CN110709736A

CN110709736A - Digenation point-containing curing composition, digenation point-containing cured material, method for producing optical member, and method for producing display device

Info

Publication number: CN110709736A
Application number: CN201880037151.0A
Authority: CN
Inventors: 中村和彦; 岩泽崇; 铃木琢实; 山县秀明; 平岩义之
Original assignee: DNP Fine Chemicals Co Ltd
Current assignee: DNP Fine Chemicals Co Ltd
Priority date: 2017-06-08
Filing date: 2018-06-06
Publication date: 2020-01-17
Also published as: JPWO2018225782A1; JP7216642B2; WO2018225782A1; TW201905117A

Abstract

The present invention provides a quantum dot-containing curable composition comprising a curable binder component, quantum dots, and a solvent, wherein the solvent comprises a solvent component having a boiling point of 165 ℃ to 260 ℃ as a first solvent, and a solvent component having a boiling point of 100 ℃ to less than 165 ℃ as a second solvent.

Description

DIGENATION POINT-CONTAINING CURING COMPOSITION, DIGENATION POINT-CONTAINING CURED MATERIAL, METHOD FOR PRODUCING OPTICAL MEMBER, AND METHOD FOR PRODUCING DISPLAY DEVICE

Technical Field

The present invention relates to a quantum dot-containing curable composition, a quantum dot-containing cured product, a method for producing an optical member, and a method for producing a display device.

Background

In recent years, Quantum Dots (QDs) which have attracted attention as light-emitting materials are semiconductor nano-sized fine particles (semiconductor nanocrystals) which exhibit specific optical and electrical properties by a Quantum confinement effect (Quantum size effect) in which electrons and excitons (exiton) are confined in nano-sized small crystals, and are expected to be applied in a wide range of fields, and also proposed as display applications. The wavelength of light emitted from the quantum dot depends on the particle diameter of the quantum dot, and light of various wavelengths can be obtained by controlling the particle diameter. In addition, quantum dots have excellent color purity because of a narrow spectral width of emission.

The quantum dot-containing layer can be formed by a wet process in which a dispersion liquid in which the quantum dots are dispersed is applied, or a dry process in which a quantum dot raw material is formed into a film by a vapor deposition method, sputtering, or the like, and the wet process tends to be used from the viewpoint of simplicity of the apparatus or process, smoothness of the obtained layer, or the like. For example, patent document 1 describes that a layer containing quantum dots is formed on a substrate surface by screen printing, contact printing, inkjet printing, or the like.

Documents of the prior art

Patent document

Patent document 1: japanese Kohyo publication No. 2010-533976

Disclosure of Invention

Problems to be solved by the invention

However, in the case of forming a quantum dot-containing layer by a wet method, there is a problem that quantum dots are easily aggregated in a dispersion liquid. Since the emission color of the quantum dot depends on the size thereof, when the quantum dot is aggregated and the crystal structure thereof is changed, the emission color may be changed and further, extinction may be caused, which is one of the large causes of the deterioration of the emission characteristics.

Further, in order to discharge ink in an accurate pattern by an ink jet method, straightness and stability at the time of discharge from a discharge head are required. However, when the quantum dot-containing layer is formed by an ink jet method, there is a problem that the ink jet head is easily clogged due to aggregation of quantum dots. Further, if the evaporation rate of the ink is too high, the viscosity of the ink increases sharply at the tip of the nozzle of the discharge head, and the ink droplets bend while flying, or are intermittently discharged at intervals, causing clogging and failing to be discharged.

Further, the ink layer formed by the ink jet method may have radial unevenness on the surface. If unevenness occurs on the surface of the quantum dot containing layer, the emission color may vary.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a content sub-dot curable composition which has excellent discharge stability in an ink jet system, suppresses aggregation of quantum dots, and can form a content sub-dot cured layer in which unevenness is reduced. Another object of the present invention is to provide a non-quantum dot cured product having reduced unevenness formed by using the non-quantum dot curable composition. Another object of the present invention is to provide a method for producing an optical member having a non-quantum dot containing cured layer in which unevenness formed by using the non-quantum dot containing curable composition is reduced. In addition, an object of the present invention is to provide a method of manufacturing a display device using the method of manufacturing an optical member.

Means for solving the problems

The quantum dot-containing curable composition of the present invention comprises a curable binder component, quantum dots, and a solvent,

the solvent contains a solvent component having a boiling point of 165 ℃ or higher and 260 ℃ or lower as a first solvent, and also contains a solvent component having a boiling point of 100 ℃ or higher and lower than 165 ℃ as a second solvent.

The quantum dot-containing curable composition of the present invention is a cured product of the quantum dot-containing curable composition of the present invention.

The method for manufacturing an optical member of the present invention includes the steps of: forming a quantum dot-containing layer by selectively attaching the quantum dot-containing curable composition of the present invention to a predetermined region on a substrate by an ink jet method; and a step of curing the quantum dot-containing layer to form a quantum dot-containing cured layer.

The method for manufacturing a display device of the present invention includes the steps of: a step of manufacturing an optical member by the method for manufacturing an optical member according to the present invention; and a step of mounting the optical member produced as described above.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a quantum dot-containing curable composition which has excellent discharge stability in an ink jet system, suppresses aggregation of quantum dots, and can form a quantum dot-containing cured layer with reduced unevenness can be provided. Further, the present invention can provide a non-quantum dot cured product with reduced unevenness formed by using the non-quantum dot curable composition. Further, according to the present invention, there can be provided a method for producing an optical member having a non-uniform non-content-quantum-dot cured layer formed using the non-content-quantum-dot curable composition. In addition, according to the present invention, a method of manufacturing a display device using the above-described method of manufacturing an optical member can be provided.

Drawings

Fig. 1 is a diagram illustrating an example of the method for manufacturing an optical member according to the present invention.

Fig. 2 is a schematic diagram showing an example of a display device obtained by the manufacturing method of the present invention.

Fig. 3 is a schematic view showing another example of a display device obtained by the manufacturing method of the present invention.

Fig. 4 is a schematic view showing another example of a display device obtained by the manufacturing method of the present invention.

Fig. 5 is a schematic view showing another example of a display device obtained by the manufacturing method of the present invention.

Fig. 6 is a view for explaining a method of evaluating unevenness of a layer containing quantum dots.

Detailed Description

The present invention will be described in detail below with reference to a quantum dot curable composition, a quantum dot cured product, a method for producing an optical member, and a method for producing a display device.

In the present invention, light includes electromagnetic waves having wavelengths in the visible and non-visible regions, and also includes radiation including, for example, microwaves and electron beams. Specifically, it refers to electromagnetic waves having a wavelength of 5 μm or less and electron beams.

In the present invention, (meth) acryloyl represents each of acryloyl and methacryloyl, (meth) acrylic acid represents each of acrylic acid and methacrylic acid, and (meth) acrylate represents each of acrylate and methacrylate.

I. Composition curable with small content of quantum dots

The quantum dot-containing curable composition of the present invention is a composition suitable for forming a quantum dot-containing layer such as a light-emitting layer and a light-converting layer of an optical member by an ink-jet method, and can be preferably used for ink-jet.

The quantum dot-containing curable composition of the present invention uses a solvent containing a first solvent having a boiling point of 165 ℃ to 260 ℃ and a second solvent having a boiling point of 100 ℃ to less than 165 ℃ in combination, and thereby can suppress aggregation of quantum dots in the quantum dot-containing curable composition and improve dispersibility. This is presumably because: among inks, particularly, among inks in an ink jet device, the stability of the solvent composition is high, and the aggregation of quantum dots can be suppressed, so that the dispersibility can be maintained. In addition, by using the content-quantum-dot curable composition of the present invention, a content-quantum-dot cured layer in which aggregation of quantum dots is suppressed can be formed. This is believed to be because: since the quantum dot-containing curable composition of the present invention has excellent dispersibility of quantum dots as described above, quantum dots can be uniformly dispersed, and since a curable binder component is used as the binder component, when the quantum dot-containing curable composition of the present invention is cured, the quantum dots are fixed by forming a crosslinked structure of the curable binder component while maintaining the uniformly dispersed state of the quantum dots.

In addition, the present invention provides a curable composition containing a plurality of quantum dots, which can form a cured layer containing a plurality of quantum dots having reduced unevenness while having excellent discharge stability in an ink jet system by using a solvent containing the specific first solvent and the specific second solvent in combination. It is considered that the specific first solvent having a suitably slow drying rate suppresses rapid drying of the partial dot curable composition, and therefore the partial dot curable composition of the present invention has improved linearity and stability when discharged from a discharge head, and further, suppresses clogging of the discharge head, thereby having excellent discharge stability. In addition, it is presumed that the reason why the content dot cured layer with reduced unevenness can be formed by using the content dot curable composition of the present invention is: since the combination of the specific first solvent and the specific second solvent has an appropriate drying rate, the flow of the solute is suppressed during the drying process when forming the quantum dot-containing layer, the generation of radial unevenness on the surface of the coating film is suppressed, and the generation of unevenness due to aggregation of the quantum dots is suppressed.

The respective components used in the content sub-point curable composition of the present invention will be described below in order from the solvent. Hereinafter, the content dot curable composition of the present invention may be referred to as an ink.

< solvent >

The solvent used for the quantum dot-containing curable composition of the present invention is characterized in that: the solvent composition contains a solvent component having a boiling point of 165 ℃ or higher and 260 ℃ or lower as a first solvent, and also contains a solvent component having a boiling point of 100 ℃ or higher and lower than 165 ℃ as a second solvent.

Since the solvent component having a boiling point of 165 ℃ or higher and 260 ℃ or lower has an appropriate drying property, the content sub-point curable composition of the present invention containing such a solvent component as the first solvent does not dry rapidly in either of the case of intermittent discharge and continuous discharge, and therefore, rapid increase and clogging of the viscosity at the tip of the nozzle of the inkjet head are not likely to occur, and the stability of the discharge direction and the discharge amount is excellent. Therefore, the partial-dot-containing curable composition of the present invention is discharged onto the surface of the substrate in a predetermined pattern by an ink-jet method, whereby a patterned partial-dot-containing curable layer can be formed accurately and uniformly.

Furthermore, the quantum dot-containing curable composition of the present invention can optimize the drying rate and suppress the aggregation of quantum dots by combining an appropriate amount of a solvent component having a boiling point of 100 ℃ or higher and lower than 165 ℃ as a second solvent in addition to the specific first solvent. Since the drying speed is moderate when the coating film containing the quantum dot curable composition is dried, the flow of the solute can be suppressed. Therefore, after being discharged onto the substrate, the substrate is melted and sufficiently leveled with the surface of the substrate, and then dried completely in a relatively short time by an appropriate drying means. Therefore, when the composition containing a quantum dot of the present invention is used, a pattern having high uniformity of film thickness with reduced unevenness can be obtained, and drying can be efficiently performed.

The solvent component used as the first solvent may be a mixed solvent of 1 kind or 2 or more kinds as long as it has the above boiling point. The proportion of the first solvent in the total amount of solvents in the quantum dot curable composition of the present invention is not particularly limited, and is preferably 30% by mass or more in terms of easily obtaining drying properties suitable for an ink jet system, and improving initial discharge properties and intermittent discharge stability of ink jet, more preferably 40% by mass or more in terms of further improving the initial discharge properties, and even more preferably 50% by mass or more in terms of further improving the intermittent discharge stability. On the other hand, the proportion of the first solvent in the total amount of solvents in the quantum dot curable composition of the present invention is preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, and particularly preferably 65% by mass or less, from the viewpoint that the second solvent can be sufficiently contained and the drying rate of the composition can be optimized.

The surface tension of the first solvent at 23 ℃ is preferably 24mN/m or more in terms of suppressing the flow-out of the quantum dot curable composition during patterning. When the first solvent is a mixed solvent of 2 or more types, the mixed solvent preferably has the surface tension as a whole.

In addition, in the case where the following wettability variable layer is formed on the surface of the substrate and exposure is performed to form an ink-receptive region in a portion of the substrate where the quantum dot-containing layer is to be formed, and the quantum dot-containing curable composition of the present invention is selectively attached to the ink-receptive region by an ink jet method, the following solvents may be selectively used as the first solvent: a contact angle (theta) after 30 seconds is measured by bringing a liquid drop into contact with a standard liquid shown in a wettability test prescribed in JIS K6768, and the contact angle is 25 DEG or more, preferably 30 DEG or more, with respect to the surface of a test piece having a critical surface tension of 30mM/m obtained by a Zisman Plot, and is 10 DEG or less with respect to the surface of a test piece having a critical surface tension of 70mN/m obtained by the same measurement method. When the first solvent is a mixed solvent of 2 or more types, it is preferable that the mixed solvent has the contact angle as a whole.

When the quantum dot curable composition is prepared using a solvent exhibiting the above behavior with respect to wettability, the composition exhibits a large repellency to the surface of the wettability-variable layer before the wettability of the wettability-variable layer is changed, and exhibits a large affinity to the surface of the wettability-variable layer after the wettability of the wettability-variable layer is changed in a direction in which hydrophilicity is increased. Therefore, the difference between the wettability of the ink-receptive region formed by selectively exposing a part of the surface of the wettability variable layer with the quantum dot curing composition and the wettability of the ink-repellent region with respect to the surrounding region thereof can be increased, and the ink that is ejected onto the ink-receptive region by the ink jet method can be uniformly spread to the corners of the ink-receptive region by wetting.

Here, the test piece having the above-described characteristics with respect to the critical surface tension may be formed of any material. As the test piece exhibiting a critical surface tension of 30mN/m, for example, the test piece having a smooth surface can be selected from the test pieces having a smooth surface of polymethyl methacrylate, polyvinyl chloride, polyvinylidene chloride, polyethylene terephthalate, and the test piece having a smooth glass surface coated with the above-mentioned polymer, surface modifier, and the like, and the test pieces can be used. Further, as the test piece showing the critical surface tension of 70mN/m, for example, a test piece obtained by coating nylon, a hydrophilized glass surface, or the like can be selected and practically used.

The first solvent is preferably 1 or more selected from the group consisting of glycol ethers, glycol ether esters, aliphatic carboxylic acids, aliphatic esters, aromatic esters, dicarboxylic acid diesters, alkoxycarboxylic acid esters, ketocarboxylic acid esters, halogenated carboxylic acids, alcohols, phenols, aliphatic ethers, alkoxyalcohols, glycol oligomers, amino alcohols, alkoxyalcohol esters, ketones, morpholines, aliphatic amines, aromatic amines, halogenated aromatic hydrocarbons, and alkanes, from the viewpoint of suppressing aggregation of quantum dots and from the viewpoint of discharge stability in an inkjet system.

More specifically, the first solvent may be selected from the following solvents: glycol ethers such as ethylene glycol monohexyl ether, diethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether; glycol ether esters such as ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate; aliphatic carboxylic acids such as 2-ethylhexanoic acid; aliphatic esters such as cyclohexyl acetate; aromatic esters such as propyl benzoate; dicarboxylic acid diesters such as diethyl carbonate; alkoxy carboxylic acid esters such as methyl 3-methoxypropionate and ethyl 3-ethoxypropionate; ketocarboxylic acid esters such as methyl acetoacetate and ethyl acetoacetate; halocarboxylic acids such as chloroacetic acid and dichloroacetic acid; alcohols or phenols such as ethanol, isopropanol, phenol, 2-methylcyclohexanol, 2-octanol, n-heptanol, diacetone alcohol; aliphatic ethers such as diethyl ether, diisoamyl ether and 1, 8-cineole; alkoxy alcohols such as 3-methoxy-3-methyl-1-butanol; glycol oligomers such as diethylene glycol and tripropylene glycol; aminoalcohols such as 2-diethylaminoethanol; alkoxyalcohol esters such as 3-methoxy-3-methylbutyl acetate and 3-methoxybutyl acetate; ketones such as diisobutyl ketone, methylcyclohexanone, and methyl-n-hexanone; morpholines such as phenyl morpholine; aliphatic or aromatic amines such as aniline; halogenated aromatic hydrocarbons such as dichlorobenzene; and alkanes such as decane, undecane, dodecane, tridecane and tetradecane.

