JP2021182126A - Quantum dot-containing composition, and quantum dot-containing member using the quantum dot-containing composition, backlight device, display device, and liquid crystal display element - Google Patents

Abstract

To provide a quantum dot-containing composition which, especially, has a superior pot life, and contains quantum dots suitable to mass-production, and a quantum dot-containing member, a backlight device, display device, and a liquid crystal display element that use the quantum dot-containing composition to have superior temporal durability.SOLUTION: A quantum dot-containing composition includes multifunctional (meth)acrylate, multifunctional thiol, a reaction retarder, and quantum dots. In the present invention, a ratio of a mol number of a (meth)acrylate group of the multifunctional (meth)acrylate and a mole number of a mercapto group of the multifunctional thiol is preferably 0.6-9.0. The quantum dot-containing member is formed by curing the quantum dot-containing composition.SELECTED DRAWING: None

Description

The present invention relates to a quantum dot-containing composition containing quantum dots, a quantum dot-containing member using the quantum dot-containing composition, a backlight device, a display device, and a liquid crystal display element.

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 Document 1 and Patent Document 2 below, materials using quantum dots are being actively developed.

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 have the problem that the emission characteristics of quantum dots deteriorate over time. In particular, the deterioration progresses significantly 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 by producing a laminated film sandwiched between barrier films provided with an airtight layer by a method is disclosed.

However, the method disclosed in Patent Document 2 has a problem that coloring by the airtight layer deteriorates the optical properties, and the airtight layer is partially damaged when the laminated film is produced, so that the airtightness is partially airtight. 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 to solve the same problems as in Patent Document 2 by the method disclosed in Patent Document 3. Further, since the (meth) allyl compound has a lower reactivity than the (meth) acrylic compound, there is a problem that the unreacted (meth) allyl compound increases and the durability deteriorates.

Further, in the invention described in Patent Document 4, it is premised that barrier layers are provided on both sides of the quantum dot layer, and a quantum dot-containing member having excellent durability without using the barrier layer is not described.

Special Table 2016-511709 Publication No. Japanese Patent No. 5940079 International Publication No. 2018/0564669 Korean Patent No. 10-1969561 Japanese Unexamined Patent Publication No. 2017-032918 Japanese Unexamined Patent Publication No. 2019-086555 Japanese Unexamined Patent Publication No. 2018-1244112 Japanese Unexamined Patent Publication No. 2017-214486

The present invention has been made in view of the above-mentioned current situation, and in particular, a quantum dot-containing composition having an excellent pot life and containing quantum dots suitable for mass production, and the quantum dot-containing composition. It is an object of the present invention to provide a quantum dot-containing member, a backlight device, a display device, and a liquid crystal display element having excellent durability over time.

The quantum dot-containing composition in the present invention is characterized by containing a polyfunctional (meth) acrylate, a polyfunctional thiol, a reaction retarder, and quantum dots.

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 0.6 or more and 9.0 or less. Is preferable.
In the present invention, it is preferable that the reaction retarder is at least one selected from a phosphorous acid-based compound and a dithiocarbamate-based compound.

In the present invention, the reaction retarder is preferably contained in a range of 0.0005% by mass or more and 1% by mass or less with respect to 100% by mass of the sum of the polyfunctional (meth) acrylate and the polyfunctional thiol.

The quantum dot-containing composition in the present invention contains a polyfunctional (meth) acrylate, a polyfunctional thiol, a reaction retarder, and quantum dots, and the reaction retarder comprises a dithiocarbamate-based compound. And.

In the present invention, it is preferable to further contain a scattering agent and a photopolymerization initiator.

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

In the present invention, the dispersion resin is further contained, and the dispersion resin is at least one selected from an acrylic resin, a polyurethane resin, a polyester resin, and a polyethyleneimine resin, and the functional group of the dispersion resin is , Phosphoric acid group, amino group, and mercapto group are preferably selected from at least one.

In the present invention, the dispersed resin is preferably contained in a 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.

The quantum dot-containing composition in the present invention contains a polyfunctional (meth) acrylate, a polyfunctional thiol, a reaction retarder, a scattering agent, a photopolymerization initiator, and a quantum dot, and contains the polyfunctional (meth) acrylate. ) The ratio of the number of moles of the (meth) acrylate group of the acrylate to the number of moles of the mercapto group of the polyfunctional thiol is in the range of 0.8 or more and 5.5 or less.

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.

The quantum dot-containing member in the present invention is characterized in that the quantum dot-containing composition described above is cured.

In the present invention, it is preferable that the quantum dot layer is formed by curing the quantum dot-containing composition and a base film covering at least one surface of the quantum dot layer.

In the present invention, a quantum dot layer obtained by curing the quantum dot-containing composition, a base film covering one surface of the quantum dot layer, and a surface of the quantum dot layer opposite to the base film. It is preferable to have an optical member that comes into contact with the.

In the present invention, the optical member is preferably a light guide plate or a diffusion plate.

In the present invention, it is preferable that the barrier layer is not arranged on the surface of the quantum dot-containing member.

The backlight device in the present invention is characterized by including the quantum dot-containing member described above.

The display device in the present invention is characterized by including the quantum dot-containing member described above.

The liquid crystal display element of the present invention is characterized in that the quantum dot-containing member described above is incorporated in a backlight device.

