8, B-10, B-12, respectively. By changing to B-16, surface-coating treatment, and purifying and preparing in the same manner as described above, quantum dot dispersion liquids QD-4 to 9 surface-coated with each compound of the present invention were obtained. Quantum dot dispersions QD-10, 11 surface-coated with bis (biphenylyl) amine (C-2) and dodecylbenzene sulfonic acid (C-3), which are not the targets of the compound of the present invention, in the same manner. Got

<Preparation of resin solution>
Paraffin wax 155 (manufactured by Nippon Seiro) was dissolved in decan so as to have an NV of 10% to prepare a resin solution 1.

A reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of xylene in a separable 4-neck flask, the temperature was raised to 80 ° C., the inside of the reaction vessel was replaced with nitrogen, and then the dropping tube was used. 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 weight average molecular weight (Mw) of 26000. After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and xylene was added to the previously synthesized resin solution so that the non-volatile content was 20% by weight. The resin solution 2 was prepared.

<Creation of inkjet ink>
(Examples 1 to 8, Comparative Examples 1 to 3)
With the ink composition shown in Table 3, weigh the quantum dot solution, the fine particle (B) solution (not added to the comparative example), the resin solution, and the solvent in this order in a container that can be sealed, and then seal and seal 3 Penetrated for minutes to create an inkjet ink.

<Evaluation method>
(Viscosity measurement)
The measurement was performed at 25 ° C. using a vibrating viscometer Viscomate VM-10A-L (manufactured by SEKONIC).
(Visual inspection)
Ink appearance It is not possible to make ink with Δ to ×, where 〇 is a transparent state without turbidity, Δ is turbidity, and × is a precipitate.
Inkjet ejection property 〇 is the one that can be ejected according to the printing pattern, × is the one that has an abnormality such as nozzle clogging, and × cannot be printed.
Appearance of printed matter The image according to the print pattern is 〇, the case where faintness is seen is 〇 △, the distorted image is Δ, and the state where the printed pattern is attached without evidence is ×, and Δ to × are inappropriate.
(Inkjet ejection test conditions)
Printing Press DimaticsMaterialsPrinter
Cartridge 10DimaticsMaterialsCartriges, 10pL
Printing pattern Lattice pattern with 1 mm intervals Substrate Round cover glass, manufactured by Matsunami Glass Industry Substrate temperature 30 ° C
Dry after printing 40 ° C for 20 minutes (quantum yield measurement)
Measuring machine Absolute PL quantum yield measuring device C9920-02
Excitation wavelength 400nm Integral range 375-425nm
Fluorescence integration range 430-800 nm
The QY maintenance rate was set to 1 at the initial stage of printing, and the ratio after 4 weeks was shown.
Note that QY represents the quantum yield.

It was confirmed that the inkjet ink of the present invention can be used for inkjet printing and can be printed with a high quantum yield. It is assumed that other coating liquids, coatings made by printing methods using ink, and printed matter have almost the same characteristics, and wavelength conversion films and color filters using these have the desired performance. It was shown that it can exert.

<Creation of electroluminescent element>
As described below, an electroluminescent device was created. In the examples, all mixing ratios indicate weight ratios unless otherwise specified. Thin-film deposition (vacuum vapor deposition) was performed in a vacuum of ^10-6 Torr under conditions where temperature control such as heating and cooling of the substrate was not performed.
Inkjet ejection test conditions Printing machine DimaticsMaterialsPrinter
Cartridge 10DimaticsMaterialsCartriges, 10pL
Print pattern solid (area in the range of 1.2 cm x 1.2 cm where a total of 6 elements of 2 mm x 2 mm are formed)
Substrate temperature 30 ° C
After printing and drying at 40 ° C. for 20 minutes, the light emitting characteristics of the element were measured using an electroluminescent element having a light emitting element area of 2 mm × 2 mm.

(Example 9)
In a container that can be sealed, weigh 1 part of quantum dot dispersion QD-1, 1 part of resin solution 1, and 30 parts of decane as a solvent, then seal and infiltrate for 3 minutes for inkjet. I made an ink.
PEDOT / PSS (poly (3,4-ethylenedioxy) -2,5-thiophene / polystyrene sulfonic acid, CLEVIOUS (registered trademark) PVP CH8000 manufactured by Heraeus) is spin-coated on the cleaned glass plate with ITO electrode. A film was formed by the method and dried at 110 ° C. for 20 minutes to obtain a hole injection layer having a film thickness of 35 nm. Next, poly (N-vinylcarbazole) was dissolved in monochlorobenzene at a concentration of 1.0% by weight, a film was formed by a spin coating method, and dried at 110 ° C. for 20 minutes to transport holes having a film thickness of 35 nm. Formed a layer. Using the prepared inkjet ink, a light emitting layer having a film thickness of 20 nm was formed by inkjet ejection printing under the above conditions, and then spin-coated with an isopropanol dispersion N-10 of zinc oxide manufactured by Avantama. A film was formed by the method to form an electron transport layer of 80 nm. Finally, aluminum (Al) was vapor-deposited at 200 nm to form an electrode, and an electroluminescent device was obtained. This element exhibited red emission at 8 V with an external quantum efficiency of 5.2% and an emission luminance of 35,000 (cd / m ² ), the peak wavelength of the emission spectrum was 658 nm, and the full width at half maximum was 50 nm. When this device was driven at a constant current at room temperature with a luminous brightness of 1000 (cd / m ² ), the luminance half life was 1000 hours or more. The luminous efficiency when driven at a current density of 10 (mA / cm ² ) is 6.5 (cd / A), and the relative brightness after 100 hours of continuous driving in an environment of 80 ° C. (= (100 hours). Later brightness) / (initial brightness)) was 0.88.

