JP2021039334A - Quantum dot-containing composition - Google Patents

Abstract

To provide a quantum dot-containing composition containing quantum dots suitable for mass production and having particularly excellent pot life.SOLUTION: Disclosed quantum dot-containing composition contains polyfunctional (meth) acrylate, polyfunctional thiol, reaction retarder, and quantum dots. In the quantum dot-containing composition, the ratio of the number of moles of the (meth) acrylate group of the polyfunctional (meth) acrylate to the number of moles of the mercapto group of the polyfunctional thiol is preferably in a range of 0.6 or more and 9.0 or less. Disclosed quantum dot containing member is composed of cured quantum dot-containing composition.SELECTED DRAWING: None

Description

The present invention relates to a quantum dot-containing composition containing quantum dots.

In recent years, in the field of image display devices such as liquid crystal displays and smartphones, there is a strong demand for improving color reproducibility in order to obtain higher-definition images. As one of the means for improving the color reproducibility, for example, as shown in Patent Documents 1 and 2 below, the development of materials using quantum dots is being actively carried out.

Patent Document 2 discloses a method of obtaining white light by exciting quantum dots that emit red light and green light using blue LED light, and conventional white light is obtained by using the white light thus obtained. Compared with the case of using an LED, the color reproducibility can be significantly improved.

However, quantum dots are vulnerable to heat, water, light, oxygen, etc., and there is a problem that the emission characteristics of quantum dots deteriorate over time. In particular, the deterioration progresses remarkably with respect to water and oxygen. There was a problem of closing it.

In order to solve this problem, for example, in Patent Document 2, a resin composition containing quantum dots is cured to produce a resin film containing quantum dots (hereinafter referred to as quantum dot film), and the surface thereof is coated or vapor-deposited. A method for preventing quantum dots from being exposed to water and oxygen is disclosed by producing a laminated film sandwiched between barrier films provided with an airtight layer by the method.

However, the method disclosed in Patent Document 2 has a problem that coloring by the airtight layer deteriorates the optical physical characteristics, and the airtight layer is partially damaged during the production of the laminated film, resulting in partial airtightness. There is a problem that the optical properties deteriorate due to the deterioration of the film. Further, since the airtightness of the end portion of the laminated film is lower than that of the central portion of the laminated film, there is a problem that discoloration occurs with time from the end portion of the quantum dot film toward the inside.

Further, in Patent Document 3, a quantum dot film is produced by dispersing and curing quantum dots in a resin composition containing a (meth) allyl compound, a (meth) acrylic compound, a photopolymerization initiator, and a thioether oligomer, and patented. Similar to Document 2, a method for preventing quantum dots from being exposed to water and oxygen by producing a laminated film sandwiched between barrier films is disclosed.

However, it has been difficult for the method disclosed in Patent Document 3 to solve the same problems as in Patent Document 2. Further, since the (meth) allyl compound has lower reactivity than the (meth) acrylic compound, there is a problem that the unreacted (meth) allyl compound increases and the durability deteriorates.

Special table 2016-511709 Patent No. 5940079 International Publication No. 2018/0564669

The present invention has been made in view of the above situation, and an object of the present invention is to provide a quantum dot-containing composition containing quantum dots, which has an excellent pot life and is suitable for mass production.

The quantum dot-containing composition in the present invention contains a polyfunctional (meth) acrylate, a polyfunctional thiol, a reaction retarder, a quantum dot, a scattering agent, a dispersion resin, and a photopolymerization initiator, and the dispersion resin. The blending amount of the above is in the range of 0.1% by mass or more and 5% by mass or less with respect to 100% by mass of the sum of the polyfunctional (meth) acrylate and the polyfunctional thiol.

In the present invention, the dispersed resin is at least one selected from acrylic resin, polyurethane resin, polyester resin, and polyethyleneimine resin, and the functional group of the dispersed resin is a phosphoric acid group and an amino group. , And, it is preferable to be selected from at least one of the mercapto groups.

In the present invention, the ratio of the number of moles of the (meth) acrylate group of the polyfunctional (meth) acrylate to the number of moles of the mercapto group of the polyfunctional thiol is in the range of 1.52 or more and 9.0 or less. Is preferable.

In the present invention, it is preferable that the scattering agent contains fine particles having at least one of melamine and a benzoguanamine structure.

By using the quantum dot-containing composition of the present invention, it is possible to mass-produce, for example, a quantum dot-containing member having excellent durability, for example, without using a barrier layer. This makes it possible to contribute to the widespread use of display members and the like having excellent color reproducibility.

It is a schematic diagram of a quantum dot. It is a vertical sectional view of the quantum dot containing member which shows the 1st Embodiment in this invention. It is a vertical sectional view of the quantum dot containing member which shows the 2nd Embodiment of this invention. It is a vertical sectional view of the quantum dot containing member which shows the 3rd Embodiment of this invention. It is a perspective view of the quantum dot containing member of this embodiment. It is a vertical sectional view of the display device using the quantum dot containing member of this embodiment. It is a vertical cross-sectional view of the display device different from FIG. 6 using the quantum dot-containing member of this embodiment. It is a vertical sectional view of the light guide member using the quantum dot containing member of this embodiment. It is a vertical sectional view of the liquid crystal display element using the quantum dot containing member of this embodiment. It is a conceptual diagram which shows the manufacturing apparatus for manufacturing the quantum dot containing member of this embodiment.

Hereinafter, embodiments of the present invention will be described in detail, but the following description is an example (representative example) of the embodiments of the present invention, and the present invention is not limited to these contents as long as the gist thereof is not exceeded. In addition, the notation of "~" used below includes both the lower limit and the upper limit values within the range.

The present inventors have developed a composition of a quantum dot-containing composition capable of improving durability without using, for example, the (meth) allyl shown in Patent Document 3. That is, in the present embodiment, when the (meth) acrylate and the thiol are included, the polyfunctional (meth) acrylate and the polyfunctional thiol are used. A sufficient degree of cross-linking can be obtained as compared with monofunctionality, and excellent durability can be obtained. On the other hand, the use of polyfunctional (meth) acrylates and polyfunctional thiols makes the reaction very fast. Therefore, a reaction retarder is added to delay the reaction and obtain excellent pot life.

As described above, the quantum dot-containing composition in the present embodiment is characterized by containing a polyfunctional (meth) acrylate, a polyfunctional thiol, a reaction retarder, and quantum dots. Hereinafter, each substance contained in the quantum dot-containing composition will be described.

<Polyfunctional (meth) acrylate (A)>
The polyfunctional (meth) acrylate has two or more (meth) acrylate groups in one molecule. In the present embodiment, a cured film can be obtained by radically polymerizing a polyfunctional (meth) acrylate and a polyfunctional thiol (B) described later with a photopolymerization initiator (F) described later. This cured film can dramatically improve the durability of the quantum dots (D) described later. Further, in producing a quantum dot-containing member (for example, a laminated film) described later, it also has a function as an adhesive for bonding two plastic films to each other.

The polyfunctional monomer used in the present embodiment is not limited to the following, but is, for example, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, and diethylene glycol. Diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, polypropylene glycol diacrylate, neopentyl glycol diacrylate, neo Pentyl glycol PO-modified diacrylate, neopentyl glycol ester diacrylate of hydroxypivalate, caprolactone adduct diacrylate of neopentyl glycol ester of hydroxypivalate, 1,6-hexanediol bis (2-hydroxy-3-acryloyloxypropyl) ether , Bis (4-acryloxypolyethoxyphenyl) propane, 1,9-nonanediol diacrylate, pentaerythritol diacrylate, pentaerythritol diacrylate monostearate, pentaerythritol diacrylate monobenzoate, bisphenol A diacrylate, EO modified bisphenol A diacrylate, PO modified bisphenol A diacrylate, bisphenol F diacrylate, EO modified bisphenol F diacrylate, PO modified bisphenol F diacrylate, EO modified tetrabromobisphenol A diacrylate, tricyclodecanedimethylol diacrylate, isocyanuric acid EO Bifunctional acrylate monomers such as modified diacrylates, 2-hydroxy-1,3-diacryloxypropane;
Glycerin PO-modified triacrylate, trimethylolpropane triacrylate, trimethylolpropane EO-modified triacrylate, trimethylolpropane PO-modified triacrylate, isocyanuric acid EO-modified triacrylate, isocyanyl acid EO-modified ε-caprolactone-modified triacrylate, 1,3 Trifunctional acrylate monomers such as 5-triacryloylhexahydro-s-triazine, pentaerythritol triacrylate, dipentaerythritol triacrylate tripropionate;
Pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate monopropionate, dipentaerythritol hexaacrylate, tetramethylolmethane tetraacrylate, oligoester tetraaacrylate, tris (acryloyloxy) phosphate, etc. Acrylate monomer and the like can be mentioned. These may be used alone, or two or more kinds may be used in combination in any combination.

The average number of functional groups per molecule of the polyfunctional (meth) acrylate (A) used in the present embodiment is preferably 2 or more, more preferably 2.5 or more, still more preferably 3 or more. is there. When the number of functional groups is 2 or more, a sufficient degree of cross-linking can be obtained as a cured film, and excellent durability can be obtained.

<Polyfunctional thiol (B)>
The polyfunctional thiol (B) used in this embodiment has two or more mercapto groups in one molecule. The polyfunctional thiol (B) is used to impart an excellent oxygen barrier property as a cured film with the polyfunctional (meth) acrylate (A).

The polyfunctional thiol (B) used in the present embodiment is not limited to the following, but is, for example, ethylene glycol bis (3-mercaptopropionate) and diethylene glycol bis (3-mercaptopropionate). , Tetraethylene glycol bis (3-mercaptopropionate), 1,2-propylene glycol bis (3-mercaptopropionate), diethylene glycol bis (3-mercaptobutyrate), 1,4-butanediol bis (3-) Mercaptopropionate), 1,4-butanediol bis (3-mercaptobutyrate), 1,8-octanediol bis (3-mercaptopropionate), 1,8-octanediol bis (3-mercaptobutyrate) ), Hexadiol bisthioglycolate, Trimethylolpropanthris (3-mercaptopropionate), Trimethylolpropanthris (3-mercaptobutyrate), Trimethylolpropanthris (3-mercaptoisobutyrate), Trimethylolpropane Tristhioglycolate, Tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, 1,3,5-tris (3-mercaptobutylyloxyethyl) -1,3,5-triazine-2,4 6 (1H, 3H, 5H) -trione, trimethylol ethanetris (3-mercaptobutylate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate) 3-Mercaptoisobutyrate), Dipentaerythritol hexakis (3-mercaptopropionate), Dipentaerythritol hexasis (3-mercaptobutyrate), Dipentaerythritol hexasis (3-mercaptoisobutyrate), Penta Examples thereof include erythritol tetrakisthioglycolate and dipentaerythritol hexacisthioglycolate. These may be used alone, or two or more kinds may be used in combination in any combination.

The average number of functional groups per molecule of the polyfunctional thiol (B) used in the present embodiment is preferably 2 or more, more preferably 2.5 or more, still more preferably 3 or more. When the number of functional groups is 2 or more, a sufficient degree of cross-linking can be obtained as a cured film, and excellent durability can be obtained.

Ratio of the number of moles of the (meth) acrylate group of the polyfunctional (meth) acrylate (A) to the number of moles of the mercapto group of the polyfunctional thiol (B) used in the present embodiment (number of moles of acrylate group / mercapto group) The number of moles) is preferably in the range of 0.6 or more and 9.0 or less, more preferably in the range of 0.8 or more and 5.5 or less, and further preferably in the range of 1.0 or more and 2.5 or less. Is. When the molar ratio of the mercapto group to the (meth) acrylate group is in the range of 0.6 to 9.0, preferably in the range of 0.8 to 5.5, a film having a high crosslink density is formed after the curing reaction. , Excellent durability can be obtained.