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 can 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 schematic diagram of a quantum dot. It is a vertical sectional view of the quantum dot containing member which shows the 1st Embodiment of 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 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 vertical sectional view of the liquid crystal display element 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 sectional drawing which shows an example of the quantum dot containing member of this embodiment. It is sectional drawing which shows an example of manufacturing of the quantum dot containing member of this embodiment. It is sectional drawing of the quantum dot containing member provided with the base film on both sides of the quantum dot layer. It is sectional drawing of the quantum dot containing member which provided the base film only on one side of the quantum dot layer by peeling off one of the base films shown in FIG. 14A. It is a conceptual diagram which shows the manufacturing apparatus for manufacturing the quantum dot containing member of this embodiment. The relationship between the wavelength (400 nm to 700 nm) and the luminance performed by using the quantum dot-containing direct-type optical element provided with the partial reflection sheet and the quantum dot-containing direct-type optical element without the partial reflection sheet is shown. It is a graph. Wavelength (400 nm to 700 nm) performed using a quantum dot-containing direct optical element (with DBEF) equipped with a partially reflective sheet and a quantum dot-containing direct optical element (with DBEF) not provided with a partially reflective sheet. ) And the brightness. The relationship between the wavelength (500 nm to 700 nm) and the luminance performed by using the quantum dot-containing direct-type optical element provided with the partial reflection sheet and the quantum dot-containing direct-type optical element without the partial reflection sheet is shown. It is a graph. Wavelength (500 nm to 700 nm) performed using a quantum dot-containing direct optical element (with DBEF) equipped with a partially reflective sheet and a quantum dot-containing direct optical element (with DBEF) not provided with a partially reflective sheet. ) And the brightness. The relationship between the wavelength (400 nm to 700 nm) and the luminance performed using the quantum dot-containing edge type optical element provided with the partially reflective sheet and the quantum dot-containing edge type optical element not provided with the partially reflective sheet is shown. It is a graph. Wavelength (400 nm to 700 nm) performed using a quantum dot-containing edge-type optical element (with DBEF) provided with a partially reflective sheet and a quantum dot-containing edge-type optical element (with DBEF) not provided with a partially reflective sheet. ) And the brightness. The relationship between the wavelength (500 nm to 700 nm) and the luminance performed by using the quantum dot-containing edge type optical element provided with the partially reflective sheet and the quantum dot-containing edge type optical element not provided with the partially reflective sheet is shown. It is a graph. Wavelength (500 nm to 700 nm) performed using a quantum dot-containing edge-type optical element (with DBEF) provided with a partially reflective sheet and a quantum dot-containing edge-type optical element (with DBEF) not provided with a partially reflective sheet. ) And the brightness.

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 within the range.

The present inventors have, for example, developed a composition of a quantum dot-containing composition capable of improving durability without using (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 monofunctional, 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. Thereby, excellent durability can be obtained without arranging the barrier layer on the quantum dot-containing member formed by using the quantum dot-containing composition. 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 the polyfunctional (meth) acrylate and the polyfunctional thiol (B) described later with the photopolymerization initiator (F) described later. This cured film can dramatically improve the durability of the quantum dots (D) described later. It also has a function as an adhesive for bonding two plastic films to each other in producing a quantum dot-containing member (for example, a laminated film) described later.

The polyfunctional monomer used in the present embodiment is not limited to the following, but is not limited to, 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, hydroxypivalic acid neopentyl glycol ester diacrylate, caprolactone adduct diacrylate of hydroxypivalic acid neopentyl glycol ester, 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-triacrylloylhexahydro-s-triazine, pentaerythritol triacrylate, dipentaerythritol triacrylate tripropionate;
Pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate monopropionate, dipentaerythritol hexaacrylate, tetramethylolmethanetetraacrylate, oligoestertetraacrylate, tris (acryloyloxy) phosphate, etc. Examples thereof include acrylate monomers. These may be used alone or in combination of two or more.

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. be. 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, and 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, Trimethylol propanetris (3-mercaptopropionate), Trimethylol propanetris (3-mercaptobutyrate), Trimethylol propanetris (3-mercaptoisobutyrate), Trimethylol propane Tristhioglycolate, Tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4 6 (1H, 3H, 5H) -trion, trimethylolethane ethanetris (3-mercaptobutyrate), 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 in combination of two or more.

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.

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) 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. Alternatively, 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) used in the present embodiment (number of moles of acrylate group /). The number of moles of the mercapto group) is preferably in the range of 1.52 or more and 9.0 or less.

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

Examples of the reaction retarder (C) used in the present embodiment include, but are not limited to, phenolic compounds, phosphorous acid compounds, dithiocarbamate compounds and the like. 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 phosphite-based compound is not limited to the following, and for example, dimethyl phosphite, diethyl phosphite, dibutyl phosphite, diisopropyl phosphite, diisobutyl phosphite, diphenyl phosphite, etc. 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, tri-o-tolyl phosphite and the like. The dithiocarbamate-based compound is not limited to the following, but is not limited to, for example, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetraisopropylthiuram disulfide, tetrabutylthium disulfide, tetramethylthium monosulfide, and dipentamethylene thiuram tetrasulfide. And so on. These may be used alone or in combination of two or more.

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

The blending 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, curing inhibition can be suppressed in the curing reaction process at the time of manufacturing 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 emission and green light emission 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, SnVS, etc.
Group IV semiconductors such as Si, Ge, SiC, SiGe;
Alternatively, semiconductors obtained by doping these with a metal element such as Mn can be mentioned. These may be used alone or in combination of two or more.

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 to be coordinated.

The ligand used in this embodiment is 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 ( Aliphatic amine compounds such as lauryl amine: C ₁₂ H ₂₅ NH ₂ , decyl _{amine: C 10} H ₂₁ NH ₂ , octyl amine: C ₈ H ₁₇ NH _2;
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, Carboxylic acid: C ₉ H ₁₉ COOH, Octanoic acid: C ₇ H ₁₅ COOH and other fatty acid compounds;
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, tributylphosphine: (C ₄ H ₉ ) ₃ P
Phosphine oxide system, trioctylphosphine oxide: (C ₈ H ₁₇ ) ₃ P = O, triphenylphosphine oxide: (C ₆ H ₅ ) ₃ P = O, tributylphosphine oxide: (C ₄ H ₉ ) ₃ P = O And the like, phosphine meter compounds and the like can be mentioned.
These may be used alone or in combination of two or more.

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, but is not limited to, for example, CdS / ZnS, CdSe / ZnS, CdSeS / ZnSe, InP / ZnS, PbSe / PbS, CdTe / ZnS, ZnCdSe / ZnS, ZnCeTe. / ZnS, ZnSe / ZnS, ZnTe / ZnS, AgInGaS / ZnS, AgInS / ZnS, etc., and a structure in which the shell portion 5b has multiple layers, such as CdS / ZnSeS / ZnS, CdSe / ZnSeS / ZnS, etc. But it's okay. 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 solution to the surface of the core portion 5a.