The first solvent is preferably selected from 3-methoxy-3-methyl-1-butanol, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 3-methoxy-3-methylbutyl acetate, diethylene glycol dibutyl ether, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, diisoamyl ether, 1, 8-cineole, diethyl adipate, dibutyl oxalate, dimethyl malonate, diethyl malonate, dimethyl succinate, diethyl succinate, 3-methoxybutyl acetate, methyl acetoacetate, cyclohexyl acetate, ethyl 3-ethoxypropionate, and mixtures thereof, in view of the dispersibility of quantum dots and the discharge stability in an ink jet system, More preferably, the amount of the organic solvent is 1 or more selected from among decane, undecane, dodecane, tridecane and tetradecane, and from the viewpoint of improving the dispersibility of the quantum dots, the organic solvent is 1 or more selected from among ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 3-methoxy-3-methylbutyl acetate, ethyl 3-ethoxypropionate and 3-methoxybutyl acetate.

In addition, the first solvent preferably has no hydroxyl group from the viewpoint of improving the storage stability of the quantum dot curable composition, and particularly when used in combination with a blocked carboxylic acid curing agent described below, is preferable from the viewpoint of improving the storage stability.

The second solvent is a solvent component having a boiling point of 100 ℃ or higher and lower than 165 ℃, and has a boiling point suitably lower than that of the first solvent. Therefore, by combining the second solvent with the first solvent, the drying speed can be appropriately adjusted without rapidly drying the quantum dot-containing layer at the tip of the nozzle of the inkjet head and by suppressing the flow of the solute during the drying of the quantum dot-containing layer. The solvent component used as the second solvent may be used alone or in combination of 2 or more kinds as long as it has the above boiling point.

Among these, the boiling point of each solvent component used in the second solvent is more preferably 105 ℃ to 160 ℃, and particularly preferably 110 ℃ to 150 ℃, from the viewpoint of improving the dispersibility of the quantum dot and easily obtaining a good coating film with reduced unevenness.

The proportion of the second solvent in the total amount of solvents in the quantum dot-containing curable composition of the present invention is not particularly limited, but is preferably 10 mass% or more, more preferably 20 mass% or more, further preferably 30 mass% or more, and particularly preferably 35 mass% or more, from the viewpoint of improving the dispersibility of quantum dots and suppressing the variation in the quantum dot-containing cured layer, and on the other hand, from the viewpoint of being able to sufficiently contain the first solvent and improve the ink ejection property, is preferably 70 mass% or less, more preferably 60 mass% or less, and further preferably 50 mass% or less.

The viscosity of the second solvent at 23 ℃ is preferably 0.5 to 6 mPas. In such a case, by including the second solvent, the viscosity of the content sub-dot curing composition can be appropriately reduced without hindering the effect of the first solvent, and the wetting and diffusing properties of the ink itself can be improved, and as a result, the ink droplets sprayed are likely to wet and diffuse to the corners of the entire content sub-dot layer forming region. As a result, even in the case of various substrates, the ink deposited can be spread to wet the edge portions of the partition walls, and the pixels can be prevented from fading or lowering the luminance. In order to attach ink to the corners of the regions, there is also a method of ejecting ink to the end portions of the regions, but in this method, ink may flow out from the gaps between the partition walls. On the other hand, the ink itself is wet and spread to the edge portions of the partition walls as in the present invention, and the ink does not flow out, which is a more preferable method. The viscosity of the second solvent at 23 ℃ is more preferably 0.5 to 3 mPas. In the case where 2 or more kinds of the second solvent are used in combination, even if the viscosity is out of the above range in the case of a single solvent, it can be preferably used as long as the viscosity of the mixed solvent is in the above range. The viscosity at 23 ℃ in the present invention can be measured by a rotational vibration type viscometer (for example, a rotational vibration type viscometer VISCOMATE VM-1G manufactured by SHANYI MOTOR).

The above-mentioned second solvent can be preferably used as long as the surface tension at 23 ℃ is 35mN/m or less. However, when the surface tension of the second solvent at 23 ℃ is 30mN/m or less, the surface tension can be appropriately reduced without inhibiting the effect exerted by the first solvent, and the wetting and diffusing properties of the ink itself are improved, so that the ink droplets deposited are likely to be wetted and diffused to the corners of the entire quantum dot layer forming region. Here, the surface tension at 23 ℃ in the present invention can be measured by a surface tension meter (Wilhelmy method) (for example, CBVP-Z, an automatic surface tension meter, manufactured by Kyowa interface science Co., Ltd.).

The second solvent may be any solvent having the above boiling point, and is preferably selected from solvents having excellent compatibility with the first solvent.

Specific examples of the second solvent include: glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, propylene glycol monopropyl ether, and diethylene glycol dimethyl ether; glycol esters including glycol ether esters such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; carboxylic acids such as isobutyric acid, propionic acid, and butyric acid; aliphatic esters such as ethyl isovalerate, hexyl formate, pentyl acetate, isopentyl acetate, ethyl lactate, methyl lactate, isopentyl propionate, butyl butyrate, and dimethyl oxalate; aliphatic carboxylic acids such as acetic acid and acetic anhydride, and anhydrides thereof; alcohols such as n-pentanol, isopentanol, 2-ethylbutanol, 1-butanol, n-hexanol, 4-methyl-2-pentanol, cyclohexanol, 2-heptanol, 3-heptanol; ketones such as ethyl-n-butyl ketone, di-n-propyl ketone, acetylacetone; alkanes such as octane and nonane; aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; aromatic ethers such as anisole; aliphatic ethers such as 1, 4-dioxane, and the like.

Among the above-mentioned second solvents, from the viewpoint of dispersibility of the quantum dots, it is preferable to use 1 or more selected from ethers including polyhydric alcohol ethers such as glycol ethers and glycerin ethers, and esters including polyhydric alcohol esters such as glycol esters and glycerin esters, aliphatic esters, alkoxycarboxylic acid esters, and ketocarboxylic acid esters. When esters and ethers as described above are used, there is an advantage in that the stability of the ink can be easily maintained even when a resin having a high reactivity is used as a binder component or the like. In addition, when glycol ethers or glycol esters are used, the wettability of the glass substrate with the second solvent is improved, and the second solvent is likely to wet and spread to the entire corners of the quantum dot layer-forming region, and is effective for preventing the discoloration of the pixels.

As the second solvent, particularly from the viewpoint of dispersibility of the quantum dots and the viewpoint of discharge stability in the inkjet system, 1 or more solvents selected from the group consisting of ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, diethylene glycol dimethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, hexyl formate, ethyl lactate, isoamyl propionate, butyl butyrate, dimethyl oxalate, 1-butanol, 1, 4-dioxane, octane, nonane, toluene, xylene, ethylbenzene and anisole are preferably used, and from the viewpoint of improvement in dispersibility of the quantum dots, more preferably from the group consisting of ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol, Toluene and propylene glycol monomethyl ether acetate, and more preferably at least 1 selected from the group consisting of ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate and propylene glycol monomethyl ether acetate.

In addition, as the solvent used in the composition having a quantum dot curability of the present invention, a combination of 1 or more of the first solvent selected from the group consisting of ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 3-methoxy-3-methylbutyl acetate, ethyl 3-ethoxypropionate, and 3-methoxybutyl acetate and 1 or more of the second solvent selected from the group consisting of ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, toluene, and propylene glycol monomethyl ether acetate is preferable in terms of improving the dispersibility of the quantum dots.

The solvent used in the present invention may further contain another solvent having a boiling point lower than 100 ℃ different from the first solvent and the second solvent, within a range not impairing the effects of the present invention. The proportion of the other solvent in the total amount of solvents used in the quantum dot curable composition of the present invention is preferably 30% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, yet more preferably 2% by mass or less, and particularly preferably 0.5% by mass or less.

The total content of the solvents including the first solvent and the second solvent in the quantum dot curable composition of the present invention is not particularly limited, but is preferably 50 mass% or more, more preferably 60 mass% or more, and even more preferably 70 mass% or more, from the viewpoint of dispersibility of the quantum dots, initial discharge from the ink jet head, intermittent discharge stability, and suppression of unevenness generated on the surface of the cured film. On the other hand, if the content of the solvent is too large, it is difficult to make the quantum dot-containing cured layer contain a sufficient amount of the quantum dots, the binder component, and the like, and therefore, it is preferably 98 mass% or less, more preferably 90 mass% or less, and still more preferably 80 mass% or less.

< curable adhesive component >

The quantum dot-containing curable composition of the present invention contains a curable binder component in order to impart film formability and adhesion to a surface to be coated and maintain the dispersibility of quantum dots in a film in a good state. In the present invention, the curable binder component is a component contained for attaching and fixing the quantum dots at predetermined positions, and is usually a mixture.

The present invention provides a curable composition containing a quantum dot, which contains a curable binder component, and which can be cured to form a cured product containing a quantum dot, wherein the cured product can inhibit aggregation of quantum dots during production and can inhibit aggregation of quantum dots over time. The composition containing a quantum dot of the present invention can provide a cured product containing a quantum dot with sufficient strength, durability, and adhesion by containing a curable binder component.

As the curable adhesive component, for example, a polymerizable adhesive component such as a photocurable adhesive component which is polymerization-curable by light such as visible light, ultraviolet light, or electron beam, or a thermosetting adhesive component which is polymerization-curable by heating can be used. The curable binder component used in the quantum dot-containing curable composition of the present invention preferably contains at least 1 of the thermosetting binder component and the photocurable binder component, from the viewpoint of easy suppression of aggregation of the quantum dots, and from the viewpoint of strength and durability. The curable binder component used in the quantum dot-containing curable composition of the present invention can be suitably selected from those having high solvent solubility of the above-mentioned solvent and high compatibility with quantum dots.

(1) Heat-curing adhesive component

As the thermosetting adhesive component, a combination of a compound having 2 or more thermosetting functional groups in 1 molecule and a curing agent is generally used, and a catalyst capable of promoting a thermosetting reaction may be further added. In addition, a polymer which is not itself polymerizable may be further used.

As the compound having 2 or more thermosetting functional groups in 1 molecule, an epoxy compound can be preferably used. Examples of the thermosetting functional group include an oxetanyl group, an isocyanate group, and a hydroxyl group in addition to an epoxy group. From the viewpoint that the solvent solubility in the specific solvent and the compatibility with the quantum dot are easily improved, a compound having 1 or more thermosetting functional groups selected from an epoxy group, an oxetane group, an isocyanate group, and a hydroxyl group in 1 molecule is preferably used.

An oxetane compound in which an epoxy group in the following epoxy compound is replaced with an oxetanyl group can be used in the same manner as the epoxy compound. In addition, a combination of a compound having 2 or more isocyanate groups in 1 molecule (polyisocyanate compound) and a compound having 2 or more hydroxyl groups in 1 molecule (polyol compound) can be converted into a polymer by forming urethane bonds between molecules through the reaction of the isocyanate groups and the hydroxyl groups. At least one of the compound having 2 or more isocyanate groups in 1 molecule and the compound having 2 or more hydroxyl groups in 1 molecule may be a polymer compound, or at least one thereof may be a urethane prepolymer.

(epoxy compound)

As the epoxy compound, an epoxy compound having 2 or more epoxy groups in 1 molecule can be preferably used. The epoxy compound having 2 or more epoxy groups in 1 molecule is an epoxy compound having 2 or more epoxy groups in 1 molecule, preferably 2 to 50, more preferably 2 to 20 epoxy groups (including a compound called an epoxy resin). The epoxy group may have an oxirane ring structure, and examples thereof include a glycidyl group, an oxyethylene group, and an epoxycyclohexyl group. Examples of the epoxy compound include known polyepoxy compounds curable with a carboxylic acid, and such epoxy compounds are widely disclosed in "handbook of epoxy resins" journal of the Japanese Industrial News Co., Ltd. (Showa 62 years), and the like, and can be used.

Examples of the epoxy compound include an epoxy group-containing (co) polymer and an epoxy group-containing monomer, and a commercially available epoxy resin may be used.

The epoxy group-containing (co) polymer is a homopolymer of a monomer containing a carbon-carbon unsaturated bond and an epoxy group (hereinafter, may be referred to as an epoxy group-containing monomer) and a copolymer thereof with a monomer copolymerizable with the epoxy group-containing monomer. The molecular form of the copolymer may be linear, may have a branched structure, or may be any form such as a random copolymer, a block copolymer, or a graft copolymer. The epoxy group-containing polymer can be obtained by a polymerization method selected from radical polymerization, ion polymerization, and the like.

Examples of the epoxy group-containing monomer include: glycidyl methacrylate (hereinafter referred to as GMA), 3, 4-epoxycyclohexylmethyl methacrylate, neopentyl glycol glycidyl ether, and the like. Examples of the monomer copolymerizable with the epoxy group-containing monomer include: alkyl (meth) acrylates, styrene, N-alkyl maleimides, and the like.

Examples of the epoxy resin include: bisphenol a-type novolac epoxy resins, cresol novolac epoxy resins, bisphenol a-type epoxy resins, bisphenol F-type epoxy resins, brominated bisphenol a-type epoxy resins, bisphenol S-type epoxy resins, diphenyl ether-type epoxy resins, p-phenylene bisphenol-type epoxy resins, naphthalene-type epoxy resins, biphenyl-type epoxy resins, fluorene-type epoxy resins, phenol novolac epoxy resins, o-cresol novolac epoxy resins, trihydroxyphenyl methane epoxy resins, 3-functional epoxy resins, tetrahydroxyphenyl ethane epoxy resins, dicyclopentadiene phenol-type epoxy resins, hydrogenated bisphenol a-type epoxy resins, bisphenol a core-containing polyhydric alcohol-type epoxy resins, polypropylene glycol-type epoxy resins, glycidyl ester-type epoxy resins, epoxypropylamine-type epoxy resins, glyoxal-type epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, and the like.

Commercially available products of bisphenol A type epoxy resins are, for example, the trade name jER828, the trade name jER157S70, and the trade name jER1001 (all manufactured by Mitsubishi chemical Co., Ltd.). The cresol novolac epoxy resin is, for example, YDCN-701 (manufactured by Tokyo chemical Co., Ltd.). Further, as the 1, 2-epoxy-4- (2-epoxyethyl) cyclohexane adduct of 2, 2-bis (hydroxymethyl) -1-butanol, a trade name of EHPE3150 (manufactured by Daicel corporation) may be used.

These epoxy compounds may be used alone or in combination of 2 or more.

(curing agent)

The curing agent used in the thermosetting adhesive component is appropriately selected depending on the kind of the thermosetting functional group contained in the thermosetting adhesive component, and is not particularly limited.

For example, when the thermosetting adhesive component contains the epoxy compound, a conventionally known carboxylic acid compound can be used as the curing agent.

Specific examples thereof include: anhydrides such as succinic anhydride, phthalic anhydride, 1, 2-cyclohexanedicarboxylic anhydride, trimellitic anhydride, 1,2, 4-cyclohexanetricarboxylic anhydride and methylhexahydrophthalic anhydride; aliphatic polycarboxylic acids such as succinic acid, adipic acid, 1,2,3, 4-butanetetracarboxylic acid, azelaic acid, sebacic acid, and decanedicarboxylic acid; aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid; alicyclic polycarboxylic acids such as tetrahydrophthalic acid, hexahydrophthalic acid, and 1,2, 4-cyclohexanetricarboxylic acid; 1 polymer carboxylic acid such as polyester resin, acrylic resin, and maleated polybutadiene resin having 2 or more carboxyl groups in the molecule; and the following blocked carboxylic acid curing agents.

Commercially available products may be used, and examples thereof include RIKACID MH700, HNA-100, and MTA-15[ all manufactured by New Japan chemical and chemical Co., Ltd ].

Among these, blocked carboxylic acid curing agents in which the carboxyl group is blocked (latent) are preferable from the viewpoints of the discharge property, the dispersibility of the quantum dot, and the storage stability of the quantum dot curable composition. That is, as the curable adhesive component, a thermosetting adhesive component containing the epoxy compound and the blocked carboxylic acid curing agent can be preferably used.

The blocked carboxylic acid curing agent is heated to release the vinyl ether compound, thereby producing a carboxylic acid compound. The resulting carboxylic acid compound is reacted with an epoxy compound. The blocked carboxylic acid curing agent can improve the storage stability of the composition because of its high temperature for deblocking, and can also improve the heat resistance and solvent resistance because of its coexistence with an epoxy group at a high concentration. When the blocked carboxylic acid curing agent is used in combination with quantum dots, the blocked carboxylic acid curing agent is preferably used because it is less susceptible to heat and light during the production process or display, can keep the distance between the quantum dots constant, and can prevent suppression of excitation.