<Reaction retarder (C)>
The reaction retarder (C) used in the present embodiment delays the reaction of the (meth) acrylate group and the mercapto group when the polyfunctional (meth) acrylate and the polyfunctional thiol are mixed, and has an excellent pot life. Is added to obtain.

The reaction retarder (C) used in the present embodiment is not limited to the following, and examples thereof include phenolic compounds, phosphorous acid compounds, and dithiocarbamate compounds. Above all, it is preferable to select at least one of a phosphorous acid-based compound and a dithiocarbamate-based compound from the viewpoint that excellent pot life can be obtained with a small amount of compounding. Examples of the phenolic compound include, but are not limited to, 4-methoxyphenol and hydroquinone. The phosphorous acid-based compound is not limited to the following, but for example, dimethyl phosphite, diethyl phosphite, dibutyl phosphite, diisopropyl phosphite, diisobutyl phosphite, diphenyl phosphite, Dibenzyl phosphite, bis phosphite (2,2,2-trifluoroethyl), trimethyl phosphite, triethyl phosphite, triisopropyl phosphite, tributyl phosphite, trihexyl phosphite, phosphite Examples thereof include triethylhexyl, trioctyl phosphite, triisodecyl phosphite, trilauryl phosphite, triphenyl phosphite, and tri-o-tolyl phosphite. The dithiocarbamate-based compound is not limited to the following, and includes, for example, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetraisopropylthiuram disulfide, tetrabutylthium disulfide, tetramethylthiuram monosulfide, and dipentamethylene thiuram tetrasulfide. And so on. These may be used alone, or two or more kinds may be used in combination in any combination.

In the present embodiment, it is more preferable to use a dithiocarbamate-based compound as the reaction retarder.

The amount of the reaction retarder (C) used in the present embodiment is 100% by mass of the sum of the polyfunctional (meth) acrylate (A) and the polyfunctional thiol (B), based on the reaction retarder (C). Is preferably contained in the range of 0.0005% by mass or more and 1% by mass or less, and more preferably 0.0005% by mass or more and 0.5% by mass or less. When the blending amount is 0.0005% by mass or more, a sufficient reaction delay effect can be obtained and a good pot life can be obtained. Further, when the blending amount is 0.5% by mass or less, the curing inhibition can be suppressed in the curing reaction process at the time of producing the quantum dot-containing member, and excellent durability can be obtained.

<Quantum dot (D)>
The quantum dots (D) used in the present embodiment are nanoparticles having a particle size of about several nm to several tens of nm, and are materials that absorb excitation light and emit light efficiently. The peak wavelength of light emission can be controlled by the composition and particle size of nanoparticles, and quantum dots that emit red light and green light are preferably used in the application of display materials. In some cases, quantum dots that emit blue light may be used, and quantum dots having a suitable wavelength can also be used in this embodiment.

The quantum dots (D) used in the present embodiment are not limited to the following, but are not limited to, for example, CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, Zn0, HgS, HgSe, HgTe, CdSeS, CdSeTe. , CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZeSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe II-VI group semiconductors such as;
GaN, GaP, GaAs, GaSb, AlN, AlP, AlP, AlAs, AlSb, InN, InP, InAs, InSb, PLAP, GaNAs, GaNSb, GaPAs, GaPSb, AINP, AINAs, AINSb, AIPAs, AIPSb, InNP, InNAs InNSb, InPAs, InPSb, GaAINP, GaAINAs, GaAINSb, GaAIPAs, GaAIPSb, GaAINAs, GaAINSb, GaAIPAs, GaAIPSb, GaInNP, GaInNAs, GaInNAsIn ;
SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSte, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSe, SnPbTe, SnPbSe, SnPbS, etc.
Group IV semiconductors such as Si, Ge, SiC, and SiGe;
Alternatively, semiconductors obtained by doping these with a metal element such as Mn can be mentioned. These may be used alone, or two or more kinds may be used in combination in any combination.

FIG. 1A shows a schematic diagram of the quantum dots 5. As shown in FIG. 1A, in order to suppress the aggregation of the quantum dots 5 used in the present embodiment and obtain excellent optical properties, a large number of organic ligands 6 are arranged on the surface of the quantum dots 5. It is preferable that the position is high.

The ligands used in this embodiment are not limited to the following, but for example, oleylamine: C ₁₈ H ₃₅ NH ₂ , stearyl (octadecyl) amine: C ₁₈ H ₃₇ NH ₂ , dodecyl ( Lauryl) amine: C ₁₂ H ₂₅ NH ₂ , decyl _{amine: C 10} H ₂₁ NH ₂ , octyl amine: C ₈ H ₁₇ NH _{2, and} other aliphatic amine compounds;
Fatty acid, oleic acid: C ₁₇ H ₃₃ COOH, stearic acid: C ₁₇ H ₃₅ COOH, palmitic acid: C ₁₅ H ₃₁ COOH, myristic acid: C ₁₃ H ₂₇ COOH, lauryl (dodecane) acid: C ₁₁ H ₂₃ COOH, Fatty acid compounds such as decanoic acid: C ₉ H ₁₉ COOH, octanoic acid: C ₇ H _{15 COOH;}
Octadecane thiol: C ₁₈ H ₃₇ SH, Hexane decane thiol: C ₁₆ H ₃₃ SH, Tetradecane thiol: C ₁₄ H ₂₉ SH, Dodecane thiol: C ₁₂ H ₂₅ SH, Decane thiol: C ₁₀ H ₂₁ SH, Octane thiol: C ₈ H ₁₇ SH and other thiol compounds;
Trioctylphosphine: (C ₈ H ₁₇ ) ₃ P, triphenylphosphine: (C ₆ H ₅ ) ₃ P, tributyl phosphine: (C ₄ H ₉ ) ₃ P
Phosphine oxides, trioctylphosphine oxides: (C ₈ H ₁₇ ) ₃ P = O, triphenylphosphine oxides: (C ₆ H ₅ ) ₃ P = O, tributylphosphine oxides: (C ₄ H ₉ ) ₃ P = O And the like phosphine meter compounds and the like.
These may be used alone, or two or more kinds may be used in combination in any combination.

As shown in FIG. 1B, the quantum dot 5 used in the present embodiment has a core shell composed of a core portion 5a and a shell portion 5b from the viewpoint of high quantum efficiency of light emission and excellent stability to light, oxygen, and the like. It is preferable to have a structure. The combination of materials of the core-shell structure is not limited to the following, and examples thereof include CdS / ZnS, CdSe / ZnS, CdSeS / ZnSe, InP / ZnS, PbSe / PbS, CdTe / ZnS, and the like. , CdS / ZnSeS / ZnS, CdSe / ZnSeS / ZnS, and the like, the shell portion 5b may have a multi-layered structure. The quantum dot 5 may be composed of only one of these types, or two or more types may be used in combination in any combination. In FIG. 1B, the boundary between the core portion 5a and the shell portion 5b is shown by a dotted line, which means that the boundary between the core portion 5a and the shell portion 5b does not have to be clearly confirmed by analysis. .. Further, the shell portion 5b may be in a state of being dissolved on the surface of the core portion 5a.

The quantum dots (D) used in the present embodiment include quantum dots exhibiting green emission having a peak wavelength of 520 to 560 nm (hereinafter referred to as green quantum dots) and red having a peak wavelength of 600 to 680 nm. Quantum dots that emit light (hereinafter referred to as red quantum dots) are preferably used. On the other hand, blue light having a peak wavelength of 430 nm to 480 nm is irradiated as excitation light, and the green quantum dots and red quantum dots that absorb the blue light emit green and red light, and further, the blue light transmitted without being absorbed. White light can be obtained by combining. Further, in order to balance the intensities of blue light, green light, and red light, quantum dots exhibiting blue light emission having a peak wavelength of 430 nm to 480 nm may be used.

The blending amount of the quantum dots (D) used in the present embodiment is 0.03% by mass or more with respect to 100% by mass of the sum of the polyfunctional (meth) acrylate (A) and the polyfunctional thiol (B). The range is preferably in the range of mass% or less, and more preferably in the range of 0.05 mass% or more and 1 mass% or less. As described above, when the blending amount of the quantum dots (D) is in the range of 0.03 to 2% by mass, sufficient emission intensity derived from the quantum dots can be obtained.

<Scattering agent (E)>
In this embodiment, the scattering agent (E) can be further included. The scattering agent (E) used in the present embodiment can scatter the excitation light of the quantum dots (D), and as a result, the optical path length can be extended, and as a result, the quantum dots emit light efficiently. The strength can be increased.

Examples of the scattering agent (E) used in the present embodiment include an organic scattering agent, an inorganic scattering agent, and an organic-inorganic hybrid scattering agent. The organic scattering agent used in the present embodiment is not limited to the following, but for example, polystyrene-based fine particles, polymethyl methacrylate-based fine particles, polyurethane-based fine particles, polyethylene-based fine particles, polypropylene-based fine particles, and the like. Examples thereof include resin fine particles such as melamine-based fine particles and benzoguanamine-based fine particles. These may be used alone, or two or more kinds may be used in combination in any combination. Further, these are generally obtained by heterogeneous polymerization such as suspension polymerization, and may be crosslinked inside the particles or have a functional group such as an acrylate group on the surface.

The inorganic scattering agent used in the present embodiment is not limited to the following, but is limited to silica particles such as colloidal silica, fumed silica, and precipitated silica, alumina particles, zirconia particles, titania particles, and oxidation. Examples thereof include inorganic oxides such as zinc particles, talc, mica, kaolin, clay and the like. These may be used alone, or two or more kinds may be used in combination in any combination. Further, these may be those whose particle surface is treated with a silane coupling agent or the like.

The organic-inorganic hybrid used in the present embodiment is not limited to the following, and examples thereof include silica fine particle-encapsulating resin fine particles, titania-encapsulating resin fine particles, and silica-modified resin fine particles. These may be used alone, or two or more kinds may be used in combination in any combination.

The scattering agent (E) used in the present embodiment has a melamine and benzoguanamine structure from the viewpoint that the scattering efficiency is high because of its high refractive index and the quantum yield is high because of its high transparency. It is preferable to use fine particles having at least one of them.

The blending amount of the scattering agent (E) used in the present embodiment is 0.05% by mass or more and 10% by mass or more with respect to 100% by mass of the sum of the polyfunctional (meth) acrylate (A) and the polyfunctional thiol (B). The range of mass% or less is preferable, and the range of 0.1 mass% or more and 8 mass% or less is more preferable.

<Photopolymerization initiator (F)>
In the present embodiment, it is preferable to further contain the photopolymerization initiator (F). The photopolymerization initiator (F) used in the present embodiment is used to efficiently proceed the curing reaction by cross-linking the polyfunctional (meth) acrylate (A) and the polyfunctional thiol (B). To. At the time of the curing reaction, it is preferable to use active energy rays such as ultraviolet rays and electron beams, and more preferably ultraviolet rays. Wavelength and irradiation amount of actinic radiation may be appropriately set, for example, ultraviolet rays having a wavelength of ^{280~400nm, 100mJ / cm 2 ~5000mJ /} cm 2, can be irradiated. Examples of the light source for generating ultraviolet rays include known light sources such as low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, and xenon lamps. These may be used alone, or two or more kinds may be used in combination in any combination.