The quantum dots (D) used in the present embodiment include quantum dots (hereinafter referred to as green quantum dots) showing green emission having a peak wavelength of 520 to 560 nm and red having a peak wavelength of 600 to 680 nm. Quantum dots exhibiting light emission (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 have absorbed this 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. Further, quantum dots having a full width at half maximum (FWHM) of 30 nm or less, preferably 25 nm or less, and more preferably 20 nm or less are preferably 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), thereby extending the optical path length, 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, polymethylmethacrylate-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 fine particles and benzoguanamine fine particles. These may be used alone or in combination of two or more. Further, these may be generally obtained by heterogeneous polymerization such as suspension polymerization, may be crosslinked inside the particles, or may 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 in combination of two or more. 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 in combination of two or more.

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 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% by mass or more and 8% by 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). NS. During 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 in combination of two or more.

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 in combination of two or more.

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, 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. As the photosensitizer, known photosensitizers can be used, for example, unsaturated ketones such as calcon 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, oxonoll derivatives and other polymethine dyes, aclysine derivatives, azine derivatives, thiadin 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, Thiospiropirane 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 this 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 dispersion 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 the in-plane variation in the brightness of the cured film made of the quantum dot-containing composition, and it is possible to suppress the decrease in the emission quantum yield due to the aggregation of the quantum dots (D).

The dispersed 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 resins, polyurethane resins, polyester resins, and polyethyleneimine resins from the viewpoint of excellent compatibility with polyfunctional (meth) acrylates (A) and polyfunctional thiols (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 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-based resin can be obtained by subjecting a polyol and a polyfunctional carbonate such as diethyl carbonate to a carbonate 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 the amino group generated after the reaction with a cyclic ester compound and performing ring-opening polymerization can also be used.

The epoxy resin can be 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) has 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 at the time of synthesizing 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 the curing process described later.

The solvent used in this 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 in combination of two or more.

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 retarder (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.

Further, a preferable form of the quantum dot-containing composition in the present embodiment includes a polyfunctional (meth) acrylate, a polyfunctional thiol, a reaction retarder, and a quantum dot, and the reaction retarder is a dithiocarbamate system. It is characterized by containing a compound. As shown in the experiment described later, the inclusion of tetraethylthiuram disulfide among the dithiocarbamate compounds makes it possible to obtain a good pot life as shown in the experiment described later.

Further, a preferable form of the quantum dot-containing composition in the present embodiment is to use a polyfunctional (meth) acrylate, a polyfunctional thiol, a reaction retarder, a scattering agent, a photopolymerization initiator, and a quantum dot. 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 0.8 or more and 5.5 or less, or is many. The ratio of the number of moles of the (meth) acrylate group of the functional (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. In Experimental Examples 1 and 2, Experimental Examples 5 to 11, and Experimental Examples 22, 23, and 26 to 32, which will be described later, favorable results were obtained in terms of haze value, total light transmittance (%), durability, and the like.

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 in combination of two or more.

<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 is optimal L, W, depending on the application. 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 near the end (edge) of the quantum dot-containing member 1 as compared with the conventional case. It is possible to effectively suppress the deterioration and fading of the quantum dot layer over time. The reason why deterioration can be suppressed by this embodiment is that the obtained quantum dot layer is a cured film having a high crosslink density due to the polyfunctional (meth) acrylate (A) and the polyfunctional thiol (B), and that it is polyfunctional. It is considered that this is because 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 in combination of two or more. 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 (primer treatment) 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 the excitation light and extract the 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 measuring 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 diffusing plate is incident on the composite quantum dot-containing member. Since the light diffused by the diffuser plate is incident on the composite quantum dot-containing member, the intensity distribution of the light 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 in the case 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 / the composite quantum dot-containing member 21 / the diffusion plate 22 / the display unit 54 can be arranged in this order. According to this, even if unevenness of emission color occurs at the joint of each quantum dot-containing member 1 due to diffused reflection or deterioration of the quantum dot due to water vapor entering from the joint, the display unit 54 displays the display unit 54. 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 in FIG. 9 is, 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, etc. The liquid crystal cell 67, the retardation film 68, and the polarizing plate 69 are laminated in this order. Although not limited, the quantum dot-containing member 1 of the present embodiment is provided, for example, between the light guide plate 61 and the diffusion sheet 62. Further, 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 underneath. The direct type is used for large displays and the like.

FIG. 10 is a structure in which the quantum dot-containing member 1 of the present embodiment is incorporated into the liquid crystal display element 60 having the structure shown in FIG. The members having the same reference numerals as those in FIG. 9 shown in FIG. 10 refer to the same members as those in FIG.

FIG. 10 has a direct-type LED sheet 80, unlike FIG. 9, and has a partially reflective sheet (partially reflective layer) 81 above the LED sheet 80. As the partially reflective sheet, "BLT" manufactured by 3M can be used.

As shown in FIG. 10, the quantum dot-containing member 1 is provided on the surface of the partially reflective sheet 81. The quantum dot-containing member 1 is coated on the surface of the partially reflective sheet 81, or the quantum dot-containing member 1 is a sheet material and the quantum dot-containing member 1 is attached to the surface of the partially reflective sheet 81. However, it does not matter.

Unlike FIG. 10, the liquid crystal display element 60 of the embodiment shown in FIG. 11 is an edge type. That is, the LED (light source) is located next to the element, and the light that has entered the light guide plate from the light source is sent upward by the light guide plate. In the embodiment shown in FIG. 11, the partial reflection sheet 81 is provided on the light guide plate 61, and the quantum dot-containing member 1 is provided on the surface of the partial reflection sheet 81.

The partial reflection sheet (partial reflection layer) 81 shown in FIGS. 10 and 11 transmits blue light and reflects red light and green light. Alternatively, the partially reflective sheet (partially reflective layer) 81 can reflect all red and green light and partially reflect blue light.

The LED emits blue light. Therefore, a part of the blue light is transmitted through the partially reflective sheet 81, and the quantum dot-containing member 1 is wavelength-converted to red light and / or green light. The wavelength-converted red light and green light are emitted upward by the partial reflection sheet 81 instead of downward.