Examples of the blocked carboxylic acid curing agent include compounds obtained by blocking carboxyl groups of a polycarboxylic acid compound with a vinyl ether compound. Examples of the preferable polycarboxylic acid compound include compounds represented by the following general formula (1).

[ chemical formula 1]

General formula (1)

(in the general formula (1), m is an integer of 0to 4 inclusive, and a is 0 or1 and n are integers of 1 to 4 inclusive. In addition, when n is 1, R¹Is a hydrogen atom or a hydrocarbon group having 2 to 8 carbon atoms, and when n is 2 to 4, R is¹A hydrocarbon group having 2 to 8 carbon atoms. R²An alkyl group having 1 to 5 carbon atoms. )

The vinyl ether compound includes, for example, a compound represented by the following general formula (2) as a preferable compound.

[ chemical formula 2]

General formula (2)

(in the general formula (2), R³A hydrocarbon group having 1 to 10 carbon atoms. )

Further, as a preferable example of the block carboxylic acid curing agent, there can be mentioned a curing agent having a structure in which a carboxyl group in the general formula (1) is blocked as shown in the following general formula (3).

[ chemical formula 3]

General formula (3)

(in the general formula (3), R³The same as the above general formula (2). )

R in the compound represented by the above general formula (1)¹Examples of the compound other than a hydrogen atom include a half ester obtained by a reaction of an alcohol compound and an acid anhydride. The alcohol compound used in the reaction may be preferably exemplified by the following compounds: monohydric alcohol compounds such as ethanol, propanol, hexanol, octanol, and isopropanol; glycol compounds such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, and cyclohexanediol; triol compounds such as glycerin, pentanetriol, hexanetriol, cyclohexanetriol, benzenetriol, and trimethylolpropane; tetrahydric alcohol compounds such as pentaerythritol; more preferred examples include hexanol, isopropanol, 1, 2-propanediol, 1, 3-propanediol, 1, 6-hexanediol, glycerol, and trimethylolpropaneAlkane and pentaerythritol.

The acid anhydride used in the above reaction may be a compound represented by the following formula (4), and specifically, 1, 2-cyclohexanedicarboxylic anhydride and 1,3, 4-cyclohexanetricarboxylic acid-3, 4-anhydride may be cited as preferable examples.

[ chemical formula 4]

General formula (4)

(in the general formula (4), R²A and m are the same as the above general formula (1). )

From the viewpoint of compatibility, it is preferable to use R in the compound represented by the above general formula (1)¹A compound which is a hydrogen atom. As R¹Compounds which are hydrogen atoms include: alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; alicyclic tricarboxylic acids such as 1,2, 4-cyclohexanetricarboxylic acid (CHTA); alicyclic tetracarboxylic acids such as 1,2,4, 5-cyclohexanetetracarboxylic acid, and the like; among them, CHTA is preferable.

The acid equivalent of the polycarboxylic acid compound is preferably 55g/mol or more, more preferably 60g/mol or more, from the viewpoint of increasing the crosslinking density and improving the toughness of the cured film, and is preferably 600g/mol or less, more preferably 500g/mol or less, from the viewpoint of compatibility. The above acid equivalent means an equivalent of carboxyl group, and is measured in accordance with JIS K-0070-3 (1992).

The above-mentioned polycarboxylic acid compounds may be used alone in 1 kind or in combination of 2 or more kinds.

Examples of the vinyl ether compound include: alkyl vinyl ethers such as isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, 2-ethylhexyl vinyl ether, and cyclohexyl vinyl ether; among them, n-propyl vinyl ether and isobutyl vinyl ether are preferable. The vinyl ether compounds can be used alone in 1 or more than 2.

The blocked carboxylic acid curing agent can be obtained by reacting the polycarboxylic acid compound with the vinyl ether compound in the presence of an acid catalyst, a solvent, and the like, if necessary, at a temperature in the range of about 20 ℃ to 150 ℃.

From the viewpoint of reaction efficiency and yield, the molar equivalent ratio of the vinyl group of the vinyl ether compound to the carboxyl group of the polycarboxylic acid compound [ (the molar equivalent ratio of vinyl group/carboxyl group) ] is preferably 2 or less. The lower limit of the molar equivalent ratio is not particularly limited, and is appropriately adjusted depending on the application, and may be, for example, 0.5 or more, or 1 or more.

Examples of the acid catalyst include an acidic phosphate ester compound.

The blocked carboxylic acid curing agent may be used alone in 1 kind or in combination of 2 or more kinds.

The molar equivalent ratio (carboxyl group and blocked carboxyl group/epoxy group) of the epoxy group in the epoxy compound to the total of the carboxyl group and blocked carboxyl group in the curing agent capable of reacting with the epoxy compound is preferably 0.2 or more, more preferably 0.5 or more from the viewpoint of heat resistance and hardness of the cured film, and is preferably 1.6 or less, more preferably 1.2 or less from the viewpoint of adhesion of the cured film.

In the quantum dot curable composition of the present invention, when the thermosetting adhesive component is used as the curable adhesive component, the total content of the compound having 2 or more thermosetting functional groups in 1 molecule such as the epoxy compound with respect to the total amount of the solid components in the quantum dot curable composition is preferably 40% by mass or more, more preferably 50% by mass or more, from the viewpoint of suppressing aggregation of quantum dots in a cured product and from the viewpoint of strength of the cured product, and on the other hand, is preferably 90% by mass or less, more preferably 80% by mass or less from the viewpoint of discharge stability and suppression of unevenness of the surface of the cured product.

In the present invention, the solid component means all components other than the solvent.

In the content-dot curable composition of the present invention, when the thermosetting adhesive component is used as the curable adhesive component, the content of the curing agent relative to the total amount of the solid components of the content-dot curable composition is preferably 5% by mass or more, more preferably 10% by mass or more, from the viewpoint of sufficiently promoting the progress of the polymerization reaction and from the viewpoint of reducing bumping and unevenness at the time of drying, and on the other hand, from the viewpoint of discharge stability and suppression of unevenness on the surface of a cured product, and from the viewpoint of storage stability, is preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 25% by mass or less.

(2) Photocurable adhesive component

As the photocurable adhesive component, a combination of a photocurable resin which can be polymerized and cured by light such as ultraviolet rays or electron beams and a photopolymerization initiator is generally used. The photocurable adhesive component preferably contains a polymer having a relatively high molecular weight in order to impart film formability and adhesion to the surface to be coated. The term "relatively high molecular weight" as used herein means that the molecular weight is higher than that of a monomer or oligomer, and the weight average molecular weight is 3,000 or more as a standard. As the polymer having a relatively high molecular weight, either a polymer having no polymerization reactivity per se or a polymer having polymerization reactivity per se may be used, or 2 or more kinds may be used in combination. The photocurable adhesive component is composed mainly of a polymer having a relatively high molecular weight, and if necessary, a polyfunctional monomer or oligomer having 2 or more photopolymerizable functional groups, a monofunctional monomer or oligomer having 1 photopolymerizable functional group, a photopolymerization initiator activated by light, a sensitizer, and the like.

As the polymer having a relatively high molecular weight, for example: (meth) acrylic resins such as (meth) acrylic copolymers and styrene- (meth) acrylic copolymers, epoxy (meth) acrylate resins, and the like; among them, from the viewpoint of dispersibility of the quantum dot, a (meth) acrylic resin such as a (meth) acrylic copolymer or a styrene- (meth) acrylic copolymer is preferably used.

Examples of the epoxy (meth) acrylate resin include an epoxy (meth) acrylate compound obtained by reacting an acid anhydride with a reaction product of an epoxy compound and an unsaturated group-containing monocarboxylic acid. The epoxy compound, the unsaturated group-containing monocarboxylic acid, and the acid anhydride can be appropriately selected from known compounds and used.

As the polymer having a relatively high molecular weight, in addition to the (meth) acrylic resin such as the (meth) acrylic copolymer and the styrene- (meth) acrylic copolymer, and the epoxy (meth) acrylate resin, a thermoplastic resin such as a polyester resin, a maleic resin, a polyolefin resin, a polyamide resin, and a polycarbonate resin may be used. Alternatively, polymers used as dispersants may also be used.

From the viewpoint of easy improvement in solvent solubility in the specific solvent and compatibility with the quantum dot, 1 or more resins selected from the (meth) acrylic resin, the epoxy (meth) acrylate resin, the polyester resin, and the maleic resin can be preferably used.

As the polymer having a relatively high molecular weight, 2 or more kinds may be used in combination, or one kind of resin may be used alone.

As the polymer having a relatively high molecular weight, a polymer having a photopolymerizable functional group such as an ethylenically unsaturated group in a side chain is preferable from the viewpoint of improving the film strength of the cured film.

In addition, from the viewpoint of dispersibility of the quantum dot, the acid value of the polymer having a relatively high molecular weight is preferably 200mgKOH/g or less, more preferably 150mgKOH/g or less, and still more preferably 125mgKOH/g or less.

The acid value is the mass (mg) of potassium hydroxide required for neutralizing an acid component contained in 1g of the solid content of the polymer, and can be measured by the method defined in JIS K0070.

In addition, from the aspect of dispersibility of the quantum dot, the polymer having a relatively high molecular weight may have an amine value, and in the case of having an amine value, the amine value is preferably 40mgKOH/g or more and 140mgKOH/g or less, preferably 120mgKOH/g or less, more preferably 100mgKOH/g or less, and further preferably 80mgKOH/g or less.

The amine value is the number of mg of potassium hydroxide equivalent to perchloric acid required for neutralizing the amine component contained in 1g of the solid component of the polymer, and can be determined by JIS-K7237: 1995 to the same laboratory.

The (meth) acrylic resin can be obtained by (co) polymerizing an ethylenically unsaturated monomer and, if necessary, another copolymerizable monomer by a known method.

As the ethylenically unsaturated monomer, for example, (meth) acrylate monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate can be preferably used. The structural unit derived from an ester group-containing ethylenically unsaturated monomer such as a (meth) acrylate monomer functions as a component for improving the solubility in a solvent and further improving the re-solubility in a solvent. The structural unit derived from a monomer means a structural unit in which a polymerizable carbon-carbon double bond (C ═ C) in the monomer is a single bond (C — C).

In the (meth) acrylic resin, the content ratio of the structural unit having an ester group is preferably 5% by mass or more, and more preferably 10% by mass or more, based on 100% by mass of the total amount of the monomer components used for synthesizing the copolymer, from the viewpoint of obtaining a good pattern. On the other hand, from the viewpoint of dispersibility of the quantum dot, the content ratio of the structural unit having an ester group is preferably 95% by mass or less, and more preferably 80% by mass or less, relative to 100% by mass of the total amount of the monomer components used for synthesizing the copolymer.

The (meth) acrylic resin preferably has a hydrocarbon ring in view of excellent adhesion of the cured film. By making the hydrocarbon ring having a bulky group in the (meth) acrylic resin, the solvent resistance of the obtained cured film, particularly the swelling of the cured film, is suppressed. The effect is not yet clarified, but it is presumed that by including a bulky hydrocarbon ring in the cured film, the movement of molecules in the cured film is suppressed, and as a result, the strength of the coating film is increased, and swelling by the solvent is suppressed.

Examples of such a hydrocarbon ring include a cyclic aliphatic hydrocarbon ring which may have a substituent, an aromatic ring which may have a substituent, and a combination thereof, and the hydrocarbon ring may have a substituent such as a carbonyl group, a carboxyl group, an oxycarbonyl group, or an amide group. Among them, when an alicyclic ring is included, the heat resistance and adhesion of the cured film are improved, and the transparency of the obtained cured film is improved.

Specific examples of the hydrocarbon ring include: hydrocarbon rings of aliphatic hydrocarbons such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornane, tricyclo [5.2.1.0(2,6) ] decane (dicyclopentane) and adamantane; aromatic rings such as benzene, naphthalene, anthracene, phenanthrene, and fluorene; a chain polycyclic ring such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, stilbene, etc., and a Cardo structure represented by the following chemical formula (i).

[ chemical formula 5]

Chemical formula (i)

The (meth) acrylic resin preferably has a maleimide structure represented by the following general formula (ii).

[ chemical formula 6]

General formula (ii)

(in the general formula (ii), R^MIs an optionally substituted hydrocarbon ring. )

R as the above general formula (ii)^MSpecific examples of the optionally substituted hydrocarbon ring in (1) include the same hydrocarbon rings as the specific examples of the hydrocarbon ring described above.

When an alicyclic ring is contained as the hydrocarbon ring, it is preferable in terms of improvement in heat resistance and adhesion of the cured film and improvement in brightness of the obtained cured film.

In addition, when the Cardo structure represented by the above chemical formula (i) is included, it is particularly preferable in terms of improvement in curability and solvent resistance of the cured film.

Examples of the ethylenically unsaturated monomer having the above hydrocarbon ring include: cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, styrene, and the like; from the viewpoint of improving the dispersibility of the quantum dot, cyclohexyl (meth) acrylate, dicyclopentyl (meth) acrylate, adamantyl (meth) acrylate, benzyl (meth) acrylate, and styrene are preferable, and cyclohexyl (meth) acrylate and styrene are particularly preferable.

In addition, as the (meth) acrylic resin, a (meth) acrylic resin containing a (meth) acrylic copolymer having a structural unit having an olefinic double bond in a side chain can be preferably used. That is, as the curable adhesive component, a photocurable adhesive component containing a (meth) acrylic resin containing a (meth) acrylic copolymer having a structural unit having an olefinic double bond in a side chain can be preferably used.

Further, as the (meth) acrylic resin, a (meth) acrylic copolymer containing a structural unit having a hydrocarbon ring and a structural unit having an olefinic double bond can be more preferably used.

In the case of a (meth) acrylic copolymer containing a structural unit having an ethylenic double bond in a side chain, in the curing step of the composition, since the (meth) acrylic resins can form a crosslinking bond with each other, the (meth) acrylic resin and the photopolymerizable compound, and the like, the film strength of the cured film is improved, and the quantum dots are fixed and the dispersibility is maintained.

When the (meth) acrylic copolymer having a structural unit having an ethylenic double bond in a side chain is used in combination with quantum dots, the copolymer is less susceptible to heat and light during the production process or display, the distance between the quantum dots can be kept constant, and suppression of excitation can be prevented.

The method for introducing an olefinic double bond into the (meth) acrylic copolymer may be appropriately selected from conventionally known methods. Examples thereof include: for example, a method of introducing a structural unit having a carboxyl group into a copolymer in advance, and adding a compound having an epoxy group and an olefinic double bond in a molecule, for example, glycidyl (meth) acrylate, to the carboxyl group to introduce an olefinic double bond into a side chain; and a method of introducing a structural unit having a hydroxyl group into the copolymer in advance, adding a compound having an isocyanate group and an olefinic double bond in the molecule, and introducing an olefinic double bond into a side chain.

Examples of the carboxyl group-containing ethylenically unsaturated monomer from which the structural unit having a carboxyl group is derived include: (meth) acrylic acid, vinylbenzoic acid, maleic acid, monoalkyl maleate, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer, and the like. In addition, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, or ω -carboxy-polycaprolactone mono (meth) acrylate may also be used. Further, an anhydride-containing monomer such as maleic anhydride, itaconic anhydride, citraconic anhydride or the like may be used as a precursor of the carboxyl group. Among them, (meth) acrylic acid is particularly preferable in view of copolymerizability, cost, solubility, glass transition temperature, and the like.

In the (meth) acrylic copolymer having a structural unit having an olefinic double bond in a side chain, the content ratio of the structural unit having an olefinic double bond in a side chain is preferably 5% by mass or more, more preferably 10% by mass or more, with respect to 100% by mass of the total amount of the monomer components, and on the other hand, is preferably 50% by mass or less, more preferably 40% by mass or less, from the viewpoint of storage stability of the composition, from the viewpoint of maintaining the dispersibility of the quantum dots.

In the (meth) acrylic copolymer having a structural unit having an olefinic double bond in a side chain, the acid value is preferably 120mgKOH/g or less, more preferably 80mgKOH/g or less, and still more preferably 70mgKOH/g or less, from the viewpoint of dispersibility of the quantum dot.

In addition, the (meth) acrylic resin preferably contains a heat-latent (meth) acrylic copolymer having a structural unit derived from a (meth) acrylate monomer containing a tertiary carbon and a structural unit having a hydroxyl group, from the viewpoints of dispersibility of quantum dots, storage stability, curability, solvent resistance of a cured film, adhesion, and heat resistance.