As the photopolymerization initiator (F) used in the present embodiment, a known photopolymerization initiator can be used, for example, diethoxyacetophenone, 2-hydroxy-1-phenylpropan-1-one, benzyl. Methyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane -1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane, oligo {2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone}, Acetphenones such as 2-hydroxy-1- {4- (2-hydroxy-2-methylpropionyl) benzyl} phenyl} -2-methylpropan-1-one;
Benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether;
Phosphines such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide;
Other examples include phenylglycoxymethyl ester. These may be used alone, or two or more kinds may be used in combination in any combination.

The blending amount of the photopolymerization initiator (F) used in the present embodiment is 0.05% by mass with respect to 100% by mass of the sum of the polyfunctional (meth) acrylate (A) and the polyfunctional thiol (B). It is preferably in the range of 5% by mass or less, and more preferably 0.1% by mass or more and 4% by mass or less.

In the present embodiment, a photosensitizer can be used in combination with the photopolymerization initiator (F) for the purpose of further enhancing the curability. Known photosensitizers can be used as the photosensitizers, for example, unsaturated ketones such as chalcone derivatives and dibenzalacetones, 1,2-diketones such as benzyl and camphorquinone, and benzoin derivatives. , Fluolene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonor derivatives and other polymethine dyes, acrydin derivatives, azine derivatives, thiazine derivatives , Oxazine derivative, Indolin derivative, Azulene derivative, Azurenium derivative, Squalylium derivative, Porphyrin derivative, Tetrapyrazinoporphyrazine derivative, Phthalocyanin derivative, Tetraazaporphyrazine derivative, Tetraquinoxalyloporphyrazine derivative, Naphthalocyanine derivative, Subphthalocyanine derivative , Pyrylium derivative, Thiopyrylium derivative, Tetraphyllin derivative, Anurene derivative, Spiropyran derivative, Spiroxazine derivative, Thiospyropyrane derivative, Metal arene complex, Organic ruthenium complex, Michler ketone derivative, Biimidazole derivative and the like. These may be used alone or in combination of two or more.

The blending amount of the photosensitizer used in the present embodiment is 0.05% by mass or more and 5% by weight with respect to 100% by mass of the sum of the polyfunctional (meth) acrylate (A) and the polyfunctional thiol (B). It is preferably in the range of% or less.

<Dispersed resin (G)>
In the present embodiment, it is preferable to further contain the dispersed resin (G). The dispersion resin (G) used in the present embodiment improves the compatibility of the quantum dots (D) and the scattering agent (E) with the polyfunctional (meth) acrylate (A) and the polyfunctional thiol (B). It is used for the purpose of making it. By improving the compatibility, it is possible to suppress in-plane variation in the brightness of the cured film made of the quantum dot-containing composition, and it is possible to suppress a decrease in the emission quantum yield due to aggregation of the quantum dots (D).

The dispersion resin (G) used in the present embodiment is not limited to the following, but is, for example, acrylic resin, polyurethane resin, polyester resin, polyolefin resin, polycarbonate resin, polyethylene imine. Examples thereof include based resins, epoxy resins, and thioether resins. In particular, at least one selected from acrylic resin, polyurethane resin, polyester resin, and polyethyleneimine resin from the viewpoint of excellent compatibility with polyfunctional (meth) acrylate (A) and polyfunctional thiol (B). Is preferable.

The acrylic resin used in the present embodiment is known such as radical polymerization, living radical polymerization, anionic polymerization, cationic polymerization, etc. of a monomer having an unsaturated group such as a (meth) acrylate group, a vinyl group, and an allyl group. It is obtained by polymerizing by the polymerization method of.

The urethane-based resin used in the present embodiment is obtained by subjecting a polyol and a polyisocyanate to a urethanization reaction using a known method.

The polyester resin used in the present embodiment is obtained by subjecting a polybasic acid and a polyol to an esterification reaction using a known method, or by ring-opening polymerization of a cyclic ester compound such as caprolactone or butyrolactone by a known method. can get.

The polyolefin-based resin is obtained by polymerizing an olefin-based monomer such as ethylene, propylene, butene, and isobutene by a known polymerization method such as coordination polymerization.

The polycarbonate resin can be obtained by reacting a polyol with a polyfunctional carbonate such as diethyl carbonate by a carbonated reaction using a known method.

The polyethyleneimine-based resin is obtained by ring-opening polymerization of an aziridine compound. Further, for example, a polyester resin grafted polyethyleneimine resin obtained by reacting a cyclic ester compound with an amino group generated after the reaction and performing ring-opening polymerization can also be used.

The epoxy resin is obtained by ring-opening polymerization of a compound having two or more glycidyl groups using a known method.

Further, from the viewpoint that excellent compatibility can be effectively obtained by adsorbing to the quantum dots (D) and the scattering agent (E), the dispersion resin (G) contains a carboxyl group, a sulfonic acid group, and a phosphoric acid. It preferably has a polar functional group such as a group, an amino group, a mercapto group, or a hydroxyl group, and more preferably a phosphoric acid group, an amino group, or a mercapto group. These are preferable not only in that excellent compatibility can be obtained, but also in that the emission quantum yield of the quantum dots (D) can be increased.

The blending amount of the dispersed resin (G) used in the present embodiment is 0.1% by mass or more with respect to 100% by mass of the sum of the polyfunctional (meth) acrylate (A) and the polyfunctional thiol (B). The range is preferably 0% by mass or less, and more preferably 0.2% by mass or more and 4% by mass or less.

In the present embodiment, it is known as a diluting solvent for the quantum dots (D), as a reaction solvent during the synthesis of the dispersed resin (G), or for the purpose of adjusting the viscosity at the time of coating the quantum dot-containing composition. You may use the organic solvent of. It is preferable that the known organic solvent is removed in a step during the curing process described later.

The solvent used in the present embodiment is not limited to the following, but is, for example, an ester solvent such as ethyl acetate, propyl acetate and butyl acetate, and a ketone solvent such as acetone, methyl ethyl ketone and methyl isobutyl ketone. , Ether solvents such as dioxane and tetrahydrofuran, aliphatic hydrocarbon solvents such as n-hexane, cyclohexane and methylcyclohexane, aromatic hydrocarbon solvents such as toluene and xylene, alcohol solvents such as methanol, ethanol and isopropanol. Examples thereof include amide-based solvents such as dimethylformamide and water. These may be used alone, or two or more kinds may be used in combination in any combination.

The quantum dot-containing composition in the present embodiment described in detail above contains a polyfunctional (meth) acrylate (A), a polyfunctional thiol (B), a reaction initiator (C), and a quantum dot (D). More preferably, the composition contains at least one of a scattering agent (E), a photopolymerization initiator (F), and a dispersion resin (G). The blending amount of each of these substances is as described above.

As the quantum dot-containing composition used in the present embodiment, known additives can be used depending on the intended purpose as long as the effects of the present embodiment are not impaired. Known additives include, for example, antioxidants, UV absorbers, antistatic agents, lubricants, surface modifiers, viscosity modifiers and the like. These may be used alone, or two or more kinds may be used in combination in any combination.

<Quantum dot-containing member>
As shown in FIG. 2, by curing the quantum dot-containing composition of the present embodiment, for example, a film-shaped quantum dot-containing member 1 containing the quantum dots (D) can be obtained.

Further, as shown in FIG. 3, for example, by forming a quantum dot layer (ink layer) 3 obtained by curing a quantum dot-containing composition on a base film 2 such as plastic, the quantum dots are contained in a laminated structure. Member 1 can be obtained. Further, the quantum dot-containing member 1 may form the quantum dot layer 3 on one side of the base film 2, but when applied to a backlight device described later, the quantum dot layer 3 may be in the form of a film. Preferably, from the viewpoint of excellent durability of the quantum dots (D), as shown in FIG. 4, the quantum dot-containing member 1 is laminated by laminating a base film 2 on both sides of a film-shaped quantum dot layer 3. It is preferably a structure. When the base film 2 and the quantum dot layer 3 are bonded to each other, a known adhesive may be used for bonding, or the quantum dot-containing composition itself of the present embodiment may be used as an adhesive. It may be bonded by curing.

FIG. 5 shows an example of a schematic diagram of the quantum dot-containing member 1 used in the present embodiment. In FIG. 5, the quantum dot-containing member 1 is formed in a thin plate shape (sheet shape, film shape) having a length dimension L, a width dimension W, and a thickness dimension T, and L, W, which are most suitable for the application. It can be changed to T. The quantum dot-containing member 1 may be formed to have a constant thickness, the thickness may be deformed depending on the location, the shape may gradually change in the length direction or the width direction, or the shape may change stepwise. It may be.

Further, the quantum dot-containing member 1 used in the present embodiment is formed by curing the quantum dot-containing composition, so that the quantum dot-containing member 1 is located closer to the end (edge) of the quantum dot-containing member 1 as compared with the conventional case. It is possible to effectively suppress the deterioration of the quantum dot layer over time and the fading of the quantum dot layer. The reason why deterioration can be suppressed by this embodiment is that the obtained quantum dot layer is a cured film having a high cross-linking density due to the polyfunctional (meth) acrylate (A) and the polyfunctional thiol (B), and the polyfunctionality. It is considered that thiol (B) can effectively suppress the invasion of oxygen.

The base film 2 of the quantum dot-containing member 1 used in the present embodiment is not limited to the following, but for example, polyester, polypropylene, polyethylene, polystyrene, AS resin, ABS resin, acrylic resin, and the like. Methacrylic resin, polyvinyl chloride, polyacetal, polyamide, polycarbonate, modified polyphenylene ether, polybutylene terephthalate, polyethylene terene terephthalate, polysulfone, polyether sulfone, polyphenylene sulfide, polyamideimide, polymethylpentene, liquid crystal polymer, epoxy resin, phenol resin , Uria resin, melamine resin, epoxy resin, diallyl phthalate resin, unsaturated polyester resin, polyimide, polyurethane, silicone resin, styrene-based thermoplastic elastomer and the like. These may be used alone, or two or more kinds may be used in combination in any combination. Among them, polyester is preferable, and polyethylene terephthalate is more preferable, from the viewpoint of excellent light transmission, thermal stability, dimensional stability, and adhesion between the base film 2 and the quantum dot layer 3. In order to improve the adhesion between the quantum dot layer 3 and the base film 2, the surface of the base material (the surface that adheres to the quantum dot layer 3) is subjected to pretreatment such as plasma treatment, corona treatment, and ozone treatment. Alternatively, an adhesive layer may be provided between the quantum dot layer 3 and the base film 2.

The average thickness of the base film 2 of the quantum dot-containing member 1 used in the present embodiment is not limited to the following, but is preferably in the range of, for example, 50 to 150 μm, and more preferably. It is in the range of 70 to 140 μm. The average thickness of the base film 2 is obtained from the average value of the values obtained by measuring the thickness of the base film 2 at three or more points using, for example, a micrometer.

The surface (outer surface) of the base film of the quantum dot-containing member 1 used in the present embodiment may be matted in order to efficiently take in excitation light and extract light emission.

The total light transmittance of the quantum dot-containing member 1 used in the present embodiment is preferably 55% or more, more preferably 65% or more. The total light transmittance is determined by measuring in accordance with the measurement method of JIS K 7136: 2000.

The haze value of the quantum dot-containing member 1 in the present embodiment is preferably 85% or more, more preferably 90% or more, still more preferably 95, from the viewpoint that the excitation light can be used efficiently. % Or more. The haze value is obtained by measuring in accordance with the measurement method of JIS K 7136: 2000.