Here, when a blue LED is used, in the configuration without the partial reflection sheet 81, when the blue light is wavelength-converted by the quantum dot-containing member 1, due to diffusion, diffuse reflection, etc., color unevenness and luminance unevenness ( Hello phenomenon) may occur. Therefore, by providing the partially reflective sheet 81 as in the present embodiment, it is possible to suppress the halo phenomenon. In particular, as shown in FIG. 10, it is effective when the number of LEDs increases in the direct type. Further, by reducing the transmission of blue light with the partially reflective sheet 81, the amount of blue light to be reused can be increased, and the brightness (emission intensity) can be improved. Therefore, high brightness can be obtained even if the quantum dots do not contain regulated heavy metals such as Cd and Pb.
The use of the quantum dot-containing member 1 of the present embodiment is not limited to FIGS. 6 to 11.

The quantum dot-containing member 1 used in the present embodiment can effectively suppress the 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 to a lighting device, a light source device, a light diffusing device, a light reflecting device, and the like, in addition to the above-mentioned backlight device, light guide member, and liquid crystal display element.

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.

Further, as shown in FIG. 12, in the quantum dot-containing member 1 of the present embodiment, the base film 2 is provided only on one side of the quantum dot layer 3, and the base film 2 on the opposite side of the quantum dot layer 3 is provided. It is possible to have a structure in which the optical member 70 is in contact with the surface. As a result, the optical member 70 can be brought into close contact with the opposite surface of the quantum dot layer 3 while protecting one side of the quantum dot layer 3 with the base film 2. As the optical member 70, a light guide plate or a diffusion plate can be preferably applied. The quantum dot-containing member 1 can be applied to a backlight device, a display device, and a lighting device.

In the quantum dot-containing member 1 shown in FIG. 12, the quantum dot-containing composition of the present embodiment is directly applied to the surface of the optical member 70, and the base film 2 is further laminated and heat-cured. It is possible to form a laminated structure of an optical member / quantum dot layer / base film.

For example, as shown in FIG. 13, the surface of the quantum dot-containing sheet 71 in which the substrate film 2 is provided only on one side of the quantum dot layer 3 is opposed to the optical member 70 so that the surface of the quantum dot-containing sheet 71 is not provided. The quantum dot-containing sheet 71 and the optical member 70 are brought into close contact with each other. At this time, the quantum dot-containing sheet 71 and the optical member 70 may be bonded via an adhesive layer, or the quantum dot-containing sheet 71 may be directly adhered to the surface of the optical member 70. be.

As shown in FIG. 14A, the quantum dot-containing sheet 71 includes, for example, a first base film 73 bonded to one side of the quantum dot layer 3 via a primer layer 72, and a first base film 73. Has a second substrate film 74, which is directly bonded to the opposite surface of the quantum dot layer 3. Thereby, both sides of the quantum dot layer 3 can be protected by the base films 73 and 74. As an example, the base films 73 and 74 can be formed of a PET film. Further, the first base film 73 can be used as a PET film, and the second base film 74 can be used as a PE film. Alternatively, a PEN (polyethylene naphthalate) film may be used instead of the PET film or the PE film.

In the quantum dot-containing sheet 71, the adhesion between the first base film 72 and the quantum dot layer 3 is stronger than the adhesion between the second base film 73 and the quantum dot layer 3. Then, as shown in FIG. 13, at the stage of attaching the quantum dot-containing sheet 71 to the surface of the optical member 70, the second base film 73 of the quantum dot-containing sheet 71 is peeled off to be exposed. The quantum dot-containing member 1 shown in FIG. 12 can be obtained by subjecting the surface of the quantum dot layer 3 to the surface of the optical member 70.

FIG. 15 shows a conceptual diagram showing a manufacturing apparatus for manufacturing the quantum dot-containing member 1 of the present embodiment. FIG. 15 discloses an example of a method for manufacturing a quantum dot-containing member 1 in which a quantum dot layer 3 is formed by applying a quantum dot-containing composition to a base film 2 and curing it, as shown in FIG. ing.

As shown in FIG. 15, the first raw fabric roll 30a for feeding out the resin film 10a to be the base film 2 and the second raw fabric roll 30b for feeding out the resin film 10b also to be 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 40.

As shown in FIG. 15, 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. do. Examples of the coating method of the quantum dot-containing composition 37 include a coating method using a known coating coater or 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. 15, 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. do. When the quantum dot-containing composition 37 does not contain a solvent, the drying portion 38 may not be used.

Next, at the bonding 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 bonded 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 beam 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 take-up 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 in an environment of an appropriate aging temperature for an appropriate time in order to completely proceed the curing reaction. 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 2 minutes of the base film used from the average thickness obtained by measuring the thickness of the quantum dot-containing member 1 at 3 points or more using a micrometer. Calculated by subtracting the thickness.

Further, using the manufacturing apparatus shown in FIG. 15, as shown in FIG. 14B, the primer layer 72 is provided only on one side of the quantum dot layer 3, and the adhesion between the quantum dot layer 3 and the base films 72 and 73 is increased. It is possible to manufacture the quantum dot-containing film member 71 having different values.

Further, using the manufacturing apparatus shown in FIG. 15, it is possible to manufacture a quantum dot-containing film member in which the base film is provided only on one side of the quantum dot layer. In this case, it is not necessary to use the second original roll 30b and the nip rolls 33 and 34.

In the above embodiments, all of the film-shaped quantum dot-containing members have been exemplified, but the shape is not limited thereto. 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, use tetrahydrofuran as the eluent, and use the HLC-8220GPC system manufactured by Tosoh Corporation, which connects two columns of TSKgel superHZM-N as a measuring instrument, to set the column temperature to 40 ° C and flow rate. It was measured 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 eluent. 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 to the column or the like.