That is, as the curable adhesive component, a photocurable adhesive component containing a (meth) acrylic resin containing a heat-latent (meth) acrylic copolymer having a structural unit derived from a (meth) acrylate monomer containing a tertiary carbon and a structural unit having a hydroxyl group can be preferably used.

The heat-latent (meth) acrylic copolymer is easily decomposed into (meth) acrylic acid and a stable compound generated on the side of the tertiary carbon atom by cleaving an O — C bond between an oxygen atom adjacent to the (meth) acryloyl group and the tertiary carbon atom adjacent thereto, the oxygen atom being derived from a structural unit of a (meth) acrylate monomer having a tertiary carbon, the structural unit being included in the (meth) acrylate monomer. Therefore, for example, in the case where the thermosetting composition containing a single-site unsaturated group in the present invention contains the aforementioned heat-latent (meth) acrylic copolymer, the structural unit derived from the tertiary carbon-containing (meth) acrylate monomer is decomposed by performing a polymerization reaction of the curable binder component in the thermosetting composition and then performing a heat treatment, thereby producing a stable compound having a (meth) acrylic unit and a tertiary carbon atom. In addition, the hydroxyl group in the heat-latent (meth) acrylic copolymer reacts with the carboxyl group of the (meth) acrylic unit formed to generate an ester crosslinked structure, thereby improving the curability of the curable composition, and the solvent resistance and heat resistance after curing. Further, it is considered that the above-mentioned heat-latent (meth) acrylic copolymer can improve the storage stability of the quantum dot-containing curable composition because the carboxyl group is blocked, and can improve the adhesion because the film thickness of the cured film can be reduced. Further, when the heat-latent (meth) acrylic copolymer is used in combination with quantum dots, the copolymer is less likely to be affected by heat and light during the production process or display, and the distance between the quantum dots can be kept constant, and suppression of excitation can be prevented, which is preferable.

The (meth) acrylate monomer having a tertiary carbon preferably has a structure in which an oxygen atom adjacent to the (meth) acryloyl group is bonded to the tertiary carbon atom. That is, the tertiary carbon-containing (meth) acrylate monomer preferably has a structure in which an oxygen atom adjacent to the (meth) acryloyl group is bonded to a tertiary carbon atom. The tertiary carbon atom means a carbon atom having 3 carbon atoms as other carbon atoms bonded to the carbon atom.

The tertiary carbon-containing (meth) acrylate monomer is preferably a compound having 1 (meth) acryloyl group in the molecule, and examples thereof include compounds represented by the following general formula (5).

CH₂＝C(R^a)-C(＝O)-O-A (5)

(R^aRepresents a hydrogen atom or a methyl group, and A represents a monovalent organic group having a structure having a tertiary carbon atom on the oxygen atom side. )

In the above general formula (5), the organic group represented by A may be represented by, for example, -C (R)^b)(R^c)(R^d) And (4) showing. In this case, R^b、R^cAnd R^dThe preferable alkyl groups are alkyl groups with the same or different carbon numbers of 1-30, and the alkyl groups can be saturated alkyl groups or unsaturated alkyl groups. Further, the compound may have a cyclic structure or may further have a substituent. In addition, R^b、R^cAnd R^dThe terminal portions may be connected to each other to form a ring structure.

In the present invention, as described below, the organic group represented by a preferably has 12 or less carbon atoms, because the O — C bond between the oxygen atom adjacent to the (meth) acryloyl group and the tertiary carbon atom in a adjacent thereto is cleaved to generate a new compound which is easily volatilized. Among them, the organic group represented by a is preferably a group derived from at least 1 selected from t-butyl (meth) acrylate and t-amyl (meth) acrylate. The organic group represented by a may have a branched structure.

Here, in the tertiary carbon-containing (meth) acrylate monomer, at least 1 of the tertiary carbon atoms bonded to the oxygen atom adjacent to the (meth) acryloyl group, preferably the adjacent carbon atoms, is bonded to a hydrogen atom. For example, when the (meth) acrylate monomer having a tertiary carbon is a compound represented by the above general formula (5) and A is-C (R)^b)(R^c)(R^d) In the case of the group represented, R is preferably^b、R^cAnd R^dAt least 1 of which comprises a carbon atom having 1 or more hydrogen atoms and which is bonded to a tertiary carbon atom. In such an embodiment, heating cleaves an O — C bond between an oxygen atom adjacent to the (meth) acryloyl group and a tertiary carbon atom adjacent thereto to produce (meth) acrylic acid, and a double bond (C ═ C) is formed between the tertiary carbon atom and the carbon atom adjacent thereto to produce a new compound more stably.

The new compound is easily volatilized, and the concentration of quantum dots in a cured product (cured film) can be increased while the thickness of the cured product (cured film) is reduced^b、R^cAnd R^dThe hydrocarbon group in (1) is preferably a saturated hydrocarbon group having 1 to 15 carbon atoms, more preferably a saturated hydrocarbon group having 1 to 10 carbon atoms, still more preferably a saturated hydrocarbon group having 1 to 5 carbon atoms, and particularly preferably a saturated hydrocarbon group having 1 to 3 carbon atoms.

Among them, the organic group represented by a is preferably at least 1 selected from the group consisting of a tert-butyl group and a tert-amyl group.

In the heat-latent (meth) acrylate copolymer, the content ratio of the tertiary carbon-containing (meth) acrylate monomer unit is preferably 5% by mass or more, more preferably 15% by mass or more, and particularly preferably 20% by mass or more, relative to 100% by mass of the total amount of the monomer components, from the viewpoint of further exhibiting the above-described effects. From the viewpoint of further improving the pattern characteristics, the upper limit of the content ratio is preferably 90% by mass or less, more preferably 75% by mass or less, and still more preferably 60% by mass or less.

The structural unit having a hydroxyl group of the heat-latent (meth) acrylate polymer is preferably a structural unit having a hydroxyl group in a side chain. As the monomer from which the above-mentioned structural unit having a hydroxyl group is derived, for example, there can be preferably mentioned: hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2, 3-hydroxypropyl (meth) acrylate.

In the heat-latent (meth) acrylate copolymer, the content ratio of the structural unit having a hydroxyl group is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, with respect to 100% by mass of the total amount of the monomer components, from the viewpoint of curability and solvent resistance, and on the other hand, from the viewpoint of suppressing whitening on the surface of a cured product, it is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less.

The heat-latent (meth) acrylate polymer preferably has a structural unit derived from (meth) acrylic acid in view of copolymerizability, cost, solubility, glass transition temperature, and the like.

In the (meth) acrylate-based copolymer, the content of the structural unit derived from (meth) acrylic acid is preferably 5 mass% or more, more preferably 10 mass% or more, with respect to 100 mass% of the total amount of the monomer components, and is preferably 35 mass% or less, more preferably 25 mass% or less, from the viewpoint of stability.

From the viewpoint of dispersibility of the quantum dot, the acid value of the heat-latent (meth) acrylate polymer is preferably 120mgKOH/g or less, more preferably 80mgKOH/g or less, and still more preferably 70mgKOH/g or less.

In addition, the heat-latent (meth) acrylate polymer preferably contains a structural unit having a tertiary amine from the viewpoint of dispersibility of the quantum dot. As the monomer from which the structural unit having a tertiary amine described above is derived, for example, there can be preferably mentioned: (meth) acrylic acid esters having an alkyl-substituted amino group such as dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and diethylaminopropyl (meth) acrylate; (meth) acrylamides having an alkyl-substituted amino group such as dimethylaminoethyl (meth) acrylamide and dimethylaminopropyl (meth) acrylamide.

In the (meth) acrylate-based copolymer, the content of the structural unit having a tertiary amine is preferably 5 mass% or more, more preferably 10 mass% or more, with respect to 100 mass% of the total amount of the monomer components, and is preferably 35 mass% or less, more preferably 25 mass% or less, from the viewpoint of stability.

From the viewpoint of dispersibility of the quantum dots, the amine value of the heat-latent (meth) acrylate polymer is preferably 40mgKOH/g or more and 140mgKOH/g or less, preferably 120mgKOH/g or less, more preferably 100mgKOH/g or less, and still more preferably 80mgKOH/g or less.

In addition, the heat-latent (meth) acrylate polymer preferably has a structural unit having an ethylenically unsaturated group in a side chain, from the viewpoint of improving the film strength of the cured film. The structural unit having an ethylenically unsaturated group in a side chain is obtained, for example, by introducing a structural unit derived from (meth) acrylic acid and adding, for example, glycidyl (meth) acrylate or the like to a carboxyl group of the structural unit and a hydroxyl group of the monomer unit having a hydroxyl group, when synthesizing the heat-latent (meth) acrylate polymer.

The heat-latent (meth) acrylate polymer can be obtained, for example, by polymerizing a (meth) acrylate monomer containing a tertiary carbon, a monomer having a hydroxyl group, and if necessary, other monomer components.

Examples of the other monomer components include: a monomer derived from the structural unit having a hydrocarbon ring, a (meth) acrylate monomer containing no tertiary carbon, a monomer derived from a structural unit having an olefinic double bond in a side chain, and the like.

In the present invention, among them, the (meth) acrylic resin preferably contains at least 1 selected from the group consisting of a (meth) acrylic copolymer having a structural unit having an ethylenic double bond in a side chain and the heat latent (meth) acrylate polymer, from the viewpoint of dispersibility of the quantum dot.

In the case where the content sub-point curable composition of the present invention contains a (meth) acrylic copolymer having a structural unit having an olefinic double bond in a side chain, the content ratio of the (meth) acrylic copolymer having a structural unit having an olefinic double bond in a side chain to the total solid content of the content sub-point curable composition is preferably 10 mass% or more, more preferably 15 mass% or more, and on the other hand, is preferably 35 mass% or less, more preferably 25 mass% or less, from the viewpoint of sufficiently containing other components, in order to sufficiently exert the effect of the (meth) acrylic copolymer having a structural unit having an olefinic double bond in a side chain.

In the case where the thermosetting (meth) acrylate-based composition of the present invention contains the heat-latent (meth) acrylate-based polymer, the content ratio of the heat-latent (meth) acrylate-based polymer to the total solid content of the thermosetting (meth) acrylate-based composition is preferably 10 mass% or more, more preferably 15 mass% or more, from the viewpoint of sufficiently exerting the effect of the heat-latent (meth) acrylate-based polymer, and on the other hand, is preferably 35 mass% or less, more preferably 25 mass% or less, from the viewpoint of sufficiently containing other components.

In the present invention, a block copolymer used as a dispersant can be preferably used as the (meth) acrylic resin from the viewpoint of dispersibility of the quantum dots. The (meth) acrylic resin of the block copolymer used as the dispersant generally has, as the block portion, a block portion containing a structural unit having an acidic group such as a carboxyl group or a basic group such as a tertiary amine, a tertiary amine salt, or a quaternary ammonium salt, and a block portion containing a structural unit having 1 or 2 or more kinds of ester groups. The structural unit having a carboxyl group, the structural unit having a tertiary amine, and the structural unit having an ester group may be the same as those described above, and other structural units having an acidic group and structural units having a basic group may be used as appropriate.

The (meth) acrylic resin used as the dispersant may be appropriately selected from commercially available resins.

From the viewpoint of dispersibility of the quantum dot, the amine value of the (meth) acrylic resin of the block copolymer used as the dispersant is also preferably 40mgKOH/g or more and 140mgKOH/g or less, preferably 120mgKOH/g or less, more preferably 100mgKOH/g or less, and still more preferably 80mgKOH/g or less.

The (meth) acrylic copolymer contained in the (meth) acrylic resin preferably has a weight average molecular weight (Mw) in the range of 1,000 to 50,000, more preferably 3,000 to 20,000. The weight average molecular weight of the (meth) acrylic copolymer is preferably 1,000 or more in view of excellent functions of the adhesive after curing, and is preferably 50,000 or less in view of improvement of the discharge property.

The weight average molecular weight (Mw) of the polymer can be measured by Shodex GPC System-21H using polystyrene as a standard substance and THF as an eluent.

The ethylenically unsaturated bond equivalent in the case where the (meth) acrylic resin has an ethylenically unsaturated group in a side chain is preferably in the range of 100 to 2000, and particularly preferably in the range of 140 to 1500, from the viewpoint of obtaining effects such as an improvement in film strength of the cured film and excellent adhesion to the substrate. When the equivalent weight of the ethylenically unsaturated bond is 2000 or less, the adhesiveness is excellent. Further, when the content is 100 or more, the proportion of other structural units such as a structural unit having a hydrocarbon ring can be relatively increased, and therefore, heat resistance and the like can be improved.

Here, the equivalent weight of the ethylenic unsaturated bond means a weight average molecular weight per 1 mole of the ethylenic unsaturated bond in the above (meth) acrylic resin, and is represented by the following numerical formula (1).

Numerical formula (1) ethylenic unsaturated bond equivalent (g/mol) ═ w (g)/m (mol)

(in the formula (1), W represents the mass (g) of the (meth) acrylic resin, and M represents the number of moles (mol) of the ethylenic double bond contained in the (meth) acrylic resin W (g))

The above-mentioned ethylenically unsaturated bond equivalent can also be determined, for example, by the following method in accordance with JIS K0070: 1992, the number of the ethylenic double bonds contained per 1g of the (meth) acrylic resin was measured and calculated.

In the content-sub-curable composition of the present invention, the content of the (meth) acrylic resin is not particularly limited, and the (meth) acrylic resin may be used alone in 1 kind or in combination of 2 or more kinds, and the content is preferably within a range of 5 to 60% by mass, more preferably 10to 40% by mass, based on the total solid content of the content-sub-curable composition. When the content of the (meth) acrylic resin is not less than the lower limit, it is preferable from the viewpoint of improving the dispersibility of the quantum dot, and when the content of the (meth) acrylic resin is not more than the upper limit, it is preferable from the viewpoint of improving the discharge property.

In the content-quantum-dot curable composition of the present invention, the above-mentioned relatively high molecular weight polymer may be used alone in 1 kind, or may be used in combination of 2 or more kinds, and the content is not particularly limited, and the above-mentioned relatively high molecular weight polymer is preferably within a range of 5 to 60% by mass, more preferably 10to 40% by mass, based on the total solid content of the content-quantum-dot curable composition. When the content of the polymer having a relatively high molecular weight is not less than the lower limit, it is preferable from the viewpoint of improving the dispersibility of the quantum dot, and when the content of the polymer having a relatively high molecular weight is not more than the upper limit, it is preferable from the viewpoint of improving the discharge property.

(polyfunctional monomer)

The polyfunctional monomer is not particularly limited as long as it can be polymerized by the following photoinitiator, and a compound having 2 or more ethylenically unsaturated double bonds is generally used, and a polyfunctional (meth) acrylate having 2 or more acryloyl groups or methacryloyl groups is particularly preferable.

The polyfunctional (meth) acrylate may be appropriately selected from conventionally known (meth) acrylates.

The polyfunctional (meth) acrylate may be used alone in 1 kind, or may be used in combination of 2 or more kinds. When excellent photocurability (high sensitivity) is required for the content-site curable composition of the present invention, the polyfunctional monomer preferably has 3 or more (trifunctional) polymerizable double bonds, and is preferably a poly (meth) acrylate of a polyol having 3 or more members or a dicarboxylic acid modified product thereof, and specifically is preferably trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, a succinic acid modified product of pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, a succinic acid modified product of dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, or the like.

The content of the above-mentioned polyfunctional monomer used in the content of the quantum dot curable composition is not particularly limited, and the polyfunctional monomer is preferably within a range of 5 to 60% by mass, and more preferably within a range of 10to 40% by mass, based on the total solid content of the quantum dot curable composition. When the content of the polyfunctional monomer is not less than the lower limit, it is preferable from the viewpoint that photocuring is easily and sufficiently performed, and the content of the polyfunctional monomer is not more than the upper limit in order to sufficiently contain other components.

(photoinitiator)

The photoinitiator is not particularly limited, and 1 or a combination of 2 or more of various photoinitiators known in the art may be used.