The quantum dot-containing member 1 of the present embodiment can be incorporated into, for example, the backlight device 55 shown in FIG. In FIG. 6, the backlight device 55 includes a plurality of light emitting elements 20 (LEDs) and a quantum dot-containing member 1 of the present embodiment facing the light emitting elements 20. As shown in FIG. 6, each light emitting element 20 is supported on the surface of the support 52. In FIG. 6, the backlight device 55 is arranged on the back surface side of the display unit 54 such as a liquid crystal display to form the display device 50.

Although not shown in FIG. 6, even if a diffuser plate for diffusing light, another sheet, or the like is interposed between the light emitting element 20 and the display unit 54 in addition to the quantum dot-containing member 1. Good.

Further, although the quantum dot-containing member 1 shown in FIG. 6 is formed of one piece, for example, a plurality of quantum dot-containing members 1 may be joined together so as to have a predetermined size. Hereinafter, a configuration in which a plurality of quantum dot-containing members 1 are connected by tiling is referred to as a composite quantum dot-containing member.

Here, the composite quantum dot-containing member is arranged in place of the quantum dot-containing member 1 of the display device 50 of FIG. 6, and the diffuser plate is arranged between the light emitting element 20 and the composite quantum dot-containing member, that is, The configuration of the light emitting element 20 / diffusion plate / composite quantum dot-containing member / display unit 54 will be considered. In such a configuration, the light radiated from the light emitting element 20 and diffused by the diffuser plate is incident on the composite quantum dot-containing member. Since the light diffused by the diffusing plate is incident on the composite quantum dot-containing member, the light intensity distribution depending on the distance from the light emitting element 20 is suppressed. Further, since the distance between the light emitting element 20 and the composite quantum dot-containing member is longer than that without the diffuser plate, the influence of the heat generated by the light emitting element 20 on the quantum dots (D) contained in the composite sheet is small. Become.

On the other hand, as shown in FIG. 7, the light emitting element 20 / composite quantum dot-containing member 21 / diffusion plate 22 / display unit 54 can be arranged in this order. According to this, even if the joint of each quantum dot-containing member 1 has uneven emission color due to diffused reflection or deterioration of the quantum dots due to water vapor entering from the joint, the display unit 54 displays the display. It is possible to appropriately suppress the occurrence of color unevenness. That is, since the light emitted from the composite quantum dot-containing member 21 is diffused by the diffusing plate 22 and then incident on the display unit 54, color unevenness in the display of the display unit 54 can be suppressed.

When the composite quantum dot-containing member 21 is used, it is preferable to arrange a diffusion plate on the light emitting surface side of the composite quantum dot-containing member 21 regardless of the application to the display device shown in FIG.

Alternatively, as shown in FIG. 8, the quantum dot-containing member 1 of the present embodiment may be provided on the surface of the light guide plate 40 to form the light guide member. As shown in FIG. 8, a light emitting element 20 (LED) is arranged on the side surface of the light guide plate 40.

Alternatively, as shown in FIG. 9, the quantum dot-containing member 1 of the present embodiment can be incorporated into the liquid crystal display element 60 having the structure shown in FIG. The liquid crystal display element 60 of FIG. 9 is shown from the bottom of the drawing, for example, a light guide plate 61, a diffusion sheet 62, a prism sheet 63, a diffusion sheet 64, a polarizing plate 65, a retardation film 66, a glass substrate / liquid crystal / color filter, and the like. The liquid crystal cell 67, the retardation film 68, and the polarizing plate 69 are laminated in this order. Although not limited to this, the quantum dot-containing member 1 of the present embodiment is provided between, for example, the light guide plate 61 and the diffusion sheet 62. The liquid crystal display element of FIG. 9 is an edge type in which LED light is incident from the side, but may be a direct type in which a plurality of LEDs are arranged directly below. The direct type is used for large displays and the like.

The use of the quantum dot-containing member 1 of the present embodiment is not limited to FIGS. 6 to 9.

The quantum dot-containing member 1 used in the present embodiment can effectively suppress a change in emission intensity with time as compared with the conventional case. Therefore, the wavelength conversion characteristics when the quantum dot-containing member 1 of the present embodiment is used for the backlight device 55, the light guide member, the liquid crystal display element, etc. can be stabilized, and the backlight device 55, the light guide member, and the like can be stabilized. The life of the liquid crystal display element can be extended.

The quantum dot-containing member 1 used in the present embodiment can be in the form of a flexible sheet. Therefore, the quantum dot-containing member 1 can be appropriately installed on a curved surface or the like.

The quantum dot-containing member 1 of the present embodiment can be applied not only to the backlight device, the light guide member, and the liquid crystal display element described above, but also to a lighting device, a light source device, a light diffusing device, a light reflecting device, and the like.

The quantum dot-containing member 1 used in the present embodiment can secure, for example, a normalized illuminance of 0.6 or more after 1000 hours of a durability test. It is preferable to secure a standardized illuminance of 0.75 or more, more preferably a standardized illuminance of 0.85 or more, and further preferably a standardized illuminance of 0.9 or more. Can be done.

FIG. 10 shows a conceptual diagram showing a manufacturing apparatus for manufacturing the quantum dot-containing member 1 of the present embodiment. FIG. 10 discloses an example of a method for manufacturing a quantum dot-containing member 1 formed by forming a quantum dot layer 3 by applying a quantum dot-containing composition to a base film 2 and curing it, as shown in FIG. ing.

As shown in FIG. 10, the first raw fabric roll 30a for feeding out the resin film 10a serving as the base film 2 and the second raw fabric roll 30b for feeding out the resin film 10b also serving as the base film 2 are wound up. It is composed of a roll 32, a joint portion 35 composed of a pair of nip rolls 33 and 34, a coating means 36, a drying portion 38, and a curing reaction portion 41.

As shown in FIG. 10, the resin film 10a is sent out from the first raw fabric roll 30a, and the quantum dot-containing composition 37 containing the quantum dots (D) is coated on the surface of the resin film 10a by using the coating means 36. To do. Examples of the coating method of the quantum dot-containing composition 37 include a coating method using a known coating coater or an impregnation coating coater. For example, a gravure coater, a curtain coater, a dip coater, a comma knife coater, a die coater, a roll coater, and the like can be exemplified.

As shown in FIG. 10, the resin film 10a coated with the quantum dot-containing composition 37 on the surface is heated by the drying portion 38 in which a heating device such as a heater or a hot air oven is installed, and the solvent contained therein is volatilized. To do. When the quantum dot-containing composition 37 does not contain a solvent, the drying portion 38 may not be used.

Next, at the joining portion 35, the interface between the quantum dot-containing composition 37 applied to the resin film 10a and the resin film 10b sent from the second raw fabric roll 30b is joined by a crimping device. At the time of joining, temperature may be applied if necessary. If the quantum dot layer 3 is not sandwiched between the resin film 10a and the resin film 10b, it is not necessary to perform the above joining operation.

Next, a quantum dot layer 3 (see FIG. 4) that has been cured by being irradiated with active energy rays by a curing reaction unit 40 in which an active energy ray irradiation device such as an ultraviolet irradiation device or an electron beam irradiation device is installed is formed. The activation energy ray irradiation may be performed before or after the joining step at the joining portion 35.

Then, the sheet-shaped quantum dot-containing member 39 made of the resin film 10a / quantum dot layer 3 / resin film 10b is wound by the winding roll 32. By cutting the wound quantum dot-containing member 39 to a predetermined size, the quantum dot-containing member 1 having a predetermined shape shown in FIG. 4 can be obtained. The quantum dot-containing composition 37 of the present embodiment has an excellent pot life, and the quantum dot-containing member 39 can be mass-produced.

The quantum dot-containing member 1 of the present embodiment can be aged for an appropriate time in an environment of an appropriate aging temperature in order to allow the curing reaction to proceed completely. The appropriate aging temperature is not limited to the following, but is preferably in the range of 20 to 60 ° C, more preferably in the range of 30 to 50 ° C. The appropriate aging time is preferably in the range of 6 to 48 hours, more preferably in the range of 10 to 24 hours.

The average thickness of the quantum dot layer 3 in the quantum dot-containing member 1 of the present embodiment is not limited to the following, but is preferably in the range of 20 to 250 μm, more preferably in the range of 50 to 200 μm, and even more preferably. Is in the range of 70 to 140 μm. When the average thickness is 20 to 250 μm, sufficient wavelength conversion efficiency can be obtained. The average thickness of the quantum dot layer 3 in the quantum dot-containing member 1 is, for example, the average of two minutes of the base film used from the average thickness obtained by measuring the thickness of the quantum dot-containing member 1 at three or more points using a micrometer. Calculated by subtracting the thickness.

In each of the above embodiments, a film-shaped quantum dot-containing member has been exemplified, but the shape is not limited to this. For example, the glass capillary is filled with the quantum dot-containing composition used in the present invention, or a stick-shaped object in which a cured product of the quantum dot-containing composition is inserted, or the LED surface is coated with the quantum dot-containing composition by potting or the like. It is possible to present a quantum dot-containing member or the like obtained by curing a quantum dot-containing composition by a form or an inkjet method.

Hereinafter, the effects of the present invention will be described with reference to Examples and Comparative Examples of the present invention. The present invention is not limited to the following examples.

<Measurement of number average molecular weight>
The number average molecular weight was measured by gel permeation chromatography (GPC) using the dispersed resin (G) as a sample. If the sample is soluble in tetrahydrofuran, tetrahydrofuran is used as the eluent, and the column temperature is set to 40 ° C. and the flow rate is set by the HLC-8220GPC system manufactured by Tosoh Corporation in which two columns of TSKgel superHZM-N are connected as a measuring device. The measurement was carried out under the condition of 0.35 ml / min. The sample was prepared by dissolving 2 mg of the sample in 5 ml of the above eluate. The number average molecular weight was calculated in terms of standard polystyrene. The number average molecular weight was not calculated for the sample that was insoluble in the eluent or the sample that could not be measured due to adsorption on the column or the like.

<Measurement of quantum yield>
Using the quantum dots (D) and quantum dot-containing members, which will be described later, as samples, the quantum yield of light emission was measured using an absolute PL quantum yield measuring device (Quantumus-QY C11347-01 manufactured by Hamamatsu Photonics Co., Ltd.) with an excitation wavelength of 450 nm. It was measured. For the quantum dots (D), a toluene solution prepared so that the absorbance at 450 nm when using a 1 cm cell was 1 was used as a sample.

<Measurement of emission peak wavelength and half width>
Using the quantum dots (D) described later as a sample, the peak wavelength and full width at half maximum of emission were measured using a spectrofluorometer (manufactured by JASCO Corporation, FP-8500) with an excitation wavelength of 450 nm. For the quantum dots (D), a toluene solution prepared so that the absorbance at 450 nm when using a 1 cm cell was 1 was used as a sample.

<Measurement of viscosity>
Using the quantum dot-containing composition described later as a sample, the viscosity was measured under 25 ° C. conditions using a B-type viscometer (TVB-10M, manufactured by Toki Sangyo Co., Ltd.).

<Measurement of film thickness>
The thickness of the obtained quantum dot-containing member, which will be described later, was determined from the average value of values measured at three or more points using a micrometer (Mitutoyo Co., Ltd., high-precision digital micrometer MDH-25MB).

<Measurement of total light transmittance and haze>
Measurement of JIS K 7136: 2000 using a spectroscopic haze meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., SH7000) using a sample of the obtained quantum dot-containing member described later cut to a width of 50 mm and a length of 50 mm. In accordance with the law, the total light transmittance and the haze value were measured three times. Then, the values averaged three times were used as the total light transmittance and the haze value.