<Measurement of quantum yield>
Using the quantum dot (D) and the quantum dot-containing member 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 dot (D) described later as a sample, the peak wavelength and full width at half maximum of light emission were measured using a spectrofluorometer (FP-8500, manufactured by Nippon Spectroscopy Co., Ltd.) 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 described later was determined from the average value 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 the obtained quantum dot-containing member described later cut to a width of 50 mm and a length of 50 mm as a sample. In accordance with the law, the total light transmittance and the haze value were measured three times. Then, the values of the three-time average were taken 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 a 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 dot powders 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% (hereinafter referred to as red quantum dots) 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, 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 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 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, 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)>
In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, nitrogen introduction pipe, and vacuum pipe, 86.9 parts of pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by Tokyo Kasei Co., Ltd.) are charged 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), SOLSERSE (registered trademark) 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 (registered trademark) PB821 (a polyester resin having an amino group manufactured by Ajinomoto Fine-Techno Co., Ltd.) was used.

<Manufacturing example (6)>
As the dispersion resin (G-6), DISPERBYK (registered trademark) -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, (meth) acrylate group amount 6.58 mmol / g, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 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). 1 copy (manufactured by Nippon Shokuhin), 0.4 copies of green quantum dots, 0.07 copies of red quantum dots, and Eposter (registered trademark) MS (manufactured by Nippon Catalyst Co., Ltd.) as a scattering agent (E). 5 parts of benzoguanamine / formaldehyde condensate particles), 0.3 parts of Irgacure (registered trademark) 184 (manufactured by BASF) as a photopolymerization initiator (F), and dispersion resin (G-1) as a dispersion resin (G). After blending 1.37 parts and shaking lightly by hand, stirring was performed with 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-1) thus obtained is It was 1.84.

<Experimental Example 2>
50 parts of A-TMPT (trimethylolpropane triacrylate, (meth) acrylate group amount 10.0 mmol / g) manufactured by Shin-Nakamura Chemical Industry Co., Ltd. as polyfunctional (meth) acrylate (A), Shikou UV-7650B (synthesized in Japan) , Urethane aclate resin, acrylate group amount 0.0004 part), TMMP (manufactured by SC Organic Chemical Co., Ltd., trimethylolpropane tris (3-mercaptopropionate), mercapto group amount as polyfunctional thiol (B) 7.53 mmol / g) as 45 parts, trimethylolpropane (manufactured by Tokyo Chemical Industry Co., Ltd.) as 0.5 part as a reaction retarder (C), and green quantum dots as 0.4 parts as quantum dots (D). , 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), and Irgacure 184 (manufactured by BASF) as a photopolymerization initiator (F). Was mixed in 0.6 parts, shaken lightly by hand, and then stirred 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-2) thus obtained is , 1.48.

<Experimental example 3>
20 parts of A-TMPT (trimethylolpropane triacrylate, (meth) acrylate group amount 10.0 mmol / g) manufactured by Shin-Nakamura Chemical Industry Co., Ltd. as polyfunctional (meth) acrylate (A), AD-TMP (New Nakamura Chemical Co., Ltd.) 30 parts of ditrimethylolpropane tetraacrylate, (meth) acrylate group base, 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) 50 parts, tetraethylthiuram 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, techpolymer (registered trademark) MBX-5 (manufactured by Sekisui Kasei Kogyo Co., Ltd., crosslinked polymethylmethacrylate particles) as a scattering agent (E) 5 parts, light 0.2 parts of Irgacure 184 (manufactured by BASF) as the polymerization initiator (F) and 1.37 parts of the dispersion resin (G-4) as the dispersion resin (G) are blended, shaken lightly by hand, and then homozygous. Stirring was performed with a disper 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-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 Industry Co., Ltd., (meth) acrylate group group amount 8.51 mmol / g), polyfunctional thiol (B) 40 parts of PEMP (SC Organic Chemical Co., Ltd., pentaerythritol tetrakis (3-mercaptopropionate), mercapto group amount 8.19 mmol / g), 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., rutile type titanium oxide) as a scattering agent (E), opt beads (registered) Trademark) 2000M (manufactured by Nissan Chemical Co., Ltd., melamine resin / silica composite particles) is 4 parts, Irgacure TPO (manufactured by BASF) is 0.3 parts as a photopolymerization initiator (F), and dispersion resin (G) is a dispersion resin (G). 1.37 parts of G-6) 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-4) thus obtained is 0. It was 87.

<Experimental Example 5>
As the polyfunctional (meth) acrylate (A), 80 parts of A-TMPT (trimethylol propantriacrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd., (meth) acrylate group amount 10.0 mmol / g) was used as the polyfunctional thiol (B). 20 parts of TMMP (SC Organic Chemical Co., Ltd., trimethylolpropanthris (3-mercaptopropionate), mercapto group amount 7.53 mmol / g), tetraethylthium 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 dispersion resin (G-6) was blended as the dispersion 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>
50 parts of A-TMPT (trimethylol propanetriacrylate, (meth) acrylate group amount 10.0 mmol / g) manufactured by Shin-Nakamura Chemical Industry Co., Ltd. as polyfunctional (meth) acrylate (A), A-DPH (New Nakamura Chemical Co., Ltd.) 5 parts of dipentaerythritol hexaacrylate, (meth) acrylate group, manufactured by Kogyo Co., Ltd., as polyfunctional thiol (B), PEMP (manufactured by SC Organic Chemical Co., Ltd., pentaerythritol tetrakis (3-mercaptopropio) Nate), 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, As the reaction retarder (C), triphenyl phosphite (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was 0.3 parts, and as the quantum dots (D), green quantum dots were 0.4 parts and red quantum dots were 0.07 parts. 7 parts of Eposter 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 (trimethylol propantriacrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd., (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., PEMP (SC Organic Chemical Co., Ltd., pentaerythritol tetrakis (3-mercaptopropio) as polyfunctional thiol (B) Nate), 35 parts of mercapto group amount 8.19 mmol / g), 0.002 part of tetraethylthiuram disulfide (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a reaction retarder (C), and green quantum dots as quantum dots (D). 0.4 part, red quantum dot 0.07 part, as a scattering agent (E), D-918 (manufactured by Sakai Chemical Industry Co., Ltd., rutile type titanium oxide) 1.0 part, as a photopolymerization initiator (F) Add 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), and 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>
40 parts of A-TMPT (trimethylolpropane triacrylate, (meth) acrylate group amount 10.0 mmol / g) manufactured by Shin-Nakamura Chemical Industry Co., Ltd. as polyfunctional (meth) acrylate (A), AD-TMP (New Nakamura Chemical Co., Ltd.) 15 parts of ditrimethylolpropane tetraacrylate, (meth) acrylate group, manufactured by Kogyo Co., Ltd., as polyfunctional thiol (B), Karenz (registered trademark) MT PE1 (Pentaerythritol tetrakis, manufactured by Showa Denko Co., Ltd.) (3-Mercaptobutyrate), mercapto group amount 7.34 mmol / g) as 45 parts, tetraethylthium disulfide (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a reaction retarder (C) 0.002 parts, as 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 ( Add 0.3 parts of Irgacure 184 (manufactured by BASF) as F) and 1.37 parts of dispersion resin (G-2) 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-8) thus obtained is , 1.60.