As the photoinitiator, there may be mentioned: aromatic ketones, benzoin ethers, halomethyl oxadiazole compounds, α -aminoketones, bisimidazoles, N-dimethylaminobenzophenones, halomethyl-S-triazine compounds, thioxanthones, and the like. Specific examples of the photoinitiator include: aromatic ketones such as benzophenone, 4 '-bisdiethylaminobenzophenone, and 4-methoxy-4' -dimethylaminobenzophenone; benzoin ethers such as benzoin methyl ether; benzoins such as ethyl benzoin; bisimidazoles such as 2- (o-chlorophenyl) -4, 5-phenylimidazole dimer; halomethyl oxadiazole compounds such as 2-trichloromethyl-5- (p-methoxystyryl) -1,3, 4-oxadiazole; halomethyl-S-triazine compounds such as 2- (4-butoxy-naphthalen-1-yl) -4, 6-bis-trichloromethyl-S-triazine; 2, 2-dimethoxy-1, 2-diphenylethan-1-one, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropanone, 1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 1-hydroxy-cyclohexyl-phenylketone, benzil, benzoylbenzoic acid methyl ester, 4-benzoyl-4' -methylbenzophenone, benzylmethyl ketal, dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 2-n-butoxyethyl-4-dimethylaminobenzoate, 2-chlorothioxanthone, 2, 4-diethylthioxanthone, 2, 4-dimethylthioxanthone, isopropylthioxanthone, 4-benzoyl-methyldiphenyl sulfide, 1-hydroxy-cyclohexyl-phenyl ketone, 2-benzyl-2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl ] -1-butanone, 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl ] -1-butanone, α -dimethoxy- α -phenylacetophenone, phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide, 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholinyl) -1-propanone, and the like.

Among them, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone, 4' -bis (diethylamino) benzophenone, and diethylthioxanthone can be preferably used.

Particularly, a photoinitiator that does not inhibit the light absorption of the quantum dot is preferable, and a photoinitiator that has a small absorption at the excitation wavelength of the quantum dot, i.e., 350nm or more or 400nm or more is preferable. Examples of such a photoinitiator include an α -hydroxyketone initiator having absorption at around 250 nm. There are 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl ] phenyl } -2-methyl-propan-1-one (Irgacure 127), 1-hydroxy-cyclohexyl-phenyl-one (Irgacure 184), 2-dimethoxy-1, 2-diphenylethan-1-one (Irgacure 651), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Irgacure 1173), 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one (Irgacure2959), and the like. The Irgacure 127, 184, 651, 1173, and 2959 are trade names and available from BASF.

The total content of the photoinitiators is preferably 5 to 15% by mass based on the total solid content of the quantum dot curable composition.

The content of the photoinitiator is usually about 0.01 to 100 parts by mass, preferably about 5 to 60 parts by mass, based on 100 parts by mass of the polyfunctional monomer.

When the content of the photoinitiator is not less than the lower limit, sufficient photocuring is facilitated, and on the other hand, when the content is not more than the upper limit, the obtained cured film is preferably reduced in yellowing and reduced in transparency.

The binder component used in the content sub-dot curable composition of the present invention is preferably blended in a ratio of the total content thereof to the total solid content of the content sub-dot curable composition of 35 to 97% by mass, more preferably 40 to 96% by mass. When the lower limit value is not less than the above-mentioned lower limit value, a cured film having excellent hardness and adhesion to a substrate can be obtained. When the amount is equal to or less than the above upper limit, the occurrence of micro wrinkles due to thermal shrinkage is preferably suppressed.

< Quantum dot >

The quantum dot used in the present invention is not particularly limited as long as it is a compound semiconductor fine particle having a size of several nm to several tens nm and is a light-emitting material that generates a quantum confinement effect (quantum size effect).

As the quantum dots, known quantum dots can be used, and 1 kind may be used alone, or 2 or more kinds may be used in combination. Known quantum dots include quantum dots (R) having an emission center wavelength in a wavelength band in a range of 600nm to 680nm, quantum dots (G) having an emission center wavelength in a wavelength band in a range of 500nm to 600nm, and quantum dots (B) having an emission center wavelength in a wavelength band in a range of 400nm to 500nm, wherein the quantum dots (R) are excited by excitation light and emit red light, the quantum dots (G) emit green light, and the quantum dots (B) emit blue light.

Specific examples of the above quantum dots include II-VI semiconductor compounds such as MgS, MgSe, MgTe, CaS, CaSe, CaTe, SrS, SrSe, SrTe, BaS, BaSe, BaTe, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, and HgTe; group IIIV semiconductor compounds such as AlN, AlP, AlAs, AlSb, GaAs, GaP, GaN, GaSb, InN, InAs, InP, InSb, TiN, TiP, TiAs, and TiSb; semiconductor crystals of group IV semiconductors containing Si, Ge, Pb, and the like, and semiconductor compounds containing 3 or more elements such as InGaP, may also be cited. Alternatively, the semiconductor compound doped with Eu may be used³⁺、Tb³⁺、Ag⁺、Cu⁺Such as rare earth metal cations or transition metal cations.

The quantum dot may contain 1 kind of semiconductor compound, or 2 or more kinds of semiconductor compounds, and may have a core-shell structure having a core containing a semiconductor compound and a shell containing a semiconductor compound different from the core. As the core-shell type quantum dot, a material having a band gap higher than that of the semiconductor compound forming the core is used as the semiconductor compound constituting the shell to enclose excitons in the core, whereby the light emission efficiency of the quantum dot can be improved. Examples of the core-shell structure (core/shell) having such a size relationship of the band gap include CdSe/ZnS, CdSe/ZnSe, CdSe/CdS, CdTe/CdS, InP/ZnS, and CuInS/ZnS.

The size of the quantum dot may be appropriately adjusted depending on the material constituting the quantum dot so as to obtain light of a desired wavelength. Quantum dots increase in energy band gap as particle size decreases. That is, as the crystal size decreases, the emission of the quantum dot shifts to the blue side, i.e., the high energy side. Therefore, by changing the size of the quantum dot, the emission wavelength can be adjusted over the wavelength region of the spectrum of the ultraviolet region, the visible region, or the infrared region.

In addition, as the quantum dot, a quantum dot in which a ligand having a coordinating group is coordinated on the surface may be used. Examples of the coordinating group include: amino, carboxyl, mercapto, phosphino, and phosphinoxide groups, and the like. Examples of the coordinating group include: hexylamine, decylamine, hexadecylamine, octadecylamine, oleylamine, myristylamine, laurylamine, oleic acid, mercaptopropionic acid, trioctylphosphine oxide, polyethylene glycol, and the like. Among them, from the viewpoint of preventing the extinction due to the surface defect, a quantum dot in which a ligand having at least 1 kind of coordinating group selected from trioctylphosphine, trioctylphosphine oxide, octadecylamine and oleylamine is provided on the surface is preferable, and a quantum dot in which a ligand having at least 1 kind of coordinating group selected from trioctylphosphine oxide, octadecylamine and oleylamine is provided on the surface is more preferable.

The quantum dot having the ligand having the coordinating group coordinated on the surface can be synthesized by, for example, the method described in j.am. chem.soc.,115, pp8706-8715(1993) or j.phys. chem.,101, pp9463-9475(1997), and a commercially available product can be preferably used.

As the quantum dot, a quantum dot whose surface is protected with a protective material may be used. Examples of the protective material include a protective material having a hydrophilic group and a hydrophobic group of 1 residue or more in one molecule, and the hydrophobic group contains at least 1 residue selected from the group consisting of triphenylamine derivatives, arylamine derivatives, oxadiazole derivatives, dinaphthylanthracene derivatives, distyrylarylene derivatives, carbazole derivatives, benzimidazole derivatives, and aluminum hydroxyquinoline complex derivatives.

Examples of the hydrophilic group include: carboxyl group, amine group, hydroxyl group, thiol group, aldehyde group, sulfonic acid group, amide group, sulfonamide group, phosphoric acid group, phosphine oxide group, etc.

The content of the quantum dots contained in the total solid content of the quantum dot curable composition of the present invention is preferably 0.1 mass% or more, more preferably 0.3 mass% or more from the viewpoint of emission intensity, and is preferably 40 mass% or less, more preferably 35 mass% or less from the viewpoint of discharge stability and dispersibility in the inkjet system.

< optional additional component >

The content sub-point curable composition of the present invention may contain various additives as needed. Examples of additives include: antioxidants, polymerization terminators, chain transfer agents, leveling agents, plasticizers, surfactants, antifoaming agents, silane coupling agents, ultraviolet absorbers, adhesion promoters, and the like.

< method for producing a curable composition containing quantum dots >

The present invention provides a thermosetting composition containing a quantum dot, which can be produced by adding the above components to the above solvent, mixing them, and dissolving or dispersing the solid components. For example, the following method can be preferably used: a curable adhesive composition in which a curable resin and a binder component such as a curing agent are dissolved or dispersed in a solvent is prepared in advance, and the curable adhesive composition, quantum dots, and optional additional components are added, and further a solvent is added and mixed. The solvent used for preparing the curable adhesive composition is preferably at least 1 selected from the first solvent and the second solvent. For example, it is preferable that at least 1 selected from the first solvent and the second solvent is further added after the preparation of the curable adhesive composition, whereby the solvent in the content-quantum-dot curable composition is a solvent including the first solvent and the second solvent.

That is, as a method for producing the composition curable with a quantum dot of the present invention, for example, a production method comprising the steps of:

preparing a curable adhesive composition containing the curable adhesive component and at least 1 selected from the first solvent and the second solvent; and

mixing the curable adhesive composition, the quantum dots, and at least 1 selected from the first solvent and the second solvent, and

the mixed solvent of the solvent in the curable adhesive composition and the solvent used in the mixing step contains the first solvent and the second solvent.

When a polymer functioning as a dispersant is used as the curable binder component, a production method including the steps of:

preparing a curable adhesive composition containing a curable adhesive component other than a polymer that functions as a dispersant, and at least 1 selected from the first solvent and the second solvent;

preparing a quantum dot dispersion by dispersing the quantum dot, a polymer functioning as a dispersant, and at least 1 selected from the first solvent and the second solvent; and

mixing the curable adhesive composition, the dispersion, and optionally at least 1 selected from the group consisting of the first solvent and the second solvent, and

< use >)

The application of the quantum dot-containing curable composition of the present invention is not particularly limited, and the composition can be used for forming a quantum dot-containing cured layer included in various optical members used in, for example, the following display devices. The quantum dot-containing curable composition of the present invention is a composition suitable for forming a quantum dot-containing layer by an inkjet method, and can be preferably used for inkjet.

Examples of the optical member include semiconductor optical members such as a light conversion member and a light emitting member.

II. curing product containing quantum dots

The quantum dot-containing cured product of the present invention can obtain desired color development because the unevenness is reduced and the aggregation of quantum dots in the cured product is suppressed.

The cured product containing quantum dots of the present invention can be obtained, for example, as follows: the quantum dot-containing layer, which is a coating film of the quantum dot-containing curable composition of the present invention, is formed by an ink jet method and cured. The method for forming the quantum dot-containing layer and the method for curing can be, for example, the same methods as those used in the method for producing an optical member described below.

When the quantum dot-containing cured product of the present invention is used as a quantum dot-containing cured layer included in various optical members such as a light conversion member and a light emitting member used in a display device described below, for example, high luminance and a wide color reproduction region can be realized.

The quantum dot-containing cured product of the present invention can be produced into a quantum dot-containing cured product having desired light emission characteristics by appropriately adjusting the type and content of quantum dots.

The color reproduction region of the quantum dot cured product of the present invention can realize red, green, Blue, and white Light emission colors using, for example, a Blue Light Emitting Diode (Blue LED) as a Light source. More specifically, in chromaticity coordinates (x, y), red color with Rx of 0.60 to 0.71 and Ry of 0.29 to 0.35, green color with Gx of 0.16 to 0.35 and Gy of 0.55 to 0.80, and blue color with Bx of 0.13 to 0.16 and By of 0.03 to 0.10 can be realized.

The chromaticity coordinates x and y are JISZ 8701: 1931 in XYZ color system.

Method for producing optical member

The method for manufacturing an optical member according to the present invention includes the steps of:

forming a quantum dot-containing layer by selectively attaching the quantum dot-containing curable composition of the present invention to a predetermined region on a substrate by an ink jet method; and

and curing the quantum dot containing layer to form a quantum dot containing cured layer.

The method for manufacturing an optical member according to the present invention may further include other steps as necessary in addition to the above-described steps.

In the method for producing an optical member of the present invention, since the above-described quantum dot-containing curable composition of the present invention is used, a quantum dot-containing cured layer in which unevenness is reduced can be formed, and since aggregation of quantum dots in the quantum dot-containing cured layer is suppressed, a desired color development can be obtained.

The quantum dot-containing cured layer can be adjusted to have desired color development characteristics by appropriately selecting the kind and content of quantum dots, and has the same color reproduction region as the above-described quantum dot-containing cured product of the present invention.

In the method for manufacturing an optical member according to the present invention, the predetermined region on the substrate is preferably a region surrounded by partition walls on the substrate.

The optical member obtained by the production method of the present invention is preferable in that high luminance and a wide color reproduction region can be realized when used as various semiconductor optical members such as a light conversion member and a light emitting member used for a display device described below.

An example of the method for manufacturing an optical member according to the present invention will be described below with reference to the drawings.

Fig. 1 is a diagram illustrating an example of the method for manufacturing an optical member according to the present invention. In the method shown in fig. 1, first, a substrate 1 of an optical member is prepared as shown in fig. 1 (a). The substrate is not particularly limited as long as it is a substrate conventionally used for optical members, and examples thereof include a transparent substrate, a Thin Film Transistor (TFT) substrate, and the like. As the transparent substrate, for example, a transparent hard material having no flexibility such as quartz glass, Pyrex (registered trademark) glass, or synthetic quartz plate, or a transparent flexible material having flexibility such as a transparent resin film or an optical resin plate can be used.

The substrate may be a substrate subjected to surface treatment for imparting gas barrier properties or the like, if necessary.

Next, as shown in fig. 1(B), partition walls 2 are formed in the regions to be the boundaries between the sub-pixels on one surface side of substrate 1. The partition walls 2 can be formed to a thickness by sputtering, vacuum deposition, or the like

And a metal thin film of chromium or the like on the left and right sides, and patterning the thin film. As a method of patterning, a general patterning method such as sputtering can be used.

The partition walls 2 may be formed of a resin binder containing light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments, and may be formed of, for example, a black matrix. As the resin binder used for the partition walls, a binder obtained by mixing 1 or 2 or more kinds of resins such as polyimide resin, acrylic resin, epoxy resin, polyacrylamide, polyvinyl alcohol, gelatin, casein, cellulose, or the like, a photosensitive resin, an O/W emulsion type resin composition, a reactive silicone emulsion, or the like can be used. The thickness of the resin partition wall can be set within the range of 0.5 to 15 μm. As a method for patterning the resin partition wall, a method of forming the partition wall into a predetermined pattern by a commonly used method such as photolithography and printing, curing the partition wall by irradiation with ionizing radiation, and baking the partition wall as needed can be used.

The partition walls 2 may or may not have ink repellency, and when the ink-repellent protrusions 3 described below are not present, the partition walls 2 preferably have ink repellency. The ink repellency can be imparted by the same method as that of the ink repellency convex portions 3 described below.

The height of the partition walls is not particularly limited, but is preferably 1.0 μm or more, more preferably 2.0 μm or more, from the viewpoint of color mixing (blocking of oblique light), and is preferably 15 μm or less, more preferably 10 μm or less, from the viewpoint of productivity of the partition walls.

As shown in fig. 1(C), the ink-repellent convex portions 3 may be formed on the pattern of the partition walls 2 as needed. The composition of the ink-repellent convex portion is not particularly limited as long as it is a resin composition having ink-repellent properties which has low affinity with the dot-containing curable composition of the present invention and repels the dot-containing curable composition. Further, transparency is not particularly required, and may be colored. For example, a material which is used for the partition walls and into which no black material is mixed may be used. Specifically, there may be mentioned 1 type or a mixture of 2 or more types of aqueous resins such as polyacrylamide, polyvinyl alcohol, gelatin, casein and cellulose, and an O/W emulsion type resin composition, for example, a composition prepared by emulsifying a reactive silicone. In the present invention, a photocurable resin is preferably used for reasons of easy handling and easy curing. Further, since the ink repellency of the ink repellent convex portion is more preferable, the surface thereof may be treated with an ink repellent treatment agent such as a silicone compound or a fluorine-containing compound.

The patterning of the ink-repellent convex portion can be performed by printing with a coating liquid using an ink-repellent resin composition, or by photolithography with a photocurable coating liquid. The height of the ink-repellent convex portion may be appropriately adjusted to prevent color mixing of the ink when applying by the ink jet method as described above, and specifically, may be varied depending on the deposition amount of the blown ink, and is preferably in the range of 0.1 to 3.0 μm in general.