(Example 10)
Weigh 1 part of quantum dot dispersion QD-4, 1 part of resin solution 2 and 30 parts of trimethylbenzene as a solvent in a container that can be sealed, then seal and infiltrate for 3 minutes. Inkjet ink was created.
Each layer was prepared in the same manner as in Example 9 except that this was replaced with the inkjet ink of Example 9 to form a light emitting layer, and an electroluminescent element was obtained. This element exhibited green emission at 8 V with an external quantum efficiency of 6.8% and an emission luminance of 53000 (cd / m ² ), the peak wavelength of the emission spectrum was 544 nm, and the full width at half maximum was 40 nm. When this device was driven at a constant current at room temperature with a luminous brightness of 1000 (cd / m ² ), the luminance half life was 1000 hours or more. The luminous efficiency when driven at a current density of 10 (mA / cm ² ) is 7.5 (cd / A), and the relative brightness after 100 hours of continuous driving in an environment of 80 ° C. (= (100 hours). Later brightness) / (initial brightness)) was 0.95.

(Example 11)
In a container that can be sealed, weigh 1 part of the quantum dot dispersion QD-6, 1 part of the resin solution 2, and then 30 parts of trimethylbenzene as the solvent, then seal and infiltrate for 3 minutes. Inkjet ink was created.
Each layer was prepared in the same manner as in Example 9 except that this was replaced with the inkjet ink of Example 9 to form a light emitting layer, and an electroluminescent element was obtained. This element exhibited green emission with an external quantum efficiency of 5.7% and an emission luminance of 49000 (cd / m ² ) at 8 V, the peak wavelength of the emission spectrum was 540 nm, and the full width at half maximum was 30 nm. When this device was driven at a constant current at room temperature with a luminous brightness of 1000 (cd / m ² ), the luminance half life was 1000 hours or more. The luminous efficiency when driven at a current density of 10 (mA / cm ² ) is 6.9 (cd / A), and the relative brightness after 100 hours of continuous driving in an environment of 80 ° C. (= (100 hours). Later brightness) / (initial brightness)) was 0.92.

(Example 12)
In a container that can be sealed, 1 part of the quantum dot dispersion QD-1, 1 part of QD-4, 2 parts of the resin solution 2, and then 60 parts of trimethylbenzene as a solvent are weighed in this order, and then sealed. Inkjet ink was prepared by infiltrating for 3 minutes.
Each layer was prepared in the same manner as in Example 9 except that this was replaced with the inkjet ink of Example 9 to form a light emitting layer, and an electroluminescent element was obtained. This element exhibited an external quantum efficiency of 6.2% and a emission brightness of 42000 (cd / m ² ) yellow emission at 8 V, and its emission spectrum had two peak wavelengths of 545 nm and 652 nm. When this device was driven at a constant current at room temperature with a luminous brightness of 1000 (cd / m ² ), the luminance half life was 1000 hours or more. The luminous efficiency when driven at a current density of 10 (mA / cm ² ) is 7.1 (cd / A), and the relative brightness after 100 hours of continuous driving in an environment of 80 ° C. (= (100 hours). Later brightness) / (initial brightness)) was 0.90.

(Comparative Example 4)
In a container that can be sealed, 1 part of the quantum dot dispersion QD-1, 1 part of QD-10, 2 parts of the resin solution 2, and then 60 parts of trimethylbenzene as a solvent are weighed in this order, and then sealed. Inkjet ink was prepared by infiltrating for 3 minutes.
Each layer was prepared in the same manner as in Example 9 except that this was replaced with the inkjet ink of Example 9 to form a light emitting layer, and an electroluminescent element was obtained. This element exhibited green emission with an external quantum efficiency of 3.2% and an emission luminance of 23000 (cd / m ² ) at 8 V, the peak wavelength of the emission spectrum was 552 nm, and the full width at half maximum was 65 nm. When this device was driven at a constant current at room temperature with a luminous brightness of 1000 (cd / m ² ), the luminance half life was 950 hours. The luminous efficiency when driven at a current density of 10 (mA / cm ² ) is 2.9 (cd / A), and the relative brightness after 100 hours of continuous driving in an environment of 80 ° C. (= (100 hours). Later brightness) / (initial brightness)) was 0.72.