<Example 9>
As polyfunctional (meth) acrylate (A), 50 parts of A-TMPT (Trimethylol propantriacrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd., (meth) acrylate group amount 10.0 mmol / g), AD-TMP (New Nakamura Chemical Co., Ltd.) Ditrimethylol propanetetraacrylate manufactured by Kogyo Co., Ltd., (meth) acrylate group amount 8.51 mmol / g) as 10 parts, polyfunctional thiol (B), PEMP (SC Organic Chemical Co., Ltd., pentaerythritol tetrakis (3-mercaptopro) Pionate), mercapto group amount 8.19 mmol / g) 40 parts, tetraethylthiuram 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 part, red quantum dot 0.07 part, as a scattering agent (E), D-918 (manufactured by Sakai Chemical Industry Co., Ltd., rutile type titanium oxide) 0.2 part, Optobeads 2000M (Nissan Chemical Co., Ltd.) (Meramine resin / silica composite particles) 4.5 parts, Irgacure 184 (manufactured by BASF) 0.2 parts as a photopolymerization initiator (F), 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 (Trimethylol propantriacrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd., (meth) acrylate group amount 10.0 mmol / g), AD-TMP (New Nakamura Chemical Co., Ltd.) Ditrimethylol propanetetraacrylate manufactured by Kogyo Co., Ltd., (meth) acrylate group amount 8.51 mmol / g) as 10 parts, polyfunctional thiol (B), PEMP (SC Organic Chemical Co., Ltd., pentaerythritol tetrakis (3-mercaptopro) Pionate), mercapto group amount 8.19 mmol / g) 40 parts, tetraethylthiuram 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 part, red quantum dot 0.07 part, as a scattering agent (E), D-918 (manufactured by Sakai Chemical Industry Co., Ltd., rutile type titanium oxide) 0.2 part, Optobeads 2000M (Nissan Chemical Co., Ltd.) (Meramine resin / silica composite particles) 4.5 parts, Irgacure 184 (manufactured by BASF) 0.2 parts as a photopolymerization initiator (F), 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>
50 parts of A-TMPT (trimethylol propanetriacrylate, (meth) acrylate group amount 10.0 mmol / g) manufactured by Shin-Nakamura Chemical Industry Co., Ltd. as polyfunctional (meth) acrylate (A), AD-TMP (New Nakamura Chemical Co., Ltd.) Ditrimethylol propanetetraacrylate manufactured by Kogyo Co., Ltd., (meth) acrylate group amount 8.51 mmol / g) as 10 parts, polyfunctional thiol (B), PEMP (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 As a reaction retarder (C), tetraethylthiolam disulfide (manufactured by Tokyo Chemical Industry Co., Ltd.) was 0.003 parts, and as quantum dots (D), green quantum dots were 0.4 parts, red quantum dots were 0.07 parts, and 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 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) are mixed lightly. 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 (trimethylolpropane triacrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd., (meth) acrylate group amount 10.0 mmol / g) was used as the reaction retarder (C). Eposter MS with 0.002 parts of tetraethylthium disulfide (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 0.4 parts of green quantum dots, 0.07 parts of red quantum dots, and scatter agent (E) as quantum dots (D). 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 compounded in 1.37 parts, shaken lightly by hand, and then stirred 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-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., trimethyl propanthris (3-mercaptopropionate), mercapto group amount 7.53 mmol / g) as a polyfunctional thiol (B), and tetraethylthiuram 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 scatter agent (E) as quantum dots (D). 5 parts of benzoguanamine / formaldehyde condensate particles manufactured by Catalyst Co., 0.4 parts of Irgacure 184 (manufactured by BASF) as a photopolymerization initiator (F), and dispersion resin (G-6) as a dispersion resin (G). 1.37 parts 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-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 Chemistry Co., Ltd., and isobornyl methacrylate as other compounds. (Made by Tokyo Kasei Co., Ltd., (meth) acrylate group amount 4.50 mmol / g) 50 parts, tetraethylthium disulfide (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a reaction retarder (C) 0.002 parts, 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), a 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 mixed, shake lightly by hand, and then the whole is shaken with a homodisper. Stirring was performed until the mixture 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-14) thus obtained is , 0.

<Experimental Example 15>
50 parts of AD-TMP (ditrimethylolpropanetetraacrylate, acrylate group amount 8.51 mmol / g) manufactured by Shin-Nakamura Chemical Industry Co., Ltd. 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) Add 0.4 part of Irgacure 184 (manufactured by BASF) and 1.37 parts of dispersion resin (G-6) as dispersion resin (G), shake lightly by hand, and then use homodisper to make the whole uniform. 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 / formyl 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 the photopolymerization initiator (F), and 54 parts of the dispersion resin (G-3) as the 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 (SC Organic Chemical Co., Ltd., pentaerythritol tetrakis (3-mercaptopropionate) mercapto group amount 8.19 mmol / g) 40 parts, quantum dots (D) 0.4 parts green quantum dots, red 0.07 parts of quantum dots, 5 parts of Epostal MS (benzoguanamine / formaldehyde condensate particles manufactured by Nippon Catalyst Co., Ltd.) 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) as the dispersion resin (G) 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-17) thus obtained is , 1.56.