In addition, in the formation of the ink repellent convex portions, surface treatment such as plasma treatment may be used to impart ink repellency. Examples of the surface treatment include reduced pressure plasma treatment or atmospheric pressure plasma treatment in which a gas containing fluorine or a fluorine compound is used as an introduced gas and plasma irradiation is performed under a reduced pressure environment or an atmospheric pressure environment. When the plasma treatment is performed in a gas containing a fluorine-based compound and oxygen, the phenomenon in which the fluorine-based compound enters the surface of the organic material occurs in the organic material in parallel with the above reaction. In particular, when the fluorine-based compound is larger than the oxygen gas, for example, in a gas atmosphere in which the amount of the fluorine-based compound is too large such that the content of the fluorine-based compound with respect to the total amount of the fluorine-based compound and the oxygen gas is 60% or more, the phenomenon of mixing the fluorine-based compound into the gas atmosphere is stronger than the oxidation reaction caused by the oxygen gas, and therefore the surface of the organic material is made nonpolar due to the phenomenon of mixing into the gas atmosphere, and the ink repellency is provided.

Although not shown in fig. 1, after the partition walls 2 and the ink-repellent convex portions 3 are formed as necessary, a functional layer (for example, a functional layer 8 shown in fig. 2) for imparting various functions may be formed as necessary on the surface of the substrate 1 in each quantum dot-containing layer forming region 4 partitioned by the pattern of the partition walls 2. The functional layer may be a layer that blocks or diffuses light from a light source or external light, or a layer that imparts both of these properties, by appropriately selecting the type and content of a colorant or light scattering particles.

Although not shown, the functional layer may be provided on the non-content dot cured layer after the non-content dot cured layer is formed. The functional layer provided on the quantum dot-containing cured layer may be, for example, a gas barrier layer.

The functional layer may be formed by appropriately selecting a material and a forming method according to the function. The functional layer can be obtained by forming a coating film of a resin composition containing a resin and, if necessary, a colorant, light scattering particles, and the like, by a known method such as a photolithography method or an ink jet method, and curing the coating film.

Next, as inks for forming the respective sub-pixels (sub-pixels), the quantum dot-containing compositions of the present invention described above in various colors were prepared as inkjet inks. Next, as shown in fig. 1(D), on the surface of the substrate 1, in each quantum dot-containing layer forming region 4 partitioned by the pattern of the partition walls 2, a quantum dot-containing layer is formed by blowing a sub-pixel forming ink of a desired color by an ink jet method. In this ink blowing step, the viscosity of the ink for forming the sub-pixels is less likely to increase at the tip of the discharge head 5, and good discharge properties can be continuously maintained. Therefore, the ink of the corresponding color can be accurately and uniformly adhered to the predetermined sub-dot layer formation region, and when the second solvent has a predetermined surface tension and viscosity, the second solvent can be spread and wetted to each corner, and the sub-pixels free from color unevenness or fading can be formed in a correct pattern. Further, since the sub-pixel forming inks of the respective colors can be simultaneously discharged onto the substrate by using the plurality of ink jet heads, the working efficiency can be improved as compared with the case of forming the sub-pixels for the respective colors.

Next, as shown in fig. 1(E), the quantum dot containing layer 6 of each color is dried and, if necessary, pre-baked, and then cured by exposure and/or heating as appropriate. In the present invention, it is preferable that the quantum dot-containing layer is dried under reduced pressure before a normal pre-baking stage, in order to suppress radial unevenness on the surface. For example, the pre-baking is performed on a heating plate at 60 to 140 ℃ for 3 to 20 minutes. Further, heating and drying under reduced pressure may be performed simultaneously. Then, when the quantum dot containing layer is appropriately exposed to light and/or heated, a crosslinking reaction occurs in the crosslinking elements of the curable resin contained in the inkjet ink, and the quantum dot containing layer is cured to form the quantum dot containing cured layer 7.

The quantum dots contained in each of the quantum dot-containing cured layers 7 may be of the same type or of different types.

The size of each sub-pixel is not particularly limited, and may be, for example, 5 μm × 5 μm or more and 200 μm × 200 μm or less. According to the manufacturing method of the present invention, a desired content sub-dot cured layer can be accurately formed on such a small sub-pixel.

The thickness of the quantum dot-containing cured layer may be, for example, about 0.01 μm to 10 μm. In addition, the thickness of the cured layer may be changed for each sub-pixel, and set to an optimum thickness for each color.

In the optical member to be manufactured in the present invention, the maximum value of the film thickness of the non-quantum dot cured layer, particularly the maximum value of the film thickness of the end portion of the non-quantum dot cured layer, is preferably 15 μm or less, and more preferably 10 μm or less. In the optical member to be manufactured in the present invention, the difference between the maximum value of the film thickness of the content sub-dot cured layer, particularly the maximum value of the film thickness of the edge portion of the content sub-dot cured layer, and the average film thickness is preferably 5 μm or less, and more preferably 2.5 μm or less. In this case, the thick film portion becomes dark, and display failure is reduced. The film thickness is a height from the substrate. The average thickness of the cured layer was calculated by dividing the volume of the coating film in the sub-pixel by the area of the cured layer surface. The maximum thickness of the end portion means the thickness of the portion having the highest thickness among the end portion swelling portions.

Thus, the optical member 101 is manufactured using the quantum dot curable composition of the present invention.

The method for manufacturing an optical member according to the present invention may further include a step of forming an overcoat layer covering the partition walls 2 and the quantum dot cured layer 7. That is, the optical member obtained by the manufacturing method of the present invention may have an overcoat 9 covering the partition walls 2 and the quantum dot cured layer 7, as shown in fig. 2 below.

The overcoat layer is provided for planarizing the optical member and preventing elution of components contained in the sub-pixels, or permeation of oxygen or moisture. The thickness of the overcoat layer can be set in consideration of the light transmittance of the material used, the surface state of the optical member, and the like, and can be set, for example, in the range of 0.01 to 2.0 μm. The overcoat layer can be formed using a material having light transmittance, gas barrier property, and the like required as a protective layer, for example, from known organic materials such as a photosensitive resin and a two-liquid curable resin, metal oxides such as silicon oxide, aluminum oxide, tantalum oxide, yttrium oxide, hafnium oxide, zirconium oxide, and titanium oxide, metal oxynitrides such as silicon nitride, inorganic materials such as metal alkoxides, silicon oxynitride, and hafnium aluminate, and organic-inorganic hybrid materials. The method for forming the overcoat layer is not particularly limited, and may be appropriately selected from known methods depending on the material used, and when the above-described inorganic material, organic-inorganic hybrid material, or the like is used, for example, a sol-gel method, a vapor deposition method, a sputtering method, or the like can be used.

In the method for producing an optical member according to the present invention, the method further includes a step of selectively changing wettability in a predetermined region of the substrate surface to form a quantum dot layer-containing region having a higher affinity with the quantum dot-containing curable composition than the surrounding region, prior to the step of forming the quantum dot-containing layer, and a method of forming the quantum dot-containing layer by selectively attaching the quantum dot-containing curable composition to the quantum dot layer-containing region by an ink jet method is preferably used in the step of forming the quantum dot-containing layer.

This is because when the ink is attached to the quantum dot-containing layer forming region having a high affinity with the quantum dot-containing curable composition, that is, having a high ink affinity, the wetting and spreading properties of the ink are further improved, and therefore, discoloration and film thickness unevenness can be more effectively prevented, and a subpixel free from occurrence of bright spots or color unevenness can be obtained.

The step of selectively changing the wettability in a predetermined region of the substrate surface to form a quantum dot-containing layer-forming region having a higher ink affinity than the surrounding region is not particularly limited, and surface treatment such as plasma treatment as described above may be used. For example, when plasma treatment is performed in a gas containing a fluorine-based compound and oxygen, unreacted groups are generated on the surface of the inorganic material by plasma discharge, and the unreacted groups are oxidized by the oxygen to generate polar groups such as carbonyl groups and hydroxyl groups, thereby imparting ink affinity. On the other hand, in the organic material, a phenomenon occurs in which a fluorine-based compound enters the surface of the organic material in parallel with the above reaction. In particular, when the fluorine-based compound is larger than the oxygen gas, for example, in a gas atmosphere in which the amount of the fluorine-based compound is too large such that the content of the fluorine-based compound with respect to the total amount of the fluorine-based compound and the oxygen gas is 60% or more, the phenomenon of mixing of the fluorine-based compound is stronger than the oxidation reaction by the oxygen gas, and therefore the surface of the organic material is made nonpolar due to the phenomenon of mixing, and the ink repellency is imparted. Therefore, when the partition walls 2 or the projections are formed on the glass substrate with the organic material and then the plasma treatment is performed under the condition that the fluorine compound is excessively present as described above, the ink affinity of the glass substrate corresponding to the content dot layer forming region becomes higher than that of the surroundings, the partition walls 2 and the projections become ink repellent, and the projections become ink repellent projections 3. The quantum dot-containing layer-formed region thus obtained is easy to wet and spread with ink, and can prevent fading and film thickness unevenness, and can prevent ink from flowing out from the convex portion corresponding to the boundary with another ink-formed region. In this case, when the partition walls 2 are formed of an inorganic material and the projections are formed thereon of an organic material, the ink affinity between the glass substrate and the partition walls 2 increases, and the projections have ink repellency.

Manufacturing method of display device

The method for manufacturing a display device of the present invention includes the steps of:

a step of manufacturing an optical member by the method for manufacturing an optical member according to the present invention; and

and a step of mounting the optical member produced as described above.

The display device manufactured by the method for manufacturing a display device according to the present invention is not particularly limited as long as it is a display device including an optical member manufactured by the method for manufacturing an optical member according to the present invention, and the configuration thereof is appropriately selected from conventionally known display devices, and examples thereof include a micro LED display device, a quantum dot light emitting display device, a liquid crystal display device, and an organic light emitting display device. The manufacturing method of the present invention is particularly preferable as a manufacturing method of a micro LED display device and a quantum dot light emitting display device in terms of realizing high luminance and a wide color reproduction region.

< micro LED display device >

In the case where the micro LED display device is manufactured by the method for manufacturing a display device according to the present invention, the step of mounting the manufactured optical member may be, for example, a step of assembling the manufactured optical member to a counter substrate including a micro LED substrate in an opposed manner.

Such a micro LED display device obtained by the manufacturing method of the present invention will be described with reference to the drawings. Fig. 2 is a schematic diagram showing an example of a display device obtained by the manufacturing method of the present invention, and is a schematic diagram showing an example of a micro LED display device. As illustrated in fig. 2, the micro LED display device 200 has a structure in which the optical member (light conversion member) 100 of the present invention described above is bonded to the counter substrate 11 having the micro LED substrate. The optical member 100 of the micro LED display device 200 has the overcoat 9, and the surface of the optical member 100 on the overcoat 9 side is assembled in an opposed manner to the opposed substrate 11. In addition, the micro LED display device 200 has the optical member 100 having the sub-pixels 10R, 10G, 10B adjusted to red, green or blue. The sub-pixel 10R adjusted to red has a sub-dot-containing cured layer 7R containing quantum dots for displaying a red emission color, and has a functional layer 8 for blocking blue light between the substrate 1 and the sub-dot-containing cured layer 7R. The sub-pixel 10G adjusted to green has a sub-dot-containing cured layer 7G containing quantum dots for displaying a green emission color, and has a functional layer 8 for blocking blue light between the substrate 1 and the sub-dot-containing cured layer 7G. The sub-pixel 10B adjusted to blue has no sub-dot containing cured layer but has the functional layer 8.

The micro LED display device obtained by the manufacturing method of the present invention is not limited to the configuration shown in fig. 2, and may be a known configuration as a micro LED display device using a semiconductor optical member (light conversion member) in general.

In addition, the counter substrate may be appropriately selected and used according to the driving method of the micro LED display device of the present invention, and the like.

The micro LED display device obtained by the manufacturing method of the present invention is not limited to the one having the structure shown in fig. 2, and examples thereof include display devices having known structures described in japanese patent laid-open nos. 2016-523450 and 2016-533030.

< Quantum dot light emitting display device >

In the case of manufacturing a quantum dot light-emitting display device by the method for manufacturing a display device of the present invention, a TFT substrate may be used as a substrate for manufacturing the optical member, and the step of mounting the manufactured optical member may be, for example, a step of assembling a light-emitting body including the manufactured optical member and a color filter in an opposed manner.

Such a quantum dot light emitting display device obtained by the manufacturing method of the present invention will be described with reference to the drawings. Fig. 3 is a schematic diagram showing another example of a display device obtained by the manufacturing method of the present invention, and is a schematic diagram showing an example of a quantum dot light emitting display device. As illustrated in fig. 3, the quantum dot light emitting display device 300 has a color filter 40, and a light emitter 80 including the optical member 74 of the present invention. The organic protective layer 50 and the inorganic oxide film 60 may be provided between the color filter 40 and the light emitter 80.

Examples of the method of laminating the light emitter 80 include a method of sequentially forming the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the optical member 74 of the present invention, the electron injection layer 75, and the cathode 76 on the upper surface of the color filter 40, and a method of bonding the light emitter 80 formed on another substrate to the inorganic oxide film 60. In the light emitter 80, known configurations can be used as appropriate for the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the electron injection layer 75, the cathode 76, and other configurations. The Quantum Dot Light Emitting display device 300 manufactured in the above manner can also be applied to a Quantum Dot Light Emitting diode (QLED) display in a passive driving manner or a QLED display in an active driving manner, for example.

< liquid crystal display device >

In the case where a liquid crystal display device is manufactured by the method for manufacturing a display device according to the present invention, the step of mounting the manufactured optical member may be, for example, a step of assembling the manufactured optical member and a substrate for driving a liquid crystal in a manner facing each other.

Such a liquid crystal display device obtained by the manufacturing method of the present invention will be described with reference to the drawings. Fig. 4 is a schematic diagram showing another example of a display device obtained by the manufacturing method of the present invention, and is a schematic diagram showing an example of a liquid crystal display device. As illustrated in fig. 4, the liquid crystal display device 400 includes an optical member (light conversion member) 100 and a liquid crystal driving substrate having a liquid crystal layer 13 on one surface side of a counter substrate 12 such as a TFT array substrate, and the liquid crystal layer 13 is provided between the optical member (light conversion member) 100 and the counter substrate 12.

The liquid crystal display device of the present invention is not limited to the configuration shown in fig. 4, and may be a known configuration as a liquid crystal display device using a semiconductor optical member (light conversion member) in general.

The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method generally used for liquid crystal display devices can be employed. Examples of such a driving method include a TN (Twisted Nematic) method, an IPS (In-Plane Switching) method, an OCB (optically compensated bend) method, and an MVA (Multi-Domain Vertical Alignment) method. In the present invention, any of these methods can be preferably used.

In addition, the counter substrate can be appropriately selected and used according to the driving method of the liquid crystal display device of the present invention.

As a method for forming the liquid crystal layer, a method generally used for manufacturing a liquid crystal cell can be used, and examples thereof include a vacuum injection method, a liquid crystal dropping method, and the like.

< organic light emitting display device >

In the case where an organic light-emitting display device is manufactured by the method for manufacturing a display device according to the present invention, the step of mounting the manufactured optical member may be, for example, a step of preparing an organic light-emitting body including the manufactured optical member, and a step of assembling the organic light-emitting body and a color filter in an opposed manner.

An organic light-emitting display device obtained by the method for manufacturing a display device of the present invention has an organic light-emitting body including the above-described optical member (light-emitting member) of the present invention.

Such an organic light emitting display device of the present invention will be explained with reference to the accompanying drawings. Fig. 5 is a schematic view showing another example of a display device obtained by the manufacturing method of the present invention, and is a schematic view showing an example of an organic light emitting display device. As illustrated in fig. 5, the organic light emitting display device 500 has a color filter 40, and an organic light emitter 81 including an optical member (light emitting member) 74' of the present invention. The organic protective layer 50 and the inorganic oxide film 60 may be provided between the color filter 40 and the organic light emitter 81. In addition, the optical member (light-emitting member) of the present invention used for an organic light-emitting display device can be made into an optical member having sub-pixels having a content sub-dot cured layer, and sub-pixels having a light-emitting layer containing an organic light-emitting compound. As the organic light-emitting compound, an organic light-emitting compound used for a light-emitting layer of a known organic light-emitting display device can be used.