<Quantum dot (D)>
In the experiment, a powder of quantum dots (hereinafter referred to as green quantum dots) having an emission peak wavelength of 530 nm (green), a half-price width of 30 nm, and a quantum yield of 90% of emission in a toluene solution, and an emission peak. Quantum dots (hereinafter referred to as red quantum dots) having a wavelength of 630 nm (red), a half-price width of 30 nm, and a quantum yield of light emission in a toluene solution of 90% were used.

<Manufacturing of dispersed resin (G)>
Dispersed resins (G-1) to (G-6) were produced according to the methods shown below. Table 1 shows the raw materials produced, the blending amount, and the properties of the obtained dispersed resin.

<Manufacturing example (1)>
25.8 parts of toluene and 56.6 parts of n-butyl methacrylate (manufactured by Tokyo Kasei Co., Ltd.) while blowing nitrogen gas into a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping tube, and nitrogen introduction tube. 3.5 parts of pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by Tokyo Kasei Co., Ltd.) was charged and stirred at room temperature for 30 minutes. Then, after raising the temperature to 90 ° C., a solution prepared by dissolving 0.02 part of 2,2'-azobis (isobutyronitrile) in 2.5 parts of toluene was added dropwise over 6 hours, and then 90 ° C. The polymerization reaction was carried out by further stirring for 3 hours. Then, after cooling to room temperature, the reaction solution was taken out, and the solvent was removed by vacuum drying to obtain a solid dispersion resin (G-1). The term "part" means "part by mass". The same applies to the following experiments.

The dispersed resin (G-1) thus obtained was an acrylic resin having a mercapto group having a number average molecular weight of 2500.

<Manufacturing example (2)>
25.7 parts of toluene and 28.9 parts of n-butyl methacrylate (manufactured by Tokyo Kasei Co., Ltd.) while blowing nitrogen gas into a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping tube, and nitrogen introduction tube. 28.9 parts of 2-ethylhexyl methacrylate and 2.1 parts of pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by Tokyo Kasei Co., Ltd.) were charged, and the mixture was stirred at room temperature for 30 minutes. Then, after raising the temperature to 90 ° C., a solution prepared by dissolving 0.02 part of 2,2'-azobis (isobutyronitrile) in 2.5 parts of toluene was added dropwise over 6 hours, and then 90 ° C. The polymerization reaction was carried out by further stirring for 3 hours. Then, after cooling to room temperature, the reaction solution was taken out, and the solvent was removed by vacuum drying to obtain a viscous liquid of the dispersed resin (G-2).

The dispersed resin (G-2) thus obtained was an acrylic resin having a mercapto group having a number average molecular weight of 3300.

<Manufacturing example (3)>
86.9 parts of pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by Tokyo Kasei Co., Ltd.) were charged in a reaction vessel equipped with a stirrer, thermometer, reflux condenser, nitrogen introduction pipe, and vacuum pipe, and vacuumed while stirring. The inside of the reaction vessel was depressurized with a pump and held for 30 minutes. Then, 13.0 parts of tris (2-acryloyloxyethyl) isocyanurate (manufactured by Tokyo Kasei Co., Ltd.) heated to 60 ° C. with stirring was added, and after stirring until uniform, 0.1 part of triethylamine was added. Then, the stirring reaction was carried out for 3 hours to obtain a viscous liquid of the dispersed resin (G-3).
The dispersed resin (G-3) thus obtained was a thioether-based resin having a mercapto group having a number average molecular weight of 2100.

<Manufacturing example (4)>
As the dispersion resin (G-4), SOLPERSE 24000GR (manufactured by Japan Lubrizol Co., Ltd., a polyethyleneimine-based resin having an amino group) was used.

<Manufacturing example (5)>
As the dispersion resin (G-5), Azisper PB821 (manufactured by Ajinomoto Fine-Techno Co., Ltd., a polyester resin having an amino group) was used.

<Manufacturing example (6)>
As the dispersion resin (G-6), DISPERBYK-111 (manufactured by Big Chemie Japan Co., Ltd., a polyester resin having a phosphoric acid group) was used.

<Manufacturing of quantum dot-containing composition>
Quantum dot-containing compositions (X-1) to (X-21) were produced according to the methods shown below. Tables 2 and 3 show the blending amount of the raw materials used in the production and the results of the following pot life evaluation.

<Experimental example 1>
As the polyfunctional (meth) acrylate (A), 60 parts of A-DCP (dimethylol-tricyclodecanediacrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd., (meth) acrylate group amount 6.58 mmol / g), polyfunctional thiol (B) ), 40 parts of EGFP-4 (manufactured by SC Organic Chemical Co., Ltd., tetraethylene glycol bis (3-mercaptopropionate), mercapto group amount 5.38 mmol / g), and hydroquinone (Tokyo Kasei Kogyo) as a reaction retarder (C). Eposter MS (manufactured by Nippon Catalyst Co., Ltd., benzoguanamine / formaldehyde condensation) as 1 part, quantum dots (D), 0.4 parts of green quantum dots, 0.07 parts of red quantum dots, and scattering agent (E). Lightly blend 5 parts of particle), 0.3 part of Irgacure 184 (manufactured by BASF) as a photopolymerization initiator (F), and 1.37 parts of dispersion resin (G-1) as a dispersion resin (G). After shaking by hand, stirring was performed with a homodisper until the whole was uniform. The ratio of the number of moles of the (meth) acrylate group of the polyfunctional (meth) acrylate (A) to the number of moles of the mercapto group of the polyfunctional thiol (B) in the quantum dot-containing composition (X-1) thus obtained is It was 1.84.

<Experimental example 2>
50 parts of A-TMPT (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trimethylolpropane triacrylate, (meth) acrylate group amount 10.0 mmol / g) as polyfunctional (meth) acrylate (A), Shikou UV-7650B (synthesized in Japan) , Urethane acrate resin, acrylate group amount 0.0004 parts), TMMP (manufactured by SC Organic Chemical Co., Ltd., trimethylolpropane tris (3-mercaptopropionate), mercapto group amount as polyfunctional thiol (B) 7.53 mmol / g) 45 parts, trimethylolpropane phosphite (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a reaction retarder (C) 0.5 parts, quantum dots (D) 0.4 parts green quantum dots , 0.07 parts of red quantum dots, 5 parts of Epostal MS (made by Nippon Catalyst Co., Ltd., benzoguanamine / formaldehyde condensate particles) as a scattering agent (E), and Irgacure 184 (manufactured by BASF) as a photopolymerization initiator (F). Was blended in 0.6 parts, shaken lightly by hand, and then stirred with a homodisper until the whole became uniform. The ratio of the number of moles of the (meth) acrylate group of the polyfunctional (meth) acrylate (A) to the number of moles of the mercapto group of the polyfunctional thiol (B) in the quantum dot-containing composition (X-2) thus obtained is , 1.48.

<Experimental example 3>
20 parts of A-TMPT (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trimethylolpropane triacrylate, (meth) acrylate group amount 10.0 mmol / g) as polyfunctional (meth) acrylate (A), AD-TMP (New Nakamura Chemical Co., Ltd.) 30 parts of ditrimethylolpropane tetraacrylate, (meth) acrylate group group amount 8.51 mmol / g manufactured by Kogyo Co., Ltd., PEMP (SC Organic Chemical Co., Ltd., pentaerythritol tetrakis (3-mercaptopro) as polyfunctional thiol (B) Pionate), mercapto group amount 8.19 mmol / g) 50 parts, tetraethylthiolam disulfide (manufactured by Tokyo Chemical Industry Co., Ltd.) as a reaction retarder (C) 0.002 parts, and green quantum dots as quantum dots (D). 0.4 part, red quantum dot 0.07 part, techpolymer MBX-5 (crossed polymethylmethacrylate particles manufactured by Sekisui Chemical Co., Ltd.) as a scattering agent (E), 5 parts, photopolymerization initiator ( Add 0.2 parts of Irgacure 184 (manufactured by BASF) as F) and 1.37 parts of dispersion resin (G-4) as dispersion resin (G), shake lightly by hand, and then use homodisper to make the whole. Stirring was performed until uniform. The ratio of the number of moles of the (meth) acrylate group of the polyfunctional (meth) acrylate (A) to the number of moles of the mercapto group of the polyfunctional thiol (B) in the quantum dot-containing composition (X-3) thus obtained is , 1.12.

<Experimental Example 4>
As the polyfunctional (meth) acrylate (A), 45 parts of AD-TMP (ditrimethylolpropanetetraacrylate manufactured by Shin-Nakamura Chemical Co., Ltd., (meth) acrylate group group amount 8.51 mmol / g), polyfunctional thiol (B) As PEMP (SC Organic Chemical Co., Ltd., pentaerythritol tetrakis (3-mercaptopropionate), mercapto group amount 8.19 mmol / g), 40 parts, DPMP (SC Organic Chemical Co., Ltd., dipentaerythritol hexakiss (3-) Mercaptopropionate), mercapto group amount 7.66 mmol / g) as 15 parts, triphenyl phosphite (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as reaction retarder (C) 0.3 parts, as quantum dots (D) , 0.4 parts of green quantum dots, 0.07 parts of red quantum dots, 0.25 parts of D-918 (manufactured by Sakai Chemical Industry Co., Ltd., rutyl type titanium oxide) as a scattering agent (E), opt beads 2000M ( 4 parts of melamine resin / silica composite particles manufactured by Nissan Chemical Co., Ltd., 0.3 parts of Irgacure TPO (manufactured by BASF) as a photopolymerization initiator (F), and dispersed resin (G-6) as a dispersed resin (G). Was mixed in 1.37 parts, shaken lightly by hand, and then stirred with a homodisper until the whole became uniform. The ratio of the number of moles of the acrylate group of the polyfunctional (meth) acrylate (A) to the number of moles of the mercapto group of the polyfunctional thiol (B) in the quantum dot-containing composition (X-4) thus obtained was 0. It was 87.

<Experimental Example 5>
80 parts of A-TMPT (trimethylolpropane triacrylate, (meth) acrylate group amount 10.0 mmol / g) manufactured by Shin-Nakamura Chemical Industry Co., Ltd. as the polyfunctional (meth) acrylate (A), as the polyfunctional thiol (B) 20 parts of TMMP (SC Organic Chemical Co., Ltd., trimethylolpropane tris (3-mercaptopropionate), mercapto group amount 7.53 mmol / g), tetraethylthiolam disulfide (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a reaction retarder (C) ) Is 0.001 part, the quantum dot (D) is 0.4 part, the red quantum dot is 0.07 part, and the scattering agent (E) is D-918 (manufactured by Sakai Chemical Industry Co., Ltd., R type). 0.2 parts of titanium oxide), 6 parts of opt beads 2000M (manufactured by Nissan Chemical Co., Ltd., melamine resin / silica composite particles), 0.8 parts of Irgacure TPO (manufactured by BASF) as a photopolymerization initiator (F), 1.37 parts of the dispersed resin (G-6) was blended as the dispersed resin (G), shaken lightly by hand, and then stirred with a homodisper until the whole became uniform. The ratio of the number of moles of the (meth) acrylate group of the polyfunctional (meth) acrylate (A) to the number of moles of the mercapto group of the polyfunctional thiol (B) in the quantum dot-containing composition (X-5) thus obtained is It was 5.31.