<Experimental Example 18>
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 (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 part of the product), 0.4 part of the green quantum dot (D), 0.07 part of the red quantum dot, and Irgacure 184 (manufactured by BASF) as the photopolymerization initiator (F). 0.4 part and 1.37 parts of the dispersed resin (G-2) were blended as the dispersed resin (G), and the mixture was lightly shaken 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-18) thus obtained is , 1.56.

<Experimental Example 19>
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 (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 part, the quantum dot (D) is 0.4 part, the red quantum dot is 0.07 part, and the scattering agent (E) is Epostal MS (Bonzoguanamine / formaldehyde condensation manufactured by Nippon Catalyst Co., Ltd.). 5 parts of the substance particles) and 1.37 parts of the dispersed resin (G-2) as the dispersed resin (G) were mixed, 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, tetraethylthium disulfide (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a reaction retarder (C). ) As 0.004 parts, as quantum dots (D), 0.4 parts as green quantum dots, 0.07 parts as red quantum dots, and as a scattering agent (E), Epostal MS (Benzoguanamine / formaldehyde condensation manufactured by Nippon Catalyst Co., Ltd.). 5 parts of the particle), 0.4 part of Irgacure 184 (manufactured by BASF) as the photopolymerization initiator (F), and 1.37 parts of the dispersed resin (G-2) as the dispersed resin (G) are mixed lightly. 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, tetraethylthium disulfide (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a reaction retarder (C). ) As 0.004 parts, as quantum dots (D), 0.4 parts as green quantum dots, 0.07 parts as red quantum dots, and as a scattering agent (E), Epostal MS (Benzoguanamine / formaldehyde condensation manufactured by Nippon Catalyst Co., Ltd.). 5 parts of the particle), 0.4 part of Irgacure 184 (manufactured by BASF) as the photopolymerization initiator (F), and 1.37 parts of the dispersed resin (G-2) as the dispersed resin (G) are mixed lightly. 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 is possible.
Δ: Increase rate is 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-tricyclodecandiacrylate) 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., EGMP-4 (Tetraethylene Glycol Bis (3-Mercaptopropionate))
TMMP: TMMP (trimethylolpropanetris (3-mercaptopropionate)) manufactured by SC Organic Chemistry Co., Ltd.
PEMP: SC Organic Chemical Co., Ltd., PEMP (Pentaerythritol Tetrakis (3-mercaptopropionate))
MT PE1: Showa Denko, Calends MT PE1 (Pentaerythritol Tetrakis (3-mercaptobutyrate))
DPMP: SC Organic Chemical Co., Ltd., DPMP (Dipentaerythritol Hexakis (3-mercaptopropionate))
D-918: D-918 (rutile type titanium oxide) manufactured by Sakai Chemical Industry Co., Ltd.
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 surface side of a PET film having a thickness of 125 μm (matting treatment on one side and primer treatment on the opposite side and 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-applied surface. .. Then, using an ultraviolet irradiation device (120 W / cm ² 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 degreeC 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 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.
◯: Floating and peeling is one. Practical is possible.
Δ: 2 floats and 2 peels. Practical lower limit.
×: 3 or more floats and peels. Not possible.
<Evaluation of durability over time>
Three sheet members (Y-1) to (Y-21) are cut into 50 mm × 50 mm pieces, and stored 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 △: 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 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). 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 fading part is less than 50 μm. Good.
◯: The fading portion is 50 μm or more and less than 150 μm. Practical is possible.
Δ: The fading portion is 150 μm or more and less than 250 μm. Practical lower limit.
X: The fading 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 significantly deteriorated.

In Experimental Example 34, since the polyfunctional (meth) acrylate (A) is not used, the quantum dot-containing composition does not cure, the adhesive strength and oxygen barrier property are insufficient, and the adhesion, durability, and edge portion are insufficient. 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 obtained. 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 discoloration were remarkably significant. 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, although a relatively good pot life was obtained, 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. rice field.

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 is too small or too large, and the cross-linking density is too high. 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 are emitted. It is a sheet member using a quantum dot-containing composition containing the body (F) in a suitable range, and has a haze value, total light transmittance, emission quantum yield of the laminate, adhesion, durability, and edges. The fading property was satisfied in a well-balanced manner.
Among the above experimental examples, Experimental Examples 29 to 32 showed excellent performance.

In Experimental Examples 29 to 32, 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, and therefore Experimental Example 1 was out of the range. A sufficient crosslink 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 is 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, a 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.

<Brightness experiment with and without partial reflection sheet>
In the experiment, the following samples were used.
(Sample 1)
Directly below BL (blue light) + QD sheet + prism (sample 2)
Direct BL (blue light) + QD coated BLT sheet + prism (sample 3)
Directly below BL (blue light) + BLT sheet + QD sheet + prism (sample 4)
Directly below BL (blue light) + QD sheet + prism + DBEF
(Sample 5)
Direct BL (blue light) + QD coated BLT sheet + prism + DBEF
(Sample 6)
Direct BL (blue light) + BLT sheet + QD sheet + prism + DBEF

The BLT sheet is a partially reflective sheet manufactured by 3M. The QD sheet contains quantum dots that emit red and green light. The QD-coated BLT sheet is obtained by coating the surface of the BLT sheet with a QD liquid containing quantum dots that emit red or green light to form a QD layer. DBEF is a reflective polarizing film (Dual Brightness Enhancement Film) manufactured by 3M.

In the experiment, the relationship between the wavelength and the brightness (emission intensity) was measured by dividing into each group of Samples 1 to 3 and Samples 4 to 6. A spectroscopic fluorometer (manufactured by JASCO Corporation, FP-8500) was used to measure the emission intensity.

FIG. 16 is a graph showing the relationship between the wavelength of 400 nm to 700 nm and the emission intensity in Samples 1 to 3. FIG. 17 is a graph showing the relationship between the wavelengths of 400 nm to 700 nm and the emission intensity in Samples 4 to 6. FIG. 18 is a graph showing the relationship between the wavelength of 500 nm to 700 nm and the emission intensity in Samples 1 to 3. FIG. 19 is a graph showing the relationship between the wavelength of 500 nm to 700 nm and the emission intensity in Samples 4 to 6. In FIGS. 18 and 19, the range of the emission intensity on the vertical axis is expanded as compared with FIGS. 16 and 17.