Examples of the method of laminating the organic light-emitting body 81 include a method of sequentially forming a transparent anode 71, a hole injection layer 72, a hole transport layer 73, an optical member (light-emitting member) 74' of the present invention which may have a light-emitting layer containing an organic light-emitting compound, an electron injection layer 75, and a cathode 76 on the upper surface of a color filter, and a method of bonding an organic light-emitting body 180 formed on another substrate to the inorganic oxide film 60. In the organic light-emitting body 81, known configurations of the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the electron injection layer 75, the cathode 76, and the like can be used as appropriate. The organic light emitting display device 500 manufactured in the above manner may be applied to, for example, an organic Electroluminescent (EL) display of a passive driving type and an organic EL display of an active driving type.

The organic light emitting display device of the present invention is not limited to the configuration shown in fig. 5, and may be a known configuration as a general organic light emitting display device.

Examples

The present invention will be specifically described below with reference to examples. The invention is not limited by these descriptions.

The weight average molecular weight was measured by Shodex GPC System-21H using polystyrene as a standard substance and THF as an eluent. The acid value was measured in accordance with JIS K0070.

Production example 1-1 Synthesis of epoxy group-containing copolymer A

In a four-necked flask equipped with a thermometer, a reflux condenser, a stirrer and a dropping funnel, 40.7 parts by mass of propylene glycol monomethyl ether acetate (hereinafter, may be referred to as PGMEA) was added in a mixing ratio shown in table 1, and the temperature was raised to 140 ℃ while stirring and heating. Subsequently, 54.7 parts by mass of a mixture (dropping component) of a monomer and a polymerization initiator having the compositions shown in Table 1 was dropped through a dropping funnel at a constant rate over 2 hours at a temperature of 140 ℃. After completion of the dropwise addition, the temperature was decreased to 110 ℃ and 4.6 parts by mass of a mixture of a polymerization initiator and PGMEA (additional catalyst component) was added, and 37.5 parts by mass of PGMEA was added at the time when the temperature of 110 ℃ was maintained for 2 hours to complete the reaction, thereby obtaining an epoxy group-containing copolymer a having the characteristics shown in table 1.

Production examples 1-2 Synthesis of epoxy group-containing copolymer B

An epoxy group-containing copolymer B having the characteristics shown in table 1 was obtained in the same manner as in production example 1-1, except that diethylene glycol monobutyl ether acetate (also referred to as BCA) was used instead of PGMEA in production example 1-1.

[ Table 1]

TABLE 1

The abbreviations in the table are as follows.

PGMEA: propylene glycol monomethyl ether acetate (boiling point: 146 ℃ C.)

BCA: diethylene glycol monobutyl ether acetate (boiling point: 247 ℃ C.)

GMA: glycidyl methacrylate

CHMA: cyclohexyl methacrylate

PERBUTYL O: tert-butyl peroxy (2-ethylhexanoate) (trade name manufactured by Nippon fat and oil Co., Ltd.)

Production example 2-1 Synthesis of adhesive acrylic resin A

A mixed solution was prepared containing 30 parts by mass of cyclohexyl methacrylate (CHMA), 25 parts by mass of 2-hydroxyethyl methacrylate (HEMA), 25 parts by mass of t-butyl methacrylate (t-BMA) and 20 parts by mass of Methyl Methacrylate (MMA). To the mixture was added PERBUTYL O2 parts by mass and n-dodecyl mercaptan 10 parts by mass, and the mixture was added dropwise to a polymerization vessel to which BCA 168 parts by mass was added at 100 ℃ for 3 hours under a nitrogen stream. After completion of the dropwise addition, the mixture was further heated at 100 ℃ for 3 hours to obtain a polymer solution containing the binder acrylic resin a as a polymer. The solid content in the polymer solution was 40 mass%, and the weight average molecular weight of the adhesive acrylic resin a was 13000.

Production example 3-1 Synthesis of adhesive acrylic resin B

A mixed solution of 48 parts by mass of cyclohexyl methacrylate (CHMA), 20 parts by mass of Methyl Methacrylate (MMA), 12 parts by mass of methacrylic acid (MAA), and 3 parts by mass of Azobisisobutyronitrile (AIBN) was added dropwise to a polymerization vessel to which 155 parts by mass of BCA was added under a nitrogen stream at 100 ℃ for 3 hours. After the completion of the dropwise addition, the mixture was further heated at 100 ℃ for 3 hours to obtain a polymer solution. The mass average molecular weight of the polymer solution was 7000.

Next, 200 parts by mass of Glycidyl Methacrylate (GMA), 0.2 parts by mass of triethylamine, and 0.05 parts by mass of p-methoxyphenol were added to the obtained polymer solution, and the mixture was heated at 110 ℃ for 10 hours, and air was bubbled through the reaction solution, thereby obtaining a binder acrylic resin B solution. The obtained adhesive acrylic resin B was a resin obtained by introducing a side chain having an olefinic double bond into a main chain formed by copolymerization of CHMA, MMA and MAA using GMA, and the solid content of the adhesive acrylic resin B solution was 40 mass%, and the acid value was 3 mgKOH/g. The weight average molecular weight of the adhesive acrylic resin B was 12000.

Production example 4-1 Synthesis of adhesive acrylic resin C

A binder acrylic resin C solution was obtained in the same manner as in the synthesis of the binder acrylic resin B of production example 3-1, except that CHMA was 40 parts by mass, MMA was 15 parts by mass, and MAA was 25 parts by mass. The obtained adhesive acrylic resin C was a resin obtained by introducing a side chain having an olefinic double bond into a main chain formed by copolymerization of CHMA, MMA, and MAA using GMA, and had a solid content of 40 mass% and an acid value of 74 mgKOH/g. In addition, the weight average molecular weight of the adhesive acrylic resin C was 12500.

Production example 5-1 Synthesis of adhesive acrylic resin D

A mixed solution of 64 parts by mass of styrene, 6 parts by mass of methacrylic acid (MAA), and 3 parts by mass of Azobisisobutyronitrile (AIBN) was added dropwise to a polymerization tank to which 125 parts by mass of BCA was added under a nitrogen stream at 100 ℃ for 3 hours. After the completion of the dropwise addition, the mixture was further heated at 100 ℃ for 3 hours to obtain a polymer solution. The weight average molecular weight of the polymer solution was 7000.

Next, 10 parts by mass of Glycidyl Methacrylate (GMA), 0.2 part by mass of triethylamine, and 0.05 part by mass of p-methoxyphenol were added to the obtained polymer solution, and the mixture was heated at 110 ℃ for 10 hours, and air was bubbled through the reaction solution, thereby obtaining a binder acrylic resin D solution. The obtained binder acrylic resin D was a resin obtained by introducing a side chain having an olefinic double bond into a main chain formed by copolymerization of styrene and MAA using GMA, and the solid content of the binder acrylic resin D solution was 40 mass%. The weight average molecular weight of the adhesive acrylic resin D was 10000.

Production example 6-1 Synthesis of adhesive acrylic resin E

A binder acrylic resin E solution was obtained in the same manner as in the production of the binder acrylic resin B of production example 3-1, except that CHMA was 34 parts by mass, MMA was 22 parts by mass, MAA was 22 parts by mass, and Glycidyl Methacrylate (GMA) was 22 parts by mass. The obtained adhesive acrylic resin E was a resin in which a side chain having an olefinic double bond was introduced into the main chain formed by copolymerization of CHMA, MMA, and MAA using GMA, and the solid content of the adhesive acrylic resin E was 40 mass%, and the acid value was 64 mgKOH/g. The weight average molecular weight of the adhesive acrylic resin E was 8700.

Production example 7-1 Synthesis of adhesive acrylic resin F

A polymer solution containing the binder acrylic resin F as a polymer was obtained in the same manner except that 30 parts by mass of CHMA, 25 parts by mass of HEMA, 25 parts by mass of t-BMA, 8.7 parts by mass of MMA, and 11.3 parts by mass of methacrylic acid (MAA) were used in the production of the binder acrylic resin a of production example 2-1. The polymer solution contained 40% by mass of solid content and had an acid value of 74 mgKOH/g. In addition, the weight average molecular weight of the adhesive acrylic resin F was 13000.

Production example 8-1 Synthesis of adhesive acrylic resin G

A polymer solution containing the adhesive acrylic resin G as a polymer was obtained in the same manner except that CHMA 9 parts by mass, dimethylaminoethyl methacrylate (DMMA)21 parts by mass, HEMA 25 parts by mass, t-BMA 25 parts by mass, and MMA 20 parts by mass were used in the production of the adhesive acrylic resin A of production example 2-1. The polymer solution contained 40% by mass of solid content and had an amine value of 75 mgKOH/g. In addition, the weight average molecular weight of the adhesive acrylic resin G was 13000.

Production examples 2-2 to 8-2 Synthesis of adhesive acrylic resins H to N

Binder acrylic resins H to N having the properties shown in Table 7 were obtained in the same manner as in production examples 2-1 to 8-1 except that PGMEA was used in place of BCA in production examples 2-1 to 8-1.

Production example 9-1 Synthesis of blocked Carboxylic acid curing agent A

In a four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, the respective components were added in the mixing ratios shown in table 2, and the temperature was raised to 70 ℃ while stirring and heating. Then, while keeping the temperature, the reaction was terminated when the acid value of the mixture became 3.0mgKOH/g or less by continuing stirring, thereby obtaining a blocked carboxylic acid curing agent A having the characteristics shown in Table 2.

Production example 9-2 Synthesis of blocked Carboxylic acid curing agent B

A blocked carboxylic acid curing agent B having the characteristics shown in Table 2 was obtained in the same manner as in production example 9-1 except that BCA was used in place of PGMEA in production example 9-1.

[ Table 2]

TABLE 2

(example 1)

(1) Preparation of adhesive composition

A Teflon (registered trademark) -coated rotor was added to the sample bottle and set in a magnetic stirrer. The epoxy group-containing copolymer a described in production example 1-1, a polyfunctional epoxy resin, and the like were added to the sample bottle in the following proportions, sufficiently stirred and dissolved at room temperature, and then a diluting solvent was added to adjust the viscosity so that the solid content became 40 mass%, stirred and dissolved, and then filtered to obtain an adhesive composition.

[ compounding ratio of adhesive composition ]

The epoxy group-containing copolymer A (40 mass% in solid content of PGMEA) of production example 1-1: 75 parts by mass

Polyfunctional epoxy resin (trade name jER154, manufactured by mitsubishi chemical corporation): 20 parts by mass

Neopentyl glycol glycidyl ether: 10 parts by mass

Blocked carboxylic acid curing agent A (solid content in PGMEA 70.8 mass%) of production example 9-1: 42 parts by mass

Dilution solvent (PGMEA): 77.3 parts by mass

(2) Preparation of composition curable with quantum dots

0.2 parts by mass of quantum dots (748056-25MG Merck), 49.51 parts by mass of the binder composition obtained above, and 50.29 parts by mass of the first solvent were sufficiently mixed to obtain a quantum dot-containing curable composition of example 1 having the compounding ratio shown in table 3.

(3) Production of optical component

A black matrix pattern having a line width of 20 μm and a film thickness of 5.0 μm was formed on a glass substrate (manufactured by Asahi glass Co., Ltd.) having a thickness of 0.7mm and 10cm × 10cm by photolithography using the curable resin composition for a black matrix.

The obtained curable composition containing a plurality of quantum dots was attached to the substrate in the region formed by the black matrix by an ink jet method.

Thereafter, the film was dried under reduced pressure at 10Torr for 120 seconds, and further prebaked on a hot plate at 80 ℃ for 10 minutes. Thereafter, the substrate was post-baked in a dust-free oven at 200 ℃ for 30 minutes, and further post-baked at 230 ℃ for 30 minutes, thereby forming a non-quantum dot cured layer (non-quantum dot cured product) having an average film thickness of 2.0 μm after drying and curing on the substrate, and an optical member was obtained.

(examples 2 to 6 and comparative examples 1 to 2 and 4)

Except that the solvents shown in table 3 were used in place of BCA in the preparation of the quantum dot curable composition containing (2) in example 1 so that the blend of the solvents in the quantum dot curable composition was the blend shown in table 3, the quantum dot curable compositions and optical members of examples 2 to 6 and comparative examples 1 to 2 and 4 were obtained in the same manner as in example 1.

(examples 7 and 8)

The content sub-point curable compositions and optical members of examples 7 and 8 were obtained in the same manner as in example 1, except that in the preparation of the adhesive composition of example 1, the composition of the adhesive components was changed so that the composition of the adhesive components became the composition shown in table 3, and a mixed solvent of PGMEA and BCA was used as a diluting solvent used for the adhesive composition in place of PGMEA so that the blending of the solvent in the content sub-point curable composition became the blending shown in table 3.

Comparative example 3

A content site curable composition and an optical member of comparative example 3 were obtained in the same manner as in example 1, except that in the preparation of the adhesive composition of example 1 (1), the composition of the adhesive component was changed so that the composition of the adhesive component was the same as that of example 7, and BCA was used instead of PGMEA as a diluting solvent used for the adhesive composition.

Comparative example 5

The content sub-point curable composition and the optical member of comparative example 5 were obtained in the same manner as in example 1, except that the composition of the adhesive component in example 1 was changed so that the composition of the adhesive component was the same as that of the adhesive component in example 7, BCA was used instead of PGMEA as a diluting solvent used for the adhesive composition, and ethyl acetate was used instead of BCA in the preparation of the content sub-point curable composition in example 1 (2).

(examples 9 to 11)

Except that a mixed solvent of PGMEA and BCA was used in place of BCA in the preparation of the quantum dot curable composition containing (2) in example 1 so that the blending of the solvent in the quantum dot curable composition was the blending shown in table 3, the quantum dot curable compositions and optical members of examples 9 to 11 were obtained in the same manner as in example 1.

(example 12)

The content sub-point curable composition and the optical member of example 12 were obtained in the same manner as in example 1, except that in the preparation of the adhesive composition of example 1, the composition of the adhesive component was changed so that the composition of the adhesive component was the same as that of the adhesive component of example 7, and a mixed solvent of PGMEA and BCA was used as a diluting solvent in place of PGMEA so that the blending of the solvent in the content sub-point curable composition was the blending shown in table 3.

(examples 13 to 16)

The content curable compositions and optical members of examples 13 to 16 were obtained in the same manner as in example 1 except that the composition of the binder component was changed so that the composition of the binder component was changed to the composition shown in table 4 in the preparation of the binder composition of example 1 (1), and the method for forming the content curable layer (content curable composition) in the production of the optical member of example 1 (3) was changed to the method described below.

< production of optical Member in embodiments 13 to 16 >

Thereafter, the film was dried under reduced pressure at 10Torr for 120 seconds, and further prebaked on a hot plate at 80 ℃ for 10 minutes. Thereafter, a conveyor type UV irradiation apparatus (manufactured by GS Yuasa) was used, and a high-output low-pressure mercury lamp was used to feed the glass at a feed rate of 1000mm/min and a feed rate of 1000mJ/cm²After the irradiation, post-baking was performed by heating at 200 ℃ for 30 minutes and further at 230 ℃ for 30 minutes in a dust-free oven, and a non-quantum dot cured layer (non-quantum dot cured product) having an average film thickness of 2.0 μm after drying and curing was formed on the substrate, thereby obtaining an optical member.

(examples 17 to 19, 24 and 29)

The curing compositions containing quantum dots and the optical members of examples 17 to 19, 24 and 29 were obtained in the same manner as in example 1 except that the composition of the binder component was changed to the composition shown in table 4 in the preparation of the binder composition (1) in example 1, and the materials and the compounding thereof were changed to the composition shown in table 4 in the preparation of the curing composition containing quantum dots in (2) in example 1.

Examples 20 to 23, 25 to 28, and 30 to 33

Examples 20 to 23, 25 to 28, and 30 to 33 were obtained in the same manner as example 1 except that the adhesive composition of example 1 was prepared by changing the composition of the adhesive component to the composition shown in table 4, the materials and the compounding thereof were changed so that the composition of the content sub-point curable composition was changed to the composition shown in table 4 in example 1 (2), and the content sub-point curable composition was prepared by changing the method of forming the content sub-point cured layer (content sub-point curable composition) to the same method as example 13 in example 1 (3).

(examples 34 to 37)

Other than changing the composition of the binder component to the composition shown in table 5 in the preparation of the binder composition (1) in example 1 and changing the materials and their blending so that the composition of the content sub-point curable composition to the composition shown in table 5 in the preparation of the content sub-point curable composition (2) in example 1, the content sub-point curable compositions and the optical members in examples 34 to 37 were obtained in the same manner as in example 1. Note that all of MEK (methyl ethyl ketone) of example 37 was contained in urethane resin (Nipporane 5253).