<Experimental example 6>
As polyfunctional (meth) acrylate (A), 50 parts of A-TMPT (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trimethylolpropane triacrylate, (meth) acrylate group amount 10.0 mmol / g), A-DPH (New Nakamura Chemical Co., Ltd.) 5 parts of dipentaerythritol hexaacrylate manufactured by Kogyo Co., Ltd., (meth) acrylate group amount 0.010 mmol / g) as polyfunctional thiol (B) PEMP (manufactured by SC Organic Chemical Co., Ltd., pentaerythritol tetrakis (3-mercaptopropio) Nate), mercapto group amount 8.19 mmol / g) 35 parts, DPMP (SC Organic Chemical Co., Ltd., dipentaerythritol hexakis (3-mercaptopropionate), mercapto group amount 7.66 mmol / g) 10 parts, As the reaction retarder (C), 0.3 part of triphenyl phosphite (manufactured by Tokyo Kasei Kogyo Co., Ltd.), as the quantum dot (D), 0.4 part of green quantum dot, 0.07 part of red quantum dot, 7 parts of Epostal MS (benzoguanamine / formaldehyde condensate particles manufactured by Nippon Catalyst Co., Ltd.) as a scattering agent (E), 0.8 parts of Irgacure 184 (manufactured by BASF) as a photopolymerization initiator (F), and a dispersion resin (G). ), 1.37 parts of the dispersed resin (G-3) was blended, shaken lightly by hand, and then stirred with a homodisper until the whole became uniform. The ratio of the number of moles of the (meth) acrylate group of the polyfunctional (meth) acrylate (A) to the number of moles of the mercapto group of the polyfunctional thiol (B) in the quantum dot-containing composition (X-6) thus obtained. Was 1.52.

<Experimental Example 7>
As polyfunctional (meth) acrylate (A), 50 parts of A-TMPT (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trimethylolpropane triacrylate, (meth) acrylate group amount 10.0 mmol / g), AD-TMP (New Nakamura Chemical Co., Ltd.) 15 parts of trimethylolpropane triacrylate, (meth) acrylate group amount 10.0 mmol / g) manufactured by Kogyo Co., Ltd., as polyfunctional thiol (B), PEMP (manufactured by SC Organic Chemical Co., Ltd., pentaerythritol tetrakis (3-mercaptopropio) Nate), 35 parts of mercapto group amount 8.19 mmol / g), 0.002 parts of tetraethylthium disulfide (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a reaction retarder (C), and green quantum dots as quantum dots (D). 0.4 parts, 0.07 parts of red quantum dots, 1.0 part of D-918 (manufactured by Sakai Chemical Industry Co., Ltd., rutyl-type titanium oxide) as a scattering agent (E), as a photopolymerization initiator (F) 0.4 parts of Irgacure 184 (manufactured by BASF), 1.0 part of dispersion resin (G-1) as dispersion resin (G), and 1.37 parts of dispersion resin (G-6) are blended lightly by hand. After shaking, stirring was performed with a homodisper until the whole was uniform. The ratio of the number of moles of the (meth) acrylate group of the polyfunctional (meth) acrylate (A) to the number of moles of the mercapto group of the polyfunctional thiol (B) in the quantum dot-containing composition (X-7) thus obtained is , 2.19.

<Example 8>
As polyfunctional (meth) acrylate (A), 40 parts of A-TMPT (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trimethylolpropane triacrylate, (meth) acrylate group amount 10.0 mmol / g), AD-TMP (New Nakamura Chemical Co., Ltd.) 15 parts of ditrimethylolpropane tetraacrylate (meth) acrylate group amount (8.51 mmol / g) manufactured by Kogyo Co., Ltd., as polyfunctional thiol (B), Karenz MT PE1 (manufactured by Showa Denko Co., Ltd., pentaerythritol tetrakis (3-mercapto)) Butylate), mercapto group amount 7.34 mmol / g) 45 parts, tetraethylthium disulfide (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a reaction retarder (C) 0.002 parts, and green quantum dots as quantum dots (D). 0.4 part, red quantum dot 0.07 part, as a scattering agent (E), 5 parts of Epostal MS (benzoguanamine / formaldehyde condensate particles manufactured by Nippon Catalyst Co., Ltd.), and Irgacure as a photopolymerization initiator (F). Mix 0.3 parts of 184 (manufactured by BASF) and 1.37 parts of dispersion resin (G-2) as dispersion resin (G), shake lightly by hand, and then use homodisper until the whole becomes uniform. Stirring was performed. The ratio of the number of moles of the (meth) acrylate group of the polyfunctional (meth) acrylate (A) to the number of moles of the mercapto group of the polyfunctional thiol (B) in the quantum dot-containing composition (X-8) thus obtained is , 1.60.

<Example 9>
As polyfunctional (meth) acrylate (A), 50 parts of A-TMPT (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trimethylolpropane triacrylate, (meth) acrylate group amount 10.0 mmol / g), AD-TMP (New Nakamura Chemical Co., Ltd.) 10 parts of ditrimethylolpropane tetraacrylate, (meth) acrylate group amount (8.51 mmol / g) manufactured by Kogyo Co., Ltd., as polyfunctional thiol (B), PEMP (manufactured by SC Organic Chemical Co., Ltd., pentaerythritol tetrakis (3-mercaptopro) Pionate), mercapto group amount 8.19 mmol / g) 40 parts, tetraethylthiolam disulfide (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a reaction retarder (C) 0.003 parts, and green quantum dots as quantum dots (D). 0.4 parts, red quantum dots 0.07 parts, as a scattering agent (E), D-918 (Sakai Chemical Industry Co., Ltd., rutyl type titanium oxide) 0.2 parts, Optobeads 2000M (Nissan Chemical Co., Ltd.) , Melamine resin / silica composite particles) 4.5 parts, Irgacure 184 (manufactured by BASF) as a photopolymerization initiator (F) 0.2 parts, Irgacure TPO 0.1 parts, as a dispersed resin (G) 1.37 parts of the dispersed resin (G-4) was blended, shaken lightly by hand, and then stirred with a homodisper until the whole became uniform. The ratio of the number of moles of the (meth) acrylate group of the polyfunctional (meth) acrylate (A) to the number of moles of the mercapto group of the polyfunctional thiol (B) in the quantum dot-containing composition (X-9) thus obtained is It was 1.79.

<Experimental Example 10>
As polyfunctional (meth) acrylate (A), 50 parts of A-TMPT (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trimethylolpropane triacrylate, (meth) acrylate group amount 10.0 mmol / g), AD-TMP (New Nakamura Chemical Co., Ltd.) 10 parts of ditrimethylolpropane tetraacrylate, (meth) acrylate group amount (8.51 mmol / g) manufactured by Kogyo Co., Ltd., as polyfunctional thiol (B), PEMP (manufactured by SC Organic Chemical Co., Ltd., pentaerythritol tetrakis (3-mercaptopro) Pionate), mercapto group amount 8.19 mmol / g) 40 parts, tetraethylthiolam disulfide (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a reaction retarder (C) 0.003 parts, and green quantum dots as quantum dots (D). 0.4 parts, red quantum dots 0.07 parts, as a scattering agent (E), D-918 (Sakai Chemical Industry Co., Ltd., rutyl type titanium oxide) 0.2 parts, Optobeads 2000M (Nissan Chemical Co., Ltd.) , Melamine resin / silica composite particles) 4.5 parts, Irgacure 184 (manufactured by BASF) as a photopolymerization initiator (F) 0.2 parts, Irgacure TPO 0.1 parts, as a dispersed resin (G) 1.37 parts of the dispersed resin (G-5) was blended, shaken lightly by hand, and then stirred with a homodisper until the whole became uniform. The ratio of the number of moles of the acrylate group of the polyfunctional (meth) acrylate (A) to the number of moles of the mercapto group of the polyfunctional thiol (B) in the quantum dot-containing composition (X-10) thus obtained is 1. It was 79.

<Experimental Example 11>
As polyfunctional (meth) acrylate (A), 50 parts of A-TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd., trimethylolpropane triacrylate, (meth) acrylate group amount 10.0 mmol / g), AD-TMP (New Nakamura Chemical Co., Ltd.) 10 parts of ditrimethylolpropane tetraacrylate, (meth) acrylate group amount (8.51 mmol / g) manufactured by Kogyo Co., Ltd., as polyfunctional thiol (B), PEMP (manufactured by SC Organic Chemical Co., Ltd., pentaerythritol tetrakis (3-mercaptopro) Pionate), mercapto group amount 8.19 mmol / g), DPMP (SC Organic Chemical Co., Ltd., dipentaerythritol hexakis (3-mercaptopropionate), mercapto group amount 7.66 mmol / g) 10 parts , 0.003 parts of tetraethylthium disulfide (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as the reaction retarder (C), 0.4 parts of green quantum dots and 0.07 parts of red quantum dots as quantum dots (D), scattered. As the agent (E), 0.2 part of D-918 (manufactured by Sakai Chemical Industry Co., Ltd., rutyl type titanium oxide), 4.5 parts of Optobeads 2000M (manufactured by Nissan Chemical Co., Ltd., melamine resin / silica composite particles), light Lightly blend 0.2 parts of Irgacure 184 (manufactured by BASF) as the polymerization initiator (F), 0.1 part of Irgacure TPO, and 1.37 parts of the dispersion resin (G-6) as the dispersion resin (G). After shaking by hand, stirring was performed with a homodisper until the whole was uniform. The ratio of the number of moles of the (meth) acrylate group of the polyfunctional (meth) acrylate (A) to the number of moles of the mercapto group of the polyfunctional thiol (B) in the quantum dot-containing composition (X-11) thus obtained is It was 1.82.

<Experimental Example 12>
As the polyfunctional (meth) acrylate (A), 100 parts of A-TMPT (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trimethylolpropane triacrylate, (meth) acrylate group amount 10.0 mmol / g) was used as the reaction retarder (C). Tetraethylthium disulfide (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as 0.002 parts, quantum dots (D) as 0.4 parts, red quantum dots as 0.07 parts, and scatter agent (E) as eposter MS 5 parts (benzoguanamine / formaldehyde condensate particles manufactured by Nippon Catalyst Co., Ltd.), 0.4 parts of Irgacure 184 (manufactured by BASF) as a photopolymerization initiator (F), and a dispersion resin (G-6) as a dispersion resin (G). ) Was blended in 1.37 parts, shaken lightly by hand, and then stirred with a homodisper until the whole became uniform. The ratio of the number of moles of the (meth) acrylate group of the polyfunctional (meth) acrylate (A) to the number of moles of the mercapto group of the polyfunctional thiol (B) in the quantum dot-containing composition (X-12) thus obtained is , 1/0 (infinity by division by zero).

<Experimental Example 13>
100 parts of TMMP (manufactured by SC Organic Chemical Co., Ltd., trimethylolpropane tris (3-mercaptopropionate), mercapto group amount 7.53 mmol / g) as a polyfunctional thiol (B), and tetraethylthiolum as a reaction retarder (C). Eposter MS (Japan) with 0.002 parts of disulfide (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 0.4 parts of green quantum dots, 0.07 parts of red quantum dots, and scattering agent (E) as quantum dots (D). 5 parts of benzoguanamine / formaldehyde condensate particles manufactured by Catalyst Co., Ltd., 0.4 parts of Irgacure 184 (manufactured by BASF) as a photopolymerization initiator (F), and dispersion resin (G-6) as a dispersion resin (G). After blending 1.37 parts and shaking lightly by hand, stirring was performed with a homodisper until the whole became uniform. The ratio of the number of moles of the (meth) acrylate group of the polyfunctional (meth) acrylate (A) to the number of moles of the mercapto group of the polyfunctional thiol (B) in the quantum dot-containing composition (X-13) thus obtained is , 0.