(Comparative Example 5)
In a container that can be sealed, weigh 1 part of Sigma-Aldrich's red InP / ZnS quantum dot dispersion, 1 part of QD-10, 2 parts of resin solution 2, and then 60 parts of trimethylbenzene as a solvent. Then, the ink was sealed and infiltrated for 3 minutes to prepare an inkjet ink.
Each layer was prepared in the same manner as in Example 9 except that this was replaced with the inkjet ink of Example 9 to form a light emitting layer, and an electroluminescent element was obtained. This element exhibited orange emission at 8 V with an external quantum efficiency of 2.7% and an emission luminance of 18,000 (cd / m ² ), and the peak wavelength of the emission spectrum was a wide peak of 585 nm. When this device was driven at a constant current at room temperature with a luminous brightness of 1000 (cd / m ² ), the luminance half life was 700 hours. The luminous efficiency when driven at a current density of 10 (mA / cm ² ) is 2.4 (cd / A), and the relative brightness after 100 hours of continuous driving in an environment of 80 ° C. (= (100 hours). Later brightness) / (initial brightness)) was 0.65.

By producing a light emitting device using the inkjet ink made of the semiconductor fine particle composition of the present invention, it was possible to produce an element having excellent light emitting characteristics and stability. It is expected that excellent characteristics can be exhibited in light emitting devices manufactured by other coating methods and printing methods using other coating liquids and inks.

Claims (14)

A semiconductor comprising semiconductor fine particles and a coating material covering the surface of the particles, wherein the coating material has a structure represented by the following general formula (1), general formula (2), or general formula (3). Fine particle composition.

General formula (1)
Y- (Ar ¹ -X ¹ -Ar ⁴ ) _n

General formula (2)
Y- (Ar ¹ -X ¹ -Ar ² -X ² -Ar ⁴ ) _n

General formula (3)
Y- (Ar ¹ -X ¹ -Ar ² -X ² -Ar ³ -X ³ -Ar ⁴ ) _n

(However, in the general formulas (1), (2) and (3), Y is an adsorbent group having an action of connecting to the surface of semiconductor fine particles, and is -OH, -C (= O) OH, -C (= O). ) O-, -C (= O) CH ₂ (O =) C-, -C (= O) O (O =) C- , -NH ₂ , = NH, -PH ₂ , = PH, -P ( = O) H ₂ , = P (= O) H, -P (= O) (OH) ₂ , = P (= O) (OH), -P (= O) (OH) O-, -SH, -SS-, -S (= O) ₂ (OH), = S (= O) ₂ , -S (= O) ₂ O-. Ar ¹ to Ar ⁴ are independent substituents. A group consisting of an aromatic ring group, a fused aromatic ring group, a heteroaromatic ring group, a condensed heteroaromatic ring group, or a structure in which 2 to 10 of the same or different two or more rings thereof are linked. Ar ¹ to Ar ³ are divalent groups and Ar ⁴ is a monovalent group, respectively. X ¹ to X ³ are independently methylene group, ethylene group, 2,2-propyridene group, and 1,1-cyclohexyli. It is either a den group or a 9,9-fluorenylidene group . N is an integer of 1 or 2.) The semiconductor fine particle composition according to claim 1, wherein Ar ¹ to Ar ⁴ are independently any of an aromatic ring group, a condensed aromatic ring group, a heteroaromatic ring group, and a condensed heteroaromatic ring group. The semiconductor fine particle composition according to claim 1 or 2 , wherein the semiconductor fine particles are quantum dots. The semiconductor fine particle composition according to any one of claims 1 to 3 , further comprising a solvent. The semiconductor fine particle composition according to any one of claims 1 to 4, wherein the solvent contains a hydrocarbon-based solvent . The semiconductor fine particle composition according to any one of claims 1 to 5, further comprising a resin. A coating liquid comprising the semiconductor fine particle composition according to any one of claims 1 to 6. A coated product using the coating liquid according to claim 7. An ink composition comprising the semiconductor fine particle composition according to any one of claims 1 to 6. An inkjet ink comprising the ink composition according to claim 9. A printed matter using the ink composition according to claim 9. A wavelength conversion film formed on a substrate by using the coating liquid according to claim 7 or the ink composition according to claim 9. A color filter formed on a substrate by using the coating liquid according to claim 7 or the ink composition according to claim 9. A light emitting device in which the light emitting layer is formed by using the coating liquid according to claim 7 or the ink composition according to claim 9.