(examples 38 to 44)

Examples 38 to 44 of the content sub-point curable composition and the optical member were obtained in the same manner as example 1 except that the preparation of the binder composition of example 1 was changed such that the composition of the binder component was changed to the composition shown in table 5, the preparation of the content sub-point curable composition of example 1 (2) was changed such that the composition of the content sub-point curable composition was changed to the composition shown in table 5, and the materials and the compounding thereof were changed such that the composition of the content sub-point curable composition was changed to the composition shown in table 5, and the formation method of the content sub-point cured layer (content sub-point curable composition) was changed to the same method as example 13 in the preparation of the optical member of example 1 (3).

(example 45)

(1) Preparation of the Dispersion

A225 mL mayonnaise bottle was charged with 65 parts by mass of PGMEA and 33 parts by mass of an acrylic block resin (trade name, BYK-LPN6919, amine number 120mgKOH/g, BYK-Chemie Japan) (solid content 60%) and stirred. To this, 2 parts by mass of quantum dots (manufactured by 748056-25MG Merck) and 100 parts by mass of zirconia beads having a particle size of 2.0mm were added, and the mixture was shaken for 1 hour by a paint shaker (manufactured by Haitian Seisakusho Co., Ltd.) to prepare a pre-crushed mixture, and then changed to 200 parts by mass of zirconia beads having a particle size of 0.1mm and dispersed for 4 hours by a paint shaker to prepare a main crushed mixture, thereby obtaining a quantum dot dispersion.

(2) Preparation of composition curable with quantum dots

An adhesive composition was prepared in the same manner as in example 1 (1) except that the composition of the adhesive component was changed to the composition shown in table 5 except for the acrylic block resin. 10 parts by mass of the quantum dot dispersion, 4.95 parts by mass of the binder composition (solid content 40%) obtained above, and 47.32 parts by mass of first solvent BCA, 21.89 parts by mass of 2 nd solvent PGMEA, 13.86 parts by mass of multifunctional monomer DPHA, and 1841.98 parts by mass of photopolymerization initiator were sufficiently mixed to obtain a content-quantum dot curable composition of example 45 having a compounding ratio shown in Table 5.

(3) Production of optical component

In the production of the optical element, the method of forming the content sub-dot cured layer (content sub-dot curable composition) was set to be the same as in example 13, thereby obtaining an optical member of example 45.

Examples 46 to 49

Except that the composition of the binder component was changed so that it became the composition shown in table 6 in the preparation of the binder composition (1) in example 1, and that Ethyl 3-Ethoxypropionate (EEP) was used instead of BCA in the preparation of the non-quantum dot curable composition (2) in example 1 so that it became the composition shown in table 6, non-quantum dot curable compositions in examples 46 to 49 were obtained in the same manner as in example 1.

An optical member was obtained in the same manner as in example 1 except that the obtained respective content of the quantum dot curable composition was used and the temperature of the post-baking was changed to 150 ℃.

(examples 50 to 60)

Except that the composition of the binder component was changed so that it became the composition shown in table 6 in the preparation of the binder composition (1) in example 1, and further that the composition of the content sub-point curable composition (2) in example 1 was changed to EEP so that it became the composition shown in table 6 instead of BCA, the content sub-point curable compositions of examples 50 to 60 were obtained in the same manner as in example 1.

In addition, in the production of the optical element, the method of forming the sub-dot cured layer (sub-dot curable composition) was the same as in example 13, and the optical members of examples 50 to 60 were obtained.

(example 61)

A content sub-point curing composition of example 61 having the compounding ratio shown in Table 6 was obtained in the same manner as in example 45 except that in example 45, EEP was changed to the composition shown in Table 6 in place of BCA.

In the production of an optical element, the method of forming the non-quantum dot cured layer (non-quantum dot curable composition) was set to be the same as in example 13, thereby obtaining an optical member of example 61.

[ evaluation ]

(1) Ink ejection property

The above-obtained compositions containing a plurality of quantum dots for each of examples and comparative examples were evaluated for ink jet ejectability by the following methods. The evaluation results are shown in tables 3 to 6.

An ink (containing quantum dot curable composition) was filled into an ink jet head, discharged from the ink jet head, and dropped to the center of a forming region of a containing quantum dot curable layer on a transparent substrate made of glass, which is divided into predetermined patterns by providing partition walls, with a droplet diameter of 30 μm. Further, after the initial discharge was stopped and the ink jet head was allowed to stand still for 30 minutes, the ink jet head was dropped from the same ink jet head to the center of another region where the quantum dot curable layer was formed at a droplet diameter of 30 μm. In such intermittent discharge, the discharge performance (initial discharge performance) when the discharge operation is performed first and the discharge performance (intermittent discharge stability) when the discharge operation is performed again thereafter are observed and evaluated according to the following criteria.

[ evaluation criteria for initial discharge Property ]

AA: the ink can be discharged from all the holes of the ink-jet head.

A: the ink jet head has a small number of holes through which ink cannot be discharged.

B: the ink jet head has about half of the holes through which ink cannot be discharged.

C: almost all the holes of the ink jet head cannot discharge ink.

[ evaluation criteria for stability of intermittent discharge ]

AA: the ink can be discharged from all the holes of the ink-jet head.

C: almost all the holes of the ink jet head cannot discharge ink.

(2) Unevenness of the flow of water

The quantum dot-containing cured layers of the optical members of the examples and comparative examples obtained above were photographed, and unevenness was evaluated according to the following evaluation criteria. That is, as shown in fig. 6, the Blue LED is disposed at a position (a position facing the camera 20) where an imaging optical axis of the camera 20 extends through an imaging region of the optical member 100, and the entire surface of the optical member 100 is imaged by the camera 20 in a state where the Blue LED is irradiated from the back side to the quantum dot containing layer. The camera 20 performs imaging by tilting 70 to 80 degrees from a direction perpendicular to the substrate of the optical member. A Blue LED was used as the light source and a monochromatic line sensor camera was used as the camera. The evaluation results are shown in tables 3 to 6.

[ evaluation criteria for unevenness ]

AA: no unevenness at all

A: slight unevenness is partially visible

B: partially visible unevenness

C: visible unevenness of the entire surface

D: visible unevenness of the entire surface

(3) Quantum dot dispersibility

Sections obtained by cutting the optical members of each example and each comparative example obtained in the above were prepared to a width of 100nm, and the optical members were measured using a transmission electron microscope: tem (transmission electron microscopy) model TecnaiG2 spots, manufactured by FEI corporation) was observed at 5 ten thousand times the cut surface of the quantum dot-containing cured layer of the cut piece. The aggregation state of the quantum dots was observed in a visual field of 500nm × 500nm, and evaluated according to the following evaluation criteria. The evaluation results are shown in tables 3 to 6.

[ evaluation criteria for dispersibility of Quantum dots ]

AA: no agglomeration was observed

A: slight agglomeration was observed

B: partial agglomeration was observed

C: a large amount of aggregates was observed

In the table, the numerical values of the content ratios (mass ratios) of the components other than the solvent represent solid content conversion values.

The abbreviations in the tables are as follows.

748056-25 MG: quantum dot manufactured by Merck

776750-5 ML: quantum dot solution manufactured by Merck

790192-25 MG: quantum dot manufactured by Merck

776777-5 ML: quantum dot solution manufactured by Merck

jER 1001: multifunctional epoxy resin, trade name, product of Mitsubishi chemical corporation

jER157S 70: multifunctional epoxy resin, trade name, product of Mitsubishi chemical corporation

Nipporane 5253: urethane resin, trade name, Tosoh corporation

Coronate L: isocyanate curing agent, trade name, Tosoh corporation

Vylon 200: polyester resin, trade name, Toyo Boseki Kabushiki Kaisha

Vylon 802: polyester resin, trade name, Toyo Boseki Kabushiki Kaisha

MALKYD No. 1: maleic acid resin, trade name, manufactured by Mitsugaku chemical Co., Ltd

MALKYD No. 31: maleic acid resin, trade name, manufactured by Mitsugaku chemical Co., Ltd

BYK 6919: acrylic Block resin, trade name, BYK-LPN6919, BYK-Chemie Japan

DPPA: dipentaerythritol pentaacrylate

Irg 184: 1-hydroxy-cyclohexyl-phenyl-ketone Irgacure 184, manufactured by BASF

BCA: diethylene glycol monobutyl ether acetate

Solfit AC: acetic acid 3-methoxy-3-methylbutyl ester

Solfit: 3-methoxy-3-methyl-1-butanol

EEP: 3-Ethoxypropionic acid ethyl ester

PGMEA: propylene glycol monomethyl ether acetate

MEK: methyl ethyl ketone

[ summary of the results ]

As shown in tables 3 to 6, in examples 1 to 61 using a mixed solvent containing a first solvent having a boiling point of 165 ℃ or higher and 260 ℃ or lower and a second solvent having a boiling point of 100 ℃ or higher and lower than 165 ℃, the quantum dot curable composition was excellent in discharge stability in the inkjet method, and therefore aggregation of quantum dots in the formed quantum dot-containing cured layer was suppressed and unevenness was reduced.

On the other hand, in comparative examples 1 and 2, since only the second solvent was used as the solvent and the first solvent was not used, the discharge stability in the inkjet system was poor, and aggregation and unevenness of quantum dots were observed in the solidified layer.

In comparative example 3, since only the first solvent was used as the solvent and the second solvent was not used, aggregation and unevenness of the quantum dots were observed in the cured layer.

In comparative example 4, since a mixed solvent of the second solvent and a high boiling point solvent that does not correspond to either of the first solvent and the second solvent was used, aggregation and unevenness of the quantum dots were observed in the solidified layer.

In comparative example 5, since a mixed solvent of the first solvent and a low-boiling point solvent that does not correspond to either of the first solvent and the second solvent was used, the discharge stability in the inkjet method was poor, and aggregation and unevenness of quantum dots were observed in the solidified layer.

Further, as shown by comparison of examples 1 to 6, when 1 or more first solvents selected from the group consisting of diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 3-methoxy-3-methylbutyl acetate, 3-methoxybutyl acetate, and ethyl 3-ethoxypropionate were used as the first solvents, the dispersibility of the quantum dots was more excellent, and when 1 or more first solvents selected from the group consisting of diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 3-methoxy-3-methylbutyl acetate, and 3-methoxybutyl acetate were used, the dispersibility of the quantum dots was further improved.

Further, it is shown from the comparison of examples 1 and 9 to 11 and the comparison of examples 7, 8 and 12 that when the proportion of the first solvent is 30 mass% or more and 80 mass% or less and the proportion of the second solvent is 20 mass% or more and 70 mass% or less in the total solvent, the dispersibility of the quantum dot is more excellent and the unevenness is reduced.

Further, examples 13 to 16 show that even when a photocurable binder component is used, the discharge stability in the inkjet system is excellent, the dispersibility of the quantum dots is excellent, and the unevenness is reduced. Among them, in example 13 using the heat latent (meth) acrylic copolymer and example 16 using the styrene- (meth) acrylic copolymer, the dispersibility of the quantum dot was excellent.

Further, examples 17 and 18 show that even if the content of quantum dots in the quantum dot curable composition is increased, the discharge stability in the inkjet system is excellent, the dispersibility of quantum dots is excellent, and the variation is reduced.

Further, examples 19 to 33 show that even when the kind of the quantum dot contained in the quantum dot curable composition and the kind of the second solvent were changed, the discharge stability in the inkjet method was excellent, the dispersibility of the quantum dot was excellent, and the variation was reduced.

Further, examples 34 to 61 show that even when the type of the binder component and the type of the first solvent contained in the quantum dot curable composition were changed to a solvent (EEP) having a lower boiling point and capable of post-baking at a low temperature, the discharge stability in the inkjet system was excellent, the dispersibility of the quantum dots was excellent, and the unevenness was reduced. When the binder component contains a polymer having an amine value, the dispersibility of the quantum dots tends to be better.

Description of the reference numerals

1 substrate

2 spacer wall

3 ink repellent convex part

4-content sub-dot layer forming region

5 ink jet head

6 quantum dot containing layer

7-content quantum dot cured layer

7G, 7R content quantum dot cured layer

8 functional layer

9 outer coating

10R, 10G, 10B sub-pixel

11 opposed substrate

12 opposed substrate

13 liquid crystal layer

20 Camera

21 Blue LED

40 color filter

50 organic protective layer

60 inorganic oxide film

71 transparent anode

72 hole injection layer

73 hole transport layer

74. 74' optical component

75 electron injection layer

76 cathode

80 luminous body

81 organic light emitting body

100. 101 optical member

200 miniature LED display device

300 quantum dot light emitting display device

400 liquid crystal display device

500 organic light emitting display device

Claims

1. A quantum dot-containing curable composition comprising a curable binder component, quantum dots, and a solvent,

2. The thermosetting composition according to claim 1, wherein the solvent contains the first solvent in a proportion of 30% by mass or more and 80% by mass or less, and the second solvent in a proportion of 20% by mass or more and 70% by mass or less.

3. The set point curable composition according to claim 1 or 2, wherein the curable adhesive component contains at least 1 of a thermosetting adhesive component and a photocurable adhesive component.

4. The content molecular point curing composition according to any one of claims 1 to 3, wherein the first solvent is 1 or more selected from glycol ethers, glycol ether esters, aliphatic carboxylic acids, aliphatic esters, aromatic esters, dicarboxylic acid diesters, alkoxycarboxylic acid esters, ketocarboxylic acid esters, halocarboxylic acids, alcohols, phenols, aliphatic ethers, alkoxyalcohols, glycol oligomers, amino alcohols, alkoxyalcohol esters, ketones, morpholines, aliphatic amines, aromatic amines, halogenated aromatic hydrocarbons, and alkanes.

5. The content molecule curing composition according to any one of claims 1 to 4, wherein the second solvent is at least 1 selected from the group consisting of glycol ethers, glycol esters, aliphatic carboxylic acids, aliphatic carboxylic anhydrides, alcohols, ketones, alkanes, aromatic hydrocarbons, aromatic ethers, and aliphatic ethers.

6. The quantum dot curable composition of any one of claims 1 to 5, wherein the first solvent is selected from the group consisting of 3-methoxy-3-methyl-1-butanol, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 3-methoxy-3-methylbutyl acetate, diethylene glycol dibutyl ether, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, diisoamyl ether, 1, 8-cineole, diethyl adipate, dibutyl oxalate, dimethyl malonate, diethyl malonate, dimethyl succinate, diethyl succinate, 3-methoxybutyl acetate, methyl acetoacetate, cyclohexyl acetate, ethyl 3-ethoxypropionate, decane, undecane, n-butyl acetate, n, 1 or more of dodecane, tridecane and tetradecane.

7. The content quantum dot curable composition according to any one of claims 1 to 6, wherein the second solvent is 1 or more selected from the group consisting of ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, diethylene glycol dimethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, hexyl formate, ethyl lactate, isoamyl propionate, butyl butyrate, dimethyl oxalate, 1-butanol, 1, 4-dioxane, octane, nonane, toluene, xylene, ethylbenzene, and anisole.

8. A cured product containing a quantum dot, which is the cured product of the composition containing a quantum dot as defined in any one of claims 1 to 7.

9. A method for manufacturing an optical member, comprising the steps of:

forming a quantum dot-containing layer by selectively attaching the quantum dot-containing curable composition according to any one of claims 1 to 7 to a predetermined region on a substrate by an ink jet method; and

and a step of curing the quantum dot-containing layer to form a quantum dot-containing cured layer.

10. The method of manufacturing an optical member according to claim 9, further comprising, before the step of forming the quantum dot containing layer, the steps of:

a step of forming a quantum dot-containing layer-forming region having a higher affinity with the quantum dot-containing curable composition than the surrounding region by selectively changing the wettability in a predetermined region of the substrate surface; and is

In the step of forming the quantum dot-containing layer, the quantum dot-containing curable composition is selectively attached to the quantum dot-containing layer formation region by an ink jet method to form the quantum dot-containing layer.

11. The method for manufacturing an optical member according to claim 9 or 10, further comprising a step of drying the quantum dot-containing layer under reduced pressure.

12. A method of manufacturing a display device, comprising the steps of:

a step of manufacturing an optical member by the method of manufacturing an optical member according to any one of claims 9 to 11; and

and a step of mounting the manufactured optical member.