<Experimental Example 14>
50 parts of PEMP (pentaerythritol tetrakis (3-mercaptopropionate), mercapto group amount 8.19 mmol / g) as polyfunctional thiol (B), manufactured by SC Organic Chemical Co., Ltd., and isobornyl methacrylate as other compounds. 50 parts (manufactured by Tokyo Kasei Co., Ltd., (meth) acrylate group amount 4.50 mmol / g), 0.002 parts of tetraethylthiuram disulfide (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a reaction retarder (C), quantum dots (D) 0.4 parts of green quantum dots, 0.07 parts of red quantum dots, 5 parts of Epostal MS (benzoguanamine / formaldehyde condensate particles manufactured by Nippon Catalyst Co., Ltd.) as a scattering agent (E), photopolymerization initiator As (F), 0.4 part of Irgacure 184 (manufactured by BASF) and 1.37 parts of dispersion resin (G-6) as dispersion resin (G) are blended, shake lightly by hand, and then the whole is homodisper. Stirring was performed until The ratio of the number of moles of the (meth) acrylate group of the polyfunctional (meth) acrylate (A) to the number of moles of the mercapto group of the polyfunctional thiol (B) in the quantum dot-containing composition (X-14) thus obtained is , 0.

<Experimental Example 15>
50 parts of AD-TMP (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., ditrimethylolpropanetetraacrylate, acrylate group amount 8.51 mmol / g) as polyfunctional (meth) acrylate (A), and octyl thioglycolate (Tokyo) as other compounds. 50 parts of mercapto group amount 4.89 mmol / g manufactured by Kasei Kogyo Co., Ltd., 0.5 part of triphenyl phosphite (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a reaction retarder (C), and quantum dots (D). 0.4 parts of green quantum dots, 0.07 parts of red quantum dots, 5 parts of Epostal MS (benzoguanamine / formaldehyde condensate particles manufactured by Nippon Catalyst Co., Ltd.) as a scattering agent (E), photopolymerization initiator (F) As a result, 0.4 part of Irgacure 184 (manufactured by BASF) and 1.37 parts of dispersion resin (G-6) as dispersion resin (G) are mixed, and after shaking lightly by hand, the whole is made uniform with homodisper. Stirring was performed until it became. The ratio of the number of moles of the (meth) acrylate group of the polyfunctional (meth) acrylate (A) to the number of moles of the mercapto group of the polyfunctional thiol (B) in the quantum dot-containing composition (X-15) thus obtained is , 0.43 / 0 (infinity by division by zero).

<Experimental Example 16>
As other compounds, 20 parts of triallyl isocyanurate (manufactured by Tokyo Kasei Kogyo Co., Ltd., allyl group amount 12.0 mmol / g) and isobornyl methacrylate (manufactured by Tokyo Kasei Co., Ltd., (meth) acrylate group amount 4.50 mmol / g) ) Is 25 parts, green quantum dots are 0.4 parts, red quantum dots are 0.07 parts, and eposter MS (benzoguanamine / formaldehyde condensate particles manufactured by Nippon Catalyst Co., Ltd.) is used as a scattering agent (E). ), 1 part of Irgacure TPO-L (manufactured by BASF) as a photopolymerization initiator (F), and 54 parts of a dispersion resin (G-3) as a dispersion resin (G), and shake lightly by hand. After that, stirring was performed with a homodisper until the whole was uniform. The ratio of the number of moles of the (meth) acrylate group of the polyfunctional (meth) acrylate (A) to the number of moles of the mercapto group of the polyfunctional thiol (B) in the quantum dot-containing composition (X-16) thus obtained is , 0/0 (infinity by division by zero).

<Experimental Example 17>
As the polyfunctional (meth) acrylate (A), 60 parts of AD-TMP (ditrimethylolpropanetetraacrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd., (meth) acrylate group amount 8.51 mmol / g) was used as the polyfunctional thiol (B). , PEMP (manufactured by SC Organic Chemical Co., Ltd., pentaerythritol tetrakis (3-mercaptopropionate) mercapto group amount 8.19 mmol / g) as 40 parts, quantum dot (D), green quantum dot 0.4 part, red 0.07 parts of quantum dots, 5 parts of Epostal MS (made by Nippon Catalyst Co., Ltd., benzoguanamine / formaldehyde condensate particles) as a scattering agent (E), and 0 parts of Irgacure 184 (manufactured by BASF) as a photopolymerization initiator (F). .4 parts, 1.37 parts of the dispersion resin (G-2) was blended as the dispersion resin (G), and after shaking lightly by hand, stirring was performed with a homodisper until the whole became uniform. The ratio of the number of moles of the (meth) acrylate group of the polyfunctional (meth) acrylate (A) to the number of moles of the mercapto group of the polyfunctional thiol (B) in the quantum dot-containing composition (X-17) thus obtained is , 1.56.

<Experimental Example 18>
As the polyfunctional (meth) acrylate (A), 60 parts of AD-TMP (ditrimethylolpropane tetraacrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd., (meth) acrylate group amount 8.51 mmol / g) was used as the polyfunctional thiol (B). , PEMP (SC Organic Chemical Co., Ltd., pentaerythritol tetrakis (3-mercaptopropionate), mercapto group amount 8.19 mmol / g) in 40 parts, triphenyl phosphite (Tokyo Kasei Kogyo) as a reaction retarder (C) 0.5 parts (manufactured by BASF), 0.4 parts of green quantum dots, 0.07 parts of red quantum dots, and Irgacure 184 (manufactured by BASF) as a photopolymerization initiator (F). 0.4 part and 1.37 parts of the dispersed resin (G-2) were blended as the dispersed resin (G), and after shaking lightly by hand, stirring was performed with a homodisper until the whole became uniform. The ratio of the number of moles of the (meth) acrylate group of the polyfunctional (meth) acrylate (A) to the number of moles of the mercapto group of the polyfunctional thiol (B) in the quantum dot-containing composition (X-18) thus obtained is , 1.56.

<Experimental Example 19>
As the polyfunctional (meth) acrylate (A), 60 parts of AD-TMP (ditrimethylolpropane tetraacrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd., (meth) acrylate group amount 8.51 mmol / g) was used as the polyfunctional thiol (B). , PEMP (SC Organic Chemical Co., Ltd., pentaerythritol tetrakis (3-mercaptopropionate), mercapto group amount 8.19 mmol / g) in 40 parts, tetraethylthiolam disulfide (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a reaction retarder (C). ) Is 0.004 parts, the quantum dots (D) are 0.4 parts, the red quantum dots are 0.07 parts, and the scattering agent (E) is Epostal MS (made by Nippon Catalyst Co., Ltd., benzoguanamine / formaldehyde condensation). 5 parts of the substance particles) and 1.37 parts of the dispersed resin (G-2) as the dispersed resin (G) were blended, shaken lightly by hand, and then stirred with a homodisper until the whole became uniform. The ratio of the number of moles of the (meth) acrylate group of the polyfunctional (meth) acrylate (A) to the number of moles of the mercapto group of the polyfunctional thiol (B) in the quantum dot-containing composition (X-19) thus obtained is , 1.56.

<Experimental Example 20>
As the polyfunctional (meth) acrylate (A), 35 parts of AD-TMP (ditrimethylolpropanetetraacrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd., (meth) acrylate group amount 8.51 mmol / g) was used as the polyfunctional thiol (B). , PEMP (SC Organic Chemical Co., Ltd., pentaerythritol tetrakis (3-mercaptopropionate), mercapto group amount 8.19 mmol / g) in 65 parts, tetraethylthiuram disulfide (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a reaction retarder (C). ) Is 0.004 parts, the quantum dots (D) are 0.4 parts, the red quantum dots are 0.07 parts, and the scattering agent (E) is Epostal MS (made by Nippon Catalyst Co., Ltd., benzoguanamine / formaldehyde condensation). Lightly blend 5 parts of particle), 0.4 parts of Irgacure 184 (manufactured by BASF) as a photopolymerization initiator (F), and 1.37 parts of dispersion resin (G-2) as a dispersion resin (G). After shaking by hand, stirring was performed with a homodisper until the whole was uniform. The ratio of the number of moles of the (meth) acrylate group of the polyfunctional (meth) acrylate (A) to the number of moles of the mercapto group of the polyfunctional thiol (B) in the quantum dot-containing composition (X-20) thus obtained is , 0.56.

<Experimental Example 21>
As the polyfunctional (meth) acrylate (A), 90 parts of AD-TMP (ditrimethylolpropanetetraacrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd., (meth) acrylate group amount 8.51 mmol / g) was used as the polyfunctional thiol (B). , PEMP (SC Organic Chemical Co., Ltd., pentaerythritol tetrakis (3-mercaptopropionate), mercapto group amount 8.19 mmol / g) in 10 parts, tetraethylthiuram disulfide (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a reaction retarder (C). ) Is 0.004 parts, the quantum dots (D) are 0.4 parts, the red quantum dots are 0.07 parts, and the scattering agent (E) is Epostal MS (made by Nippon Catalyst Co., Ltd., benzoguanamine / formaldehyde condensation). Lightly blend 5 parts of particle), 0.4 parts of Irgacure 184 (manufactured by BASF) as a photopolymerization initiator (F), and 1.37 parts of dispersion resin (G-2) as a dispersion resin (G). After shaking by hand, stirring was performed with a homodisper until the whole was uniform. The ratio of the number of moles of the (meth) acrylate group of the polyfunctional (meth) acrylate (A) to the number of moles of the mercapto group of the polyfunctional thiol (B) in the quantum dot-containing composition (X-21) thus obtained is , 9.36.

<Evaluation of pot life of quantum dot-containing composition (X)>
For the obtained quantum dot-containing compositions (X-1) to (X-21), the viscosity of the quantum dot-containing composition immediately after production was measured, and then the quantum dot-containing composition was transferred to a sample tube with a lid. The viscosity of the quantum dot-containing composition was measured again after allowing to stand in a roller-type stirrer for 24 hours in an environment of 25 ° C. The viscosity immediately after production and the rate of increase in viscosity after 24 hours were calculated from the following formulas, and the pot life of each quantum dot-containing composition was evaluated.
Viscosity increase rate (%) = (viscosity after 24 hours / viscosity immediately after preparation) x 100
Viscosity after 24 hours (cps)
Viscosity immediately after creation (cps)

The evaluation criteria are shown below.
⊚: Increase rate is less than 120%. Good.
〇: Increase rate of 120% or more and less than 150%. Practical use is possible.
Δ: Increase rate of 150% or more and less than 200%. Practical lower limit.
X: Increase rate of 200% or more or gel formation. Not practical.