As shown in FIGS. 16 and 17, the blue emission intensity was high in Samples 1 and 4 having no partially reflective sheet. On the other hand, in the samples 2, 3, 5, and 6 having the partially reflective sheet, the blue emission intensity could be suppressed.

Further, as shown in FIGS. 18 and 19, in Samples 1 and 4 having no partially reflective sheet, the red emission intensity and the green emission intensity were lowered, and in comparison with this, Sample 2 having the partially reflective sheet, In 3, 5 and 6, the red emission intensity and the green emission intensity could be increased.

(Sample 7)
Edge BL (blue light) + QD sheet + prism (sample 8)
Edge BL (blue light) + QD coated BLT sheet + prism (sample 9)
Edge BL (blue light) + BLT sheet + QD sheet + prism (sample 10)
Edge BL (blue light) + QD sheet + prism + DBEF
(Sample 11)
Direct BL (blue light) + QD coated BLT sheet + prism + DBEF
(Sample 12)

Edge BL (blue light) + BLT sheet + QD sheet + prism + DBEF
Samples 7 to 12 are experimental examples in which an edge BL is used instead of the BL directly under the samples 1 to 6. That is, Samples 1 to 6 have a direct type configuration shown in FIG. 10, and Samples 7 to 7 have an edge type configuration shown in FIG.

FIG. 20 is a graph showing the relationship between the wavelengths of 400 nm to 700 nm and the emission intensity in Samples 7 to 9. FIG. 21 is a graph showing the relationship between the wavelength of 400 nm to 700 nm and the emission intensity in the samples 10 to 12. FIG. 22 is a graph showing the relationship between the wavelength of 500 nm to 700 nm and the emission intensity in Samples 7 to 9. FIG. 23 is a graph showing the relationship between the wavelength of 500 nm to 700 nm and the emission intensity in the samples 10 to 12. In FIGS. 22 and 23, the range of the emission intensity on the vertical axis is expanded as compared with FIGS. 20 and 21.

As shown in FIGS. 20 and 22, the blue emission intensity is higher in the sample 7 and the sample 10 having no partially reflective sheet, and in comparison with this, in the samples 8, 9, 11 and 12 having the partially reflective sheet. , The blue emission intensity could be suppressed.

Further, as shown in FIGS. 22 and 23, in the samples 7 and 10 having no partially reflective sheet, the red emission intensity and the green emission intensity were lowered, and in comparison with this, the sample 8 having the partially reflective sheet, In 9, 11 and 12, the red emission intensity and the green emission intensity could be increased.

As described above, by using the partially reflective sheet, it is possible to increase the luminance emission intensity and the green emission intensity while suppressing the blue emission intensity, and the white light emitted by wavelength-converting the light from the blue LED. It was found that the brightness can be increased and the uneven brightness can be suppressed.

There was no significant difference in emission intensity between the case where the QD was applied to the surface of the BLT sheet and the case where the QD sheet was laminated on the BLT sheet.

In the present invention, it is possible to obtain a quantum dot-containing composition having excellent pot life and effectively suppressing changes in emission intensity over time and a quantum dot-containing member using the same, and using the quantum dot-containing member of the present invention. 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 (19)

A quantum dot-containing composition comprising a polyfunctional (meth) acrylate, a polyfunctional thiol, a reaction retarder, and quantum dots. 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 0.6 or more and 9.0 or less. The quantum dot-containing composition according to claim 1. The quantum dot-containing composition according to claim 1 or 2, wherein the reaction retarder is at least one selected from a phosphorous acid-based compound and a dithiocarbamate-based compound. 3. The reaction retarder is characterized by being contained in a range of 0.0005% by mass or more and 1% by mass or less with respect to 100% by mass of the sum of the polyfunctional (meth) acrylate and the polyfunctional thiol. The quantum dot-containing composition according to. A quantum dot-containing composition comprising a polyfunctional (meth) acrylate, a polyfunctional thiol, a reaction retarder, and a quantum dot, wherein the reaction retarder contains a dithiocarbamate-based compound. The quantum dot-containing composition according to any one of claims 1 to 5, further comprising a scattering agent and a photopolymerization initiator. The quantum dot-containing composition according to claim 6, wherein the scattering agent contains fine particles having at least one of melamine and a benzoguanamine structure. In addition, it contains a dispersion resin
The dispersed resin is at least one selected from an acrylic resin, a polyurethane resin, a polyester resin, and a polyethyleneimine resin.
The quantum dot-containing composition according to any one of claims 1 to 7, wherein the functional group of the dispersion resin is selected from at least one of a phosphoric acid group, an amino group, and a mercapto group. thing. 8. The dispersion resin is characterized by being contained in a 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. The quantum dot-containing composition according to. It contains a polyfunctional (meth) acrylate, a polyfunctional thiol, a reaction retarder, a scattering agent, a photopolymerization initiator, and quantum dots.
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 0.8 or more and 5.5 or less. 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 in the range of 1.52 or more and 9.0 or less. The quantum dot-containing composition according to claim 10. A quantum dot-containing member obtained by curing the quantum dot-containing composition according to any one of claims 1 to 11. The quantum dot-containing member according to claim 12, further comprising a quantum dot layer obtained by curing the quantum dot-containing composition and a base film covering at least one surface of the quantum dot layer. .. Optics that abuts the quantum dot layer obtained by curing the quantum dot-containing composition, the base film that covers one surface of the quantum dot layer, and the surface of the quantum dot layer opposite to the base film. The quantum dot-containing member according to claim 13, wherein the member has a member. The quantum dot-containing member according to claim 14, wherein the optical member is a light guide plate or a diffusion plate. The quantum dot-containing member according to any one of claims 12 to 15, wherein the barrier layer is not arranged on the surface of the quantum dot-containing member. A backlight device comprising the quantum dot-containing member according to any one of claims 12 to 16. A display device comprising the quantum dot-containing member according to any one of claims 12 to 16. A liquid crystal display element according to any one of claims 12 to 16, wherein the quantum dot-containing member is incorporated in a backlight device.

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