The meanings of the abbreviations in Tables 2 and 3 are as follows.
A-DCP: A-DCP (dimethylol-tricyclodecanediacrylate) manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
A-TMPT: A-TMPT (trimethylolpropane triacrylate) manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
AD-TMP: AD-TMP (ditrimethylolpropane tetraacrylate) manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
A-DPH: A-DPH (dipentaerythritol hexaacrylate) manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
UV-7650B: Shikou UV-7650B (urethane acrylate) manufactured by Nippon Synthetic Chemical Industry Co., Ltd.
EGMP-4: SC Organic Chemical Co., Ltd., EGFP-4 (Tetraethylene Glycol Bis (3-Mercaptopropionate))
TMMP: Made by SC Organic Chemistry, TMMP (trimethylolpropane tris (3-mercaptopropionate))
PEMP: SC Organic Chemical Co., Ltd., PEMP (Pentaerythritol Tetrakis (3-mercaptopropionate))
MT PE1: Showa Denko, Calends MT PE1 (Pentaerythritol Tetrakis (3-mercaptobutyrate))
DPMP: Made by SC Organic Chemistry, DPMP (Dipentaerythritol Hexakis (3-mercaptopropionate))
D-918: Sakai Chemical Industry Co., Ltd., D-918 (rutile type titanium oxide)
MBX-5: Techpolymer MBX-5 (crosslinked polymethyl methacrylate particles) manufactured by Sekisui Plastics Co., Ltd.
MS: Epostal MS (benzoguanamine / formaldehyde condensate particles) manufactured by Nippon Shokubai Co., Ltd.
2000M: Nissan Chemical Industries, Ltd., Optobeads 2000M (melamine resin / silica composite particles)
Irg184: BASF, Irgacure 184 (alkylphenone-based photopolymerization initiator)
TPO: BASF, Irgacure TPO (acylphosphine oxide-based photopolymerization initiator)
TPO-L: BASF, Irgacure TPO-L (acylphosphine oxide-based photopolymerization initiator)

<Manufacturing of quantum dot-containing members>
Using the quantum dot-containing compositions (X-1) to (X-21) of Experimental Examples 1 to 21, sheet members (Y-1) to (Y-21) having a laminated structure were obtained according to the methods shown below. .. Tables 4 and 5 show the properties of the quantum dot-containing composition and sheet member used in the production and the results of the following performance tests.

Quantum dot-containing compositions (X-1) to (X-21) are placed on the primer-treated side of a PET film having a thickness of 125 μm (one side is matted and the other side is primed and has no barrier layer). Using a roll coater, the cured film made of the quantum dot-containing composition was applied so that the thickness was about 100 μm, and a PET film having the same composition and a thickness of 125 μm was bonded so that the primer-treated surface side became the ink-coated surface. .. Then, using an ultraviolet irradiation device (120 W / cm2 high-pressure mercury lamp), ^{ultraviolet irradiation was performed so that the integrated light amount was 1000 mJ / cm 2} , and the curing treatment was performed. Then, it was allowed to stand at 40 ° C. for 12 hours to complete the curing reaction. In this way, sheet members (Y-1) to (Y-21) having a thickness of about 350 μm were obtained.

(performance test)
<Evaluation of haze value and total light transmittance>
The haze values of the sheet members (Y-1) to (Y-21) and the total light transmittance were measured by the above-mentioned method.
<Evaluation of emission quantum yield of sheet member>
The emission quantum yields of the sheet members (Y-1) to (Y-21) were measured by the above-mentioned method. The evaluation criteria are shown below.
⊚: Quantum yield is 85% or more. Good.
〇: Quantum yield is 75% or more and less than 85%. Practical use is possible.
Δ: Quantum yield is 65% or more and less than 75%. Practical lower limit.
X: Quantum yield is less than 65%. Not practical.
<Evaluation of adhesion>
Using a 100 mm × 100 mm blade manufactured by Dumbbell, 10 sheet members (Y-1) to (Y-21) were punched out. At this time, the presence or absence of floating or peeling of the end portion of the sheet member was visually evaluated. The evaluation criteria are shown below.
◎: No floating or peeling. Good.
◯: One float and one peeling. Practical use is possible.
Δ: 2 floats and 2 peels. Practical lower limit.
X: 3 or more floats and peels. Not possible.
<Evaluation of durability over time>
Three sheet members (Y-1) to (Y-21) are cut out to 50 mm × 50 mm, respectively, and stored over time for 1000 hours under the following three level conditions. Emission peaks of green light and red light before and after storage over time. The strength maintenance rate was calculated by the following formula.
Maintenance rate of emission peak intensity (%) = (emission peak intensity after 1000 hours storage / emission peak intensity before storage) × 100
The storage conditions over time are as follows.
Condition 1: 60 ° C 90% RH with blue LED lighting Condition 2: 65 ° C 95% RH without blue LED lighting Condition 3: 85 ° C without blue LED lighting The evaluation criteria for durability over time are shown below.
⊚: Maintenance rate is 90% or more. Good.
〇: The maintenance rate is 75% or more and less than 90%. Practical useable Δ: Maintenance rate is 60% or more and less than 75%. Practical lower limit ×: Maintenance rate is less than 60%. Impractical

<Evaluation of edge fading of sheet members>
In the above evaluation of durability over time, the length of the part of the sheet members (Y-1) to (Y-21) that had been stored for 1000 hours under condition 1 was discolored from the end with a digital microscope (Keyence Co., Ltd.). 3 points were measured using VHS-5000), and the fading property was evaluated from the average value of the lengths. The evaluation criteria are shown below.
⊚: The faded part is less than 50 μm. Good.
◯: The faded part is 50 μm or more and less than 150 μm. Practical use is possible.
Δ: The faded portion is 150 μm or more and less than 250 μm. Practical lower limit.
X: The faded part is 250 μm or more. Not practical.

As shown in Tables 4 and 5, in Experimental Example 33, since the polyfunctional thiol (B) was not used, the oxygen barrier of the cured film was insufficient, and the durability and the edge fading property were remarkably deteriorated.

In Experimental Example 34, since the polyfunctional (meth) acrylate (A) was not used, the quantum dot-containing composition was not cured, the adhesive strength and oxygen barrier property were insufficient, and the adhesiveness, durability, and edge portion were not used. The fading property was significantly deteriorated.

In Experimental Example 35, since a monofunctional (meth) acrylate was used instead of the polyfunctional (meth) acrylate (A), the crosslink density of the cured film was insufficient, sufficient oxygen barrier properties could not be obtained, and durability and durability were improved. The edge fading was significantly worsened.

In Experimental Example 36, since a monofunctional thiol was used instead of the polyfunctional thiol (B), the crosslink density of the cured film was insufficient, sufficient oxygen barrier properties could not be obtained, and durability and edge fading were remarkable. It got worse.

In Experimental Example 37, a monofunctional (meth) acrylate and a low-reactivity polyfunctional allylate are used instead of the polyfunctional (meth) acrylate (A), so that the reaction retarder (C) is not used. However, a relatively good pot life was obtained, but the degree of cross-linking of the cured film was insufficient, sufficient oxygen barrier properties could not be obtained, and durability and edge fading were significantly deteriorated.

In Experimental Example 38, since the reaction retarder (C) was not used, significant thickening occurred in about 10 minutes after uniformly stirring, and various performance evaluations of the laminated body could not be performed because coating was not possible. It was.

Experimental Example 39 is an example in which the scattering agent (E) is not used. Although the durability and edge fading were excellent, it was found that the excitation light was not wavelength-converted by the quantum dots (D), making it difficult to select a sufficient optical path length.

Experimental Example 40 is an example in which the photopolymerization initiator (F) is not used. In this example, the cross-linking reaction hardly proceeded due to the irradiation with ultraviolet rays, and delamination occurred, so that various performance evaluations of the laminated body could not be performed. Therefore, a photopolymerization initiator (F) is used, or an additive that replaces the photopolymerization initiator (F) is required.

In Experimental Examples 41 and 42, the ratio of the number of moles of the (meth) acrylate group of the polyfunctional (meth) acrylate to the number of moles of the mercapto group of the polyfunctional thiol was too small or too large, and the crosslink density was too large. However, sufficient oxygen barrier properties could not be obtained, and durability and edge discoloration tended to deteriorate.

On the other hand, in Examples 22 to 32, the polyfunctional (meth) acrylate (A), the polyfunctional thiol (B), the reaction retarder (C), the scattering agent (D), the photopolymerization initiator (E), and the quantum dot emission It is a sheet member using a quantum dot-containing composition containing the body (F) in a suitable range, and has haze value, total light transmittance, emission quantum yield of the laminate, adhesion, durability, and edge. The fading property was satisfied in a well-balanced manner.
Among the above experimental examples, Experimental Examples 29 to 32 showed excellent performance.

Experimental Examples 29 to 32 were outside the range of Experimental Example 1 because the average number of functional groups per molecule of the polyfunctional (meth) acrylate (A) and the polyfunctional thiol (B) was in a suitable range of 2.5 or more. A sufficient cross-linking density of the cured film was obtained, and excellent durability and edge fading were obtained.
Since Experimental Examples 29 to 32 used the dispersant (G), an excellent emission quantum yield was obtained as compared with Experimental Example 23 in which the dispersant (G) was not used.

Since Experimental Examples 29 to 32 use melamine and / or fine particles having a benzoguanamine structure as a scattering agent, excellent emission quantum yields were obtained as compared with Experimental Examples 24 and 28 which were not used. ..

In Experimental Examples 29 to 32, the ratio of the number of moles of the (meth) acrylate group of the polyfunctional (meth) acrylate to the number of moles of the mercapto group of the polyfunctional thiol was in a more preferable range of 1.0 to 2.5. Therefore, a sufficient cross-linking density of the cured film was obtained as compared with Experimental Examples 25 and 26 outside the range, and excellent durability and edge fading were obtained.

In Experimental Examples 29 to 32, since the dispersant (G) uses at least one selected from acrylic resin, polyurethane resin, polyester resin, and polyethyleneimine resin, thioether resin is used. Compared with Experimental Example 27, the compatibility of the quantum dots (D) was improved, and an excellent emission quantum yield was obtained.

In the present invention, a quantum dot-containing composition having excellent pot life and capable of effectively suppressing changes in emission intensity over time and a quantum dot-containing member using the same can be obtained, and the quantum dot-containing member of the present invention can be used. It is possible to realize a backlight device, a light guide member, a display device, a liquid crystal display element, and the like having stable wavelength conversion characteristics.

1, 39: Quantum dot-containing member 2: Base film 3: Quantum dot layer 5: Quantum dot 5a: Core part 5b: Shell part 6: Organic ligand 10a, 10b: Resin film 20: Light emitting element 21: Composite quantum Dot-containing member 22: Diffusing plate 30a: First raw fabric roll 30b: Second raw fabric roll 32: Winding roll 33, 34: Nip roll 35: Joint portion 36: Coating means 37: Quantum dot-containing composition 38: Drying unit 40: Light guide plate 41: Curing reaction unit 50: Display device 52: Support 54: Display unit 55: Backlight device 60: Liquid crystal display element 61: Light guide plate 62, 64: Diffusion sheet 63: Prism sheet 65, 69 : Polarizing plates 66, 68: Phase difference film 67: Liquid crystal cell

Claims (4)

It contains a polyfunctional (meth) acrylate, a polyfunctional thiol, a reaction retarder, a quantum dot, a scattering agent, a dispersion resin, and a photopolymerization initiator.
The blending amount of the dispersed resin is in the range of 0.1% by mass or more and 5% by mass or less with respect to 100% by mass of the sum of the polyfunctional (meth) acrylate and the polyfunctional thiol. Stuff. The dispersed resin is at least one selected from an acrylic resin, a polyurethane resin, a polyester resin, and a polyethyleneimine resin, and the functional groups of the dispersed resin are a phosphoric acid group, an amino group, and a mercapto. The quantum dot-containing composition according to claim 1, wherein the group is selected from at least one of the groups. The ratio of the number of moles of the (meth) acrylate group of the polyfunctional (meth) acrylate to the number of moles of the mercapto group of the polyfunctional thiol is in the range of 1.52 or more and 9.0 or less. The quantum dot-containing composition according to claim 1 or 2. The quantum dot-containing composition according to any one of claims 1 to 3, wherein the scattering agent contains fine particles having at least one of melamine and a benzoguanamine structure.

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